Ultra-High Temperature Materials IV: Refractory Carbides III (W Carbides) 3031071743, 9783031071744

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Ultra-High Temperature Materials IV

Igor L. Shabalin

Ultra-High Temperature Materials IV Refractory Carbides III (W Carbides) A Comprehensive Guide and Reference Book

123

Igor L. Shabalin Materials and Physics Research Centre The University of Salford Salford, UK Department of High Temperature Materials National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute” Kyiv, Ukraine

ISBN 978-3-031-07174-4 ISBN 978-3-031-07175-1 https://doi.org/10.1007/978-3-031-07175-1

(eBook)

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

This book is dedicated to the Heroes of Ukraine, who are defending the freedom of their country

Preface

This book is the fourth volume in my Ultra-High Temperature Materials (UHTM) book series, which is devoted to the materials having melting (sublimation or decomposition) points around or above 2500 °C. In the preface to Volume I I have already detailed all the motives that led me to the creation and establishment of this series of books, so here I believe it is enough only to refer to the ideas mentioned earlier in the prefaces to Volume I, II and III. This volume is not only the continuation of three books published previously. As an author, considering the system of references and addenda adopted in the UHTM book series in a whole, I must explain that this book accumulates all the information presented in the previous volumes. Thus, it is a serious warning to any reader/user of this book that he/she will be unlikely satisfied with the process of learning the subjects or searching for the necessary information in this book without the direct usage of all the volumes jointly. Once more, many thanks to all the colleagues, including especially those, who were contacting me through my personal account in the Research Gate network (https://www.researchgate.net/profile/Igor_Shabalin), for their useful feedback on the chapters of Volume I, II and III. Now I again ask everybody, who has any remarks, observations, or possible corrections and personal opinions, concerning this book and its contents, to send all of them directly to my university e-mail or Research Gate account. It will be extremely useful for me to consider all your responses before preparation and publishing of the next volumes of the UHTM book series. To prepare this book series for the publication would not have been possible for me without the permanent encouragement and kind support (direct assistance, sometimes) I have got for the last years from my friends and colleagues. Unfortunately, some of them had passed away in the period after the publication of Volume III, as it happened recently with Prof. Sergei N. Kulkov (Tomsk State University, Russia). The bright memory of such people, with whom I worked together and communicated in my everyday life, is an important part of the driving force in my work. With the release of this volume, I would like to honour the memory of all those colleagues, who are no longer with us. For the invaluable and kind assistance in the preparation of this volume, I would like gratefully to acknowledge Dr. Alexey S. Kurlov (Institute of Solid State Chemistry, Russian Academy of Sciences, Yekaterinburg, Russia), Prof. Igor Yu. Konyashin (Element Six GmbH, Burghaun, Germany), Prof. Anna Biedunkiewicz (West Pomeranian University of Technology, Szczecin, Poland), Dr. Patrick A. Burr (University of New South Wales, Sydney, Australia), Prof. Gopal

vii

viii

Preface

S. Upadhyaya (formerly Indian Institute of Technology, Kanpur), Dr. Sree S. Roy (University of Manchester, Manchester, UK), Dr. Wayne Y. Wang (University of Salford, Manchester, UK), Prof. Alexander I. Savvatimskiy (Joint Institute for High Temperatures, Russian Academy of Sciences, Moscow, Russia), Prof. Irina V. Medvedeva (Institute of Metal Physics, Russian Academy of Sciences, Yekaterinburg, Russia), Prof. Anders E. W. Jarfors (Jönköping University, Sweden), Prof. Yury G. Gogotsi (Drexel University, Philadelphia, USA), Prof. Artem R. Oganov (Stony Brook University, New York, USA), Dr. Suneel K. Kodambaka (University of California, Los Angeles, USA), Dr. Sergei A. Zykov (Institute of Metal Physics, Russian Academy of Sciences, Yekaterinburg, Russia), Dr. Alexander G. Trifonov (Joint Institute for Power and Nuclear Research, National Academy of Sciences of Belarus, Minsk, Belarus), Prof. Mikhaylo S. Kovalchenko (Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kyiv, Ukraine), Dr. Oleksii Yu. Popov (Taras Shevchenko National University, Kyiv, Ukraine), Prof. Tetiana A. Prikhna (Institute of Superhard Materials, National Academy of Sciences of Ukraine, Kyiv, Ukraine), Prof. Petro I. Loboda (National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine), Prof. Koichi Niihara (Nagaoka University of Technology, Japan), Dr. Vladimir M. Vishnyakov and Prof. John S. Colligon (University of Huddersfield, Huddersfield, UK), Prof. Levan Chkhartishvili (Georgian Technical University, Tbilisi, Georgia), Prof. Shiro Shimado (Hokkaido University, Sapporo, Japan), John Cloughley (E4 Structures, Manchester, UK), Prof. László A. Gömze and Dr. Ludmila N. Gömze (University of Miscolc, Hungary). I sincerely apologize, if I have missed to mention the assistance of anybody else from the variety of scientists and researchers all around the world, I have contacted with concerning the issues connected with the topics of this book. I express my appreciation for the encouragement and pleasant cooperation with Stephen Soehnlen, former editor of Springer Science + Business Media, who made initial efforts to initiate my interest to “writing thick books” more than 10 years ago, and with Mieke van der Fluit (now retired), Hisako Niko, Rebecca Sauter, Ambrose Berkumans and all other members of Springer Nature B.V. team. I also acknowledge Bob Bramah (Salford Sports Injury Clinic, University of Salford, Manchester, UK) and all his team for their kind assistance and support in my physiotherapeutic treatment. I could not have done my work well without the care I have got in the clinic. Lastly, I wish to thank my best friends Ondrej Obediar and Mark Frith and all my relatives for their steadfast support during the last years, which were necessary to accomplish the preparation of Volume IV for its publication.

Professor Igor L. Shabalin Manchester, UK March 2022

Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Tungsten Carbides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Electro-Magnetic and Optical Properties . . . . . . . . . . . . . . . . . . . . . . 2.4 Physico-Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Nuclear Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6 Chemical Properties and Materials Design . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Addendum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.1 Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.2 Thermal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.3 Electro-Magnetic and Optical Properties . . . . . . . . . . . . . . . . . . . . . . A.4 Physico-Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.5 Nuclear Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.6 Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.7 Porosity-Property Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Index (Physical Properties) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Index (Chemical Systems) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 9 11 11 34 49 58 123 131 581 831 831 831 831 832 832 832 833 870 885 895

ix

About the Author

In his professional career Igor Logan Shabalin has got more than 50 years of experience in Ultra-High Temperature Materials Design, Science and Engineering. He was born in the Urals, Russia, graduated in Technology of Less-Common Metals and received his M.Sc. and Ph.D. degrees from the Ural Polytechnic Institute (UPI), Yekaterinburg (former – Sverdlovsk), Russia. He has held academic positions at the UPI (now – Ural Federal University) and was the founder of the Special Research Laboratory for Aerospace Industry (ONIL-123). As head of the laboratory and member of several scientific and technological councils, he established collaboration between universities and industry by running a variety of R&D projects and was involved in the management of some world leading programmes in rocketry and spacecraft development in the USSR Ministry of Aerospace Industry (MOM). In 2003 Professor Igor L. Shabalin immigrated to the United Kingdom. He joined the University of Salford, Manchester, as a researcher in Materials in 2005. As I. L. Shabalin has developed his personal original approach to a special subclass of engineering materials – hetero-modulus composites and hybrids in ceramics, his research activity focuses mainly on high and ultra-high temperature ceramic composites with graphene-like (carbon and boron nitride) constituents. I. L. Shabalin has discovered in Russia in the 1980-90s and formulated later in the UK – mesoscopic temperature-pressure-dependent phenomenon in the solid-state gas-exchange chemical reactions (surface processes) termed as “ridge effect”. From 1971 up to date he has published about 300 scientific and technical papers and holds more than 40 patents. In 2014 Prof. I. L. Shabalin was awarded the title of Honoured Professor of the Department of High Temperature Materials (National Technical University of Ukraine), which was founded by Grigorii V. Samsonov, one of the world-famous scientists of the 20th century in the field of physics and chemistry of non-oxide refractory compounds.

xi

Abstract

This series of books represents a thorough treatment and consideration of ultrahigh temperature materials – chemical elements and compounds with melting (sublimation or decomposition) points around or over 2500 °C. In the fourth volume are included physical (structural, thermal, electro-magnetic, optical, mechanical, nuclear) and chemical (about 1300 binary, ternary and multi-component systems, including those used for contemporary materials design, data on diffusion, wettability and interaction with various metals, compounds, chemicals, gases and aqueous solutions) properties of tungsten monocarbide δ-WC1±x and γ-WC1–x phases, tungsten semicarbide α-W2+xC, β-W2+xC, ε-W2+xC and γ-W2±xC phases as well as materials on their bases. The tungsten carbide materials are widely applied in the general technological and engineering practice in the wide range from cryogenic to ultra-high temperatures as parts of highly strong and hard materials (alloys) and special steels. This book will be of interest to various researchers, engineers, postgraduate, graduate and undergraduate students alike. For the named materials, readers/users are provided with the complete qualitative and quantitative assessment, which is based on the latest updates in the field of fundamental physics and chemistry, nanotechnology, materials science, design and engineering.

xiii

1 Introduction

It is quite symbolic that in the series of books on Ultra-High-Temperature Materials [1-3], Volume IV, which is a kind of "equator" of the entire publication, is dedicated specifically to tungsten carbides. In comparison with all other refractory metals and compounds, materials based on tungsten carbide are the most widely applied in contemporary technologies and industrial production. These ultra-high temperature phases are formed by the elements, carbon C and tungsten W, which themselves have the highest melting points of any substance known in nature. Thus, among this type of compounds and materials [4-15], tungsten monocarbides and semicarbides [16-21] (marked out with bold borders in Table 1.1) occupy a central and special position, determined by their special structures, properties, and applications. The Noble prize winner Henri Moissan in 1893 was the first [22], who had synthesized tungsten carbide, more accidentally than specially, while seeking the ways to produce artificial diamond through heating sugar and tungsten oxides in a special furnace. The sugar acted as a reducing agent for the oxides to produce tungsten carbides remelted at ultra-high temperatures. Unfortunately, it became clear very soon that the discovered compound, demonstrating some desirable and interesting characteristics, had no chance for technical applications as a refractory material due to its extremely high brittleness. However, this imperfection was largely corrected by metal additives to carbide and the creation of so-called cermet (ceramic-metal) materials, mainly produced by powder metallurgy methods [16, 18]. Indeed, the temperature range for using the cermets is significantly reduced due to the lower melting point of metals, primarily cobalt, compared to tungsten carbide, but the process of powder consolidation of the similar compositions can be greatly simplified, due to their sintering in the presence of a liquid phase [19, 21]. Thus, it became possible to realize for practical purposes the high potential of tungsten carbides in terms of hardness and elastic characteristics, which, as already mentioned in the Introduction to Volume III [3], correlate with a high melting temperature, since all these physical constants are a consequence of the high strength of the chemical bond in refractory carbides. Undoubtedly an ultra-high temperature material in its primary nature, tungsten carbide is used in a number of ultra-high temperature ceramic composites [23-25] intended for service for various times at temperatures > 2700 K, although it has found its widest application at ambient, moderate or elevated temperatures as a hard and wear-resistant material in conventional metalworking in the form of sintered hard alloys and high speed steels and has thus produced a real technical revolution in the world. Compared to the elements of carbon C and tungsten W forming these compound, tungsten monocarbide δ-WC1±x is relatively less stable, that is expressed in its lower heat of formation, ability to decompose by a peritectic reaction and significant dis-

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 I. L. Shabalin, Ultra-High Temperature Materials IV, https://doi.org/10.1007/978-3-031-07175-1_1

1

21

Sc

22

Ti

23

V

5/VB

24

Cr

Mn

25

26

Fe

27

Co

28

Ni

29

Cu

6/VIB 7/VIIB 8/VIIIa 9/VIIIb 10/VIIIc 11/IB

30

Zn

5

B

Mg

12

20

Ca

K2C2 CaC2 ScC1–x TiC1–x (?) (~2400) (2270) (3070) Sc4C3+x (1860) Sc3C4–x (1800)

K

19

Na2C2 Mg2C3 (?) (~700) MgC2 (~2200)

Na

V2±xC Cr23C6±x Mn23C6 Meta(2190) (1610) (1035) stable V4C3–x Cr7C3±x Mn15C4 (1320) (1770) (1020) V6C5±x Cr3C2–x Mn3C (~1220) (1820) (~1050) VC1–x Mn5C2 (2800) (1170) Mn7C3 (1340)

Metastable

Metastable

–

–

14

Si

–

Ga

31

–

Ge

32

Al4C3 SiC (2100) (2545)

Al

C

6 N

P

As –

33

–

15

–

7

Se CSe2 (?)

34

CS2 (?) CS (?)

S

–

O

16

8

F

Cl

–

Ar

–

Ne

–

–

Kr

36

18

10

He

(continued)

Br –

35

–

17

–

9

2

12/IIB 13/IIIA 14/IVA 15/VA 16/VIA 17/VIIA 18/VIIIA

13

Be

4/IVB

11

4

3/IIIB

B4±xC (2450)

Li

–

H

2/IIA

Li2C2 Be2C (~600) (~2100) BeC2 (?)

3

1

1/IA

Table 1.1 Melting (or decomposition) points Tm (C) of the binary compounds of chemical elements with carbon (carbides) in the periodic table [1-15, 35]

2 1 Introduction

40

Zr

Fr

(?)

87

Ra

(?)

88

89

(?)

Ac**

Rf

(?)

104

Hf

72

BaC2 La2C3–x HfC1–x (2000) (1415) (3950) LaC2±x (2400)

La*

(?)

57

56

Ba

Y

Y2±xC ZrC1–x (950) (3450) YC1±x (~2380) Y4C5 (1530) Y3C4–x (~1600) Y2C3–x (~1500) YC2±x (~2380)

39

Cs

55

SrC2 (1800)

(?)

Sr

38

Rb

37

Table 1.1 (continued)

Nb

Mo

42

43

Tc

Ta

Db

(?)

105

Ta2±xC (3335) Ta4C3–x (2525) Ta6C5±x (1160) TaC1–x (3990)

73

W

Sg

(?)

106

W2±xC (2790) WC1–x (2780) WC1±x (2780)

74

(?)

Bh

–

Re

107

75

Nb2±xC Mo2±xC TcC1–x (3080) (2520) (?) Nb4C3–x Mo3C2-x (1750) (2550) Nb6C5±x MoC1–x (~1100) (2600) NbC1–x MoC (3600) (1220)

41

(?)

Hs

108

–

Os

–

Ru

76

44

(?)

Mt

109

–

Ir

–

Rh

77

45

Ds (?)

110

–

Pt

–

Pd

78

46

(?)

Rg

–

Au

–

Ag

111

79

47

–

Cd

Cn (?)

112

–

Hg

80

48

In

Tl

Nh (?)

113

–

81

–

49

(?)

Fl

–

Pb

–

Sn

114

82

50

Sb

Bi

(?)

Mc

115

–

83

–

51

Te

Po

(?)

Lv

116

–

84

–

52

I

At

(?)

(?)

Og

–

Rn

118

86

–

Xe

54

(continued)

Ts

117

(?)

85

–

53

1 Introduction 3

**

*

Ce

Th

ThC1±x (2630) ThC2–x (2660)

90

Ce2C3 (~1600) CeC2±x (2300)

58

Pr

Pa

PaC (?) PaC2 (?)

91

Pr2C3–x (1550) PrC2±x (2320)

59

Table 1.1 (continued)

Nd

U

Pm

93

Np

(?)

61

UC1±x NpC1–x (2530) (?) U2C3 Np2C3 (1820) (?) UC2–x NpC2 (2510) (?)

92

Nd2C3–x (1620) NdC2 (2260)

60

Sm

63

Eu

Gd

64

Pu

95

Am

Pu3C2 Am2C3 (575) (?) PuC1–x AmC2 (1655) (?) Pu2C3–x (2040) PuC2 (2230)

94

Cm

(?)

96

Sm3–xC Eu3–xC Gd3–xC (?) (?) (?) Sm2C3–x Eu2C3 Gd2C (1325 ?) (?) (?) SmC2 EuC2 Gd2C3–x (~2300) (1700 ?) (?) GdC2 (2370)

62

Tb

66

Dy

Ho

67

68

Er

69

Tm

70

Yb

71

Lu

Bk

(?)

97

Cf

(?)

98

Es

(?)

99

(?)

Fm

100

(?)

Md

101

No (?)

102

(?)

Lr

103

Tb3–xC Dy3–xC Ho3–xC Er3–xC Tm3–xC Yb3–xC Lu3–xC (?) (?) (?) (?) (?) (?) (?) Tb2C3–x Dy2C Ho2C Er15C19 Tm15C19 YbC1–x Lu15C19 (?) (?) (?) (?) (?) (?) (?) TbC2 Dy2C3–x Ho2C3–x ErC2 TmC2 Yb4C5+x LuC2 (~2150) (?) (?) (2250 ?) (2180 ?) (?) (?) DyC2 HoC2 TmC3 Yb15C19 (2250 ?) (2270 ?) (?) (?) Yb3C4±x (?) YbC2 (?)

65

4 1 Introduction

1 Introduction

5

solution in cubic carbides of 4-5 groups, in contrast to which the tungsten carbide has a hexagonal crystal lattice. The properties of tungsten monocarbide δ-WC1±x are determined by the features of its electronic structure occurring from the combination of tungsten W, which is a very weak electron donor, with carbon C atoms, in which the sp3-hybridized configurations are unstable under these conditions and electron delocalization is observed. This makes it impossible to form a face-centered cubic (fcc) monocarbide lattice, similar to that in the transition metals of groups 4-5 – Ti, V, Zr, Nb, Hf and Ta (see Volumes II and III), or another cubic lattice under normal conditions, and leads to the formation of a hexagonal monocarbide structure. The delocalization of the valence electrons of carbon C atoms results in thermodynamic instability of such a structure, but it allows to obtain a higher symmetry due to the dissolution of tungsten monocarbide in the cubic carbides of metals of 4-5 groups within the limits accepting the preservation of the cubicity of the latters. This also causes the moderate hardness of tungsten monocarbide δ-WC1±x and its remarkable property that this phase has some plasticity at ambient and moderate temperatures, unlike most refractory carbide phases. The combination of hardness, plasticity and the ability to recrystallize in molten metals, inherent in tungsten carbide, led to its application as the main component of sintered hard alloys, which were proposed 100 years ago by Karl Schröter [26-27] and until now, practically did not change significantly in composition, despite numerous attempts to remove tungsten monocarbide δ-WC1±x from them, as a compound of such a scarce metal as tungsten. The principle of development and creation of sintered hard alloys is to apply for the processing of materials, mainly various metals, steels and alloys, a highly hard (but often brittle!) carbide phase component, "cemented" in order to increase the strength of the entire cutting tool as a whole by ductile (tough) metals, primarily cobalt, as well as nickel, iron and/or their alloys [17]. In the case of plasticity of a carbide component, while maintaining its sufficiently high hardness, the total plasticity of the cutting edge of the tool (its so-called "pliability") is composed of the plasticity of the "cementing" metal (binder) and grains of the carbide phase, that can smooth out a sharp transition from hard to plastic component in a hard alloy and allows processing ductile materials with the occurrence of lower stresses in them, and brittle materials – with a longer preservation of the cutting edge. Somewhat ductile compared to other hard carbides, tungsten monocarbide δ-WC1±x is therefore a difficult to replace component of hard alloys; instead of it, only such hard components that are less ductile, but have some other positive properties, can be employed. Among other various applications of tungsten carbides in technology, it is undoubtedly necessary to note their use in arc-resistant electrical contact materials for circuit breakers. These contact composite materials can withstand extreme arcing conditions generated by a short circuit with minimal material loss due to their acceptable contact resistance at “rated” currents after arcing and non-welding to each other at high and ultra-high currents. This set of stringent conditions is only fulfilled by carefully engineered tungsten carbide – metal composites, which can comply with independent material properties like superior conductivity and high boiling point [28]. Modification of various composite materials based on metal or

6

1 Introduction

polymer matrices with tungsten carbide leads to a significant increase in the possible operating temperature of such materials, along with a noticeable increase in hardness, strength, and obvious enhancement in wear- and/or erosion-resistance of parts made from these composite materials [29-30]. Owing to the delocalized electrons of the carbon C atom in tungsten monocarbide δ-WC1±x mentioned above, this phase is an active electron donor that determines its catalytic activity in many chemical processes such as redox and hydrogenation reactions, it provides a promising industrial application of tungsten monocarbide as a catalyst. The observed catalytic behaviour of δ-WC1±x is estimated as “platinumlike” [31-32], which is not found for metallic tungsten W, so the carbide can be considered a promising replacement for precious metal-based catalysts and electrocatalysts, due to the similarity of its electronic structure and characteristics to those of Pt and Pd. Much progress in using tungsten carbides has been made to demonstrate their superior properties in a variety of electrochemical reactions, such as the oxygen reduction reaction (ORR), methanol oxidation reaction (MOR), hydrogen evolution reaction (HER) and others [33-35]. Therefore, the successful applications of proton exchange membrane fuel cells and electrolyzers are directly connected with the development of various compositions of advanced tungsten carbides electrocatalysts that are not only highly active but also economical and durable. Experimentally, hexagonal semicarbide γ-W2±xC was found to be the most active phase as a catalyst being slightly more active than hexagonal monocarbide δ-WC1±x and more than twice as active as cubic γ-WC1–x (NaCl-structured) [36]. However, according to theoretical analysis [37], the latter has the density of states close to the Fermi level twofold greater than that of semicarbide and 6 times greater that of δ-WC1±x. The formation of cubic tungsten monocarbide γ-WC1–x phase, with the great deficit of carbon C atoms in its crystal lattice, occurs in the tungsten-carbon system due to the localization of valence electrons of carbon C atoms in the range of high temperatures near the effective nucleus of tungsten W atoms with a corresponding reduction in the non-localized part of the electrons [17]. The high-temperature cubic form of monocarbide phase is of great interest to researchers, both in theoretical terms and in the aspect of discovering new technical possibilities for its applications at ultra-high temperatures. The particularly promising areas of research on γ-WC1–x are preparation of superhard coatings and thin films based on it as well as its various types of nanostructures and doping of this carbide phase with nitrogen N and oxygen O interstitial atoms in order to synthesize carbonitride and oxycarbide modifications of cubic carbide phase. Researchers find no fewer interesting properties in the semicarbide phase of tungsten, which is already of great technical importance. This phase exists in four crystalline polymorphic forms (hexagonal (γ), orthorhombic (β), and two trigonal (α and ε)) and is a thermodynamically stable (in the range of 1500-3050 K) hightemperature compound. With tungsten monocarbide δ-WC1±x phase, semicarbide forms fine-grained eutectic alloys, which are termed as "relites". Tungsten semicarbide W2±xC and alloys based on it or with its participation are characterized by very high wear- and erosion-resistance, they are applied to produce hardfacing

1 Introduction

7

layers or various protective coatings on fast-wearing parts of machines, mechanisms and various drilling tools. Continuing to develop further the earlier claimed ideas, the author would like to remind again and attract your attention to the fact that the refractory carbides, including δ-WC1±x, γ-WC1–x and W2±xC phases, possess the amazing structural, physico-mechanical, thermophysical and physico-chemical properties. Similarly to the cubic refractory carbides of transition metals of 4-5 groups of the periodic table described in Volumes II-III, these phases belong to the family of metal-like (or interstitial) carbides formed by d- and f-elements. The extraordinary behaviour of these compounds is caused by the specific chemical bonds between interstitial atoms of carbon C and metallic atoms, which include and combine metallic, ionic and covalent types of interatomic bonding (interaction) [14-15, 38]. The heterodesmic character of chemical bonding in transition metal refractory carbides is almost always accompanied by non-stoichiometry phenomenon and existence of wide homogeneity region (variability of composition) of the carbide phases (see Volumes II and III). However, in opposite to the cubic refractory carbides of transition metals, hexagonal tungsten monocarbide δ-WC1±x phase has no homogeneity ranges at temperatures < 2300 K at all and rather limited ranges at the higher temperatures – from WC0.95÷0.98 to WC1.02 (see section C – W in Table I-2.13; hereafter “I-0.00”, “II-0.00” and “III-0.00” are used to mark the sections, figures and tables of Volumes I, II and III of this UHTM book series, respectively). Tungsten monocarbide δ-WC1±x differs significantly from the refractory carbides considered and discussed in the previous Volumes II and III of this book series on ultra-high temperature materials and has a complex of very peculiar, technically very important physical and physico-chemical properties that allowed it to become the first ultra-high-temperature material that has become so widespread in modern technologies and applied in various branches of contemporary industry. The specificity of the structures and properties of tungsten carbides and materials based on them, along with the author's desire to collect and systematize, if possible, all the available information on these issues, led to the fact that the special separate volume in this book series, which is currently being presented to readers/users under the number of 4, is devoted only to the tungsten carbides. Such a huge size of Volume IV is in no way due to any author’s preferences, but it is only a reflection of the information boom in the scientific and research literature on materials science and nanotechnology that has occurred in the last decade and was directly related to the studies and investigations in the field of tungsten carbides and the applications of materials containing these compounds in technological and industrial practice. In the general chapter of Volume IV, jointly for all existing in the tungstencarbon W-C system phases (δ-WC1±x, γ-WC1–x and W2±xC), the special section devoted to their structural features (partial variant of tungsten-carbon phase diagram, system and type of crystal structures, possible slip systems, synthesized or theoretically predicted nanostructures, density of structures) advances the thorough and comprehensive description of data available in the literature on thermal, electromagnetic and optical, physico-mechanical and nuclear physical properties of the phases over very wide temperature ranges and given in the corresponding sections.

8

1 Introduction

The chemical properties of tungsten carbides and developed approaches to the design of materials based on them or containing them are considered in the final section by the analysis of interaction of the carbide phases with metals, non-metals, various refractory (carbides, nitrides, oxides, borides, silicides, intermetallides) and other chemical compounds, gases and some common chemicals (acids, alkalis and salts in aqueous solutions and melts), diffusion processes and parameters of wettability by various melts in the wide range of temperatures. Similarly to that it was produced earlier in Volumes I, II and III, the most reliable data (in author’s opinion) on the general physical and physico-chemical properties of the ultra-high temperature materials included in all the volumes of the book series are summarized in Addendum. Indeed, all the data in Addendum are based on the information given before in the corresponding chapters of the volumes; however, every reader/user of the book has to be reminded that in the case of refractory carbides these data relate only to the near-stoichiometric (or sometimes carbon-richest) compositions of the corresponding carbide materials. The full amount of data on the structures and properties of refractory carbides, which was available in literature at the moment, when the publication of this UHTM book series began, was turn up to be too enormous, so it has been decided to divide all the information on carbide materials into several books (volumes). Honestly, it was desire of my readers/users, who took advantage of the feedback, to make the real content of the books in the series – much “deeper” than “wider”. Thus, Volume IV is the third one, which is devoted to ultra-high temperature carbide materials. It continues the topic of transition metal carbides of 4-6 groups, giving each reader/user the opportunity to obtain the most complete information on tungsten carbides. As far as possible, due to the reduction in the number of systems under the consideration, the author has tried to include in Volume IV all the latest data on these refractory carbide materials, including nanotechnological advances as well as the computer simulation results of the properties of these carbides based on the density functional theory theoretical approaches and methods. From Table 1.1, where all the ultra-high temperature carbide systems relegated according to the classification adopted in this UHTM book series are shaded gray, it is clear that the next volume(s) of series will include data on metallic carbide systems, such as molybdenum, thorium and uranium carbides, as well as non-metallic refractory carbide systems, such as silicon and boron carbides. There are no special sections devoted to the manufacturing methods of ultra-high temperature carbides in the chapters of this book series; however, anybody can find a lot of useful information on these issues in the sections, where the chemical properties of individual carbides and general principles of carbide containing materials design are described. As a kind reminder, the special author’s remarks for readers/users of the book are following: when it is not indicated specially, the value of percentage reported in the text of the book is given in mass percent;

1 Introduction

9

some experimental and/or theoretically calculated data presented in the text, which are a bit doubtful in author’s opinion, as they have not been confirmed in the literature sufficiently, are denoted specially by the question marks; for the most of chemical elements and compounds, considering as reagents in the relation to the major refractory carbide phases in the corresponding sections on chemical properties and materials design, all their known phase modifications (polymorphs) are marked, but just for a reminder as the necessary information on some of them is sometimes not available in literature Finally, it is necessary to recommend all the readers/users to become acquainted with the introductions to the previous volumes [1-3], as those novel approaches to the description of materials that were substantiated there are also employed by the author in Volume IV.

References 1. Shabalin IL (2014) Ultra-high-temperature materials I. Carbon (graphene/graphite) and refractory metals. Springer Science, Dordrecht, London 2. Shabalin IL (2019) Ultra-high-temperature materials II. Refractory carbides I (Ta, Hf, Nb and Zr carbides). Springer Nature, Singapore 3. Shabalin IL (2020) Ultra-high-temperature materials III. Refractory carbides II (Ti and V carbides). Springer Nature, Dordrecht 4. Kotelnikov RB, Bashlykov SN, Galiakbarov ZG, Kashtanov AI (1968) Osobo tugoplavkie elementy i soedineniya (Extra-refractory elements and compounds). Metallurgiya, Moscow (in Russian) 5. Kieffer R, Schwarzkopf P (1953) Hartstoffe und Hartmetalle (Refractory hard metals). Springer, Vienna (in German) 6. Storms EK (1967) The refractory carbides. Academic Press, New York, London 7. Toth LE (1971) Transition metal carbides and nitrides. Academic Press, New York, London 8. Samsonov GV, Upadhyaya GS, Neshpor VS (1974) Fizicheskoe materialovedenie karbidov (Physical materials science of carbides). Naukova Dumka, Kyiv (in Russian) 9. Upadhyaya GS (1996) Nature and properties of refractory carbides. Nova Science, Commack, New York 10. Kosolapova TYa (1971) Carbides: properties, production and applications. Plenum Press, New York 11. Kosolapova TYa, ed (1990) Handbook of high-temperature compounds: properties, production and applications. Hemisphere, New York 12. Pierson HO (1996) Handbook of refractory carbides and nitrides. Noyes Publications, Westwood, New Jersey 13. Lengauer W (2000) Transition metal carbides, nitrides and carbonitrides. In: Riedel R (ed) Handbook of ceramic hard materials, pp. 202-252. Wiley-VCH, Weinheim, New York 14. Andrievskii RA, Lanin AG, Rymashevskii GA (1974) Prochnost tugoplavkikh soedinenii (Strength of refractory compounds). Metallurgiya, Moscow (in Russian) 15. Andrievskii RA, Spivak II (1989) Prochnost tugoplavkikh soedinenii i materialov na ikh osnove (Strength of refractory compounds and materials based on them). Metallurgiya, Chelyabinsk (in Russian) 16. Schwarzkopf P, Kieffer R (1960) Cemented carbides. Macmillan, New York 17. Samsonov GV, Vitryanyuk VK, Chaplygin FI (1974) Karbidy volframa (Tungsten carbides). Naukova Dumka, Kyiv (in Russian)

10

1 Introduction

18. Upadhyaya GS (1998) Cemented tungsten carbides. Production, properties and testing. Noyes Publications, Westwood, New Jersey 19. Tretyakov VI (1976) Osnovy metallovedeniya i tekhnologii proizvodstva spechennykh tverdykh splavov (Fundamentals of metal science and production technology of sintered hard alloys). Metallurgiya, Moscow (in Russian) 20. Kurlov AS, Gusev AI (2013) Tungsten carbides. Structure, properties and application in hardmetals. Springer, Heidelberg 21. Konyashin I, Ries B (2022) Cemented carbides, 1 st ed. Elsevier, Amsterdam, Berlin 22. Moissan H (1893) Preparation au four électrique de quelques mètaux réfractaires: tungsténe, molybdène, vanadium (Preparation of some refractory metals: tungsten, molybdenum, vanadium – in electric furnace). C R Acad Sci 116:1225-1227 (in French) 23. Zhang SC, Hilmas GE, Fahrenholtz WG (2008) Improved oxidation resistance of zirconium diboride by tungsten carbide additions. J Am Ceram Soc 91(11):3530-3535 24. Zhang SC, Hilmas GE, Fahrenholtz WG (2011) Oxidation of zirconium diboride with tungsten carbide additions. J Am Ceram Soc 94(4):1198-1205 25. Binner J, Porter M, Baker B, Zou J, Venkatachalam V, Diaz VR, D’Angio A, Ramanujam P, Zhang T, Murthy TSRC (2020) Selection, processing, properties and applications of ultra-high temperature ceramic matrix composites, UHTCMCs – a review. Int Mater Rev 65(7):389-444 26. Ortner HM, Ettmayer P, Kolaska H (2014) The history of the technological progress of hardmetals. Int J Refract Met Hard Mater 44:148-159 27. Ortner HM, Ettmayer P, Kolaska H, Smid I (2015) The history of the technological progress of hardmetals. Int J Refract Met Hard Mater 49:3-8 28. Ray N, Kempf B, Wiehl G, Mützel T, Heringhaus F, Froyen L, Vanmeensel K, Vleugels J (2017) Novel processing of Ag-WC electrical contact materials using spark-plasma sintering. Mater Design 121:262-271 29. Huang G, Hou W, Shen Y (2018) Evaluation of the microstructure and mechanical properties of WC particle reinforced aluminium matrix composites fabricated by friction stir processing. Mater Charact 138:26-37 30. Mohan N, Mahesha CR, Rajaprakash BM (2013) Erosive wear behaviour of WC filled glass epoxy composites. In: Hassan MB (ed) Proc. Malaysian Int. tribology conf. (MITC 2013), Sabah, Malaysia, 18-20 Nov 2013. Proc Eng 68:694-702 31. Levy RB, Boudart M (1973) Platinum-like behaviour of tungsten carbide in surface catalysis. Science 181(4099):547-549 32. Bennett LH, Cuthill JR, McAlister AJ, Erickson NE, Watson RE (1974) Electron structure and catalytic behaviour of tungsten carbide. Science 184(4136):563-565 33. Nikiforov AV, Petrushina IM, Christensen E, Alexeev NV, Samokhin AV, Bjerrum NJ (2012) WC as a non-platinum hydrogen evolution electrocatalyst for high-temperature PEM water electrolysers. Int J Hydrogen Energy 37:18591-18597 34. Yang X, Kimmel YC, Fu J, Koel BE, Chen JG (2012) Activation of tungsten carbide catalysts by use of an oxygen plasma pretreatment. ACS Catal 2:765-769 35. Do Rêgo UA, Lopes T, Bott-Neto JL, Tanaka AA, Ticianelli EA (2018) Oxygen reduction electrocatalysis on transition metal – nitrogen modified tungsten carbide nanomaterials. J Electroanal Chem 810:222-231 36. Neylon MK, Choi S, Kwon H, Curry KE, Thompson LT (1999) Catalytic properties of early transition metal nitrides and carbides: n-butane hydrogenolysis, dehydrogenation and isomerization. Appl Catal A 183:253-263 37. Gao Y, Song X, Liu X, Wei C, Wang H, Guo G (2013) On the formation of WC1–x in nanocrystalline cemented carbides. Scripta Mater 68(2):108-110 38. Gubanov VA, Ivanovskii AL, Zhukov VP (1994) Electronic structure of refractory carbides and nitrides. Cambridge University Press, Cambridge, New York

2 Tungsten Carbides 2.1 Structures Tungsten forms with carbon several chemical compounds (see also section C – W in Table I-2.13): tungsten monocarbide δ-WC1±x phase (hexagonal structured), having almost invariable composition (at least at temperatures < 2000 °C) and thermally stable in the wide range of temperatures, tungsten monocarbide γ-WC1–x phase (cubic structured) with a wide homogeneity range and very limited temperature interval of existence (at least in the pure form) and low-temperature (ordered) α-W2+xC, intermediate β-W2+xC (or ε-W2+xC phase (ordered) as an alternative to α- and β-phases) and high-temperature (disordered) γ-W2±xC phase modifications of tungsten semicarbide [1-13, 205]; the presence of metastable W3C [94-101, 200, 523, 943, 1331, 3057-3064, 4491], W8C [102, 3065] and W12C [519, 3064, 3066] structures (or W3+xC, Pm(–3)n) in some W-C-containing materials was also reported. In the intensive thermal loading conditions (non-equilibrium) leading

Fig. 2.1 Ultra-high and high temperature partial variant of tungsten – carbon equilibrium phase diagram [2-6, 8-13, 36, 41-87, 90-91, 108, 111, 117, 123-125, 128, 136-137, 141, 149-157, 169, 200, 202, 205, 214-219, 498, 625, 976, 1902, 1985, 1892, 1995, 2500, 2502, 2576, 2637, 2725, 2734, 3993-3994, 4001, 4385, 4505, 4644, 4677]

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 I. L. Shabalin, Ultra-High Temperature Materials IV, https://doi.org/10.1007/978-3-031-07175-1_2

11

12

2 Tungsten Carbides

to the escape of carbon atoms from the surface of materials, the sequence of transformations δ-WC1±x → γ-WC1–x → α-W2+xC → W3+xC → W was shown experimentally [97]. An ultra-high and high temperature partial variant of tungsten – carbon (W-C) equilibrium phase diagram is given in Fig. 2.1 (see also δ-WC1±x – C – W and α/β/ε/γ-W2±xC – C – W sections in Table 2.21). Alternative phase diagrams for the high-temperature W2C-WC region specially were constructed by Sara [41] and Kurlov and Gusev [68], a hypothetical metastable W-C phase diagram was considered by Velikanova et al. [86]. The modified variant of W-C phase diagram, where the place of surface carbides, in particular formed by carbon on W (100), is considered in the sequence of phase equilibria, was proposed by Gall et al. [103-105]. As it was shown by first principles calculations [82-83, 219], depending on their stability all the phases in the W-C system can be arranged in the following series: δ-WC1±x > ε-W2+xC > β-W2+xC > γ-W2±xC > α-W2+xC > γ-WC1–x, where δ-WC1±x, ε-W2+xC and β-W2+xC are stable, γ-W2±xC is metastable and α-W2+xC and γ-WC1–x are unstable; whereas the metallic properties (metallicity) of the phases decreases in the sequence: γ-WC1–x > ε-W2+xC > γ-W2±xC > β-W2+xC > α-W2+xC > δ-WC1±x. The C/W atomic radii ratio for δ-WC1±x calculated on the basis of Pauling’s atomic size of W (0.1394 nm, CN = 12) is 0.553 [7, 12, 45], or 0.57 [11, 118]; the ratio of W radii (in nm) for γ-WC1–x in Me/MeC is 0.137/0.153 (11.8 % expansion of W atoms in carbide) [8-9]. The C/W atomic radii ratio in tungsten semicarbide γ-W2±xC phase is 0.55 [200], or 0.57 [11, 198]. Tungsten monocarbide δ-WC1±x is the only binary phase in the system, which is thermodynamically stable at room temperature and has almost no solid solubility at temperatures up to ~2100 °C; it becomes C-deficient between this temperature and its incongruent melting point. The main element of δ-WC1±x lattice is a trigonal prism of W atoms. There is some ambiguity in the crystal structure of δ-WC1±x, because it could be also considered as trigonal; furthermore, the DFT calculations carried out by Nabarro et al. [244] have showed that the trigonal structure is lower in energy than the hexagonal one by ~0.4 eV per formula unit. The existence of polytypic structure in δ-WC1±x was reported by Perezhogin et al. [385] with a polytype having tetragonal lattice (I41md) with parameters a = 0.2840 nm and c = 1.010 nm (Z = 4). The band theory has shown that in δ-WC1±x phase the C atom carries an excess negative charge of (–1.4) [70, 112]. The δ-WC1±x – C peritectic melting transition is proposed to use as an ultra-high temperature fixed point for the metrological purposes [71-79]. The structural features of all the tungsten carbide bulk phases (except for W3+xC) are presented in Tables 2.1 and 2.2. The β-W2+xC (Pbcn) → ε-W2+xC (P(–3)1m) transformation was interpreted as a first-order phase transition [67, 223, 258], while the ε-W2+xC (P(–3)1m) → γ-W2±xC (P63/mmc) transformation – as a second-order phase transition [67]. Thus, in accordance to the alternative viewpoints, during the cooling procedure the disordered γ-W2±xC phase, likely, converts at ~1800 °C to the ordered ε-W2+xC modification (not shown on the diagram in Fig. 2.1), which at temperatures ~1000 °C can transform into β-W2+xC phase [184-185, 209, 214-216, 222-223]. The identification of γ-W2±xC, β-W2+xC, α-W2+xC and ε-W2+xC phase modifications by the means of XRD analysis is notably

2.1 Structures

13

Table 2.1 Structural properties (crystal structure, density) of tungsten monocarbide phases Crystal structure Formula

System

Type

Space group

a

Lattice parameters , nm a

c

Z

c/a

b

Density c, References g cm−3

δ-WC1±x Hexagonal WC d P(–6)m2 0.2880e

0.2800e

0.9722e

1

–

[3604]

f

f

0.9770f

1

–

[70]

0.2889e

0.2818e

0.9754e

1

–

[39]

0.28890.2902g

0.28410.2858g

0.98170.9872g

1

–

[32]

0.2890

0.2820

0.9758

1

–

[681]

0.2893

0.2832

0.9786

1

–

[170]

0.2894

0.2819

0.9741

1

–

[215]

0.2896h

0.2839h

0.9804h

1

–

0.2897i

0.2827i

0.9758i

1 15.83

[11, 28, 150]

0.2899

0.2831

0.9766

1

–

[675, 888, 1033, 1054]

1

–

[130, 1013]

1

–

[110]

0.2880

0.2900j

0.2810

–

–

0.2900k

0.2480k

0.2900i, l

0.2830i, l 0.9759i, l 1 15.78

0.2900m

0.2830m

0.9759m

1 15.77

[3, 6, 15]

0.2900

0.2831

0.9762

1 15.67

[4, 12, 29, 43, 117118, 621]

0.2900n

0.2880n

0.9931n

1

–

[420]

0.2900

0.2881

0.9934

1

–

[580, 584585]

0.2901

0.2830

0.9755

1

–

[586]

0.2902o

0.2831o

0.9755o

1

–

[34]

p

p

p

1

0.2902

–

[138, 201]

0.2833

0.9759

1 15.77

[200, 580]

0.2903q

0.2840q

0.9783q

1

–

[67]

0.2903r

0.2841r

0.9786r

1

–

[176]

s

s

s

1

–

[127]

0.29030.2909t

0.28310.2844t

0.97460.9783t

1

–

[67]

0.2904u

0.2833u

0.9756u

1

–

[1017]

v

v

0.9762v

1

–

[113]

0.28360.2849w

0.97590.9780w

1

–

[125]

0.2904

0.29040.2916w

0.2843

0.9769

[11, 27, 68, 423, 452, 457, 3604]

0.2903

0.2903

0.2834

0.8552k

[325]

0.2835

0.9793

(continued)

14

2 Tungsten Carbides

Table 2.1 (continued) 0.2905x

0.2827x

0.9731x

i

i

i

0.2905

[35]

1 15.70

[20, 4446]

0.2836y

0.9762y

1

–

[113]

0.2905z

0.2837z

0.9766z

1

–

[2567]

0.2905

0.2838

0.9769

1

–

[106, 4198]

0.2905

0.2840

0.9776

1

–

[86]

0.2906a1

0.2825a1 0.9721a1 1

–

[6, 16]

0.2906x

0.2825x

1

–

[36, 123]

1

–

[1407, 1439]

1

–

[84-85, 4198]

0.2906

0.2830

a2, a3

0.9759

–

0.2905y

a2, a3

0.2835

1

0.9721x 0.9738

a2, a3

0.2906

0.2836

0.2906i, a4

0.2837i, a4 0.9763i, a4 1 15.68

[1-9, 13-14, 18, 21-24, 31, 46, 48, 53, 68, 70, 107, 109, 114-117, 137, 698]

0.2906a5

0.2837a5 0.9763a5 1

–

[93, 951]

0.2906

0.28370.2840

1

–

[4198]

0.2906a6

0.2838a6 0.9766a6 1

–

[121, 142]

0.2906

a7

0.2838

0.9759

a7

0.97630.9773 0.9766

a7

1 15.64

[42, 69, 92, 108, 323, 530, 3866, 4533]

0.2906a8

0.2838a8 0.9766a8 1

–

[543-544]

0.2906i

0.2839i

0.9769i

1

–

[6, 17, 120, 136, 598]

0.2906

0.2840

0.9773

1

–

[4198]

0.29060.2907a9

0.2835- 0.9752- 1 0.2837a9 0.9763a9

–

[884]

0.2907b1

0.2823b1 0.9711b1 1

–

[3762]

0.2907b2

0.2837b2 0.9759b2 1 15.65

0.2907

i

0.2907 0.2907

0.2837

i

0.2838 i

0.2839

0.9759

i

0.9763 i

0.9766

i

[19]

1 15.67

[7, 25, 30, 45, 90, 126]

1

[134]

–

1 15.65

[26]

0.2907b3

0.2895b3 0.9960b3 1

–

[37]

0.2908b4

0.2822b4 0.9704b4 1

–

[129]

0.2908b5

0.2837b5 0.9756b5 1

–

[595]

0.2908

0.2841

0.9770

1

–

[88]

0.2908h

0.2842h

0.9773h

1

–

[363]

(continued)

2.1 Structures

15

Table 2.1 (continued) 0.2909b6 0.2910

b7

0.2830

b7

0.9725

b7

1

–

[40]

0.2910b8

0.2843b8 0.9770b8 1

–

[1065]

0.2912

0.2846

1

–

[4309]

0.2913b9

0.2838b9 0.9742b9 1

–

[122]

c1

0.2851c1 0.9774c1 1

–

[3658]

0.2917c2

0.2811c2 0.9640c2 1

–

[91]

0.2918c3, c4 0.2847c4 0.9757c4 1

–

[140, 4503]

0.2919

0.9773

c4

1

–

[38]

0.2844c5 0.9743c5 1

–

[135]

0.2920u

0.2840u

0.9726u

1

–

[768]

x

x

x

1

0.9719x

–

[139]

0.2923x

0.2841x

1

–

[917]

0.2924c6

0.2849c6 0.9746c6 1

–

[1000]

0.2924x

0.2850x

1

–

[39]

0.2925c7

0.2850c7 0.9744c7 1

–

[1065]

0.2926

c6

0.2929b3 0.2930

c8

0.2844

0.9740

c4

[154, 212, 314, 385, 553, 3604]

0.2919c5 0.2922

0.2843

1 15.61

[133]

0.2840

c4

0.9759

–

0.2910

0.2916

γ-WC1–xd2 Cubic

0.2829b6 0.9725b6 1

0.2849

c6

– 0.2830

0.9733

0.9747x 0.9736

c6

– c8

0.9659

c8

1 15.40

[33, 81-82, 92]

1

[119]

–

1

–

[396]

0.2930c4

0.2854c4 0.9741c4 1

–

[141]

0.2932c9

0.2853c9 0.9731c9 1

–

[132]

0.2935d1

0.2859d1 0.9741d1 1

–

[89]

NaCl Fm(–3)m 0.41150.4124d3

–

–

4

–

[153]

0.4140d4

–

–

4

–

[161, 175]

0.4160

–

–

4

–

[5, 178]

0.41600.4248d5

–

–

4

–

[158]

0.4171d6

–

–

4

–

[1465]

0.4178

–

–

4

–

[3, 59]

0.4180d7

–

–

4

–

[110, 154, 203]

0.4192d8

–

–

4

–

[164]

0.4210

–

–

4

–

[497]

0.4215d9, e1

–

–

4 17.18

[2-3, 6, 41, 128, 156, 159, 161, 202, 267, 598, 625]

(continued)

16

2 Tungsten Carbides

Table 2.1 (continued) 0.42150.4240

–

–

4

–

[10]

0.4220e2

–

–

4

–

[2-3, 6-7, 46-47, 53, 67, 80, 8485, 136, 199]

0.4222

–

–

4

–

[151]

0.42220.4263e3

–

–

4

–

[148]

0.42250.4237d3

–

–

4

–

[153]

0.4229

–

–

4

–

[147]

0.4230

–

–

4

–

[4]

a8

–

–

4

–

[543-544]

0.4235e4

–

–

4

–

[439]

0.4236

–

–

4

–

[524, 4417, 4499]

0.4240e5

–

–

4

–

[2-3, 68-69, 143-144]

0.4240e3

–

–

4

–

[160-161]

0.4241d8

–

–

4

–

[8-9]

0.42410.4244e6

–

–

4

–

[172]

0.4248i

–

–

4

–

[2, 145, 156, 607, 625]

0.4250

–

–

4

–

[2, 149, 179, 499]

0.42510.4254r

–

–

4

–

[167-169, 177]

0.4252e7

–

–

4

–

[2-3, 143144]

0.4264e8

–

–

4

–

[524]

0.4265i

–

–

4

–

[2, 146]

0.4266i, e9

–

–

4 17.27

[1-3, 8-9, 143-144]

0.4270

–

–

4

–

[5, 54]

0.4272f1

–

–

4

–

[171]

0.4286f2

–

–

4

–

[166]

0.4230

0.4241r

0.4291

f

[176]

–

–

4

–

[37]

0.4302f3

–

–

4

–

[524]

0.4310d5

–

–

4

–

[157]

(continued)

2.1 Structures

17

Table 2.1 (continued) 0.4320f, f4

–

–

4

–

[173, 975]

b7

–

–

4

–

[770]

0.4336f5

–

–

4

–

[4276]

0.4351x

–

–

4

–

[36, 123]

0.4360f6

–

–

4

–

[770]

x

–

–

4

–

[770]

0.4374x

–

–

4

–

[195]

0.4380f7, f8

–

–

4

–

[162-163]

c4

–

–

4

–

[174]

0.4382f9

–

–

4

–

[165]

0.4394c4

–

–

4

–

[141]

0.4328

0.4362

0.4380

0.4398g1 – – 4 – [81-83] a When it is not indicated specially, a value reported is for near-stoichiometric composition and room temperature b Number of formula units per lattice cell c Calculated from XRD, electron or neutron diffraction patterns d The WC structure type is proposed to be a partially disordered NiAs structure type (the only carbide phase to be isomorphous with δ-WC1±x is γ-MoC) [27] e Calculated for the stoichiometric phase on the basis of density functional theory (DFT) with the local density approximation (LDA) f Calculated for the stoichiometric phase by the ab initio pseudopotential local-orbital method g Nanostructured powders (specific surface area – 24 m2 g–1), the lattice parameters determined by different precision experimental methods h Nanoparticles with the estimated mean crystallite size of 38 nm (the addition of 0.1% La2O3–x leads to increase of lattice parameters to a = 0.2916 nm and c = 0.2843 and decrease of mean particle size to 28.5 nm [363]) i Content C – 50.0 at.% j Calculated on the basis of DFT by the plane-wave pseudopotential method k Nanopowders with mean crystallite size – ~6 nm and specific surface area – ~30 m2 g–1 l Nanorods (diameter – 50-70 nm, length – 200-300 nm); nanoneedles (diameter – ~50 nm and length – ~1 μm); nanotubes (outer diameter – 30-70 nm, for the maximum outer diameter: inner diameter – 20 nm with wall thickness – 25 nm, length – 1-5 μm) m Content C – 49.6-49.7 at.% n Nanorods (diameter – 30-50 nm, length – 200-500 nm) o Qusongite (natural mineral); the basic empirical formula is (W0.98Cr0.02)C0.97 (or W0.998C1.003, in the accordance to microprobe analysis in [131]) p Fine powders (average crystallite size – 99 nm, lattice strain – 0.00523) q For δ-WC1±x (x = 0) phase in contact with metallic W phase in the series of W-C alloys with contents C from 28 to 32 at.% r Ultra-fine powders prepared by plasma dynamic synthesis s Nanocrystalline δ-WC1±x phase investigated using synchrotron X-ray diffraction t For δ-WC1±x phases in contact with W2±xC phases in the series of W-C alloys with contents C from 33 to 48 at.% u Calculated on the basis of DFT within the generalized gradient approximation (GGA) of the Perdew-Wang (PW91) scheme v Determined by Rietveld refinement for δ-WC1±x phase in alloys containing 18 vol.% Co w For δ-WC1±x phases in contact with ε-W2+xC phases and α-C (graphite) in arc plasma melt-cast

18

2 Tungsten Carbides

three-phase composites (the lattice parameters directly depend on C/W ratio in the composites) x Calculated for the stoichiometric phase on the basis of DFT within the GGA using the PerdewBurke-Ernzerhof (PBE) functional y Determined by Rietveld refinement for pure δ-WC1±x phase (compare with note v in this table) z For the δ-WC1±x phase constituent in Co- and Ni-containing hard alloys a1 Content C – 49.3 at.% a2 Mesoporous δ-WC1±x materials containing γ-W2±xC and γ-WC1–x minor phases a3 Nanocrystalline δ-WC1±x with mean particle size – ~5 nm and specific surface area – 76 m2 g–1 a4 Minimal interatomic distances: W-W – 0.286 nm and W-C – 0.222 nm (at 298 K); the lattice parameters at various temperatures (calculated on the basis of experimental measurements from several sources): a = 0.2904 nm, c = 0.2835 nm, c/a = 0.9762 (20-50 K); a = 0.2904 nm, c = 0.2835 nm, c/a = 0.9762 (100 K); a = 0.2908 nm, c = 0.2839 nm, c/a = 0.9760 (500 K); a = 0.2916 nm, c = 0.2845 nm, c/a = 0.9758 (1000 K); a = 0.2919 nm, c = 0.2848 nm, c/a = 0.9756 (1200 K); a = 0.2922 nm, c = 0.2851 nm, c/a = 0.9755 (1400 K); a = 0.2926 nm, c = 0.2853 nm, c/a = 0.9753 (1600 K) a5 Synthesized by electrothermal explosion (ETE) under pressure (variant of self-propagating hightemperature synthesis (SHS)) in the presence of semicarbide W2±xC phase a6 The precision determination of lattice parameters by means of Rietveld analysis a7 The lattice parameters measured experimentally at higher temperatures and pressures: a = 0.2835 nm, c = 0.2786 nm, c/a = 0.9829 (300 K, 30 GPa); a = 0.2849 nm, c = 0.2797 nm, c/a = 0.9817 (1273 K, 29 GPa); a = 0.2857 nm, c = 0.2802 nm, c/a = 0.9809 (1673 K, 28 GPa) a8 Phase constituent of ultra-thin and thin films prepared by atomic layer deposition method a9 Single crystal δ-WC1.00, content: O – 0.01-0.05 % b1 Content C – 48.7 at.% b2 Content C – 49.5 at.% b3 Calculated for the stoichiometric phase on the basis of DFT within the GGA b4 Powders of δ-WC1±x phase synthesized by mechanical alloying with 8 h milling duration b5 Content C – 49.7 at.% b6 At 0 K; calculated for the stoichiometric phase on the basis of DFT using the Troullier-Martins norm-conserving pseudopotentials within the GGA of PW91 scheme (the evaluated contraction of lattice parameters at excess pressure of 60 GPa: a/a0 = 0.958 and c/c0 = 0.969) b7 Calculated for the stoichiometric phase on the basis of DFT within the GGA of the PerdewBurke-Ernzerhof scheme for solids (PBEsol) b8 Calculated for the stoichiometric phase on the basis of DFT by the projector augmented wave (PAW) method using the PBE potentials within the GGA with the undampened D3 Van-der-Waals correction term of Grimme b9 Nanocrystalline powder consisting of particles with an average size of 20 nm c1 For a carbide phase constituent of δ-WC1±x – Hadfield steel hard alloys c2 Calculated using specially developed bond-order potential (BOP) scheme c3 Bulk materials prepared by pulse current activated sintering (PCAS) method from fine powders (mean grain size – 0.4 μm) densified to 78 % relative density c4 Calculated for the stoichiometric phase on the basis of DFT by the PAW method using the PBE potentials within the GGA c5 Calculated for the stoichiometric phase on the basis of DFT by the PAW method using the PBE potentials within the GGA (the evaluated contraction of lattice parameters at excess pressure of 100 GPa: a/a0 = 0.940 and c/c0 = 0.952) c6 At 0 K; calculated for the stoichiometric phase on the basis of DFT by the full-potential linearized augmented-plane-wave (FP-LAPW) method within the GGA c7 Calculated for the stoichiometric phase on the basis of DFT by the PAW method using the PBE potentials within the GGA

2.1 Structures c8

19

Nanoparticles of δ-WC1±x (mean size – 10-60 nm) distributed in a C cellular matrix Calculated for the stoichiometric phase on the basis of DFT by PAW method using the PW91 scheme within the GGA d1 Calculated for the stoichiometric phase on the basis of DFT by the all-electron PAW method within the GGA using the PBE functional d2 Due to a eutectoid transformation (see Fig. 2.1), which proceeds at a very high velocity, the phase γ-WC1–x decomposes, forming γ-W2±xC and δ-WC1±x, so the conventional quenching methods do not allow to prepare pure single-phase samples of γ-WC1–x (the compositions of obtained samples, according to the reports in literature, extend in the range from 33 to 50 at.% C); the addition of ~ 1-2 at.% metals of 4 group (Ti, Zr, Hf) to the W-C alloys with 38-40 at.% C leads to the formation (stabilization) of γ-WC1–x phase (a = 0.4225÷0.4230 nm) in the quenched materials [86] d3 Thermal-plasma (CH4-containing) synthesized powders with various C contents d4 Ultra-disperse nanocrystalline particles and coatings on the surface of MWCNT (presumed that nonstoichiometric γ-WC1–x phase is more likely to be stable only in the case of nanocrystallites); see also the assumption made by Babad-Zakhryapin et al. [161] d5 Coatings deposited by magnetron sputtering on several substrates d6 Nanoparticles on α-C (black) support (for electrocatalysis purposes), mean size – ~3 nm d7 Nanopowders with mean crystallite size – ~4 nm and specific surface area – ~ 30-100 m2 g–1 d8 Synthesized by the ampoule reaction of CaC2 with WCl4 d9 Content C – 45.1 at.% e1 Encapsulated carbide nanoparticles e2 Content C – 37.9 at.% e3 More likely, materials were contaminated with O and N e4 Phase constituent of W-Mo-C-nanowire (diameter – 15-20 nm) e5 Content C – 41.5-41.9 at.% e6 Powders synthesized by the electrical explosion of W wire in liquid paraffin e7 Content C – 45.9 at.% e8 Reactive r.f. sputtering deposited thin films (single-phase, unbiased) investigated by XRD using the Rietveld method; content C – ~47 at.% e9 Minimal interatomic distances: W-W and C-C – 0.298 nm, W-C – 0.211 nm (at 298 K) f1 Crystalline hollow nanowires γ-W(C1–xOy) (0.64 ≤ x ≤ 0.87, 0.11 ≤ y ≤ 0.13) as small as 32 nm in diameter and with length/diameter aspect ratio of as much as 200 f2 The cubic phase formed in nanocrystalline δ-WC1±x – Co cemented carbides on the WC/WC interfaces (it exists extending for ~ 4-5 atomic layers) f3 Reactive r.f. sputtering deposited thin films (γ-WC1–x – α-W2+xC multi-phase, with a negative substrate bias of –40 V, domain size – ~5 nm) investigated by XRD using the Rietveld method; total content C – ~41 at.% f4 Calculated for the stoichiometric phase on the basis of total energy approach using ab initio pseudopotentials and Wigner form within the LDA f5 Prepared at temperature 1800 °C, higher pressures 3.5-6.0 GPa and Ti additive f6 Calculated for the stoichiometric phase on the basis of DFT within the GGA using the revised Perdew-Burke-Ernzerhof (RPBE) functional f7 Calculated for the stoichiometric phase on the basis of DFT by the plane-wave pseudopotential method within the LDA f8 Calculated for the stoichiometric phase using of density-functional perturbation theory (DFPT) f9 Calculated for the stoichiometric phase on the basis of DFT by the plane-wave pseudopotential code Dacapo method using the PW91 scheme within the GGA g1 Calculated for the stoichiometric phase on the basis of DFT by FP-LAPW method using the PBE potentials within the GGA c9

20

2 Tungsten Carbides

Table 2.2 Structural properties (crystal structure, density) of tungsten semicarbide phases Crystal structure Formula

α-W2+xC

System Trigonal

Type antiCdI2

Space group

a

Lattice parameters , nm a

c

P(–3)m1 0.2787d

–

0.4549d 1

–

[524]

0.29700.2994e

–

0.4712- 1 0.4781e

–

[148]

0.2974

–

0.4728

1

–

[4604]

0.2980f

–

0.4710f 1

17.41

[60, 190, 207, 4520]

0.2985g

–

0.4717g 1

–

[2, 46, 6869]

0.2990f

–

0.4710f 1

17.29

0.2990

–

0.4720

1

–

0.2990f

–

0.4730f 1

17.22

0.2992

–

0.4721

1

–

[3, 10, 58, 178, 197, 2725]

0.2992h

–

0.4722h 1

–

[44, 84-85]

0.29940.2912

–

0.4724- 1 0.4823

–

[156, 624625]

0.2995

–

0.4726

1

–

[136]

0.2997

–

0.4727

1

–

[299]

0.2997i

–

0.4728i 1

17.14

0.3000j

–

0.4730j 1

–

[212]

f

–

0.4728f 1

–

[2, 46, 6869, 137]

0.3003f

–

0.4730f 1

17.07

0.3025

–

0.4730

–

0.4766

0.3027

[189]

[17, 543544]

[188]

1

–

[13, 44]

1

–

[214]

–

0.4655

1

–

0.3057l

–

0.4697l 1

16.59

0.3060m

–

0.4703m 1

–

[196]

n

–

0.4688n 1

–

[141]

ε-Fe2N P(–3)1m 0.5153o

–

0.4681o 3

–

[214-216]

0.5170p

–

0.4716p 3

–

[48] [213]

0.3070

k

[191] [206, 4635]

k

0.3043

Trigonal

Density c, References g cm−3

b

0.3001

ε-W2+xC

Z

b

q

–

0.4716

3

–

0.5179r

–

0.4719r 3

–

[201]

0.5181f

–

0.4722f 3

17.23

[187]

0.5176

q

[36] [82-83, 219]

(continued)

2.1 Structures

21

Table 2.2 (continued) 0.5181s

–

0.4722s 3

17.15

0.5181t

–

0.4728t 3

–

[194, 214216]

0.5183u

–

0.4724u 3

–

[181]

f

–

0.4721f 3

–

[1-3, 48, 180, 151]

0.5185v

–

0.4723v 3

–

[2, 181]

f

–

0.4727f 3

–

[194, 214216]

0.5190f

0.5184

0.5188

–

0.4724f 3

17.17

w

–

0.4724w 3

–

[183-185]

0.51900.5195x

–

0.4720- 3 0.4744x

–

[125]

0.5190

–

0.4729

3

–

[134]

0.5196y

–

0.4721y 3

–

[48] [36]

0.5190

–

0.4752

3

–

0.5235k

–

0.4777k 3

–

0.5253l

–

0.4772l 3

16.59

0.5260n

–

0.4786n 3

–

[141]

m

–

0.4706m 3

–

[196]

0.5182z 4

–

[208]

4

–

[67, 208, 211]

0.4720a2 0.5980a2 0.5170a2 4

–

[60, 207] [184-185]

0.5357 Orthorhombic

ζ-Fe2N Pbcn (Mo2C, PbO2–x)

0.4718z 0.4719

0.4720

a1

f

0.6018z 0.6017

f

0.5181

f

4

– –

[208]

0.4720

0.6036

0.5190

4

–

[186, 207]

0.4721f

0.6030f

0.5180f 4

17.10

0.4725k

0.6057k

0.5195k 4

–

[36]

0.4726- 0.6013- 0.5178- 4 0.4732a4 0.6025a4 0.5195a4

–

[67]

0.4728a5 0.6009a5 0.5193a5 4

–

[2-3, 48, 53, 58, 6869, 108, 128, 137, 156, 180, 267, 625]

0.6002

0.5200

a1

[917] [82-83, 219]

0.4720a3 0.6016a3 0.5180a3 4

0.4736

0.6010

a1

k

[2, 204]

k

0.5211

β-W2+xC

[2, 182, 592]

4

17.06

0.4745m 0.6088m 0.5211m 4

–

[196]

0.4756k

–

[917]

0.6093k

0.5198

[3, 10, 186, 209, 2725]

0.5244k 4

[1, 8-9]

(continued)

22

2 Tungsten Carbides

Table 2.2 (continued)

γ-W2±xC

Hexagonal W2C (antiNiAs)

0.4759l

0.6097l

0.5227l 4

16.63

0.4761n

0.6113n

0.5243n 4

[82-83, 219]

–

[141]

P63/mmc 0.2971a6

–

0.4831a6 1

–

[3875]

0.29770.2992a7

–

0.4707- 1 0.4722a7

–

[67]

0.2980f

–

0.4710f 1

–

[4, 10-12, 43, 118, 584, 621]

0.2980f

–

0.4730f 1

17.33

[20]

0.29800.2984a8

–

0.4712- 1 0.4715a8

–

[67]

0.2982a9

–

0.4714a9 1

–

[67]

b1

–

0.4716b1 1

–

[48]

0.2985b2

–

0.4717b2 1

–

[46]

0.2986

–

0.4712

1

–

[584, 586]

0.2990b3

–

0.4690b3 1

–

[6, 199]

b4

–

0.4720b4 1

–

[6, 53, 58, 170, 199, 204]

0.2991b5

–

0.4722b5 1

–

[67]

0.2991

–

0.4725

1

–

[220-221]

0.2992

–

0.4721

1

–

[2-3, 10, 180, 186, 192, 209]

–

0.4722b6 1

17.24

[2, 5-6]

–

0.4722f 1

17.22

[193]

–

0.4722b7 1

–

0.2985

0.2990

0.2992b6 0.2992

f

0.2992b7 0.2993

b8

b8

[208, 598]

–

0.4717

1

–

0.2993f

–

0.4727f 1

17.19

[22-24]

0.2994

–

0.4724

1

17.18

[3, 13, 26, 44, 108, 189]

0.2994

–

0.4729

1

–

[220-221]

0.29940.2996b9

–

0.4723- 1 0.4726b9

–

[67]

0.29940.2998c1

–

0.4725- 1 0.4736c1

–

[67]

0.29940.3002c2

–

0.4723- 1 0.4732c2

–

[67]

0.2995c3

–

0.4721c3 1

–

[67]

0.2995

–

0.4726

1

–

[593]

–

0.4728c4 1

–

[214-216]

–

[208]

0.2995c4 0.2996

c5

–

0.4719

c5

1

[208]

(continued)

2.1 Structures

23

Table 2.2 (continued) 0.2996c6

–

0.4724c6 1

–

[3866]

1

–

[698]

0.4851a6 1

–

[3875]

0.4725- 1 0.4730c8

–

[67]

–

0.4728

1

–

[225, 377]

–

0.4726c9 1

–

[208]

–

0.4731d1 1

–

[93, 951]

c7

–

0.4726

0.2996a6

–

0.29960.3003c8

–

0.2997 0.2998c9 0.2999d1

0.2996

c7

b3

–

0.4720

1

–

[60, 207]

0.3000d2

–

0.4730d2 1

–

[46, 48, 314]

0.3001f

–

0.4728f 1

–

–

0.4736d3 1

17.34

[1, 8-9, 12, 45, 151, 200, 580, 584]

0.3002

–

0.4728

1

–

[888, 1033, 1054]

0.3002

–

0.4750- 1 0.4760

–

[2, 46, 6869, 137]

0.3003d4

–

0.4738d4 1

–

[176]

0.3025b5

–

0.4726b5 1

–

[6, 16]

0.3000

0.3001

0.3029

d3

a6

b3

a6

[46]

–

0.4867

1

–

[3875]

0.3033l

–

0.4741l 1

16.61

[82-83, 219]

0.3043k

–

0.4707k 1

–

[36]

n

–

0.4687n 1

–

[141]

0.30700.3080d5

–

0.5040- 1 0.5120d5

–

[769]

0.3190m

–

0.4626m 1

–

[196]

0.3070

– – 0.4730d6 1 – [769] a When it is not indicated specially, value reported is for near-stoichiometric compositions b Number of formula units per lattice cell c Calculated from XRD, electron or neutron diffraction patterns d c/a = 1.632; content C – ~23 at.%; reactive r.f. sputtering deposited thin films (α-W2+xC – γ-WC1–x multi-phase with total content C – ~41 at.%, with a negative substrate bias of –40 V, average domain size – ~5 nm) investigated by XRD using the Rietveld method e More likely, materials were contaminated with O and N f Content C – ~33.3 at.% g c/a = 1.580; content C – 29.1 at.% h c/a = 1.578; content C – 30.6-31.5 at.% i c/a = 1.578; phase constituent of ultra-thin and thin films prepared by atomic layer deposition method j c/a = 1.577; nanostructured phase with particle size of ~10 nm formed on high-surface-area C materials

24 k

2 Tungsten Carbides

Calculated for the stoichiometric phase on the basis of density functional theory (DFT) within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional l Calculated for the stoichiometric phase on the basis of DFT by the full-potential linearized augmented-plane-wave (FP-LAPW) method within the GGA m Calculated for the stoichiometric phase on the basis of DFT by Vanderbilt ultra-soft pseudopotential (USPP) within the GGA using Perdew-Wang (PW91) scheme n Calculated for the stoichiometric phase on the basis of DFT by the projector augmented wave (PAW) method using the PBE potentials o c/a = 0.908; content C – 31.5 at.%; ordered phase (the corresponding lattice parameters of the disordered γ-W2±xC phase are a = 0.2995 nm and c = 0.4728 nm) p c/a = 0.912; content C – 29.5 at.% q c/a = 0.911; content C – 30.5 at.% r c/a = 0.911; content C – 29.4 at.% s c/a = 0.911; content C – 31.0 at.% t c/a = 0.913; content C – 32.3 at.% u c/a = 0.911; content C – 29.8-30.3 at.% v c/a = 0.911; content C – 30.6-31.0 at.% w c/a = 0.910; content C – 31.4 at.% x For semicarbide phases in contact with δ-WC1±x phases and α-C (graphite) in arc plasma meltcast three-phase composites (lattice parameters directly depend on C/W ratio in the composites) y c/a = 0.909; content C – 32.8 at.% z Ordered structure prepared by annealing at 850-1200 °C (exposure > 540 h) in contact with monocarbide δ-WC1±x and metallic W phases, parameters of approximately hexagonal lattice: a = 0.2996±0.0002 nm, c = 0.4719±0.0004 nm, c/a = 1.575±0.002 a1 Content C – 32.0 at.%; semicarbide β-W2+xC phase of eutectoid composition (metastable state, rhombic distortion of the W sublattice of the carbide phase) a2 Semicarbide β-W2+xC phase in contact with monocarbide δ-WC1±x phase a3 Content C – 30.5 at.%; ordered structure prepared by annealing at 850-1200 °C (exposure > 540 h) in contact with metallic W phase, parameters of approximately hexagonal lattice: a = 0.2993±0.0001 nm, c = 0.4717±0.0004 nm, c/a = 1.576±0.002 a4 Semicarbide β-W2+xC phase in two/three-phase alloys annealed at 900 °C (exposure – 850 h); total content C – 28.0-37.0 at.%, parameters of approximately hexagonal lattice: a = (0.2994±0.0001)÷(0.3002±0.0002) nm, c = (0.4723±0.0001)÷(0.4732±0.0002) nm a5 Content C – 32.6 at.% a6 Semicarbide γ-W2±xC phase in selective laser melted Ni-W-C materials, acquired from transmission electron microscopy (TEM) selected area diffraction patterns (SADP) a7 Semicarbide γ-W2±xC phase in cast and quenched from high temperatures two-phase alloys with metallic W phase (total content C – 28.5-30.5 at.%) a8 Semicarbide γ-W2±xC phase in cast two-phase alloys with metallic W phase (total content C – 24.0-28.0 at.%) a9 c/a = 1.581; content C – 29.0 at.% b1 c/a = 1.580; content C – 29.5 at.% b2 c/a = 1.580; content C – 29.2 at.% b3 c/a = 1.569; semicarbide γ-W2±xC phase in contact with metallic W phase b4 c/a = 1.573÷1.579; semicarbide γ-W2±xC phase in contact with monocarbide δ-WC1±x phase b5 Content C – 31.0 at.%; semicarbide γ-W2±xC phase in cast single-phase alloys b6 c/a = 1.578; content C – 34.2 at.% b7 c/a = 1.578; content C – 30.5 at.% (cast alloys) b8 c/a = 1.576, content C – 30.5 at.%; parameters of approximately orthorhombic lattice:

2.1 Structures

25

a = 0.4720±0.0003 nm, b = 0.6016±0.0003 nm, c = 0.5180±0.0003 nm b9 Semicarbide γ-W2±xC phase in two/three-phase alloys annealed at 1300 °C (exposure > 100 h); total content C – 28.0-35.0 at.% c1 Semicarbide γ-W2±xC phase in cast two-phase alloys with monocarbide δ-WC1±x phase (total content C – 35.0-48.0 at.%) c2 Semicarbide γ-W2±xC phase in two/three-phase alloys annealed at 900 °C (exposure – 850 h); total content C – 28.0-37.0 at.%, parameters of approximately orthorhombic lattice: a = 0.4726÷0.4732 nm, b = 0.6013÷0.6025 nm, c = 0.5178÷0.5195 nm c3 c/a = 1.576, content C – 32.0 at.%; semicarbide γ-W2±xC phase in cast and quenched from high temperatures single-phase alloys c4 c/a = 1.579, content C – 31.5 at.%; disordered phase (the corresponding lattice parameters of the ordered ε-W2+xC phase are a = 0.5153 nm and c = 0.4681 nm) c5 c/a = 1.575; parameters of approximately orthorhombic lattice: a = 0.4718±0.0003 nm, b = 0.6018±0.0003 nm, c = 0.5182±0.0003 nm (total content C – 35.0 at.%) c6 Content C – 32.4 at.%; semicarbide γ-W2±xC phase in laser engineered hard alloys c7 c/a = 1.578; combined content C – 30.9 at.% (contents: non-combined C < 0.05%, O < 0.023%, N ≤ 0.003%, Mo < 0.01%) c8 Semicarbide γ-W2±xC phase in cast and quenched from high temperatures two-phase alloys with monocarbide δ-WC1±x phase (total content C – 32.5-36.0 at.%) c9 c/a = 1.576; prepared in cast alloys in contact with monocarbide δ-WC1±x phase (total content C – 35.0 at.%) d1 c/a = 1.578; synthesized by electrothermal explosion (ETE) under pressure (variant of selfpropagating high-temperature synthesis (SHS)) in the presence of monocarbide δ-WC1±x phase d2 c/a = 1.577; content C – 32.8 at.% d3 c/a = 1.578, V = 0.1108 nm3; minimal interatomic distances: W-W – 0.278 nm, C-C – 0.299 nm and W-C – 0.215 nm (at 298 K) d4 c/a = 1.578; phase constituent in ultra-fine powders prepared by plasma dynamic synthesis d5 Parameters of W2±xC phase in W2±xC – WS2–x alloy nanoflowers d6 For W2±xC nanosheets

difficult, as their patterns differ only in the region of small angles and their main α (100), β (021) + (002), γ (100) and ε (210) planes/peaks are overlapping each other [2, 18, 80]. The structural features of the tungsten mono- and semicarbide phases are presented in Tables 2.1 and 2.2 (see also Fig. 2.23 and Table 2.20). The variation of the lattice parameter of tungsten monocarbide γ-WC1–x cubic phase with C content in its homogeneity region is shown in Fig. 2.2; the following equation (given in a modified form), described this relationship for 0 ≤ x ≤ 0.4 in γ-WC1–x, was proposed by Kurlov and Gusev [2, 68, 69] on the basis of available experimental sources: a = 0.4260 – 0.0009x – 0.0236x2,

(2.1)

where a is the lattice parameter, nm and x is the value of index in γ-WC1–x formula. The incorporation of C into the γ-WC1–x lattice can be much higher than that predicted by the phase diagram, especially in the metastable and nanostructured materials. The variations of the lattice parameters of tungsten semicarbide α-W2+xC phase with composition in its homogeneity region are given in Fig. 2.3. The effects of temperatures on the lattice parameters of δ-WC1±x, γ-WC1–x and ε-W2+xC phases

26

2 Tungsten Carbides

Fig. 2.2 Lattice parameter of tungsten monocarbide γ-WC1–x phase as a function of phase composition: 1 – melted and rapidly quenched from the liquid state by the use of special apparatus alloys [143-144], 2 – fused and quenched [146], 3 – [145], 4 – heated and quenched in molten Sn [41], 5 – heated and rapidly quenched in molten Sn [46, 80], 6 – data summarized on the basis of several sources by Samsonov and Upadhyaya [8-9], 7 – data summarized on the basis of several sources by Kurlov and Gusev [2, 68, 69]

are demonstrated in Fig. 2.4; the compression effects on the unit cell of tungsten monocarbide δ-WC1±x in the wide ranges of ultra-high pressures, studied at several temperatures experimentally as well as theoretically, are shown in Figs. 2.5 and 2.6, respectively. The similar effect on γ-WC1–x was computed and analysed by Mishra and Chaturvedi [92]. Due to interactions between d-states of W atoms and sp-states of C atoms, chemical bonding in tungsten monocarbide δ-WC1±x is not simply covalent or ionic, but more likely of complicated covalent-ionic-metallic mixed type [89, 243-244]. At ambient and higher (at least – up to 1000-1200 °C) temperatures, the preferred slip systems in δ-WC1±x lattice structure, mainly determined by microdurametric studies, are (1010) , (1010) and (1010) [84-85, 107, 229246, 443, 445, 629-630, 795, 817, 991-993, 1020]; the last one is called by some authors as the primary slip system [107, 232, 240, 243-244], despite the claims that slip can occur on the different planes [84-85, 234-236, 246]. According to the atomistic simulations, the main slip system is (1100) ; in detail, when the compression is perpendicular to the (1120) or (1100) prismatic planes, is the soft direction of the δ-WC1±x crystal [1019]. The (1010) plane is the most ener-

2.1 Structures

27

Fig. 2.3 Lattice parameters of tungsten semicarbide α-W2+xC as a function of phase composition: 1 – hot-pressed, subsequently homogenized at 2200 °C under high purity He of ambient pressure and rapidly quenched into a molten Sn bath preheated to 300 °C alloys, data summarized by Rudy et al. (c/a ratio vs. composition linear relationship from c/a = 1.580 at 29.3 at.% C to c/a = 1.577 at 33.1 at.% C for single-phase semicarbide materials is not shown on the plot) [6, 22-24, 26, 46-48, 80]; 2 – arc-melted in pure Ar shielding atmosphere, subsequently annealed and then quenched materials, data summarized by Kublii and Velikanova [67, 208]; 3 – hot-pressed in vacuum [6, 16]; 4 – sintered [6, 199]; 5 – [6]; 6 – ultra-fine two-phase powders prepared at 1500 °C in vacuum (exposure – 0.5 h) [20]; 7 – sintered [4, 10-12, 43] (data for two-phase (W2C+W, or W2C+WC) materials are marked with partly-filled signs, for single-phase materials – unfilled signs, for each literature source a form of signs does not change with changing in a type of materials)

getically favourable plane for the separation of tungsten monocarbide δ-WC1±x crystal, as each W atom breaks bonds with only two C atoms, and similarly each C atom retains four C-W bonds and breaks only two bonds [245]. The minimal (shortest) Burgers vector of δ-WC1±x (⅓) b = 0.291 nm [85]. For parameters of formation and migration of various lattice point defects in δ-WC1±x see Table 2.19 in section 2.5. The only slip system, which is responsible for plastic deformation in tungsten semicarbide W2±xC phase and subsisting in the wide range of temperatures (from room temperature up to 2200 °C), is the basal (0001) type slip, existing due to the motion of dislocations in the semicarbide lattice basal plane (0001), as it was preciously studied in detail in numerous works [247-257]. The past three decades have been marked by the obvious and massive discoveries and achievements in nanotechnology and their applications in all the human activities [556-558]. Plenty of different nanostructures and nanoarchitectu-

28

2 Tungsten Carbides

See figure legend on the next page

2.1 Structures

29

Fig. 2.4 Lattice parameters of tungsten carbides as functions of temperature for the various phases: a – tungsten monocarbide δ-WC1±x (x = 0): 1 – extrapolation of data calculated by Reeber and Wang [115] and summarized on the basis of several sources [14, 21, 31, 114, 116, 228], 2 – experimental data (lattice parameters c = 0.2876÷0.2885 are not shown on the plot) [226-227]; b – tungsten monocarbide γ-WC1–x (x ≈ 0.18): 3 – summarized on the basis of several sources [224, 228], 4 – estimated using an empirical approach by Singh and Wiedemeier [159]; c – tungsten semicarbide ε-W2+xC (x = 0.22, contents: O – 0.04%, N < 0.01%): 5 – measured by hightemperature X-ray powder diffraction method by Lönnberg [187]

res based on tungsten mono- and semicarbide phases have been synthesized recently, in particular, there are: nanopowders, nanoparticles, nanocubes and nanoclusters (massive variety of conditionally zero-dimensional (0D-) nanostructures in the wide range of sizes from 1-3 nm to submicrometer dimensions, different shapes and compositions, including nano-particles conjugated with carbon nanostructures (see section 2.1 in Volume 1), such as nanotubes, nanocages, nanocapsules, spherical and tubular nanoonions, nanoshells, graphene and graphene oxide layers, and other carbon element forms like activated and mesoporous carbons, biochars, carbon fabrics etc.) [32, 110, 121-122, 124, 127, 138, 167-168, 170, 175, 203, 212, 259-414, 433, 450, 452, 959, 1160, 1164, 1166-1167, 1169, 1172-1173, 1177-1179, 1326, 1386, 1409-1410, 1418-1419, 1423, 1433, 1437-1438, 1453, 1456, 1458, 1469, 1477, 1490, 1500, 1504, 1511, 1521, 1559, 1589-1592, 1600, 1603, 1609, 1620, 1632-1633, 1636, 1638-1639, 1646, 1656, 1665-1666, 1683, 1687, 1691, 1696,

30

2 Tungsten Carbides

Fig. 2.5 Experimentally determined variations of the lattice parameters of tungsten monocarbide δ-WC1±x phase with ultra-high pressure at several temperatures: 1 – 99.99 % purity powder (mean particle size < 1 μm, a0 = 0.2906 nm, c0 = 0.2838 nm, c0/a0 = 0.9766), the values of experimental pressures at higher temperatures (up to 1200 °C) are accepted in accordance with the calculations based on the Dorogokupets-Devaele equation of state for MgO [42]; 2 – fine powder (a0 = 0.2908 nm, c0 = 0.2841 nm, c0/a0 = 0.9770), ruby, NaCl and Au were used as internal pressure calibrants [88]; 3 – nanocrystalline phase (mean particle size – ~25 nm, a0 = 0.2903 nm, c0 = 0.2843 nm, c0/a0 = 0.9793), ruby was used as an internal pressure calibrant [127]

1704-1705, 1708, 1729, 1733, 1751, 1754, 1777, 1872, 1880, 2034-2035, 2060, 2073, 2126, 2253, 2303, 2316, 2372, 2376-2379, 2644, 2757, 2843, 2851, 2954, 2986, 3865, 4259, 4282, 4367-4369, 4493, 4499-4501, 4640]; nanopolyhedrons (with the mean size of ~400 nm) [415]; nanorods (variety of conditionally one-dimensional (1D-) nanostructures with diameters – 25-200 nm, typical lengths – 150-600 nm (sometimes – up to 2-10 μm and even 200 μm) and high specific surface areas (> 20-30 m2 g–1), including hollow nanorods, e.g. with inner/outer diameters – ~ 50/100 nm) [372, 387, 408, 418-433, 442, 1161, 1170, 1648];

2.1 Structures

31

Fig. 2.6 Theoretically calculated variations of the lattice parameters of stoichiometric tungsten monocarbide δ-WC1±x (x = 0) phase with ultra-high pressure at several temperatures: 1 – on the basis of density functional theory (DFT) by the all-electron projector augmented wave (PAW) method within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional (a0 = 0.2935 nm, c0 = 0.2859 nm, c0/a0 = 0.9741) [89]; 2 – on the basis of DFT by the plane-wave ultra-soft pseudopotential total energy method using Broyden-FletcherGoldfarb-Shanno (BFGS) scheme (a0 = 0.2903 nm, c0 = 0.2843 nm, c0/a0 = 0.9793) [127]; 3 – on the basis of DFT using the Troullier-Martins norm-conserving pseudopotentials within the GGA of Perdew-Wang (PW91) scheme (a0 = 0.2909 nm, c0 = 0.2829 nm, c0/a0 = 0.9725) [133]; 4 – on the basis of DFT by the full-potential linearized augmented-plane-wave (FP-LAPW) method within the GGA (a0 = 0.2926 nm, c0 = 0.2849 nm, c0/a0 = 0.9736) [92]

nanoneedles and whiskers (conditionally one-dimensional (1D-) nanostructures with diameter – ~50 nm and length – ~1 μm) [420, 424, 435, 452-453, 457, 1567]; nanowires (variety of conditionally one-dimensional (1D-) nanostructures with typical diameters and lengths – 15÷500 nm and 0.2÷15 μm, respectively, having sometimes quasi-rectangular cross-sections with approximate dimensions in the wide range of ~ (250÷500) nm × (250÷1500) nm and including various hollow,

32

2 Tungsten Carbides

mesoporous, amorphous (or partly amorphous), hybrid/composite and nanocarbon-conjugated nanowires) [171, 404, 421, 424, 434-444, 452, 704, 753-757, 2415]; nano- and microfibers (variety of conditionally one-dimensional (1D-) nanostructures with linear dimensions in the very wide ranges from 30 nm to 40 μm and from few micrometers to several centimeters for diameter and length, respectively, including nanocarbon-conjugated fibers and nanofibers with the specific surface areas of 45-50 m2 g–1) [372, 446-451]; nanotubes (variety of conditionally one-dimensional (1D-) nanostructures, experimentally synthesized straight, coiled or zigzag in shape, outer diameter – 30-80 nm, for maximum outer diameter: inner diameter – 20 nm with wall thickness – 25 nm, length – 0.5-5.0 μm; for the theoretically DFT-simulated single-walled tungsten monocarbide nanotubes the W-W, C-W and C-C bond lengths were calculated to be 0.2914 nm, 0.2082 nm and 0.2913 nm in a zigzag (4, 0) nanotube and 0.2921 nm, 0.2060 nm and 0.2921 nm in a zigzag (10, 0) nanotube, respectively) [421, 424, 452-456]; various nanoarrays of nanopillars (nanorods) or nanobelts (hierarchic nanostructures (or nanoarchitecture), some nanoarrays are composed of thin nanobelts, e.g. with length – ~600 nm, width – ~200 nm and thickness – ~30 nm, and nano-belts are composed of omnifarious nanoparticles) [431-433, 1161, 1170, 1175]; nanoflowers (hierarchic nanostructures (or nanoarchitectures), exhibiting abundant flower-shaped active sites, in the range from 200 to 400 nm in size) [563, 769]; nanoplatelets, nanowalls, nanosheets and nanoslices (variety of conditionally two-dimensional (2D-) nanostructures, plane nanostructures with various characteristics and linear dimensions from 20 to 800 nm (sometimes 3-D nanostructures with thickness – up to 90 nm), including multi-phase, ordered, mesoporous nanoplates with specific surface area > 30 m2 g–1, average diameter of pores – 3-4 nm and various characteristics) [404, 420, 424, 436, 458-463, 704, 769, 1530, 1607, 1659, 1742, 2358]; nanocoatings, thin and ultra-thin films (massive variety of conditionally twodimensional (2D-) nanostructures, deposited on various substrates with thicknesses from 5-10 nm up to 10-20 μm, including composite films with metastable tungsten carbide (W3+xC-like with 0 ≤ x ≤ 9) phase and different crystalline (graphene-like, diamond-like) and amorphous carbon phase constituents and nanocrystalline films with ultra-small grain sizes – up to ~ 1-2 nm) [94-96, 99-101, 157-158, 175-177, 272, 422, 433, 435, 464-555, 565, 709, 731, 755, 757, 842, 844-846, 979, 1066, 1162, 1168, 1389, 1403-1405, 1490, 2148-2149, 2262, 4022, 4426-4427, 4429-4433, 4439]; hollow microspheres or hemisphere-shaped structures (hierarchic nanostructures (or conditionally 2.5D-nano-structures) with average diameters in the range from

2.1 Structures

33

0.5 to 5.0 μm and wall thickness of ~50 nm, having specific surface areas – up to ~400 m2 g–1) [416-417, 1382-1384, 1467, 1474, 1506, 1647, 1654, 1661, 1663, 1671, 1745]; nanocrystalline bulk materials (massive variety of three-dimensional (3D-) nanostructures, including composite and hybrid materials with quite different structural types) [2, 127, 166, 260-263, 269, 275, 294, 317-318, 562, 577] were reported up to date in the numerous works published in literature. Monocarbide γ-WC1–x (cubic) phase is stable in the bulk materials only at very high temperatures; however, at rather lower temperatures, it can form as thin interfacial structures or nanoparticles [4385]. Revolutionary advances in physics and chemistry of 2D-atomic crystals [556558] resulted in the discovery of an entirely new widespread family of metal carbides in the 2D-molecular state termed as MXenes, due to their origins from MAX phases and similarities of their structures to molecular graphene, with the general formula of (M′yM″1−y)n+1(CzN1−z)nTx, where M′ and M″ are early transition metals (co-host carbide or carbonitride metals), 1 ≤ n ≤ 4 and T are functional surface groups OH, O, F, Cl and others [559-561, 563-564]. Taking no account of the obtainment of 2D nanometer-thin crystals of Mo, Ta and W carbides by Xu et al. [565], who used a chemical vapour deposition method for the synthesis and growth of these crystals, Meshkian et al. [566] were the first to synthesize W-based MXenes; successfully to achieve it, step-by-step they had to predict by DFTcalculations, synthesize and then selectively etch the new W-based i-MAX phases [568], where W is a co-host carbide metal jointly with Sc or Y. As a result of complex investigations, 2D-molecular W1.33C (or (W4/3□2/3)C) MXenes (atomic laminates) with ordered metal divacancies were produced, followed later by the preparation of 2D-nanolamellar (W,Ti)4C4–x (with the refined formula of (W2.1Ti1.6)C2.6) realized by Anasori et al. [567]. Several works published during the last years were devoted to the theoretical prediction of possible synthesis ways and physical and chemical properties of 2D-nanolayered tungsten containing carbide phases [569-576]. Theoretically calculated sequence for the fully stoichiometric W-C phases with respect to their densities β-W2+xC > γ-W2±xC > ε-W2+xC > α-W2+xC > δ-WC1±x > γ-WC1–x [82] is not agreed with the following sequence: α-W2+xC > γ-W2±xC > γ-WC1–x ≥ ε-W2+xC > β-W2+xC > δ-WC1±x (see also Tables 2.1 and 2.2), which is based on the experimental data from different diffraction measurements and gives us directly for each phase the following approximate values in g cm–3: 17.40, 17.35, 17.27, 17.23, 17.10, 15.70, respectively; it is necessary to note that all the DFTcalculated lattice parameters in [82] are much higher than the experimental data and result in the certainly lower values for phase densities. According to Taimatsu et al. [785], the measured bulk density of single-phase α-W2+xC materials (spark-plasma sintered at 1700 °C, porosity – ~2 %) almost linearly decreased within the phase homogeneity region from 16.85 g cm–3 for W2.24C to 16.65 g cm–3 for W1.99C, while being corrected to porosity the density showed no apparent dependence on carbon

34

2 Tungsten Carbides

content, averaging close to 17.2 g cm–3. The recommended values for the bulk (or pycnometric) densities of highly pure (single-phase) poreless tungsten monocarbide δ-WC1±x and semicarbide W2±xC materials at room temperature are 15.6-15.7 and 17.2-17.3 g cm–3, respectively [1, 3-5, 11-13, 43, 45, 85, 87, 118, 150-151, 200, 553, 577-591, 594, 608, 621, 627, 698, 735, 812-813, 858, 895, 995-997, 1022, 2062, 2734, 4505].

2.2 Thermal Properties The tungsten mono- and semicarbide phases have their melting points higher than 2500 °C (see Fig. 2.1). Compared with the transition metal carbides of 4-5 groups, which were described in the previous volumes, the melting point temperatures of tungsten carbides are lower than those of carbides 4-5 groups, but also, in opposite to them, much lower than that of their forming metal W; these parameters are almost the same for both polymorphs of monocarbide and the semicarbide phase, in opposite to the carbides of 5 group, where the semicarbides have noticeably lower melting points than those of monocarbide phases. The maximum congruent melting temperature of γ-W2±xC phase is observed at a composition of W~2.3C and that of γ-WC1–x – at WC0.60÷0.65 [2, 6-9, 47-48, 57, 68-69, 86, 128, 613]. The general thermodynamic properties of tungsten mono- and semicarbide phases are summarized in Tables 2.3 and 2.4, respectively. For the molar heat capacity of tungsten monocarbide δ-WC1±x phase, cp = f(T, K), J mol–1 K–1, the following relationships were recommended in the literature: for WC~1.0 (in the range of temperatures from 298 to 2000 K) [12, 151, 580, 584, 610, 622] cp = 33.39 + (9.079×10–3)T,

(2.2)

for WC~1.0 (in the range of temperatures from 298 to 3060 K) [613, 616] cp = 51.34 + (8.619×10–3)T – (1.121×106)T –2,

(2.3)

for WC0.99 (in the range of temperatures from 1275 to 2640 K) [151, 595-596] cp = 41.86 + (7.472×10–3)T,

(2.4)

for WC0.99 (in the range of temperatures from 298 to 3000 K) [6, 85] cp = 41.54 + (8.987×10–3)T – (5.465×10–7)T 2 – (3.906×105)T –2.

(2.5)

For the molar heat capacity of tungsten semicarbide W2±xC phases cp = f(T, K), J mol–1 K–1, the following relationships were recommended in the literature:

2.2 Thermal Properties

35

Table 2.3 General thermodynamic properties of tungsten monocarbide δ-WC1±x phase Characteristics

Symbol a

Unit

Value

References

–1

35.14±0.8

[13, 118, 151, 598, 613]

35.19±0.8

[8-9, 43, 200, 586, 594, 601602, 605, 639, 659]

35.36

[115]

37.70

[45]

38.07±9.5

[8-9, 12, 579580, 584, 604, 610, 622, 626, 654]

40.20±0.6

[201, 618, 623]

40.46±1.7

[6, 596-598, 619, 641]

40.58±1.7b

[1, 51, 599, 637]

40.90±4.6c

[56, 637]

Standard heat of formation (at 298.15 K) –ΔH°298 kJ mol

44.00±3.0

Standard molar entropy (at 298.15 K and S°298 101.3 kPa)

Standard molar heat capacity (at 298.15 K c◦p,298 and 101.3 kPa)

–1

J mol K

[56, 637]

44.40±0.8

[49]

48.80

[201, 637]

J mol–1 K–1 32.10

–1

d

[632]

32.38

[1, 51, 599, 618]

35.56±6.3

[12, 151, 200, 579, 585, 610, 622, 659]

37.66±6.3

[118, 584]

39.75±2.1

[13, 613, 616]

41.80±4.2

[637-638]

35.37

[1, 51, 115, 599, 618]

35.69±2.1

[12, 200, 151, 579, 584-585, 610, 626, 659]

36.11

[118, 584]

38.13

[674, 981]

39.75e

[6-7, 45, 85, 595-596, 600, 641]

41.29±4.2

[13, 613, 616]

(continued)

36

2 Tungsten Carbides

Table 2.3 (continued) Specific heat capacity (at 298.15 K) f

c

J kg–1 K–1

Molar enthalpy (heat) of vaporization (dissociation) g

ΔĤv

kJ mol–1

Melting (decomposition) point h

Tm

K (°C)

180.0

[1016]

184.0

[584, 627]

210.8

[13]

741.4

[654]

2800 (2530) [627] 2870 (2600) [118, 621] 2900 (2630) [13, 614, 622] 2920±50 (2650±50)

[13, 44]

2950 (2680) [120] 2995 (2720) [12-13, 580, 584, 611-612, 626, 639, 654] 3021±1 (2748±1)

[71-79]

3030 (2755) [6, 41, 641] 3050±4 (2775±4)

[6, 46-47, 61, 583, 618, 633, 641, 2000]

3054±4 (2780±4)

[1, 13, 44, 609, 735, 4586]

3058±5 (2785±5)

[13, 128, 151, 156, 579, 613, 617, 625, 4171]

3060 (2790) [1032] 3070 (2800) [584, 627, 2734] 3100 (2830) [553] 3140±50 (2870±50)i

[11, 13, 44-45, 200, 586, 608, 631, 1022, 2986, 4505]

3170 (2900) [150, 816] 3250 (2975) [584-585] Boiling point

a

Tb

K (°C)

6270 (6000) [11-13, 553, 580, 585-586, 626, 646, 4171]

Enthalpy (heat) of complete dissociation (atomization) of fully stoichiometric phase from solid state at 298,15 K (–ΔatH°298, kJ mol–1): 1573 [151], 1590 [605], 1600±50 [121, 604], 1610±7 [1], 2040 [606]; formation energy Ef, eV f-u–1 (kJ mol–1), calculated on the basis of density functional theory (DFT) by the full-potential linearized augmented-plane-wave (FP-LAPW) method within the generalized gradient approximation (GGA), is –0.339 (–32.71) [82], calculated on the basis of DFT by the projector augmented wave (PAW) method using the Perdew-Burke-Ernzerhof (PBE) potentials, is –0.374 (–36.09) [141] and estimated on the basis of molecular dynamics (MD) simulation within a second-nearest-neighbor modified embedded-atom method (2NN MEAM)

2.2 Thermal Properties

37

potential, is –0.560 (–54.03) [90] b Recommended value on the basis of several sources c Obtained from e.m.f. measurements (BaF2 – β-BaC2 solid solutions) on a galvanic cell with Cr3C2–x d Obtained from e.m.f. measurements (BaF2 – β-BaC2 solid solutions) on a galvanic cell with α-Mo2+xC e Carbon content – 49.7 at.% f Approximate specific heat capacity c, J kg–1 K–1, of δ-WC1±x materials at higher temperatures: 210-270 (at 730 °C), 270-330 (at 1730 °C) and 330-350 (2730 °C) [13, 581] g For the dissociation of stoichiometric δ-WC1±x phase, according to the reaction: (δ-WC1±x)solid = (W2±xC)solid + Cgas; molar enthalpy (heat) of dissociation at the congruent vaporization (calculated on the basis of thermodynamical data) ΔĤv = 793.2 kJ mol–1 h High-pressure melting curve was determined up to 3800 K (3500 °C) [647] i Melting temperature for the interval of pressures from ambient up to 8 GPa [631] Table 2.4 General thermodynamic properties of near-stoichiometric semicarbide W2±xC phases a Characteristics

Symbol

Unit

c

Standard heat of formation (at 298.15 K) –ΔH°298 kJ mol

Standard molar entropy (at 298.15 K and S°298 101.3 kPa)

Molar enthalpy difference

–1

Value b

References

26.36±2.5

[5-6, 49, 596598, 618-619, 637]

29.66±20.9

[579, 584, 626]

30.54±2.5

[49]

31.59±1.7

[598, 615]

46.05±16.7

[8-9, 13, 151, 200, 580, 603, 613, 616, 654, 659]

54.39

[586]

J mol–1 K–1 56.07

[618]

H298 – H0 kJ mol–1

81.59±4.2

[13, 613, 616]

91.00d, e

[201]

1.363d

[201]

Standard molar heat capacity (at 298.15 K c◦p,298 and 101.3 kPa)

J mol–1 K–1 70.42d, f

Specific heat capacity (at 298.15 K)

c

J kg–1 K–1

201.9

[13]

Molar enthalpy (heat) of vaporization (dissociation) g

ΔĤv

kJ mol–1

757.3

[654]

Melting point

Tm

K (°C)

3000±15 (2730±15)h

[4, 43, 45, 200, 580, 584, 626627, 654]

76.65±5.9

[201] [13, 579, 613, 616, 618]

3010 (2735) [6, 639] 3020 (2750) [118, 621] 3028±15 (2755±15)

[1]

(continued)

38

2 Tungsten Carbides

Table 2.4 (continued) 3050±12 (2780±12)

[61, 583]

3060 (2785) [156, 625] 3068 (2795) [13, 151, 579, 613, 617-618] 3120±50 (2850±50)

[44]

3130±50 (2860±50)

[11, 586, 608609]

3150 (2880) [11] 3270 (3000) [2734] Boiling point a

Tb

K (°C)

6270 (6000) [11-13, 580, 586, 626]

Temperature of α-W2+xC ↔ β-W2+xC transformation is ~2300 (~2030) K (°C) [580], ~2370 (~2100) K (°C) [128, 156, 625]; temperature of β-W2+xC ↔ γ-W2±xC transformation is 2650±30 (2380±30) K (°C) at carbon content – 33.4 at.% [128, 156, 625], 2727±20 (2455±20) K (°C) at carbon content – ~33.3 at.% [1, 580], 2760±30 (2490±30) K (°C) at carbon content – 32.6 at.% [128, 156, 625], 2798 (2525) [613] with enthalpy (heat) of transformation ΔHtr = 29.7 kJ mol–1 [584, 627] b When it is not indicated specially, value reported is for quasi-stoichiometric composition c Enthalpy (heat) of complete dissociation (atomization) of fully stoichiometric phase from solid state at 298,15 K (–ΔatH°298) is 2450±13 kJ mol–1 [1]; formation energies Ef, eV f-u–1 (kJ mol–1), calculated on the basis of density functional theory (DFT) by the full-potential linearized augmented-plane-wave (FP-LAPW) method within the generalized gradient approximation (GGA), for α-, β-, ε-W2+xC and γ-W2±xC modifications of tungsten semicarbide are +0.191 (+18.43), –0.017 (–1.64), –0.044 (–4.25) and +0.019 (+1.83), respectively [82-83], calculated on the basis of DFT within the GGA using the Perdew-Burke-Ernzerhof (PBE) functional, for α-, β-, ε-W2+xC and γ-W2±xC modifications are +0.195 (+18.82), –0.054 (–5.21), –0.009 (–0.87), –0.087 (–8.39), respectively [36], calculated on the basis of DFT by Vanderbilt ultra-soft pseudopotential (USPP) within the GGA using Perdew-Wang (PW91) scheme, for α-, β-, ε-W2+xC and γ-W2±xC modifications are +0.010 (+0.96), –0.231 (–22.29), +0.815 (–78.64), –0.186 (–17.95), respectively [196], calculated on the basis of DFT by the projector augmented wave (PAW) method using the PBE potentials, for α-, β-W2+xC and γ-W2±xC modifications are +0.030 (+2.89), – 0.180 (–17.37), +0.030 (+2.89), respectively [141] and estimated on the basis of molecular dynamics (MD) simulation within a second-nearest-neighbor modified embedded-atom method (2NN MEAM) potential, for β-W2+xC and γ-W2±xC modifications (at 0 K) are –0.097 (–9.36), – 0.347 (–33.77), respectively [90] d For semicarbide W2±xC phase (with carbon content – 29.4 at.%), containing the following impurities: δ-WC1±x – 33.1 %, θ-Fe3C – 0.3% and α-C (graphite) – 0.2 %, on the basis of its molar mass M (W~2.40C) = 453.23 g mol–1 e Molar entropy at 1000 K is 159.8 J mol–1 K–1 on the basis of accepted molar mass M (W~2.40C) = 453.23 g mol–1 f Molar heat capacity at 1000 K is 92.1 J mol–1 K–1 and at 2000 K is 98.4 J mol–1 K–1 (estimated assuming a linear heat capacity increase with temperature) on the basis of accepted molar mass M (W~2.40C) = 453.23 g mol–1 g For the dissociation of stoichiometric W2±xC phase, according to the reaction: (W2±xC)solid = 2(W)solid + Cgas; molar enthalpy (heat) of dissociation at the congruent vaporization (calculated on the basis of thermodynamical data) ΔĤv = 810.4 kJ mol–1 h Content C – ~33.3 at.%

2.2 Thermal Properties

39

for W~2.0C (in the range of temperatures from 298 to 3070 K) [613, 616] cp = 89.75 + (1.088×10–2)T – (1.456×106)T –2,

(2.6)

for W~2.40C (in the range of temperatures from 10 to 1000 K) summarized and computed on the basis of several sources (given in a modified form) [201, 595, 632, 634] cp = 48.95 + (1.491×10–2)T – (2.539×10–6)T 2 – (9.146×105)T –2.

(2.7)

For the specific heat capacity of tungsten monocarbide WC0.99 materials, c = f(t, °C), J kg–1 K–1, the following relationship was recommended (for the range of temperatures from 1000 to 2300 °C) [13, 45, 595]: c = 214.2 + (3.840×10–2)(t + 273).

(2.8)

The experimentally determined and theoretically calculated variations of molar heat capacity c with temperature for tungsten monocarbide and semicarbide phases are demonstrated on the basis of several sources in Fig. 2.7. The thermodynamic functions of tungsten monocarbide δ-WC~1.0 are tabulated by Wicks and Block [622], Krzhizhanovskii et al. [584] and Grønvold et al. [201] in the range of 298.152000 K, by Barin [618] in the range of 298.15-2500 K, by Storms [6], Toth [7], Chang [634-635] and Turchanin A and Turchanin M [596] in the range of 298.153000 K and by Schick [613] in the range of 298.15-3058 K; the thermodynamic functions of tungsten semicarbide are tabulated by Schick [613], Pankratz et al. [636] and Barin [618] for W~2.0C phase in the range of 298.15-3068 K and by Grønvold et al. [201] for W~2.40C (W2C0.833) phase in the ranges of 0-1000 K and 298.15-2000 K. At the ambient temperatures single-phase (non-stoichiometric) cubic tungsten monocarbide γ-WC1–x (DFT-calculated formation energy Ef = +0.562 eV f-u–1 (+54.22 kJ mol–1) [82], or +0.526 eV f-u–1 (+50.75 kJ mol–1) [141], MD-estimated energy formation Ef = +0.1 eV f-u–1 (+9.65 kJ mol–1) [90]), which is thermodynamically stable only in the range of temperatures from its melting point (~3020 (~2750) K (°C) [583, 607], ~3030 (~2760) K (°C) [2, 68-69], 3060±5 (2785±5) K (°C) [128, 156, 625]) to its decomposition (to γ-W2±xC + δ-WC1±x) point (~2800 (~2525) K (°C) [2, 68-69, 607], ~2810 (~2535) K (°C) at carbon content – 37.538.0 at.% [128, 156, 625]), has molar heat capacity cp = 39.77 J mol–1 K–1 [607]. Vaporization of any ultra-high temperature materials in a vacuum is an important factor limiting the working capacity and technical applications of materials [5-9, 13, 16, 598, 643, 654]. Afore at 2000 K (1980 °C), the vapour pressure of C above the δ-WC1±x surface reaches 2.67×10–4 Pa [585]. According to Hoch et al. [640], who studied the vaporization process of tungsten semicarbide phases with approximate compositions of W1.81÷2.61C (with the obvious presence of monocarbide phase) by the Langmuir method in the interval of temperatures from 2255 K (1980 °C) to

40

2 Tungsten Carbides

See figure legend on the next page

2.2 Thermal Properties

41

◄ Fig. 2.7 Variations of molar heat capacity c of tungsten carbide phases with temperature: a – data obtained experimentally at constant pressure, cp (1 – W~2.0C, on the basis of several sources [613, 618]; 2 – δ-WC~1.0, on the basis of several sources [13, 613]; 3 – δ-WC0.99±0.01, contents: N < 0.1%, Fe – 0.4%, Si – 0.3% [581, 600, 620]; 4 – δ-WC0.99, on the basis of several sources [6-7, 595-596]; 5 – δ-WC~1.0, summarized on the basis of several sources [618]; 6 – δ-WC~1.0, on the basis of several sources [584, 622]; 7 – δ-WC~1.0 [118, 581]) and b – theoretically calculated values for stoichiometric δ-WC1±x phase (at constant pressure, cp: 8 – calculated on the basis of Debye-Grüneisen modeling approaches [115]; 9 – calculated on the basis of density functional theory (DFT) by the all-electron projector augmented-wave (PAW) method within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional for zero pressure [89]; 10 – calculated using the same scheme for the ultra-high pressure (100 GPa) environment [89] and at constant volume, cv: 11 – calculated on the basis of DFT using TroullierMartins norm-conserving pseudopotentials within GGA of Perdew-Wang (PW91) scheme for zero pressure [133]); data on low-temperature measurements (1.5-15 K) of cp for δ-WC1±x phase [628] and DFT calculations within the GGA using PBE functional (1-50 K) of cp for α-W2+xC, ε-W2+xC, β-W2+xC, γ-W2±xC, γ-WC1–x and δ-WC1±x phases [36] are not shown on the plot directly

2755 K (2480 °C), the vapour pressure of C, PC, Pa and general evaporation rate G, g cm–2 s–1 increase noticeably with the temperature growth from 2.90×10–4 and 9.24×10–9 to 8.62×10–2 and 2.49×10–6, respectively; the vapour pressure of C above the surface of tungsten carbides was revealed to be very close to that of C above the surface of pure graphite phase, and evaporation rates from both surfaces were found to be commensurable within the limits of measurement errors. The preferential vaporization of C atoms (with the evaporation coefficient of C1 being near unity) from δ-WC1±x [6], having a limited homogeneity range (see section 2.1), leads to the essential loss of C in the crystal lattice and subsequent transition of the vaporization process to the δ-WC1±x + W2±xC and then to W2±xC + W two-phase regions [16, 640, 645]. At high and ultra-high temperatures in vacuum tungsten monocarbide δ-WC1±x phase does not dissociate into the elements (no evidence of congruent vaporization was observed), it disproportionates into semicarbide W2±xC at temperatures > 2350 K (2080 °C), according to the following scheme [598, 642]: (δ-WC1±x)solid = (W2±xC)solid + Cgas, for this process in the temperature range of 1000-3000 K (730-2730 °C), on the basis of thermodynamical calculations, the following simplified relationships were derived for the vapour pressure of C, PC, Pa and total pressure of all the components of vapour phase above δ-WC1±x, PΣ, Pa, respectively [654]: lgPC = – (3.878×104)/T + 13.17,

(2.9)

lgPΣ = – (3.892×104)/T + 13.31,

(2.10)

where T is temperature, K; at the vaporization from the exposed surface due to a lack of equilibrium vapour above the solid phase, semicarbide phases dissociate

−

lgPΣCx d, Pa

−

−

−

−

−

lgPW, Pa

lgPC, Pa

lgPC2, Pa

lgPC3, Pa

lgPΣ b, Pa

8.329

−

lg(ΣC/W) e

0.63

99.37

158.12

−14.906

−14.909

1500 (1230)

8.39

91.61

10.91

−8.521

−8.559

2000 (1730)

6.426

−

−

−

−

−

−12.100

−18.507

2500 (2230)

5.931

−2.177

−7.755

25.40

74.60

2.94

−5.644

−5.771

5.842

−1.156

−6.606

34.89

65.11

1.87

−4.632

−4.818

W – W2±xC phases equilibrium

2350 (2080)

5.717

0.611

−4.688

54.42

45.58

0.840

−2.897

−3.238

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

65.43

34.57

0.528

−1.908

−2.369

3000 (2730)

(88.91)

(11.09)

(0.125)

(1.622)

(0.667)

4000 (3730)

−1.908

−7.777

−5.667

−2.386

−2.084

5.653

1.595

−3.627

1.546

−3.257

−1.435

1.066

1.371

5.505

5.034

0.014

W2±xC – C phases equilibrium

2800 (2530)

Temperature, K (°C)

Congruent dissociation of quasi-stoichiometric W2±xC

5.878

−5.423

−11.063

W2±xC – δ-WC1±x phases equilibrium

lgPW, Pa

W

C

−

−

(ΣC/W) c

100.0

−

Contents, vol.%:

−

lgPΣ b, Pa

1000 (730)

lgPC, Pa

Parameters

(continued)

3.459

−1.033

0.785

2.977

3.284

4.775

6.393

2.085

(96.32)

(3.68)

(0.038)

(3.671)

(2.237)

5000 (4730)

Table 2.5 Parameters of the gaseous phase in the W – C system in the conditions of W – W2±xC, W2±xC – δ-WC1±x and W2±xC – C phases equilibrium and congruent dissociation of quasi-stoichiometric W2±xC, calculated on the basis of thermodynamic data a [642]

42 2 Tungsten Carbides

−

−

−

C2

C3

W

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

−

66.70

0.02

33.28 − 66.79

0.11

33.10 −

66.80

0.003

0.21

32.98

Σ (Total) − − − − − − 100.0 100.0 100.0 a The values in parentheses/brackets are obtained by extrapolation b Total gas pressure in the system c The ratio between the number of all C species (C, C2, C3… Ci) and number of W atoms in gaseous phase d Total pressure of all C species (C, C2, C3… Ci) e Logarithm of the ratio between the number of all C species (C, C2, C3… Ci) and number of W atoms in gaseous phase f For the general calculation of ultra-high temperature process of congruent dissociation of quasi-stoichiometric W2±xC, the existence of C4, C5 and C6 components is negligible

−

C

Contents f, vol.%:

Table 2.5 (continued)

2.2 Thermal Properties 43

44

2 Tungsten Carbides

into the elements, but as the evaporation rate of W is essentially lower than that of C [644] (see also Table A.5), the solid surface of materials is to be enriched with W metal: (W2±xC)solid = 2(W)solid + Cgas, for this process in the range of 1000-4700 K (730-4430 °C) temperatures, on the basis of thermodynamical calculations, the following simplified relationships were derived for the vapour pressure of C, PC, Pa and total pressure of all the components of vapour phase above W2±xC, PΣ, Pa, respectively [654]: lgPC = – (3.956×104)/T + 13.24,

(2.11)

lgPΣ = – (4.140×104)/T + 14.18,

(2.12)

where T is temperature, K. More likely, the congruent vaporization of W2±xC (W2±xC)solid = 2(W)gas + Cgas could be expected only in the interval of temperatures > 3000 K (2730 °C). The results of thermodynamic calculations of parameters of the gaseous phase in the W− C system in the various equilibrium conditions at high and ultra-high temperatures are given in Table 2.5. The evaporation rate G, g cm–2 s–1 of C from δ-WC1±x in the temperature range from 2250 K (1975 °C) to 2920 K (2650 °C) is described satisfactorily by the following temperature dependence, proposed earlier by Vlasov and considered in detail by Bolgar et al. [598]: lgG = – [(34.310±1.430)×103]/T + (6.317±0.571),

(2.13)

where T is temperature, K. The vaporization processes of tungsten carbides in some special conditions, mainly also connected with loss of C, and theoretical modeling of gas phase species in the W – C system were considered in several published works as well [648-653]. The values of general thermodynamic properties and vapour pressures for tungsten carbides are given in Addendum in comparison with all other ultra-high temperature materials in the wide ranges of temperatures. At room temperature the thermal conductivity λ of tungsten carbide phases lies in the wide interval of temperatures from ~30 up to ~200 W m–1 K–1 [1, 3-4, 1213, 43, 45, 85, 118, 151, 200, 553, 581, 600, 607, 610, 626-627, 655-658, 660666, 682, 735, 1016, 1993, 2000, 2734]. The variations of thermal conductivity with temperature for tungsten carbide materials on the basis of several sources are shown in Fig. 2.8 in the wide ranges from cryogenic to ultra-high temperatures. Depending on the correspondence between its electron and phonon constituents determined by the intrinsic defects and impurities, the thermal conductivity of δ-WC1±x can either grow or decline with the temperature growth [658]. Nonetheless, tungsten monocarbide has the highest value of this property of any of

2.2 Thermal Properties

45

Fig. 2.8 Variation of thermal conductivity λ with temperature for tungsten carbide materials: 1 – hot-pressed, high-purity δ-WC~1.0, porosity 5 % [581, 600, 660]; 2 – recommended values for δ-WC1±x [13]; 3 – recommended values for W2±xC [13]; 4 – δ-WC1±x [1, 118, 151, 200, 607, 610, 627]; 5 – W2±xC [3, 12-13, 85, 151, 200, 626]; 6 – W2±xC [627]; 7 – hot-pressed δ-WC1.02, corrected to porosity [85, 658]; 8 – hot-pressed, high-purity δ-WC~1.0, mean grain size – 44 μm, contents of metallic impurities < 0.1 % [45, 655]; 9 – δ-WC1±x [662, 665]; 10 – hot-pressed δ-WC 8) [716-717]. For moderate and elevated temperatures in the range of 300-1250 K (20-1000 °C) Kurlov et al. [2, 69, 281, 292, 718] proposed the following equation, which describes the magnetic susceptibility – temperature relationships, typical for the temperature dependence of Pauli paramagnetism: χ (T) = A + BT 2,

(2.22)

where χ is the magnetic susceptibility of δ-WC1±x, T is temperature, K, and A and B are the constants calculated from the experimental data, which, for example, for the molar susceptibility χm (SI) of highly purified powdered δ-WC1.00 (mean particle size – 4-9 μm, contents: O – 0.10%, N < 0.02%, Me1 (Fe, Co, Ni) < 0.00001%, Me2 (Gd, Dy, Tb, Ho, Er, Tm) < 0.000005%) are equal to ~140×10–6 cm3 mol–1 and ~3.2×10–11 cm3 mol–1 K–2, respectively. The decrease in the susceptibility χ of conventional δ-WC1±x materials with an increase in temperature, which is observed in practice [715], mainly indicates the presence of some ferromagnetic impurities (most likely Fe) in the carbide materials [2]. The behaviour of plasma-chemically synthesized, nanocrystalline powders of δ-WC1±x, concerning their magnetic properties, was studied by Kurlov et al. [2, 281, 292, 718] and W-C-based thin films with diamagnetic properties – by Taylor [464] and Miki et al. [709]. According to the first principles calculations carried out by Suetin et al. [82-83, 219], the Pauli paramagnetic susceptibility (or paramagnetism of conduction electrons), as a constituent of the sum of few contributions to the complete magnetic susceptibilities of W-C phases, decreases in the following order: γ-WC1–x > ε-W2+xC > γ-W2±xC > β-W2+xC > α-W2+xC > δ-WC1±x. Dielectric and electromagnetic attenuated properties of δ-WC1±x were studied by Yang et al.

2.3 Electro-Magnetic and Optical Properties

53

Fig. 2.10 Room-temperature reflectance spectrum of polished hot-pressed δ-WC1±x materials from the ultraviolet to infrared wavelength regions [724]

[1014]. No experimental data on the magnetic properties of tungsten monocarbide γ-WC1–x and semicarbide W2±xC phases are available in the literature. The optical spectroscopy properties of δ-WC1±x and various bulk and film tungsten carbide containing materials were studied by several researchers [8-9, 495, 719-729]. The reflectance spectrum of hot-pressed δ-WC1±x from the ultraviolet (UV) to infrared (IR) wavelength regions obtained by Ivanchenko [724] at ambient temperatures is shown in Fig. 2.10. The optical properties are also anisotropic, e.g. the reflectance (for λ = 0.60 μm) was found to be 0.57±0.02 – for the basal and 0.51±0.01 – for the prismatic surfaces of δ-WC1±x single crystals [884]. Optical absorption and reflection spectra in the IR diapason (4001400 cm–1) were explored by Kammori et al. [721], Xiong [722] and Hoffmann et al. [495]; the latter ones have observed the IR bands (vibrational modes) located at 1144 cm–1, which was assigned to γ-WC1–x, and 1067 cm–1 and 1220 cm–1, which were assigned to δ-WC1±x phase. To investigate tungsten carbide materials, X-ray reflection, emission and photoelectron spectroscopy methods were employed by Page et al. [32], Yanagihara et al. [723], Yamada et al. [727], Qin and Gao [725], Lin et al. [716], Katrib et al. [726, 1323-1324], Vidick et al. [1279], Weigert et. Al [1475], Nakazawa and Okamoto [1273] and some others, electron spectroscopy methods – by Ramqvist et al. [719], Wickersham et al. [731] and Smetyukhova et

54

2 Tungsten Carbides

al. [729] and γ-ray absorption spectroscopy on 182W, 184W and 186W isotopes – by Hershkowitz et al. [1072]. At the common conditions δ-WC1±x and W2±xC materials, having primarily a metallic bond type, are mostly steel gray in their colours (with a gray-green tint inherent to W2±xC) [1, 8-9, 11-12, 45, 151, 584, 586, 626]. According to Samsonov et al. [1, 8-9, 12, 151, 584, 626, 730, 733], who carried out measurements on powdered tungsten carbides coatings (thickness – ~100 μm , mean grain size – 2-3 μm) in the range of temperatures from 800 to 1800 °C, the normal monochromatic emittance (spectral emissivity) ελ,T (λ = 0.65 μm) of tungsten monocarbide δ-WC1±x slightly varies with temperature, decreasing correspondingly in the interval of 0.73 ≥ ελ,T ≥ 0.69, while the ελ,T (λ = 0.65 μm) of tungsten semicarbide W2±xC does not depend on temperature at all, being equal to 0.78 in all the temperature ranges investigated. For a reactively sputter-deposited coatings, containing γ-WC1–x phase mainly, Wickersham et al. [731] reported ελ,T to be as small as 0.35, in contrast with similar carbon-rich coatings. In the range of 1430-2230 °C, on the polished surface of bulk δ-WC1±x materials, using graphite as a reference, Ozaki and Zee [732] have obtained ελ,T (λ = 0.81 μm) = 0.82, this value was found to be independent on temperature within the range examined and to increase up to 0.90, when the surface roughness of materials increased (the similar effect of roughness on ελ,T was also observed in the earlier works [734]), but the emissivity ελ,T considerably decreased (up to 0.71) after thermal treatment at temperatures > 2050 °C, as the surface of materials was converted from δ-WC1±x to W2±xC, owing to the thermal exposure procedure in ultra-high vacuum. While in the range of temperatures from 730 to 2230 °C Kotelnikov et al. [13] recommend for the W2±xC materials, on the basis of earliest research, the value of ελ,T (λ = 0.665 μm) to be declining with temperature growth in the interval of 0.48 ≥ ελ,T ≥ 0.45. Jointly with some data already mentioned above, the variations of normal monochromatic emittance ελ,T with wavelength λ and temperature for tungsten mono- and semicarbide based materials [16] are shown in Fig. 2.11, which assists to systematize the behaviour of the W-C materials in different environments. The normal integral (total) emittance εT of δ-WC1±x, measured on the surface of hot-pressed materials in Ar atmosphere in the very wide range of temperatures from 520 to 2640 °C, showed a rather complicated character of the εT = f(T) function, which could be described as a sinusoid-like curve estimated around 0.4-0.5 at the lowest and highest temperatures with maximum of 0.7-0.8 at 800-1200 °C and minimum of 0.3-0.4 at 1500-2300 °C [600], that is in the obvious disagreement with the data reported by Riethof et al. [736], who observed an almost linear increase for the normal emittance εT of δ-WC1±x from 0.20 at 1330 °C to 0.33 at 2730 °C. For the interval of 1130-2330 °C, Bradshaw and Matthews [11, 670] recommended the values of integral (total) emittance εT for the W2±xC materials to be in the interval of 0.26 ≤ εT ≤ 0.35, increasing with temperature growth. The thermionic emission characteristics (electron work function and Richardson constants) of tungsten carbides are collected in in Table 2.10. The re-

2.3 Electro-Magnetic and Optical Properties

55

Fig. 2.11 Variation of normal monochromatic emittance (spectral emissivity) ελ,T with wavelength λ for different tungsten carbide materials in various temperature intervals: a – based on δ-WC1±x: at 800-1700 °C – coating on Ta cylinder prepared from the layer of fine-powdered paste (mean particle size – 2-3 μm, thickness – ~100 μm) suspended in liquid polymer binder and finally dried (ελ,T declines with temperature growth) [1, 8-9, 12, 151, 584, 626, 730, 733], at 1130-1530 °C (shaded area) – polished and cleaned surface, measured in Ar at ~10 kPa (ελ,T increases with temperature growth at λ > X and declines – at λ < X) [16, 734], at 1300-2100 °C – polished surface [734], at 1300-2100 °C (*) – rough (dull) surface [734], at 1430-2230 °C – polished surface, measured in ultra-high vacuum [732], at 1430-2230 °C (*) – rough surface, measured in ultra-high vacuum [732]; b – based on W2±xC: at 730-2230 °C – recommended by Kotelnikov et al. (ελ,T declines with temperature growth) [13], at 800-1800 °C – coating on Ta cylinder prepared from the layer of fine-powdered paste (mean particle size – 2-3 μm, thickness – ~100 μm) suspended in liquid polymer binder and finally dried [1, 8-9, 12, 151, 584, 626, 730, 733], at 1330-2130 (shaded area) – polished and cleaned surface, measured in Ar at ~10 kPa (ελ,T increases with temperature growth at λ > X and declines – at λ < X) [16, 734], at 1430-2230 °C – surface layer of W2±xC formed due to the decomposition of δ-WC1±x after thermal treatment in ultra-high vacuum [732]; probable X-points or isosbestic points of the families of ε – λ curves, where |1/ελ,T ×dελ,T/dT|λ=X = 0, supposed by the author are marked specially

56

2 Tungsten Carbides

Table 2.10 Thermionic emission characteristics (electron work function and Richardson constant) of tungsten carbide phases Compo- Work function a, Richardson Temperature sition φ = φ0 + (dφ/dT)avT, constant, A, range, °C eV 104 A m–2 K–2 W2±xC

Remarks b

References

2.60

–

–

FeM

[1, 737738, 748, 760]

~ 4.0-4.6

–

–

TiM

[1155]

4.05

–

–

TM, calculated with the [1, 738] usage of isotherms of surface tension

4.27-4.34

–

–

FeM, Fowler-Nordheim [1, 738, plot method, in vacuum 747] ~0.0133 μPa

4.31c

–

–

FeM, in vacuum 0.016 [769] μPa; W2±xC nanosheets (mean size < 0.1×0.1 μm)

–

–

FeM

–

TiM, Richardson plot [1, 13, 737method, average value of 738, 746, four measurements 760]

–

PhES; nanocrystalline [543] thin films (minimal thickness – ~5 nm, mean grain size – ~2 nm), prepared by atomic layer deposition methodd

4.42 4.58±0.08

190

[737-738]

4.63

–

γ-WC1–x 4.40

–

4.40

–

–

TM, calculated by the [770] projector augmented wave (PAW) method for (011) surface of stoichiometric phase (x = 0)

4.50

–

–

TM, calculated by the [770] projector augmented wave (PAW) method for (001) surface of stoichiometric phase (x = 0)

4.7-4.8

–

–

PhES; γ-W(CxNy) thin nanocrystalline films (thickness – 3 nm) prepared by atomic layer deposition followed by annealing at 900 °C

1200-1400 FeM, Fowler-Nordheim [651, 764plot method, in vacuum 767] 0.013-0.13 μPa; “ribbed crystals” (x ≈ 0.5)

[1882]

(continued)

2.3 Electro-Magnetic and Optical Properties

57

Table 2.10 (continued) 4.89-4.91

–

–

PhES; γ-W(CxNy) thin [4433] nanocrystalline films (thickness – 5 nm) prepared by remote plasma atomic layer deposition

5.16

–

–

TM, calculated by linear- [762] muffin-tin-orbital method with atomic sphere approximation (LMTO-ASA) for (100) surface of stoichiometric phase (x = 0)

~ 5.2-5.5e

–

–

TM, calculated by the [770] projector augmented wave (PAW) method for (111) surface of stoichiometric phase (x = 0)

–

TiM, Richardson plot method; gaseous (CH4) carburization materials

δ-WC1±x 3.60

2.7

[1, 738]

3.60f

–

3.73

–

–

FeM, Fowler-Nordheim [517, 763] plot method; thin films on the surface of W tip

3.79

–

–

FeM, Fowler-Nordheim [493] plot method, in vacuum 1-10 μPa; thin films on the surface of W tip

3.83 + (2.5×10–4)T

–

–

TiM; powdered materials [1, 738739]

4.2±0.1g

–

–

PhES; thin nanocrystal- [1882, line films (thickness – 3- 4436] 6 nm) prepared by plasma-enhanced atomic layer deposition method

4.42h

244

1190

TiM; solid state diffusion [1, 737carburization (saturation 738, 744by C) materials 745, 760]

~1700

TiM, Richardson plot [761] method; powdered materials pasted on Ta substrate

4.51-4.57

–

1620-1870 TiM; powdered coating on substrate treated by low-temperature Cs plasma (pCs = ~13 Pa)

[1, 738, 741-742, 758]

4.52-4.59

–

1580-1840 TiM; powdered coating on substrate

[1, 738, 741-742]

(continued)

58

2 Tungsten Carbides

Table 2.10 (continued) ~ 5.2-6.4e

–

–

TM, calculated for (0001) [1, 123, surface by unrelaxed line- 740] arized augmented-planewave (LAPW) method

~ 5.3-6.2e

–

–

TM, DFT-calculated for (0001) surface

[123, 768]

6.70±0.10

–

–

SiM, surface ionization of Ag atoms

[1, 738, 743]

a

T is temperature, K Methods applied for the determination of work function (FeM – field emission method, TM – theoretical method, TiM – thermionic emission method, PhES – photoelectron spectroscopy, SiM – surface ionization method) and manufacturing methods for the fabrication of a particular material (or its constitution) are marked c The work function of the W2±xC – WS2–x alloy nanoflowers, containing W2±xC nanosheets, could be tuned up to 4.95 eV by modulating the synthetic conditions d Consisted of W2±xC, δ-WC1±x and non-stoichiometric γ-WC1–x phases e Minimal values are for W-terminated surfaces, maximal – for C-terminated surface f Value of effective electron work function g Strongly non-stoichiometric materials (contents C – ~30 at.%) h Effective electron work function is φeff ≈ 4.30 eV (for working temperature Tw = 0.65Tm) b

ported values of emission current density for tungsten semicarbide W2±xC materials are 1.9×10–3, 2.24 and 6.8×103 A m–2 at 730 °C, 1230 °C and 1730 °C, respectively [13]; δ-WC1±x based materials can be safely operated with the maximum emission densities of ~104 A m–2 at 1500-1600 °C for 300 h [759]. Field emission properties of various W-C materials were reported in several works [493, 517, 651, 748, 763-767, 771-773], secondary ion emission was studied by Cherepin et al. [774]. The recommended values of electrical resistivity, magnetic susceptibility, integral and spectral emittances and thermionic emission characteristics (electron work function and Richardson constant) for tungsten carbide materials are given in the wide range of temperatures in comparison with all other ultra-high temperature materials in Addendum.

2.4 Physico-Mechanical Properties The physico-mechanical properties of tungsten carbides are the most important characteristics for their applications in the engineering practice. Crystallizing mainly with hexagonal or orthorhombic structural symmetry (see section 2.1), the tungsten carbides exhibit more appreciable anisotropy of mechanical characteristics than refractory transition metal carbides of 4 and 5 groups. All the tungsten carbide phases are known as extremely hard substances [1, 3-9, 13, 43, 45, 84-85, 87, 118]. At room temperature the hardness HV, GPa of tungsten monocarbide δ-WC1±x materials was evaluated as 10.0 (for spark-plasma sintered

2.4 Physico-Mechanical Properties

59

materials, porosity – 22 %, 294 N load) [140], 12.7 (for sintered materials, 2.94 N load) [815], 13.5 (for plasma-pressure compacted materials, 4.9 N load) [841], (14.4÷15.3)±(0.2÷0.5) (for spark-plasma sintered materials, porosity – ~1 %, mean grain size – ~4 μm, 9.8 N load) [902], 15.5±0.6 (for reactive hot-pressed materials, porosity – 3.5±0.3 %, 29.4 N load) [661], 15.7-19.6 (for sintered materials) [12, 594, 776, 807], ~16.0-22.0 (for highly dense sintered materials, 4.9 N load) [4, 7, 43, 847, 850], 16.8 (for sintered materials, porosity – 5 %, 9.8 N load) [898], ~17.0 (for chemical vapour deposited (CVD) coatings and sintered materials) [101, 810], 17.4 (for functional coatings) [474, 808], 17.4±1.9 (for reactive hot-pressed materials, porosity – 2.1±0.1 %, 29.4 N load) [661], 17.6±0.3 (for hot-pressed materials and reactive spark-plasma sintered materials, porosity – ~1 %, mean grain size – ~2.5 μm, 9.8-98 N load) [675, 784, 786-787, 822-823], 17.6-19.6 (for sintered materials and coatings) [3, 579, 594, 679, 782], 17.6-27.4 (for chemical vapour deposited (CVD) coatings and thin films) [100], 17.7±0.3 (for hot-pressed materials, porosity – 1 %, mean grain size – 2.5 μm, 49 N load) [784], (17.7÷19.7)±0.5 (for hot-pressed materials, porosity – 4-6 %, mean grain size – 0.3-1.0 μm, 98 N load) [868], 18.1 (for sintered materials, 2.94 N load) [815], (18.2÷18.6)±(0.2÷0.3) (for reactive spark-plasma sintered materials, porosity – 1 %, mean grain size – 2.5 μm, 2.94-9.8 N load) [784], 19.0±0.4 (for hot-pressed materials, porosity – 1 %, mean grain size – 1.4 μm, 98 N load) [784], 19.1±0.4 (for spark-plasma sintered materials, porosity – 1-4 %, mean grain size – 1-2 μm, 19.6-98 N load) [784, 926], 19.2±0.3 (for hot-pressed materials, porosity – 1 %, mean grain size – 1.4 μm, 49 N load) [784], 19.6-23.5 [588, 594, 804], 19.7±0.5 (for poreless hot-pressed materials, mean grain size < 1 μm, 9.8 N load) [955], 19.9±0.5 (for spark-plasma sintered materials, porosity – 1-3 %, mean grain size – 0.4-2.0 μm, 9.8-98 N load) [342, 784], 20.2±0.4 (for spark-plasma sintered materials, porosity – 1 %, mean grain size – 1-2 μm, 4,9 N load) [784], 20.4-20.6 (for sintered materials, 0.49-1.96 N load) [4, 6, 43, 202, 589, 591, 669, 680, 777, 779, 794, 803], 20.6±0.5 (for hot-pressed materials, porosity – 3 %, mean grain size – 2.1±0.6 μm, 98 N load) [905], 20.9±0.4 (for spark-plasma sintered materials, porosity – 7 %, mean grain size – ~80 nm, 98 N load) [909], 21.2 (for plasma-activated sintered materials, mean grain size – ~1 μm, 98 N load) [936], 21.4 [805], 21.5 (for hot-pressed and annealed materials, 9.8 N load) [790], 21.6 (for sintered materials) [3, 780], 21.6-26.5 (for pressureless sintered materials, porosity < 1 %, mean grain size < 0.3 μm, 294 N load) [870], 22.0 (for hot-pressed materials) [1, 45], 22.2 (for spark-plasma-sintered materials, porosity – 0.4 %, mean grain size – 0.4 μm, 98 N load) [941], 23.0 (for sintered materials, porosity – ~1 %, 196 N load) [578, 590, 848-849], 23.5 (0.29-0.49 N load) [3-4, 11, 43, 581, 679, 778, 796, 812-814, 816], 24.0±0.3 (for poreless spark-plasma sintered materials, mean grain size – 0.5 μm, 9.8 N load) [938, 948], 24.3 (for sparkplasma sintered materials, porosity – 1-2 %, mean grain size – 0.4 μm, 98-294 N load) [847, 860, 863], 24.6-26.5 (for materials prepared by the high-frequency induction-heated sintering (HFIHS) method, porosity – 1.5-3.0 %, mean grain size – 0.3-0.6 μm, 98-196 N load) [861, 865, 931], 24.9±0.1 (for hot-pressed materials,

60

2 Tungsten Carbides

poreless, mean grain size – 0.4 μm, 98 N load) [784], 25.0 (for spark-plasma sintered materials, porosity < 1 %, 98 N load) [942], 25.0±0.3 (for poreless hotpressed materials, mean grain size – 0.4 μm, 49 N load) [784], 25.3±0.4 (for poreless spark-plasma sintered materials, mean grain size – ~0.4 μm, 9.8-98 N load) [866-867, 895], 25.4±1.8 (for highly densified spark-plasma sintered materials, mean grain size – 0.25-0.30 μm, 98 N load) [869, 897], 25.5 (for sparkplasma sintered materials, porosity – 1 %, mean grain size – ~0.2 μm, 196 N load) [859], 25.7±0.3 (for poreless spark-plasma sintered materials, mean grain size – ~0.4 μm, 19.6 N load) [784], 25.8±0.4 (for spark-plasma sintered materials, porosity – 0.5 %, mean grain size – ~0.4 μm, 9.8 N load) [902], 26.0 (for poreless spark-plasma sintered materials, 294 N load) [852-853], 26.0±0.3 (for hot-pressed materials, porosity – 2.5±0.1 %, 29.4 N load) [661], 26.0-26.5 (for pressureless sintered materials, 9.8 N load) [945], 26.1 (for materials prepared by the pulsed current activated sintering (PCAS) method, porosity – 0.5-1.0 %, 294 N load) [947, 949], 26.2±0.1 (for poreless materials prepared by the pulsed electric current sintering (PECS) method, mean grain size < 0.3 μm, 294 N load) [857], 26.2±0.3 (for poreless reactive spark-plasma sintered materials, mean grain size – 0.4 μm, 9.8 N load) [784], 26.4 (for poreless spark-plasma sintered materials, 98 N load) [950], (26.5÷27.1)±(0.2÷0.5) (for spark-plasma sintered materials, porosity ≤ 1 %, mean carbide grain size – 0.3-0.4 μm, 2.94-98.0 N load) [784, 878, 909, 946], (27.4÷28.1)±0.1 (for poreless materials prepared by the pulsed electric current sintering (PECS) method, mean grain size < 0.3 μm, 49-98 N load) [857], 27.5 (for single-phase spark-plasma sintered materials, porosity – 1 %, mean grain size – 0.4 μm, 294 N load) [925], (27.7÷28.0)±0.2 (for materials prepared by the highfrequency induction-heated sintering (HFIHS) method, porosity – 1.0-1.5 %, mean grain size – 0.1-0.4 μm, 98-294 N load) [666, 850, 862, 864, 929], 28.7 (for materials prepared by the high-pressure – high-temperature (HPHT) technique, porosity – 0.8 %, mean grain size – ~0.2 μm, 98 N load) [666, 930], 28.7±0.3 (for materials prepared by the pulsed current activated sintering (PCAS) method, porosity – 1 %, mean grain size – 85 nm, 196 N load) [928, 932], ~ 29.0-30.0 (for spark-plasma sintered materials, porosity – 0.2 %, mean grain size – 0.3 μm, 98 N load) [344, 666, 956], (29.2÷28.8)±(0.5÷0.8) (for spark-plasma sintered materials, porosity – 0.8-1.2 %, mean grain size – 0.15-0.16 μm, contents: non-combined C – (0.17÷0.18)±(0.1÷0.2) %, O – (0.3÷0.4)±(0.01÷0.02) %, 19.6 N load) [2986], 29.6 (for materials prepared by the high-frequency induction-heated sintering (HFIHS) method, porosity – 1 %, mean grain size – 90 nm, 98 N load) [328, 666, 896], 31.0±0.1 (for poreless materials prepared by the pulsed electric current sintering (PECS) method, mean grain size < 0.3 μm, 9.8 N load) [857], 31.1-34.0 (for spark-plasma sintered materials, porosity – 0.3 %, mean grain size – 0.1-0.3 μm, 19.6 N load) [380, 398, 666, 921-922, 933], 31.2 (for spark-plasma sintered materials, porosity – 3 %, mean grain size – 90-150 nm, 19.6 N load) [893], 33.0±0.4 (for hot-pressed materials, prepared by the high-pressure – hightemperature treatment, 29.4 N load) [952] (the nanoindentation hardness measurements of δ-WC1±x phase constituent in Co containing hard alloys carried

2.4 Physico-Mechanical Properties

61

out with a Berkovich 3-sided pyramid indenter resulted in the maximum values of 150-170 GPa (1 mN load) [833]). The room-temperature hardness HV, GPa of tungsten semicarbide W2±xC materials was evaluated as 11.5 (for arc-cast materials, 9.8 N load), 14.2 [6, 202], (16.8÷17.8)±(0.2÷0.5) (for spark-plasma sintered materials, porosity – 2 %, 2.9419.6 N load) [785], (17.0÷17.6)±(0.2÷0.3) (for hot-pressed materials, porosity – 1 %, 49-98 N load) [784], (17.6÷17.7)±(0.3÷1.0) (for hot-pressed materials, porosity – 1 %, 19.6-49 N load) [784], (18.9÷20.6)±(0.3÷0.6) (for spark-plasma sintered materials, porosity – 1 %, 0.98-2.94 N load) [784], 19.5 (0.29-1.96 N load) [3-4, 43, 624, 777-778, 791, 934], 19.6-24.5 (for sintered materials) [588, 594, 802], (20.6÷23.9)±(0.6÷0.8) (for hot-pressed materials, porosity – 1 %, 0.49-0.98 N load) [784], 21.8 [13], 29.4-33.3 (0.49 N load) [11, 118, 150, 200, 474, 581, 594, 796], 34.3 (for chemical vapour deposited (CVD) coatings, thickness – up to 18 μm) [519]. The variations of hardness HV and microhardness Hμ with test force load P at room temperature for tungsten monocarbide and semicarbide materials are shown in Fig. 2.12. The comparison of hardness values measured with the different loads may be proceeded, using the following empirical equation [474]: lnH = A + BlnP,

(2.23)

where H is the hardness, P is the load applied for hardness measurements, and A and B are the constants, which are dependent on the samples of materials and can be determined only experimentally. The collected data on hardness HV/HK and microhardness Hμ of single crystal and polycrystalline tungsten carbide materials are listed in Tables 2.11-2.12. The appropriate and rather important note to these tables is that generally the hardness of mixtures of carbide phases is higher than that of pure individual carbides, due to the higher inner stresses observed in the microstructures consisting of carbide mixtures [519]. The reported hardness HK, GPa of tungsten monocarbide δ-WC1±x materials is 7.9 (for single crystal (1010) surface, direction, or parallel to axis c, 9.8 N load) [824], 17.6 (for single crystal (1010) surface, direction, or perpendicular to axis c, 9.8 N load) [824], 17.6 (for sintered materials, 0.98 N load) [594, 697], 18.3-18.4 (for sintered materials, 0.98 N load) [11, 608, 793, 796], 18.8 (for single crystal (0001) surface, 9.8 N load) [824], 20.6 (for sintered materials) [792], (22.2÷22.9)±(0.6÷0.9) (for sintered materials, 19.6 N load) [954], 23.0 (0.49 N load) [594, 806], 23.1 (for fine-grained hot-pressed materials, 9.8 N load) [824]; hardness HRA, kgf mm–2 is 81 [12, 85, 151, 579, 626, 780], 8687 (for sintered materials, porosity – 3-7 %) [792], 89-93 (for materials sintered with the use of ultra-fine powders) [414], 89.5 [4171], ~90 (for sintered materials) [150], 92 (for hot-pressed materials, porosity < 1 %, content Co – 0.1-0.2 %) [11, 150, 851], 94 (for spark-plasma sintered materials, mean grain size < 0.35 μm) [871], 95.5 (for modified hot isostatic pressed (HIP) materials, poreless) [1006], 96.5 (for modified pulsed current sintered materials, porosity < 1 %) [999], 98 (for

62

2 Tungsten Carbides

Fig. 2.12 Variation of hardness HV (1-5) and microhardness Hμ (6-11) with applied test force load P at room temperature for tungsten carbides materials: 1 – reactive spark-plasma sintered W~2.0C, porosity – 1 % [784]; 2 – reactive spark-plasma sintered W2.18C, porosity – 1 % [785]; 3 – spark-plasma sintered δ-WC1±x, poreless, mean grain size – 0.4 μm (no preferential texture) [784]; 4 – spark-plasma sintered δ-WC1±x, porosity – 1 %, mean grain size – 1.4 μm (no preferential texture) [784]; 5 – spark-plasma sintered δ-WC1±x, porosity – 1 %, mean grain size – 2.5 μm (no preferential texture) [784]; 6 – hot-pressed δ-WC1±x, prepared from the powders, which were synthesized in very different conditions (carburization of WO3 and W powders in the range of temperatures from 1450 to 2000 °C), reported by Vinogradov et al. [1]; 7 – single crystal δ-WC1±x (0001) plane, measured by Luyckx and Demanet [798]; 8 – single crystal δ-WC1±x (0001) plane, measured by Luyckx et al. [835]; 9 – single crystal δ-WC1±x (0001) plane, measured by Corteville and Pons [3, 231, 881-882]; 10 – single crystal δ-WC1±x (0010) plane, measured by Corteville and Pons [3, 231, 881-882]; 11 – single crystal δ-WC1±x (0001) plane, measured by Haglund [3]; data reported by Roebuck et al. [904] from the scanning indentation mechanical microprobe (SIMM) measurements of δ-WC1±x grains in metal matrix composites for the loading range of 0.1 N ≤ P ≤ 0.5 N, demonstrating the decay of hardness for basal (0001) and prismatic (parallel to direction) planes from 107.0 GPa to 42.3 GPa and from 47.5 GPa to 23.4 GPa, respectively, are not shown on the plot

2.4 Physico-Mechanical Properties

63

Table 2.11 Microhardness Hμ (or hardness HV/HK) of tungsten monocarbide δ-WC1±x single crystals and individual grains of δ-WC1±x phase constituents in several materials at ambient conditions Surface (0001)

Indenter diagonal direction Microhardness Hμ, GPa a 18.0±0.7b

17.8±0.2b c

References [883] [883]

–

d

57.1±3.4

[920, 923]

–

52.5±2.5e

[920, 923]

–

43.0±0.8f

[924]

–

42.8±2.2g

[920, 923]

–

h

40.4±1.6

[908, 914915]

–

34.4±1.9i

[920, 923]

–

34.0

j

[798]

–

33.4-35.8j

[835]

–

33.3k

[3]

–

33.1l

[798]

–

30.1

m

[798]

–

29.9±4.7n

[927]

–

29.7-31.6l

[835]

–

29.6-31.3m

[835]

o

–

28.9±0.1

[916]

–

28.4p

[3]

–

25.6±0.2q

[903]

–

~ 25.0-30.0r

[872]

s

–

24.5±1.0

[3, 85, 231, 881-882]

–

23.8t

[798]

–

23.5

[8-9]

–

23.5u

[3]

–

23.5v

[900]

–

23.3-24.6t

[835]

–

22.0

w

–

~22.0x, y

[831, 904]

–

21.9-24.6z

[3, 230]

–

21.2±1.0a1

[3, 85, 231, 881-882]

–

20.7a2

[3]

–

20.6±0.4a3

[7, 229, 798]

–

20.4

a4

[798]

–

20.0-21.2a4

[835]

[3]

(continued)

64

2 Tungsten Carbides

Table 2.11 (continued) –

(0010)

(1010) (1010)

19.6a1

–

19.6

[884]

–

19.6a6

[887]

–

19.3±1.0a7

[3, 85, 231, 881-882]

–

19.1±1.0a8

[3, 85, 231, 881-882]

–

18.8a9

[824]

–

14.2±1.0s

[3, 85, 231]

–

13.9±1.0a1

[3, 85, 231]

–

13.3±1.0

a8

[3, 85, 231]

–

13.2±1.0a7

[3, 85, 231]

–

~ 40.0-55.0r

[872]

25.2b2

[245]

b1

23.5 b4

(1010)

(1100) (0110) (1101)

[3]

x, a5

z

[8-9, 230]

17.6b3

[824]

12.0b5

[245, 233234]

9.8z

[8-9, 230]

7.9b6

[824]

–

36.2±2.1d

[920, 923]

–

33.1±2.3

e

[920, 923]

–

32.8±2.0h

[908, 914915]

–

30.1±2.0g

[920, 923]

28.0±1.0f

[924]

–

25.5±1.7j

[920, 923]

–

22.0±9.6n

[927]

–

21.9±0.1

[916]

–

17.2±0.1q

[903]

–

~14.0y

[904]

–

12.7-17.6

[884]

b7

b1

23.6

[245]

b4

9.5b8

[245, 233234]

–

~11.0

[831]

–

10.6±0.5a3

[7, 229, 798]

–

21.4v

[900] a3

– 10.4±0.2 [7, 229, 798] – 21.3v [900] (2110) a Perpendicular direction to the axis a on the basal plane b 0.98 N load, Knoop measurement (HK), the average values of at least 3 specimens in each

2.4 Physico-Mechanical Properties

65

direction, which indicate no discernible hardness variation between them c Parallel direction to the axis a on the basal plane d 3 mN load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 5% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter and calculated by the Oliver-Pharr method e 3 mN load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 15% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter and calculated by the Oliver-Pharr method f 0.01-0.02 N load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 7.5% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter and atomic force microscopy (AFM) and calculated by the Oliver-Pharr method g 0.01 N load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 5% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter and calculated by the Oliver-Pharr method h 0.01 N load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 7.5% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter (with a tip radius less than 20 nm) and calculated by the Oliver-Pharr method i 0.01 N load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 15% Co hard alloy by means of nanoindentation using a Berkovich diamond indenter and calculated by the Oliver-Pharr method j 0.245 N load, measured by Luyckx and Demanet k 0.049 N load, measured by Haglund l 0.49 N load, measured by Luyckx and Demanet m 0.98 N load, measured by Luyckx and Demanet n The average statistical value obtained for the δ-WC1±x phase constituent in δ-WC1±x – 11% Co hard alloy by means of nanoindentation measurements with a Berkovich diamond tip using Oliver-Pharr calculation method o 0.01 N load, measured on δ-WC1±x grains (crystals) in δ-WC1±x – 9% Co hard alloy by means of nanoindentation and atomic force microscopy (AFM) p 0.098 N load, measured by Haglund q 0.25 N load, measured by means of nanoindentation using a Berkovich diamond tip and calculated by the Oliver-Pharr method using a fused silica sample for the tip calibration r Data evaluated from the nanoindentation of δ-WC1±x phase constituent (individual grains) in δ-WC1±x – 12 % Co hard alloy, obtained from nanocrystalline powders; all the indentations (with a Berkovich diamond tip with radius < 20 nm) were programmed to reach 30 nm in depth under a displacement control program with load at 5 μN s–1 until the maximum depth is reached s 0.196 N load, Vickers measurement (HV) t 1.96 N load, measured by Luyckx and Demanet u 0.196 N load, measured by Haglund v Theoretical evaluation based on the electronegativity approach w 0.49 N load, measured by Haglund x Average value for the surface y Derived (corrected) from the scanning indentation mechanical microprobe (SIMM) measurements (0.2 N load) on the δ-WC1±x grains in metal matrix composites z 0.98 N load, Knoop measurement (HK) a1 0.49 N load, Vickers measurement (HV) a2 0.98 N load, measured by Haglund a3 9.8 N load a4 4.9 N load, measured by Luyckx and Demanet a5 0.098 N load a6 0.98 N load a7 0.82 N load, Vickers measurement (HV) a8 0.98 N load, Vickers measurement (HV)

66

2 Tungsten Carbides

a9

9.8 N load, Knoop measurement (HK) Perpendicular direction to the axis c b2 0.98 N load, Knoop measurement (HK), the average value of at least 4 measurements (with the long indentor diagonal perpendicular to the axis c), minimal and maximal values are 24.5 and 25.7 GPa, respectively b3 9.8 N load, Knoop measurement (HK), with the long indentor diagonal perpendicular to the axis c b4 Parallel direction to the axis c b5 0.98 N load, Knoop measurement (HK), the average value of at least 4 measurements (with the long indentor diagonal parallel to the axis c), minimal and maximal values are 11.7 and 12.3 GPa, respectively b6 9.8 N load, Knoop measurement (HK), with the long indentor diagonal parallel to the axis c b7 0.98 N load, Knoop measurement (HK), the average value of at least 4 measurements (with the long indentor diagonal perpendicular to the axis c), minimal and maximal values are 23.1 and 24.2 GPa, respectively b8 0.98 N load, Knoop measurement (HK), the average value of at least 4 measurements (with the long indentor diagonal parallel to the axis c), minimal and maximal values are 9.4 and 9.6 GPa, respectively b1

Table 2.12 Microhardness Hμ (or hardness HV/HK) characteristics of various tungsten carbide phases (polycrystalline materials) at ambient conditions Composi- Microhardness Hμ (or tion hardness HV/HK), GPa

Remarks

References

W~12.0C

28.4

Chemical vapour deposited (CVD) coatings, maximum thickness – 25 μm

[519]

W~3.0C

30.4

Chemical vapour deposited (CVD) coatings, maximum thickness – 20 μm

[519]

19.6-24.5

0.98 N load, chemical vapour deposited (CVD) coatings

[101]

17.6-27.4a

Functional coatings prepared by various techni- [94, 96] ques on different substrates

α-W2.24C

16.8

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.21C

17.4

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.18C

21.2±0.3

0.245 N load, reactive spark-plasma sintered ma- [785] terials, porosity – 1 %

20.2±0.3

0.49 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

19.5±0.5

0.98 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

18.2±0.4

1.96 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

17.8±0.2

2.94 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

17.6±0.5

4.9 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

(continued)

2.4 Physico-Mechanical Properties

67

Table 2.12 (continued) 17.0±0.3

19.6 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1 %

(16.9÷17.4)±0.4

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 1-2 %

α-W2.16C

17.3

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.13C

17.3

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.09C

17.5

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.07C

17.5

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.05C

17.4

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2.03C

17.3

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W~2.0C

29.4-31.9c

0.49 N load, fine-grained thin films (coatings), [157] prepared by d.c. non-reactive magnetron sputtering deposition on Mo and cemented carbide substrates, thickness – 3-11 μm

26.0c

Nanocrystalline films deposited by a filtered ca- [494] thodic vacuum arc technique

17.1

9.8 N load, reactive spark-plasma sintered mate- [785] rials, porosity – 2 %

α-W2+xC

25.2

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

ε-W2+xC

25.4

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

β-W~2.0C

34.3

Chemical vapour deposited (CVD) coatings, maximum thickness – 18 μm

β-W2+xC

25.4

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

γ-W~2.7C

~16.0b

0.2-20 mN load, thin films with microstructures [498] ranging from nanocrystalline to epitaxial ones

γ-W2±xC

24.9

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

W2.04÷2.33C 31.0±1.4

0.245-0.98 N load, chemical vapour deposited (CVD) coatings with mean grain size – 0.2-0.5 μm

[519]

[550]

(continued)

68

2 Tungsten Carbides

Table 2.12 (continued) W~2.0C

29.4-33.3

0.49 N load

[11, 118, 150, 200, 474, 579, 581, 796]

30.0

On the basis of several sources

[2734]

25.9±2.1

0.245 N load, synthesized from W-C powdered mixtures by eruptive heating in a solar furnace

[221]

23.9±0.8

0.49 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

23.8

0.98 N load, middle layers (thickness – ~20 μm) [910] of coatings fabricated by spark-plasma sintering technique with the use of α-C (graphite) powder

21.8

Recommended value on the basis of several sour- [13] ces

21.1e

0.98 N load

20.6±0.6

0.98 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

20.0-24.0

Materials prepared by chemical vapour deposition (CVD)

20.0±0.5

1.96 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

19.9±0.4

0.98 N load, fused materials, mean grain size – 76 μm (see also section 2.5)

[85, 888, 1033]

19.6-24.5

Sintered materials

[588, 594, 802]

19.6-24.5f

0.98 N load, chemical vapour deposited (CVD) coatings

[101, 810]

19.5

0.29-0.49 N load, sintered materials

[3-4, 43, 624, 777778, 791]

19.5

1.96 N load, measured on equiaxed dendrites as a [934] phase constituent in cermet materials

18.9±0.3

2.94 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

18.7

0.29 N load

[3, 85]

18.6

Chemical vapour deposited (CVD) coatings on metal substrate, thickness – 30 μm

[101]

18.3±0.3

4.9 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

18.1-20.6

0.98 N load, fused materials (with hardness ani- [1, 3] sotropy)

17.7-20.2g

0.98 N load, fused materials (on the face surface [3, 783] of materials grains were oriented mainly by the (1012) planes), mean grain size – 76 μm

17.7±0.3

9.8 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

d

[11, 608]

[1083]

(continued)

2.4 Physico-Mechanical Properties

69

Table 2.12 (continued) 17.7±1.0

19.6 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

17.6±0.3

49 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

17.0±0.2

98 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %

15.1

1.96 N load, measured on directional dendrites as [934] a phase constituent in cermet materials

14.2

–

[6, 202]

11.5h

9.8 N load, arc-cast materials with columnar microstructure, porosity 4-5 %

[838]

9.3h

9.8 N load (B4±xC indenter), arc-cast materials with columnar microstructure, porosity 4-5 %

[838]

γ-WC~0.6

~21.0

0.2-20 mN load, nanocrystalline films, prepared [498] by the magnetron sputtering (co-evaporation of W with C60) deposition on Al2O3 (012) substrate, thickness – 0.5 μm, mean grain size < 3 nm

γ-WC~0.7

26.0-28.9

0.49 N load, fine-grained thin films (coatings), [157] prepared by r.f. non-reactive magnetron sputtering deposition on Mo and cemented carbide substrates, thickness – 3-11 μm

26.0±2.0

0.49 N load, thin films (coatings) prepared by d.c.[844-845] reactive magnetron sputtering deposition on stainless steel substrates, thickness – 4-5 μm

γ-WC0.74- 40.0±2.1 γ-WC1.01

0.245-0.98 N load, chemical vapour deposited (CVD) ultra-fine grained coatings with lower grain size (up to 5-10 nm)

γ-WC~0.8

~14.0

0.2-20 mN load, nanocrystalline films, prepared [498] by the magnetron sputtering (co-evaporation of W with C60) deposition on Al2O3 (012) substrate, thickness – 0.5 μm, mean grain size < 3 nm

γ-WC~0.9

22.0i

10 mN load, single-phase nanocrystalline thin [509-510] films (coatings), prepared by r.f. reactive sputtering deposition on Si (100) substrates, thickness – 0.1-0.4 μm, (200) textured

γ-WC1–x

39.3

0.245 N load, thin films (coatings) prepared by r.f. reactive sputtering deposition, mean grain size ≤ 12 nm, (200) textured

[470]

37.2

Chemical vapour deposited (CVD) coatings, maximum thickness – 12 μm

[519]

36.0-41.0i

Nanocrystalline coatings, prepared by the reac- [842] tive magnetron sputtering deposition on steel substrates

34.8

Theoretical estimation based on Pugh’s (modulus) ratio

34.3

0.5 mN load, thin films (coatings) prepared by r.f. [504] reactive sputtering deposition on steel substrates

[550]

[953]

(continued)

70

2 Tungsten Carbides

Table 2.12 (continued) 33.0±0.9j

0.01 N load, monolithic coatings deposited by [177] high-speed plasma spraying technique on Cu substrate, thickness – 10-15 μm, mean grain sizes – around 1-10 μm

31.4k

0.098 N load, single-phase films (coatings), pre- [100, 465] pared by the reactive magnetron sputtering deposition on stainless steel substrates

(30.1÷33.5)±(2.1÷3.6)l Coatings (thin films) prepared by the high-target [546-547] utilization sputtering (HiTUS) technique on various substrates, thickness – 0.4-0.8 μm 29.1±1.1

0.098 N load, spark-discharge produced powders [828] with particle sizes from 5 to 40 μm

27.4-29.4

0.98 N load, as a phase constituent in various multi-phase cast materials

25.0-30.0

0.49-0.98 N load, powders prepared by the spark- [880] discharge technique

25.0l

Thin films, prepared by mist chemical vapour deposition (CVD) method, thickness – 0.5-1.0 μm

[555]

23.5

DFT-calculated for the stoichiometric phase within the local density approximation (LDA)

[37]

22.3

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

21.8

DFT-calculated for the stoichiometric phase by [195] using Vanderbilt ultra-soft pseudopotential within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) and MonkhorstPack (MP) scheme

19.5i

Thin films (coatings) prepared by the magnetron [499] sputtering deposition on steel substrates, thickness – 0.2 μm, (200) textured

~19.0i

Thin films (coatings) prepared by the magnetron [503] sputtering deposition, (200) textured

18.5i

Thin films (coatings) prepared by the magnetron [499] sputtering deposition on steel substrates, thickness – 0.2 μm, (111) textured

17.8

Evaluation based on the correlation analysis of available data on physical properties of cubic transition metal carbides

[607]

14.7-18.7i

Multilayered thin films prepared by the magnetron sputtering deposition on steel substrates, thickness – 0.5 μm (5-45 layers)

[499]

δ-WC0.93

18.0±2.0

0.78-0.98 N load, hot-pressed and annealed mate- [819-820] rials

δ-WC0.97

18.1±1.0

0.98 N load, hot-pressed materials, porosity – 2-4 %

[86]

[788-789]

(continued)

2.4 Physico-Mechanical Properties

71

Table 2.12 (continued) δ-WC1.00

25.0

High-pressure (5.8 GPa) sintered materials, poro- [827] sity – 4 %, contents: non-combined C – 0.04%, Co, Fe, Ni – 0,0005-0.003 %

δ-WC1.01

17.0-20.5

Single-phase fused materials, prepared by the electrothermal explosion (ETE) under pressure (variant of self-propagating high-temperature synthesis (SHS))

δ-WC~1.0

38.8m

0.29 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1450 °C)

37.4m

0.29 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1800 °C)

36.3m

0.29 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 2000 °C)

35.8n

0.98 N load, hot-pressed materials

[4380]

35.8

DFT-calculated theoretical value

[3955]

35.0±1.8

0.245-0.98 N load, chemical vapour deposited (CVD) coatings

[550]

34.7n

1.96 N load, hot-pressed materials

[4380]

[93, 951]

m

0.29 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of W at 1450 °C)

33.3m

0.29 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of W at 1800 °C)

33.0±0.4

29.4 N load, materials prepared by high-pressure [952] (10 GPa) – high-temperature (1300 °C) hot-pressing (exposure – 10 min)

32.4-33.1

DFT-calculated values obtained by different methods and approaches

[35]

32.0

Theoretically evaluated value

[876]

34.5

31.5

m

0.49 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1450 °C)

31.5n

2.94 N load, hot-pressed materials

[4380]

31.2-31.5

0.98 N load, arc-plasma melted materials

[843]

31.2

19.6 N load, single-phase spark-plasma sintered [893] materials, porosity – 3 %, mean grain size – 90150 nm

31.1-34.0

19.6 N load, single-phase spark-plasma sintered [380, 398, materials, porosity – 0.3 %, mean grain size – 666, 9210.1-0.3 μm 922, 933]

31.0±0.1

9.8 N load, single-phase materials prepared by [857] the pulsed electric current sintering (PECS), poreless, mean grain size < 0.3 μm

31.0m

0.49 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1800 °C)

31.0

Evaluation based on the microscopic theory of hardness

o

[907]

(continued)

72

2 Tungsten Carbides

Table 2.12 (continued) 30.8n

4.9 N load, hot-pressed materials

[4380]

30.4

Materials heat-treated at 1400 °C under quasihydrostatic pressure of 10 GPa

[3]

30.0±3.0

Theoretically calculated value

[874-875, 877, 919]

29.6±0.8

0.49 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

29.6

98 N load, materials prepared by the high-frequ- [328, 666, ency induction-heated sintering (HFIHS) techni- 896] que, porosity – 1 %, mean grain size – 90 nm

29.4

0.49 N load, sintered materials

29.3-33.4

Evaluation based on the hardness-elasticity cor- [889, 892] relations

29.3

Recommended value

p

[6, 150]

[874]

(29.2÷28.8)±(0.5÷0.8) 19.6 N load, spark-plasma sintered, single-phase [2986] materials, porosity – 0.8-1.2 %, mean grain size – 0.15-0.16 μm, contents: non-combined C – (0.17÷0.18)±(0.1÷0.2) %, O – (0.3÷0.4)±(0.01÷0.02) % ~ 29.0-30.0q

98 N load, spark-plasma (field assisted) sintered [344, 666, materials, porosity – 0.2 %, mean grain size – 0.3 956] μm

28.8±0.9

0.98 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

28.8r

Coatings prepared by chemical vapour deposition [943] (CVD) under atmospheric pressure conditions

28.7±0.3

196 N load, materials prepared by the pulsed cur- [928, 932] rent activated sintering (PCAS) technique, porosity – 1 %, mean grain size – 85 nm

28.7

98 N load, materials prepared by the high-pres- [666, 930] sure – high-temperature (HPHT) technique, porosity – 0.8 %, mean grain size – ~0.2 μm

28.5m

0.49 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of W at 1800 °C)

28.5±0.7

Hot-pressed materials (porosity – 2-5 %) in the [818] work-hardened conditions of outer surface layer

28.1±0.1

49 N load, pure materials prepared by the pulsed [857] electric current sintering (PECS), poreless, mean grain size < 0.3 μm

28.0

98 N load, single-phase materials, prepared by [666, 850] the high-frequency induction-heated sintering (HFIHS) technique, porosity – 1.5 %, mean grain size – 0.4 μm

27.9

98-294 N load, materials prepared by the highfrequency induction-heated sintering (HFIHS), porosity – 1.5 %, mean grain size < 0.3 μm

[862, 864]

(continued)

2.4 Physico-Mechanical Properties

73

Table 2.12 (continued) 27.7±0.2

196 N load, materials prepared by the high[929] frequency induction-heated sintering (HFIHS) technique, porosity – 2 %, mean grain size – 0.1 μm

27.5

294 N load, single-phase spark-plasma sintered [925] materials, porosity – 1 %, mean grain size – 0.4 μm

27.4-31.4s

Materials heat-treated at 2400 °C under all-round [3, 782] compression of 9.8 GPa (non-annealed)

27.4±0.1

98 N load, single-phase materials prepared by the [857] pulsed electric current sintering (PECS), poreless, mean grain size < 0.3 μm

27.3±3.3t

0.245 N load, synthesized from W-C powder mixtures by eruptive heating in a solar furnace

27.1±1.1

98 N load, reactive spark-plasma sintered materi- [918] als, porosity – 5 %, mean grain size – 0.6 μm

27.1±0.2

2.94 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

27.0±0.4

49 N load, materials prepared by oscillatory pres- [4496] sure sintering (OPS), porosity – 1.4 %

26.8±0.2

4.9 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

26.8

294 N load, spark-plasma sintered materials, porosity – 0.5-1 %, mean grain size – 0.4 μm

26.7±0.2o

98 N load, high-pressure (low-temperature) [909] spark-plasma sintered materials, porosity < 1 %, mean grain size – 0.3 μm

26.5±0.5

98 N load, spark-plasma sintered materials, poro- [946] sity – 0.1 %, mean grain size – 0.3 μm

26.5

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 1800-1850 °C, temperature of WO3 reduction – 1200 °C)

26.5

–

[221]

[878, 3127]

[937]

26.4±0.4

98 N load, materials prepared by the pulsed elec- [4481] tric current sintering (PECS) technique, porosity – ~ 1-2 %

26.4

98 N load, spark-plasma sintered materials, poro- [950] sity – 0.1 %

26.4

Theoretical value based on the calculation within [889-890] Tian’s model

26.2±0.1

294 N load, single-phase materials prepared by [857] the pulsed electric current sintering (PECS) technique, poreless, mean grain size < 0.3 μm

26.2±0.3

9.8 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

(continued)

74

2 Tungsten Carbides

Table 2.12 (continued) 26.1u

294 N load, materials prepared by the pulsed current activated sintering (PCAS) technique, porosity – 0.5-1.0 %

26.1

Materials prepared by the high-frequency induc- [1007] tion-heating sintering (HFIHS) technique, porosity – ~1 %, mean grain size – 70 nm

26.0-26.5

9.8 N load, pressureless sintered materials

[945]

26.0±0.3v

29.4 N load, hot-pressed materials, porosity – 2.5±0.1 %

[661]

26.0

98 N load, materials prepared by the high-frequ- [940] ency induction-heated sintering (HFIHS) technique, porosity – 2 %, mean grain size – 0.1 μm

26.0n

98 N load, spark-plasma sintered materials, pore- [942] less

~26.0

Polycrystalline reactive pulsed laser deposited thin films

[479]

25.8±0.4n

9.8 N load, spark-plasma sintered materials, porosity – 0.5 %, mean grain size – 0.4 μm

[902]

25.7±0.3

19.6 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

25.7

9.8 N load, single-phase spark-plasma sintered materials, poreless, mean grain size – ~0.5 μm

25.5

196 N load, single-phase spark-plasma sintered [859] materials, porosity – 1 %, mean grain size – ~0.2 μm

25.5

294 N load, single-phase spark-plasma sintered materials, prepared from nanopowders (mean grain size – 40-70 nm), with poreless and finegrained microstructures

25.4±0.6

98 N load, spark-plasma sintered materials, poro- [869] sity – 1.5 %, mean grain size – 0.25-0.30 μm

25.4±1.8

98 N load, reactive spark-plasma sintered materi- [897] als, highly densified, mean grain size – 0.27 μm

25.3±0.4

9.8-98 N load, spark-plasma sintered materials, poreless, mean grain size – ~0.4 μm

[866-867]

25.3

98 N load, fine-grained spark-plasma sintered materials, poreless

[895]

25.1±0.2

98 N load, spark-plasma sintered materials, poro- [4160] sity – 0.7 %

25.0-26.5

98 N load, single-phase materials prepared by the [861, 865] high-frequency induction-heated sintering (HFIHS) combustion technique, porosity – 1.5 %, mean grain size – 0.4-0.6 μm

25.0±0.3

49 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

25.0

98 N load, single-phase spark-plasma sintered materials, porosity – 0.8 %

[947, 949]

[317]

[852-853]

[942]

(continued)

2.4 Physico-Mechanical Properties

75

Table 2.12 (continued) ~25.0

Carbide domains embedded in Co matrix (binder) [846] in δ-WC1±x – Co hard alloys

24.9±0.1

98 N load, reactive spark-plasma sintered mate- [784] rials, poreless, mean grain size – 0.4 μm

24.6

196 N load, materials prepared by the high-frequ- [931] ency induction-heated sintering (HFIHS) technique, porosity – 3 %, mean grain size – 0.3 μm

24.6

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 2200 °C)

24.3

98-294 N load, single-phase spark-plasma (field- [847, 860, activated) sintered materials, porosity – 1-3 %, 863] mean grain size – ~0.4 μm

24.2

Highly dense spark-plasma sintered materials, mean grain size – 0.7-0.8 μm

24.0-26.0w

20 mN load, magnetron sputtering deposited coa- [481] tings on steel substrates

24.0±0.3

9.8 N load, spark-plasma sintered materials, pore- [938, 948] less, mean grain size – 0.5 μm

24.0±0.3

298 N load, spark-plasma sintered materials with [854-856, single-phase and low porous microstructures 4141]

24.0

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 1800-1850 °C, temperature of WO3 reduction – 700-900 °C)

24.0

98 N load, spark-plasma sintered materials, poro- [4463] sity < 0.5 %

24.0

1.96 N load, sintered materials

24.0

Recommended value on the basis of several sour- [13, 662] ces

23.8

Hot-pressed and annealed materials (porosity – 2-5 %) in the recrystallized (at 1380 °C) conditions

[818]

23.5

Chemical vapour deposited (CVD) coatings, maximum thickness – 10 μm

[519]

23.5

0.29-0.49 N load

[3-4, 11, 43, 581, 679, 778, 796, 812814, 816]

23.5

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 1600-1650 °C)

23.4±1.1

0.49 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

23.4x

9.8-118 mN load, sputtering deposited thin films [474] (coatings), thickness – 0.2 μm

23.2

Thin films, prepared by reactive r.f. magnetron [95-96] sputtering deposition on stainless steel substrates

[1008]

[873-874]

(continued)

76

2 Tungsten Carbides

Table 2.12 (continued) 23.1e

9.8 N load, hot-pressed materials with fine-grai- [824] ned microstructures

23.1

Single-phase materials prepared by the high-fre- [911] quency induction-heated pressing (HFIHP) technique

~23.0i

Thin films (coatings) prepared by magnetron sputtering deposition

23.0

196 N load, spark-plasma sintered materials, po- [848-849] rosity – 1 %

23.0e

0.49 N load, sintered materials

22.9±0.9e

19.6 N load, sintered materials, structured with a [954] bimodal grain size distribution with a large number of grains in the submicron range and in the 24 μm size

22.9

98 N load, spark-plasma sintered materials

22.8

Calculated by using the modified microhardness [912] model based on first principles

22.5

– y

[503]

[594, 806, 2000]

[4329]

[587]

22.4±0.6

Arc-plasma melted (followed by an in situ fur- [4154] nace cooling) materials with δ-WC1.00±0.01 initial composition

22.3±1.4

0.98 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

22.2±0.6e

19.6 N load, sintered materials, structured with a [954] broad uniformly-distributed range of grain sizes from submicron to 2-4 μm

22.2

98 N load, single-phase spark-plasma sintered [941-942] materials, porosity – 0.4 %, mean grain size – 0.4 μm

22.1±0.7

0.49 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 2.5 μm

22.1

98 N load, materials prepared by pulsed current [2076] activated sintering (PCAS) technique, porosity – 12 %, mean grain size – 0.16 μm

22.1

Sintered materials

[935]

22.0-28.0

Recommended values

[894]

22.0

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 1500-1550 °C)

22.0

Recommended value on the basis of several sour- [45, 2734] ces

22.0

Theoretical value obtained for the stoichiometric [36] phase by the DFT calculation within the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional

21.6-35.3

–

[780, 1993]

(continued)

2.4 Physico-Mechanical Properties

77

Table 2.12 (continued) 21.6-26.5

294 N load, vacuum pressureless sintered mate- [870] rials (with usage of nanocrystalline powders), porosity < 1 %, mean grain size < 0.3 μm

21.5

196 N load, materials prepared by the high-frequ- [4239] ency induction-heated sintering (HFIHS) technique, porosity – 3.6 %, mean grain size – 0.15 μm

21.5

9.8 N load, hot-pressed and annealed materials

21.5m

0.98 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1450 °C)

21.5

DFT-calculated value

21.4

Hot-pressed materials (powders prepared by car- [1, 106] burization of W at 1450 °C, temperature of WO3 reduction – 650-850 °C), porosity – 4-11 %, mean grain size – 0.7 μm

21.4 21.2

[790]

[889, 891]

–

[805]

98 N load, nearly single-phase materials prepared [936] by the plasma-activated sintering (PAS) technique, mean grain size – 1.1 μm

(21.1÷21.9)±(0.1÷0.2) 0.49 N load, as a phase constituent with mean grain sizes – (6.0÷12.7)±(0.1÷0.8) μm in fully densified cermet materials

[944]

21.1±0.6

1.96 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

21.0m

0.98 N load, hot-pressed materials (powders pre- [3] pared by carburization of WO3 at 1800 °C)

21.0

Recommended on the basis of several sources

20.9±1.1

0.098 N load, spark-discharge produced powders [828] (particle size – 5-40 μm) after vacuum annealing (at 900 °C)

20.9±0.4

98 N load, high-pressure (low-temperature) [909] spark-plasma sintered materials with single-phase microstructures, porosity – 7 %, mean grain size – ~80 nm

20.8±1.3

98 N load, ultra-high temperature flash sintered [4676] materials (UFS) (with the presence of 2.1 % α-W2+xC and 2.3 % α-C (graphite) phases) porosity – 5.4 %, mean grain size – 0.8±0.1 μm

20.8

0.98 N load, top layers (thickness – ~2 μm) of [910] coatings fabricated by spark-plasma sintering technique with the use of α-C (graphite) powder

20.6±0.5

98 N load, hot-pressed materials, porosity – 3 %, [905] mean grain size – 2.1±0.6 μm

20.6

Recommended as a carbide matrix hardness in δ-WC1±x – Co hard alloys

[800, 811]

20.6

Functional coatings

[680, 803]

[120]

(continued)

78

2 Tungsten Carbides

Table 2.12 (continued) 20.6e

–

[792]

20.6

Evaluation based on the electron holding energy [906] per unit volume

20.4

0.49-1.96 N load, sintered materials

20.3-25.7

Single-phase materials prepared by pulsed cur- [1009] rent activated sintering (PCAS) technique, porosity – 1-4 %, mean grain size – 50-900 nm

20.3±0.5

0.98 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 2.5 μm

20.3±0.7

2.94 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

20.2±0.4

4.9 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

20.0m

0.98 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of W at 1800 °C)

19.9±0.5

98 N load, spark-plasma sintered (with pulsed [342] current) materials, porosity – 3 %, mean grain size – 0.4-1.0 μm, mean crystallite size – 70 nm

19.9±0.4

9.8 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 1.4 μm

19.7±0.5z

9.8 N load, modified hot-pressed materials, pore- [955] less, mean grain size < 1 μm

~19.6a1

10 mN load, thin films prepared by plasma beam [1162] sputtering technique, thickness – 0.17±0.01 μm

19.6

–

[4, 6, 43, 202, 589, 591, 594, 669, 777, 779, 794]

[588]

19.5±0.8

1.96 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 2.5 μm

19.4

0.49-0.98 N load, hot-pressed materials (powders [3, 781] prepared by carburization of W at 1380-1400 °C)

19.2a2

0.98 N load, spark-plasma sintered (with pulsed [899] current) materials, mean grain size – 5.5 μm

19.1±0.4

19.6-98 N load, spark-plasma sintered materials, [784] porosity – 1 %, mean grain size – 1.4 μm

19.1

98 N load, spark-plasma sintered materials, poro- [926] sity – 4 %

18.6±0.3

2.94-4.9 N load, reactive spark-plasma sintered [784] materials, porosity – 1 %, mean grain size – 2.5 μm

18.5a3

0.98 N load, materials sintered in vacuum and [1, 85, 673] annealed, porosity – 4.0 %, mean grain size – 4.0 μm, contents: non-combined C – 0.11%, O – 0.05%, N – 0.005%

(continued)

2.4 Physico-Mechanical Properties

79

Table 2.12 (continued) 18.3-18.4e

0.98 N load

18.2±0.2

9.8 N load, reactive spark-plasma sintered mate- [784] rials, porosity – 1 %, mean grain size – 2.5 μm

18.1

2.94 N load, sintered (in high vacuum) materials [815]

18.1

196 N load, single-phase materials prepared by [4241] pulsed current activated sintering (PCAS), porosity – 13 %, mean grain size – 92 nm

18.0-20.6

Materials prepared by powder metallurgy methods (with hardness anisotropy)

18.0m

1.47 N load, hot-pressed materials (powders pre- [1, 3] pared by carburization of WO3 at 1450 °C)

[11, 608, 793, 796]

[1, 8-9]

17.8

0.49 N load, hot-pressed and annealed materials [821]

(17.7÷19.7)±0.5

98 N load, single-phase hot-pressed materials, [868] porosity – 4-6 %, grain size – 0.3-1.0 μm, crystallite size – 70-90 nm

17.6-27.4

Chemical vapour deposited (CVD) thin films (coatings)

17.6±0.3

19.6-98 N load, reactive spark-plasma sintered [784] materials, porosity – 1 %, mean grain size – 2.5 μm

17.6

0.29-1.47 N load, hot-pressed materials, porosity [3, 675, ≤5% 786-787, 822-823]

17.6

Sintered materials and coatings

[3, 579, 782]

17.6e

0.98 N load, sintered materials

[594, 697]

17.5

Sintered materials (powders prepared by carburi- [1, 106] zation of W at 2200 °C, temperature of WO3 reduction – 1200 °C), porosity – 3-6 %, mean grain size – 1 μm

17.4±1.9

29.4 N load, reactive hot-pressed materials with [661] single-phase microstructure, porosity – 2.1±0.1 %

17.4±0.4

0.29 N load

[3, 12, 779]

17.4

Functional coatings

[474, 808]

17.3m

1.47 N load, hot-pressed materials (powders pre- [3] pared by carburization of WO3 at 1800 °C)

17.1

0.98 N load, materials prepared by sintering in high vacuum

[815]

17.0

0.29-0.98 N load

[3, 11, 118, 150, 796797, 4171]

16.9±0.6

0.98 N load, hot-pressed materials, poreless (see [85, 888, also section 2.5) 1033]

16.8

9.8 N load, sintered (in Ar atmosphere) materials, [898] porosity – 5 %

[100]

(continued)

80

2 Tungsten Carbides

Table 2.12 (continued) 16.7-23.5

–

[582-583, 809]

16.7-17.6

0.29-0.49 N load

[3, 85, 151, 780, 802]

~16.7

Chemical vapour deposited (CVD) coatings and [101, 810] sintered materials

16.7

0.29 N load

16.6

Sintered materials (powders prepared by carburi- [1, 106] zation of W at 1450 °C, temperature of WO3 reduction – 650-850 °C), porosity – 3-6 %, mean grain size – 1 μm

16.2±0.4i

Thin films prepared by d.c. magnetron sputtering [913] deposition, thickness – ~0.7 μm

16.2±0.2

0.98 N load, materials sintered (in Ar protective [577] atmosphere) from spherical nanopowders with mean particle size – ~50 nm

16.2

0.49 N load, sintered (in high vacuum) materials [815]

16.2

294 N load, spark-plasma sintered materials, po- [4465] rosity – 9 %

16.1m

1.47 N load, hot-pressed materials (powders pre- [3] pared by carburization of W at 1800 °C)

~ 16.0-22.0

4.9 N load, highly densified sintered materials (with hardness anisotropy)

[4, 7, 43, 847, 850]

15.9

Single-phase sintered materials

[12, 776]

15.5±0.6

29.4 N load, reactive hot-pressed materials with [661] single-phase microstructure, porosity – 3.5±0.3 %

15.4

98 N load, highly dense hot-pressed materials

15.2

1.96 N load, hot-pressed and annealed materials, [825] porosity ≤ 5 %, mean grain size – 10-30 μm

[3, 85]

[2062]

(14.4÷15.3)±(0.2÷0.5) 9.8 N load, single-phase spark-plasma sintered [902] materials, porosity – 0.9-1.2 %, mean grain size – ~4 μm 13.9a4

Ion sputtering deposited thin films (coatings) on [475] glass substrates, thickness – 0.2 μm

13.5

4.9 N load, plasma-pressure compacted materials, [841] porosity – 4 %

13.3e, a5

0.098 N load, amorphous thin films prepared by [472] pulsed laser deposition, thickness – 70 nm

13.0-13.5

Average hardness of crystals (over all possible [798, 800] crystallographic planes, see Table 2.11) derived experimentally from the Hall-Petch relationships

12.7-21.6a6

0.98 N load, hot-pressed materials (with hardness [3, 783] anisotropy), poreless, mean grain size – 28 μm

12.7

2.94 N load, materials prepared by sintering in high vacuum

[815]

(continued)

2.4 Physico-Mechanical Properties

81

Table 2.12 (continued) 10.0 9.5±0.1

294 N load, spark-plasma sintered materials, po- [140] rosity – 22-24 %

98 N load, hot-pressed materials, porosity – 10 [3867] %, mean grain size – 5.2 μm a In the presence of metallic W and/or W monocarbide, as second phases b Hardness was evaluated by the nanoindentation technique using a triangular Berkovich diamond tip c In the presence of monocarbide γ-WC1–x and W metallic phases d In the presence of traces of monocarbide δ-WC1±x and W metallic phases e Knoop measurement (HK) f The presence of W3+xC phase is probable g Degree of microhardness anisotropy – 0.35 h In the presence of δ-WC1±x phase (up to 5 vol.%) i Hardness was evaluated by the nanoindentation technique using a Berkovich diamond tip and calculated by the Oliver-Pharr method j Hardness was evaluated by the nanoindentation technique; in the presence of 0.5 % δ-WC1±x phase k For the mixed-phase films (coatings), containing also δ-WC1±x and W3+xC phases and noncombined C, the value of microhardness Hμ drops up to 23.2 GPa l Measured by means of nanoindentation with constant strain rate 0.05 s–1; in the presence of noncombined disordered C m Data reported by Vinogradov et al. n In the presence of semicarbide W2±xC phase o In the presence of W2±xC and γ-WC1–x phases p Microhardness before treatment Hμ = 17.6 GPa, after post-treatment annealing at 1300 °C (exposure – 4 h) microhardness declined to Hμ = 29.5 GPa q In the presence of ~2 vol.% W2±xC phase in the materials r Measured by means of nanoindentation; in the presence of W metallic phase s Microhardness before treatment Hμ = 17.6 GPa, after post-treatment annealing at 1530 °C (exposure – 1.5 h) microhardness declined to Hμ = 18.3 GPa t In the presence of traces of semicarbide W2±xC phase u The hardness decreased up to 22.9 GPa after annealing at 1300 °C (exposure – 48 h) v Containing 4.3% W2±xC phase w Microhardness was measured by the dynamical microindentation method using a Berkovich diamond indenter and hardness values were deduced by the Oliver-Pharr analysis method x In the presence of W2±xC phase, measured by ultramicrohardness tester [832]; the value of hardness HV deduced from dislocation data is 24.55 GPa y Determined by a UMIS nanoindentation system z With addition 5 vol.% SiC a1 Containing metallic W phase a2 At 294 N load hardness HV = 16.2 GPa a3 At 1000 °C microhardness Hμ = 3.9 GPa a4 In the presence of W2±xC phase, measured by Vickers diamond microindentation hardness tester a5 The hardness after 80 keV N2+ ion beam (Φ = 3.0×1016 cm–2) irradiation increased up to 20.3 GPa a6 Degree of microhardness anisotropy – 0.75

82

2 Tungsten Carbides

Fig. 2.13 Hardness of δ-WC1±x tungsten monocarbide crystals as a function of the angle between indenter and axis c (or the rotational angle of measured surface from the basal orientation (crosssectional orientation dependence)): 1 – variation of the hardness HK (0.98 N load) on the first order prismatic (1010) surface of single crystal δ-WC1±x tungsten monocarbide [883]; 2 – variation of the derived (corrected) hardness data on the of δ-WC1±x grains (crystals) as a phase constituent of metal matrix composites from the measurement by scanning indentation mechanical microprobe (SIMM) method [904]; 3 and 4 – variations of nanoindentation hardness HIT on δ-WC1±x grains (crystals) as a phase constituent of δ-WC1±x – 7.5% Co hard alloys with the usage of atomic force microscopy (AFM) and Oliver-Pharr hardness calculation method with loading 0.02 N and 0.01 N, respectively [924]; Inset – hardness of δ-WC1±x tungsten monocarbide crystals as a function of the rotational angle from (1010) to (2110) surfaces: 5 and 6 – variations of nanoindentation hardness HIT on δ-WC1±x grains (crystals) as a phase constituent of δ-WC1±x – 7.5% Co hard alloys with loading 0.02 N and 0.01 N, respectively [924] in φ, deg – H, GPa scale

2.4 Physico-Mechanical Properties

83

Fig. 2.14 Variations of the hardness HV (9.8 N load) at room temperature with deviation from the stoichiometry (carbon content) within the homogeneity range of tungsten semicarbide α-W2+xC phase (single-phase materials prepared by reactive spark-plasma sintering at 1700 °C, porosity – 2 %) [785]

Fig. 2.15 Variations of the hardness HK (9.8 N load) of single crystal tungsten monocarbide δ-WC~1.0 along the different surfaces and directions with temperature: 1 – (0001), 2 – (1010) , (with the long indentor diagonal perpendicular to the axis c), 3 – (1010) (with the long indentor diagonal parallel to the axis c) [85, 243-244, 824, 829, 879]

84

2 Tungsten Carbides

Fig. 2.16 Variations of the hardness HV (2-3, 6, 8-10, 12-15), HK (4) and microhardness Hμ (1, 5, 7, 11) of tungsten carbide materials with temperature: 1 – δ-WC0.97, hot-pressed and annealed, porosity – 2-4 %, 0.98 N load (for lower temperatures) and 0.69 N load (for higher temperatures) [788-789, 1025]; 2 – δ-WC1±x [3, 778]; 3 – δ-WC~1.0, measured by the mutual indentation technique, 1.19 kN load [814]; 4 – δ-WC~1.0, hot-pressed, fine-grained, 9.8 N load [243-244, 824, 1016]; 5 – δ-WC1±x, 0.49 N load [1, 673]; 6 – δ-WC1±x, recommended on the basis of several sources [13]; 7 – δ-WC1±x, hot-pressed, porosity – 2 %, 1.47-9.8 N load [3, 786-787, 822]; 8 – δ-WC~1.0, sintered (in high vacuum), 2.94 N load [815]; 9 – δ-WC1±x [837, 839]; 10 – δ-WC~1.0, hot-pressed and annealed, 9.8 N load [790]; 11 – δ-WC~1.0, hot-pressed and annealed, 0.69 N load [790]; 12 – δ-WC1±x sintered (in high vacuum), 2.94 N load [815]; 13 – W2±xC, arc-cast alloys with columnar microstructure, containing 5 vol.% δ-WC1±x phase, porosity – 4-5 %, 9.8 N load (measured by B4±xC indentor) [838, 1016]; 14 – δ-WC1±x [830]; 15 – δ-WC~1.0, sintered, porosity – 1 %, ≤ 1.47 N load [816]; Inset – exponential microhardness Hμ – reciprocal temperature relationship for hot-pressed and annealed δ-WC0.97 materials (porosity – 2-4 %, 0.69 N load) [788-789] in (lnHμ – 1/3lnT) – 1/T, 10–4 K–1 scale (when it is not indicated specially, data reported are for near-stoichiometric compositions)

2.4 Physico-Mechanical Properties

85

spark-plasma sintered materials) [834] and hardness in the Mohs (mineralogical) scale is ≥ 9 [4-5, 12, 43, 151, 581, 586, 4675]. The anisotropy of hardness characteristics of tungsten monocarbide δ-WC1±x materials is illustrated clearly in Fig. 2.13, where the variation of hardness HK with direction on the first order prismatic (1010) surface of a δ-WC1±x single crystal is plotted jointly with the related data obtained from the nanoindentation hardness HIT measurements of δ-WC1±x grains as a phase constituents of composite materials; the character of hardness function follows the crystal symmetry with the difference bet-ween the softest and hardest (or parallel and perpendicular to the axis c, respectively) directions on the surface being ~50 %. According to Roebuck et al. [904], who studied the hardness anisotropy of δ-WC1±x grains in metal matrix composites with the use of the developed scanning indentation mechanical microprobe (SIMM) method, the measured hardness H of a δ-WC1±x crystal (grain) H = Hb – (Hb – Hp) sinθ ,

(2.24)

where Hb is the basal (0001) plane hardness, Hp is the prismatic plane hardness and θ is the angle between the basal plane and the plane of the measurement. The reported hardness HK, GPa of tungsten semicarbide W2±xC is 21.1 (0.98 N load) [11, 608]; hardness HRA, kgf mm–2 is 80 [12, 85, 151, 579, 626, 780] and hardness in the Mohs (mineralogical) scale is ≥ 9 [4-5, 11-12, 43, 151, 581, 586, 670, 780]. For non-stoichiometric tungsten semicarbide materials, the variation of hardness HV with carbon content within the homogeneity range of W2±xC phase is demonstrated in Fig. 2.14. The hardness of metastable cubic tungsten monocarbide γ-WC1–x was estimated theoretically as high as 17.8 GPa (based on the correlation analysis) [607] and 34.8 GPa (based on Pugh’s (modulus) ratio) [953], the experimentally measured hardness values, GPa: ~14.0 (for γ-WC~0.8 nanocrystalline thin films (coatings) prepared by the magnetron sputtering deposition, thickness – 0.5 μm, mean grain size < 3 nm, 0.2-20 mN load) [498], 14.7-18.7 (for multilayered thin films prepared by the magnetron sputtering deposition, thickness – 0.5 μm) [499], 18.519.5 (for thin films prepared by the magnetron sputtering deposition) [499, 503], ~21.0 (for γ-WC~0.6 nanocrystalline thin films (coatings) prepared by the magnetron sputtering deposition, thickness – 0.5 μm, mean grain size < 3 nm, 0.220 mN load) [498], 22.0 (for γ-WC~0.9 nanocrystalline thin films (coatings) prepared by means of r.f. reactive sputtering deposition, thickness – 0.1-0.4 μm, 10 mN load) [509-510], 25.0 (for chemical vapour deposited (CVD) thin films, thickness – 0.5-1.0 μm) [555], 25.0-30.0 (for spark-discharge produced powders, 0.49-0.98 N load) [880], 26.0±2.0 (for γ-WC~0.7 thin films (coatings) prepared by means of d.c. reactive magnetron sputtering deposition, 0.49 N load) [844-845], 26.0-28.9 (for γ-WC~0.7 thin films (coatings) prepared by means of r.f. nonreactive magnetron sputtering deposition, 0.49 N load) [157], 27.4-29.4 (for γ-WC1–x phase constituents in multi-phase cast materials, 0.98 N load) [86],

86

2 Tungsten Carbides

29.1±1.1 GPa (for spark-discharge produced powders, 0.098 N load) [828], (30.1÷33.5)±(2.1÷3.6) (for thin films prepared by the high-target utilization sputtering (HiTUS) technique, thickness – 0.4-0.8 μm) [546-547], 31.4 GPa (for thin films (coatings) prepared by the reactive magnetron sputtering deposition, 0.098 N load) [100, 465], 33.0±0.9 (for monolithic coatings deposited by the highspeed plasma spraying technique, 0.01 N load) [177], 34.3 (for thin films prepared by means of r.f. reactive sputtering deposition, 0.5 mN load) [504], 36.0-41.0 (for nanocrystalline films and coatings prepared by the reactive magnetron sputtering deposition) [842], 37.2 GPa (for chemical vapour deposited (CVD) coatings, maximum thickness – 12 μm) [519], 40.0±2.1 (for γ-WC~0.74÷1.01 chemical vapour deposited (CVD) ultra-fine grained coatings, 0.245-0.98 N load) [550], while the DFT-calculated values are 21.8 GPa [195] and 23.5 [37]. The hardness HV of metastable W3+xC phase is evaluated as 19.6-24.5 GPa (0.98 N load) [101], or 17.6-27.4 GPa (in the presence of metal W and/or W monocarbide, as second phases) [94, 96] and its microhardness Hμ is 30.4 GPa [519], similarly to all other tungsten carbide phases its hardness in the Mohs (mineralogical) scale is ≥ 9 [151, 798]. The microhardness Hμ of W~12C chemical vapour deposited (CVD) coatings (with maximum thickness – 25 μm) is 28.4 GPa [519]. The hardness H of polycrystalline tungsten monocarbide δ-WC1±x is dependent on its grain size in the materials in accordance with the Hall-Petch relationship [798-801, 879, 902]: H = H0 + k0L−1/2,

(2.25)

where H0 is the average hardness of δ-WC1±x crystals (over all their possible crystallographic planes), GPa, k0 is the Hall-Petch coefficient, related to the ease of slip transfer across grain boundaries and L is the mean grain size, μm, of the randomly oriented grains; Lee and Gurland [800] obtained the following values for the relationship constants: H0 = 13.55 GPa and k0 = 7.16 GPa μm1/2 (for room temperature conditions), only slightly different results for H0 and k0 were reported by Sigl and Exner [798-799] – 13.03 GPa and 7.44 GPa μm1/2, respectively, and Nino et al. [902] obtained for tungsten carbide spark-plasma sintered materials (without the presence of non-combined C) – 10.90 GPa and 8.93 GPa μm1/2, respectively. The Hall-Petch relationship is widespread and often employed in materials engineering practice, including contemporary nanotechnology. In the case of nanocrystalline materials, such as tungsten carbide thin films (see section 2.1), the “negative slope effect”, when k0 < 0, can be observed [475]; if the grain size is below a critical dimension, the hardness of nanomaterials can decrease with its grain size decreasing, that is considered within the modified Hall-Petch relationship theory [475]. Similarly to other ceramic materials, the hot hardness (or hardness temperature dependence) of tungsten monocarbide δ-WC1±x materials can be expressed by a simple exponential relationship [836-837, 840], such as

2.4 Physico-Mechanical Properties

87

Fig. 2.17 Variations of ultimate flexural (bending) strength σf of tungsten carbide materials with temperature: 1 – δ-WC~1.0, sintered, porosity – 14-16 % [12, 585, 626, 961-962, 968]; 2 – W2.30C, cast alloys, data reported by Voronkova [13]; 3 – δ-WC1±x [4, 8-9, 12, 43, 581, 626, 4380]; 4 – δ-WC~1.0, sintered [118, 735]; 5 – δ-WC1±x [11]; 6 – δ-WC~1.0, sintered, prepared from the powders synthesized by the 2-step low-temperature reduction of WO3, porosity – 3-6 %, mean grain size – 1 μm [1, 106]; 7 – δ-WC~1.0, sintered, prepared from the powders synthesized by the 1-step high-temperature reduction of WO3, porosity – 3-6 %, mean grain size – 1 μm [1, 106]; 8 – W~2.0C, hot-pressed, porosity – 2-5 % [8-9, 581, 776]; 9 – δ-WC1±x [4, 11, 43, 45, 608, 776, 4481]; 10 – δ-WC~1.0, sintered, porosity < 2 %, data reported by Bruyak et al. [13, 45]; 11 – δ-WC~1.0, sintered [582-583, 966]; 12 – δ-WC~1.0, materials prepared by the high-frequency induction-heated pressing (HFIHP) technique, poreless [911]; 13 – δ-WC~1.0, spark-plasma sintered, porosity – 4 %, 3-point bending scheme [926]; 14 – δ-WC~1.0, sintered, porosity – ~ 1-2 % [581, 964, 4160]; 15 – δ-WC~1.0, hot-pressed, porosity – (2.1÷3.5)±(0.1÷0.3) %, 3-point bending scheme [661]; 16 – δ-WC1±x [873, 4496]; 17 – δ-WC~1.0, sintered, highly densified, structured with a broad uniformly-distributed range of grain sizes from submicron to 2-4 μm (Weibull modulus – 14.5), 4-point bending scheme [954]; 18 – δ-WC~1.0, spark-plasma sintered [1004]; 19 – δ-WC~1.0, modified hot-pressed materials (with addition 5 vol.% SiC), poreless, mean grain size < 1 μm, 4-point bending scheme [955]; 20 – δ-WC~1.0, spark-plasma sintered [834]; 21 – δ-WC~1.0, sintered, highly densified, structured with a bimodal grain size distribution with a large number of grains in the submicron range and in the 2-4 μm size (Weibull modulus – 4.3), 4-point bending scheme [954, 4171]; 22 – δ-WC~1.0, spark-plasma sintered, porosity – ~1 %, mean grain size – 0.52±0.07 μm, 3-point bending scheme [1021]; 23 – δ-WC~1.0, highly densified, spark-plasma sintered, mean grain size – 0.7-0.8 μm [1008]; 24 – δ-WC~1.0, modified hot isostatic pressed (HIP) materials, poreless [1003, 1006] (data reported by Csanádi et al. [2981] from microcantilever bending testing for average fracture strength of δ-WC1±x grains in δ-WC1±x – Co alloys σf = 12.3±3.8 GPa (σf, max ≈ 20.5 GPa) and average fracture strength of δ-WC1±x/δ-WC1±x boundaries σf′ = 4.1±2.5 GPa are not shown on the plot); Inset – variation of yield stress σf* at 4-point bending test with temperature for hot-pressed/recrystallized δ-WC~1.0 materials (porosity – 4 %, containing non-combined C) [967] in lgσf*, MPa – 1/T, 10–4 K–1 scale (when it is not indicated specially, data reported are for near-stoichiometric compositions)

88

2 Tungsten Carbides

Fig. 2.18 Variations of ultimate compressive strength σc of tungsten carbide materials with temperature: 1 – δ-WC~1.0, spark-plasma sintered [873]; 2 – δ-WC1±x [873]; 3 – δ-WC1±x [12-13, 85, 626, 886]; 4 – δ-WC1±x [1003, 1005]; 5 – δ-WC~1.0, sintered [150]; 6 – δ-WC~1.0, hot-pressed, porosity < 1 %, data reported by Bruyak et al. [12-13, 626]; 7 – W2±xC, cast alloys (in the presence of δ-WC1±x phase) [3, 13, 85]; 8 – δ-WC~1.0, data corrected to porosity (see formula (A.20) in Table III-A.11, applied with a = 500) [823, 4505]; 9 – δ-WC1±x [1, 151]; 10 – δ-WC~1.0, hot-pressed, porosity < 1 % [3, 13, 85]; 11 – δ-WC~1.0, hot-pressed, porosity < 1 %, data reported by Struk [12]; 12 – δ-WC~1.0, porosity – 3 %, data reported by Kharchenko [3, 85, 965]; 13 – δ-WC~1.0, porosity – 8 %, data reported by Kharchenko [3, 85, 965]; 14 – δ-WC1±x [4, 8-9, 43, 581]; 15 – δ-WC~1.0, sintered [118]; compression strain values ε are indicated for curves 1 and 4 at corresponding temperatures, reported by Tumanov et al. with the value of specific deformation energy at room temperature – ~460 N cm–3 [3, 1029-1030]); data on nano-compression testing by the use of depth sensing indentation technique for the prismatic and basal planes of δ-WC1±x single crystal micropillars (indexes a and c relate to the directions along the main axes a and c (or parallel and perpendicular to the (0001) plane), respectively: the values of yield stresses σc, a* = 6.3±1.0 GPa and σc, c* = 6.6±0.8 GPa and ultimate strengths σc, a = 7.2±0.8 GPa and σc, c = 12.5±1.7 GPa [915] are not shown on the plot (when it is not indicated specially, data reported are for near-stoichiometric compositions)

2.4 Physico-Mechanical Properties

89

Table 2.13 Fracture toughness (critical stress intensity factor) KIC characteristics of various tungsten carbide materials Composi- Fracture toughness KIC, tion MPa m1/2

Remarks

References

α-W~2.0C

3.6a

Reactive spark-plasma sintered materials, poro- [785] sity – 2 %

δ-WC1.01

(3.0÷6.2)±(0.1÷0.3)a

Sintered materials, porosity – 0.5 %, mean grain [987] size – 1-4 μm

δ-WC~1.0

21.7±0.3a

Hot-pressed materials

13.7±0.8

a

[2062]

Materials prepared by high-pressure (10 GPa) – [952] high-temperature (1500 °C) hot-pressing (exposure – 10 min) with abnormal grain growth microstructure

11.1±3.7b, c

Hot-pressed materials, porosity – 2.5±0.1 %

9.8a

Materials prepared by the pulsed current activa- [947] ted sintering (PCAS) technique, porosity – 0.51.0 % (after annealing at 1300 °C, exposure – 48 h)

9.5±0.2b

Single-phase hot-pressed materials, porosity – 3.5±0.3 %

[661]

9.4±0.3a, d

Spark-plasma sintered materials, porosity – 0.7 %

[4160]

9.4

Single-phase materials prepared by the high-fre- [911] quency induction-heated pressing (HFIHP) technique, poreless

9.0-15.0a

Single-phase spark-plasma sintered materials, porosity – 1-3 %, mean grain size – ~0.2 μm (tended to decrease with increasing hardness)

8.9a

Materials prepared by the high-pressure – high- [666, 930] temperature (HPHT) technique, porosity – 0.8 %, mean grain size – ~0.2 μm

8.9a

Nearly single-phase materials prepared by the plasma-activated sintering (PAS) technique, mean grain size – 1.1 μm

8.7±1.1a, e

The inherent characteristics of prismatic facets of [903] carbide particles (10-20 μm) embedded in metal matrix of δ-WC1±x – 8.5 % Co hard alloys

8.5-9.8a

Single-phase materials prepared by pulsed cur- [1009] rent activated sintering (PCAS) technique, porosity – 1-4 %, mean grain size – 50-900 nm

8.4a

Spark-plasma sintered materials, mean grain size [871] < 0.35 μm

8.1±0.6a

Materials prepared by high-pressure (10 GPa) – [952] high-temperature (1000 °C) hot-pressing (exposure – 10 min)

[661]

[859]

[936]

(continued)

90

2 Tungsten Carbides

Table 2.13 (continued) 7.9±0.3a, f

Spark-plasma sintered materials, porosity – 0.7 %

[4160]

7.8a

Single-phase spark-plasma sintered materials, porosity – 0.4 %, mean grain size – 0.4 μm

[941-942]

7.6

–

[873]

7.5±0.7b

Single-phase hot-pressed materials, porosity – 2.1±0.1 %

7.5±0.2a

Spark-plasma sintered materials, porosity – 4 % [926]

7.5

Sintered materials, mean grain size – 6 μm

7.5a

Spark-plasma sintered materials, porosity – 9 % [4465]

7.5a

Single-phase materials prepared by pulsed cur- [4241] rent activated sintering (PCAS), porosity – 13 %, mean grain size – 92 nm

7.3±1.2b, g

Hot-pressed materials, porosity – 1.6±0.7 %

7.2-7.3a

Spark-plasma (field assisted) sintered materials, [344, 666, porosity – 0.2 %, mean grain size – 0.3 μm 956]

7.2±2.4a, e

The inherent characteristics of basal facets of [903] carbide particles (10-20 μm) embedded in metal matrix of δ-WC1±x – 8.5 % Co hard alloys

7.2a, h

High-pressure (low-temperature) spark-plasma sintered materials, porosity < 1 %, mean grain size – 0.3 μm

7.2a

Materials prepared by the high-frequency induc- [1007] tion-heating sintering (HFIHS) technique, porosity – ~1 %, mean grain size – 70 nm

7.1±0.2a

Hot-pressed materials, porosity – 10 %, mean grain size – 5.2 μm

7.0-8.3a

Materials prepared by the high-frequency induc- [328, 666, tion-heating sintering (HFIHS) technique, poro- 850, 862, sity – ~ 1-4 %, mean grain size – 90-400 nm 864, 896, 4239]

7.0±1.2a, h

Hot-pressed materials

7.0±0.2

a

[661]

[85, 1027]

[661]

[909]

[3867]

[4380]

Materials prepared by the pulsed current activa- [928, 932] ted sintering (PCAS) technique, porosity – 1 %, mean grain size – 85 nm

7.0a

Hot isostatic pressing (HIP) sintered materials with fine-grained microstructure

[666, 939]

6.8±0.7 i, j

Modified hot-pressed materials, poreless, mean grain size < 1 μm

[955]

6.7±0.2a

Spark-plasma sintered materials, porosity – 0.1 %, mean grain size – 0.3 μm

[946]

6.7

Spark-plasma sintered materials, porosity – 0.1 % [950, 4329]

(6.6÷8.7)±(0.7÷0.8)a

Spark-plasma sintered (with pulsed current) ma- [899] terials, mean grain size – 5.5 μm

(continued)

2.4 Physico-Mechanical Properties

91

Table 2.13 (continued) 6.6-7.2a

Single-phase spark-plasma (field-activated) sin- [847, 860, tered materials, porosity – 1-5 %, mean grain 863] size – ~0.4 μm

6.5a

Pressureless sintered materials

[945]

6.3±0.2a, c

Hot-pressed materials, porosity – 2.5±0.1 %

[661]

6.3a, k

Spark-plasma sintered materials, porosity – 0.5 %, mean grain size – 0.4 μm

[871, 3127]

6.2a

Spark-plasma sintered materials, porosity – 1 % [878]

6.1-6.2a

Materials prepared by the high-frequency induc- [929, 940] tion-heating sintering (HFIHS) technique, porosity – 2 %, mean grain size – 0.1 μm

6.1±0.4a

Spark-plasma sintered materials, porosity < 0.5 %

[4463]

6.0±0.5

Spark-plasma sintered materials with singlephase and low porous microstructures

[855-856, 1015]

6.0a

Materials prepared by the high-frequency induc- [931] tion-heating sintering (HFIHS) technique, porosity – 3 %, mean grain size – 0.3 μm

6.0a

Sintered (in Ar atmosphere) materials, porosity –5%

[898]

6.0a

Materials prepared by pulsed current activated sintering (PCAS) technique, porosity – 12 %, mean grain size – 0.16 μm

[2076]

6.0

Theoretically calculated on the basis of Prantskyavichyus’s approach

[85, 1028]

5.9±0.3a

Spark-plasma sintered materials, poreless, mean [866-867] grain size – ~0.4 μm

5.9±0.2a

Materials prepared by oscillatory pressure sinte- [4496] ring (OPS), porosity – 1.4 %

5.9a

Spark-plasma sintered materials, porosity – 0.5 %, mean grain size – 0.4 μm

5.8±0.2a

Spark-plasma sintered materials, porosity – 1 %, [3470] mean grain size – 0.27 μm

5.8±0.4a

Spark-plasma sintered materials with singlephase and low porous microstructures

5.8a

Calculated from the indentation measurements, [847] single-phase spark-plasma (field-activated) sintered materials, porosity – 7 %

5.7-6.2a

Spark-plasma sintered materials, poreless, mean [938, 948] grain size – 0.5 μm

5.7±0.2a, g

Hot-pressed materials, porosity – 1.6±0.7 %

[661]

5.3±0.4a

Single-phase hot-pressed materials, porosity – 2.1±0.1 %

[661]

5.3a

Fine-grained spark-plasma sintered materials, poreless

[895]

[902]

[4141]

(continued)

92

2 Tungsten Carbides

Table 2.13 (continued) 5.26±0.09l

Sintered materials, structured with a broad uni- [954] formly-distributed range of grain sizes from submicron to 2-4 μm

(5.2÷6.7)±(0.3÷0.4)a

Single-phase spark-plasma sintered materials, porosity – 3 %, mean grain size – 90-150 nm (tended to decrease with increasing hardness)

[893]

5.0

On the basis of several sources

[2734]

4.9±0.3a

Materials prepared by the pulsed electric current [4481] sintering (PECS) technique, porosity – ~ 1-2 %

4.9±0.1a

Single-phase hot-pressed materials, porosity – 3.5±0.3 %

(4.8÷5.3)±0.2a

Single-phase spark-plasma sintered materials, [2986] porosity – 0.8-1.2 %, mean grain size – 0.15-0.16 μm, contents: non-combined C – (0.17÷0.18)±(0.1÷0.2) %, O – (0.3÷0.4)±(0.01÷0.02) %

4.69±0.04l

Sintered materials, structured with a bimodal [954] grain size distribution with a large number of grains in the submicron range and in the 2-4 μm size

4.5a

Single-phase spark-plasma sintered materials, porosity – 1 %, mean grain size – 0.4 μm

4.4±0.2a

Single-phase materials prepared by the pulsed [666, 857] electric current sintering (PECS), poreless, mean grain size < 0.3 μm

4.3-6.7a

Single-phase spark-plasma sintered materials, porosity – 0.3-1.7 %, mean grain size – 0.1-0.3 μm

4.3-6.0a

Spark-plasma sintered materials, porosity – 1 % [848-849]

4.2-4.8a

Single-phase materials prepared by the high-fre- [861, 865] quency induction-heated combustion (HFIHS) technique, porosity – 1.5 %, mean grain size – 0.4-0.6 μm

4.1-5.1a

Single-phase spark-plasma sintered materials, [852-853] prepared from nanopowders (mean grain size – 40-70 nm), with poreless and fine-grained microstructures

4.0-7.0a

Vacuum pressureless sintered materials (with usage of nanocrystalline powders), porosity < 1 %, mean grain size < 0.3 μm

[870]

4.0±0.3a

Hot-pressed materials, porosity – 10 %, mean grain size – 0.7±0.3 μm

[905]

3.9±0.1a

Hot-pressed materials, porosity – 3 %, mean grain size – 2.1±0.6 μm

[905]

3.9a

Materials as-prepared by the pulsed current acti- [947, 949] vated sintering (PCAS) technique, porosity – 0.51.0 % (without any heat treatment or annealing)

[661]

[925]

[380, 398, 666, 921922, 933]

(continued)

2.4 Physico-Mechanical Properties

93

Table 2.13 (continued) 3.6a

Spark-plasma sintered materials, porosity – ~ 22-24 %

[140]

3.2±0.5a

Reactive spark-plasma sintered materials, highly [897] densified, mean grain size – 0.27 μm a Calculated from the indentation measurements b Determined by the single notch edge beam (SNEB) method c Containing 4.3 % W2±xC phase d Calculated using the Niihara formula e With the usage of a cube corner indenter f Calculated using the Anstis formula g Containing 5.4 % W2±xC phase h In the presence of semicarbide W2±xC phase i Determined by the chevron-notched beam (SNB) method j With the addition of 5 vol.% SiC k Containing some amounts of γ-WC1–x and W2±xC phases l Determined by the single-edge precracked beam (SEPB) method

H = H0exp(–At),

(2.26)

where H is the hardness, GPa, t is temperature, °C and H0 and A are the empirical coefficients, which were determined for monocarbide δ-WC1±x materials in the temperature range of 0-720 °C as 23.0 GPa and 3.62×10–4 °C –1, respectively [836]. The variations of the hardness HV/HK and microhardness Hμ of various single crystal and polycrystalline tungsten carbide materials with temperature based on several sources are presented in Figs. 2.15-2.16 (data on tungsten carbide based hard alloys are not given there to avoid some kind of confusion, which was produced, for example, by including the data reported by Westbrook and Stover [958] for the hot hardness of δ-WC1±x – 6 % Co hard alloys to compare with behaviour of other refractory transition metal carbides with single-phase compositions [7]). For more detailed physico-mechanical analysis of the hardnesstemperature relationships of single-phase transition metal carbides at elevated and higher temperatures, the following equation, which was derived from the connection between hardness, determined by the indentation technique, and yield point (stress) of materials, can be employed (confirmed experimentally for δ-WC1±x materials in the range of 500-2200 °C) [3, 788-790, 957]: H = BT 1/3 exp(– Q/3RT),

(2.27)

where H is hardness, GPa, B is the parameter allowing for the effect of deformation rate, Q is the activation energy of the process, R is the gas constant and T is temperature, K. The equation reflects the direct connection of hardness of metal carbides with the plastic deformation, which is controlled by the mechanism of thermally activated slip of dislocations. From the hot hardness measurements Kovalchenko et al. [3, 788-789] evaluated Q in δ-WC1±x grains (crystals) as high as ~150 kJ mol–1 (see also Inset to Fig. 2.16) and proposed for δ-WC1±x the fol-

94

2 Tungsten Carbides

Table 2.14 Ductile-to-brittle transition temperatures of tungsten monocarbide δ-WC1±x materials Composition δ-WC~1.0

a, b

Characteristics

Temperature, K (°C)

References

20 (290)

Single crystal materials

[232, 242, 993]

δ-WC~1.0 c

1420 (1150)

Materials prepared by activated sintering, porosity – 0.5-1.0 %

[947, 955]

δ-WC~1.0 d

1500 (1230)

Hot-pressed and annealed, porosity – ~4 %

[84-85, 967]

δ-WC~1.0 e 1770 (1500) Sintered materials [1, 1026] a Flexure (3-point bending tests) b Indentation technique for the subsurface layers (0001) treated by implantation with 100 keV N+-ion fluences in the range of 3.0×1016 – 1.5×1017 cm–2 (the depth of ion implantation – ~0.2 μm) c Fracture toughness tests d Flexure (4-point bending tests) e Determined by the analysis of temperature dependence of yield stress

Table 2.15 Formal creep characteristics (activation energy Q, stress exponent constant n) of tungsten monocarbide δ-WC1±x materials at various temperature and stress ranges Composition

Load type a

Temperature range, °C

Stress range, Activation energy b, Exponent RefeMPa Q, kJ mol–1 constantb, n rences

δ-WC~1.0 c F

1050-1400

100-200

250

2 (or 1)d

[990]

F

1050-1400

160-500

250

1

[990]

F

1200-1400

25-100

250

2

[990]

δ-WC~1.0 e F

1200-1300

70-270

250

~3

[990]

1400

50-150

250

2

[990]

F

F 1500 30-150 250 1 MeV) fluence Φ for produced by ceramic technologies (hot-pressed, slip-cast, explosion-pressed) tungsten monocarbide δ-WC1±x materials irradiated at 300-1100 °C [1033, 1047-1053]

2.5 Nuclear Physical Properties

127

Table 2.20 The effect of thermal neutron irradiation on the structure and physical properties of tungsten carbide materials [888, 1033, 1054-1055]

Characteristics

Unit

Temperature, °C

After irradiation with different thermal neutron fluences Φ, 1020 cm–2

Initial values

0.37

0.75

1.5

γ-W2±xC (arc-melted materials) Lattice parameters: a

nm

~50

relative change Δa/a

%

~50

–

c

nm

~50

0.4728

relative change Δc/c

%

~50 –

c/a relative change Δ(c/a)/(c/a)

~50

%

~50

ρ

μΩ m

~50

relative change Δρ/ρ

%

~50

GPa

~50

0.3002

– 1.575 –

0.3001

0.2999

0.2996

–0.03

–0.10

–0.20

0.4733

0.4743

0.4756

0.11

0.32

0.59

1.577

1.582

1.587

0.13

0.44

0.76

Electrical resistivity: 1.67±0.13 2.02±0.12 2.18±0.09 –

2.64±0.32

21.0

30.5

58.1

27.0±0.8

22.7±0.9

25.1±0.8

Microhardness: Hμ

relative change ΔH/H %

19.9±0.4

~50

–

35.7

14.1

26.1

Accumulated energy a ΔE: per gram

J g−1

~50

−

3

10

17

per mole

kJ mol−1 ~50

−

1.19

3.98

6.77

−

30

100

160

0.2903

0.2903

a

Effective temperature ΔT K

~50

δ-WC1±x (hot-pressed materials) Lattice parameters: a

nm

~50

0.2899

relative change Δa/a

%

~50

–

c

nm

~50

0.2831

relative change Δc/c

%

~50

–

~50

0.9765

%

~50

–

ρ

μΩ m

~50

relative change Δρ/ρ

%

~50

GPa

~50

–

c/a relative change Δ(c/a)/(c/a)

0.2901 0.07

0.14

0.14

0.2832

0.2836

0.2840

0.04

0.18

0.32

0.9762

0.9769

0.9783

–0.03

0.04

0.18

Electrical resistivity: 0.20±0.01 0.71±0.07 1.33±0.05 1.85±0.05 –

248

552

807b

25.5±1.2

28.4±0.9

31.1±0.8

50.1

68.0

84.0c

Microhardness: Hμ

relative change ΔH/H %

~50

16.9±0.6 –

(continued)

128

2 Tungsten Carbides

Table 2.20 (continued) Accumulated energy a ΔE: per gram

J g−1

~50

−

13

32

42

per mole

kJ mol−1 ~50

−

2.46

6.25

8.20

−

130

330

430

Effective temperature a ΔT K

~50

δ-WC1±x – W2±xC (two-layered diffusion-type coatings on metallic W) d Microhardness: Hμ

GPa

≤ 70-90

15.8

≤ 70-90

relative change ΔH/H %

–

−

−

24.5e

−

−

55.1e

–

–

1.10e

Overall microbrittleness index: z

–

≤ 70-90

0.54

relative change Δz/z % ≤ 70-90 – – – 103.7e Given for additional information b From this value the property return after annealing (exposure 1 h) is: at 200 °C – Δρ/ρ ≈ 730 %, at 400 °C – Δρ/ρ ≈ 470 %, at 600 °C – Δρ/ρ ≈ 160 %, at 800 °C – Δρ/ρ ≈ 60 % and at 1000 °C – Δρ/ρ ≈ 40 % c From this value the property return after annealing (exposure 1 h) is: at 200 °C – ΔH/H ≈ 85 %, at 400 °C – ΔH/H ≈ 75 %, at 600 °C – ΔH/H ≈ 25 %, at 800 °C – ΔH/H ≈ 18 % and at 1000 °C – ΔH/H ≈ 1.5 % d Consisting of thin layer of δ-WC1±x and thick layer of W2±xC phases e After irradiation with thermal neutron fluence Φ = 1.0×1020 cm–2 (a small number of cracks appeared after the exposure) a

The retention of hydrogen isotopes in tungsten carbides, which are proposed to be employed as plasma-facing materials, is an important issue for the development of nuclear fusion devices; so plenty of various research works consider and interpret this problem in different details [525, 1058, 1081-1099, 1152-1153]. The 1.5 keV D3+ ions implantation of W2±xC (chemical vapour deposited materials) with fluence Φ = ~3×1019 cm–2 at 20-300 °C showed that the D retention in W2±xC is higher than that in metallic W due to the presence of C and differences in carbide and metal microstructures and recoil carbon induced damage [1083]. At ambient temperatures in the course of 10 keV D+ ions irradiation of chemical vapour deposited coatings γ-WC0.8÷0.9 with thickness – 10-15 μm and mean grain size – 2-3 nm, containing ~10 % γ-W2±xC phase, as a value of Φ increases, the concentration of D atoms in the implanted zone reaches a maximum value of ~0.03 D atoms per WC unit (density assumed to be 5.3×1022 WC units per 1 cm3), while the D atom profile (Φ = ~1×1019 cm–2) shows a long tail extending to ~2.5 μm, i.e. far beyond the implantation zone; at the elevated temperatures (~380 °C) D atoms are retained in the zone with the maximum concentration in the ion stopping zone not exceeded ~0.01 D atoms per WC unit [1086]. The behaviour study of δ-WC1±x, irradiated at 50 °C by 1 keV D2+ ions with a fluence up to Φ = 1×1018 cm–2 and flux φ = 1×1014 cm–2 s–1, showed that almost all of D atoms, retained in the carbide, were desorbed in the range of temperatures from 25 to 430 °C and the residue – at ~700 °C, the D2 desorbed at the higher temperatures originates from the D atoms trapped by C, and this retention was considerably

2.5 Nuclear Physical Properties

129

small and saturated at lower D2+ fluence; the D2 desorption at lower temperatures takes place in three stages: two of them are attributed to the desorption of D atoms retained in the interstitial sites and another one, marked by the highest peak on the thermal desorption spectra, corresponds to the D atoms trapped by the C vacancies, which are induced by chemical sputtering of C atoms by energetic D2+ ions [1087]. By the means of first principles studies, it was found that the most stable interstitial site for the H atoms is the projection of the octahedral interstitial site on W basal plane followed by the site near the projection of the octahedral interstitial site on C basal plane, and the migration of interstitial H atoms in δ-WC1±x is preferable in the direction along the c axis [1094]. The object-oriented MonteCarlo simulations were successfully applied to study the implantation profile of 2 MeV protons in δ-WC1±x [1092]. Low-energy (10-100 eV) H isotope ions and He ions bombardment, as it was shown by the molecular dynamics (MD) simulations on D ions [1088], can lead to the erosion and amorphization of surface layers of tungsten monocarbide δ-WC1±x and semicarbide W2±xC materials and preferential sputtering of C atoms from the irradiated layers [1090-1091, 1153]. The MD simulations of cumulative co-bombardment of crystalline tungsten carbides by D ions with C, W, He, Ne or Ar impurities (performed for 0.1-0.3 keV ion energies, temperature of 330 °C and ion flux φ = 3.38×1024 cm–2 s–1) have indicated that the irradiated surface changed from crystalline to amorphous, and D atoms were trapped in the carbide, followed by the D2 accumulation into bubbles, which resulted in some cases to a blistering-like effect [1093, 1152]. A Monte Carlo simulation study on retention and reflection processes at room temperature from tungsten monocarbide under high fluence of He ions (φ = 1×1014 cm–2 s–1) was carried out by Ono et al. [1154]. Employing the deuteron flux of 9×1015 cm–2 s–1 (consisted of 97 % D3+, 2 % + D2 and 1 % D+) for the implantation process in a W-C multilayer system deposited by magnetron sputtering, Wang and Jacob [1096] proved that D diffusion in the system can be reduced substantially by the formation of tungsten monocarbide δ-WC1±x and can be almost completely suppressed by the formation of tungsten semicarbide W2±xC phase. Oya et al. [1097] showed that the sequential co-implantation of He+ (φ = 1×1013 cm–2 s–1, Φ = 1×1017 cm–2) and D2+ (φ = 1×1014 cm–2 s–1, Φ = 1×1018 cm–2) ions, carried out at room temperature, increases the D retention in ion-implanted δ-WC1±x at temperatures < 160 °C due to the formation of dense and large He bubbles, which act as D diffusion barriers toward the bulk, even if the damage was introduced by He+ ions in the materials. The erosion behaviour of δ-WC1±x under 0.02-1.5 keV D3+ ions bombardment (Φ = 3×1015 cm–2) at room temperature results in the preferential sputtering (loss) of C and respective changes of the surface composition of carbide materials due to the threshold effects caused by the large W/C mass ratio [1132]. Massive experience has been accumulated on the problems related to the interaction of tungsten carbides with the ion fluxes of different nature and intensities. At the same time, in the accordance with the requests of industrial

130

2 Tungsten Carbides

manufacturing, the research in this direction were devoted for the most part to the containing tungsten monocarbide δ-WC1±x hard alloys (cermet systems with the metals of Fe group) [98, 1101-1131, 1133-1143, 1146, 1150, 1159, 1165]. The comparison between the behaviour of massive δ-WC1±x and W2±xC samples and a δ-WC1±x – 8 % Co hard alloy, which were subjected to the same procedure of 40 keV 15N+ ions implantation (Φ = 1×1017 cm–2, N concentration profile in all the materials was studied using the 15N (p, αγ) 12C reaction), has allowed to conclude that the metal binder plays an important role (more likely as a short circuit) for N diffusion in the hard alloy, and W2±xC structure, having a lot of vacancies, where N atoms possibly end up in the non-occupied interstitial sites, is less favourable to the easy mobility of N than that of δ-WC1±x [1112]. The 0.1 MeV N+ ions implantation of single crystal δ-WC1±x (0001) with the fluences Φ ranging from 3.0×1016 cm–2 to 1.5×1017 cm–2 (depth of ion penetration was ~0.2 μm), carried out by Luyckx et al. [993, 1144], led to the dislocationinduced cracks at lower ion fluences and to the cracks, which followed paths of maximum tensile stress and were unrelated to cleavage planes, at higher ion fluences; while the sub-surface layer of the δ-WC1±x crystals, in which the ions come to stop, underwent a ductile-to-brittle transition (see also Table 2.14). Fine powders of tungsten monocarbide δ-WC1±x (mean grain size < 5 μm), irradiated by 7 MeV Si+ ions (Φ ≤ 1014 cm–2), were characterized with a maximum increase of ≥ 1.0 % in volume of the unit cell and the saturation density of defects to be ~1022 cm–3, but there was no evidence for the formation of a non-crystalline condition [1145]. The implantation of tungsten carbide substrates by Pt+ ions (Φ > 1016 cm–2) causes their catalytic activity to become higher than that of smooth Pt metal, but this functional property decreases noticeably with increasing Kr+ ion fluence used for mixing in the ion beam [1147, 1157-1158]. The 80 keV N2+ ions beam (Φ = 3.0×1016 cm–2) treatment (irradiation) of the pulsed laser deposited tungsten carbide films induced recrystallization in as-deposited amorphous thin films and a significant increase in the hardness of these films [472]; the 0.16 MeV Ar+ (with Φ varied from 1.0×1016 cm–2 to 2.0×1017 cm–2 at temperatures in the range of 25-190 °C) and 0.16 MeV N+ (with Φ varied from 5.0×1015 cm–2 to 2.0×1017 cm–2 at 150 °C) ions implantations of δ-WC1±x magnetron sputtered films (thickness – 50-120 nm) induced the formation of new phases on the interfaces due to the interaction of irradiated δ-WC1±x with Ti based alloy substrates [1148-1149]. Ar+ ion bombardment can be employed as reducing agent enabled to optimize the preparational conditions of tungsten carbides [726]. The 45 keV N+ ions irradiation (Φ = 1.0×1017 cm–2) of W-C-B multi-layers induced the formation of δ-WC1±x and γ-WC1–x phases, while the implanted N+ ions bonded with both W and C atoms there [1151]. The interactions of thermal beams of D2, He, Ne and Ar with tungsten carbide overlayers formed on metallic W were studied by Weinberg and Merrill [1098-1100]. Nuclear properties of tungsten carbides in comparison with all other ultra-high temperature materials are also given in Addendum.

2.6 Chemical Properties and Materials Design

131

2.6 Chemical Properties and Materials Design The comprehensive data on the chemical properties, compatibility (in the connection with both environmental resistance and composite materials design) and interaction behaviour of tungsten carbide phases in the wide range of temperatures with elements (metals, non-metals) are summarized in Table 2.21, with refractory and some other compounds, including polymers – in Table 2.22 and with gaseous media – in Table 2.23. The data on the oxidation resistance of tungsten carbide materials listed there are also accompanied by the graphic information in Fig. 2.25; the isothermal oxidation kinetics of bulk tungsten monocarbide δ-WC1±x materials presented in it can be termed in the context of ridge-effect model proposed by Shabalin [1185-1187] with a ridge temperature at air conditions (for a certain partial pressure of O2) around 800 °C, since the kinetics curves at temperatures ≥ 1200 °C are not reproducible and representative because of the random fracture of oxide scales on the surface of δ-WC1±x; similar phenomena are also called as “kinetics inversion” or “negative kinetics” [20312033]. The general catalytic and adsorption activities jointly with special electro- and photocatalytic, solar conversion and bioactivity properties of single-phase tungsten carbides, as well as the characteristics of complex (composite) electrocatalysts, catalysts and sorbents containing them, are described and considered in a massive number of research works [1, 3, 32, 110, 154, 169, 212, 259, 274, 277, 287-288, 298-299, 313, 327, 336, 352-353, 356, 369, 375, 387-392, 397, 401, 403-405, 407-410, 412, 415-418, 422, 425, 428-429, 431, 439-440, 444, 447, 450-451, 454, 460-463, 468, 502, 505-508, 542, 725-726, 770, 1147, 11571158, 1161, 1166-1167, 1170, 1172, 1175, 1177, 1179, 1188-1781, 1790, 1792, 1794, 1798, 1801, 1814, 1838-1839, 1842, 1851, 1883, 1907-1917, 2303, 2312, 2315-2316, 2328, 2356, 2358, 2377-2379, 2396-2397, 2407, 2415, 2420-2421, 3143, 3510, 4544], including directly the following chemical reactions and/or processes: adsorption of carbon dioxide [1738]; adsorption of carbon monoxide [1452, 1553, 1644, 1685, 1738]; adsorption of hydrogen [1459, 1491, 1567, 1625, 3510]; adsorption of thiophene [212]; adsorption of water [1738] anaerobic digestion of manure [1733]; conversion (hydrolysis, hydrogenolysis) of cellulose [1440, 1466, 1479, 1503, 1519, 1538, 1668, 1725, 1739, 1749, 3835]; conversion (reforming), thermal decomposition and oxidation of methane [388, 407-408, 1340-1341, 1343, 1349, 1360, 1374, 1387, 1470, 1476, 1627, 1684, 1699, 1713, 1908];

132

2 Tungsten Carbides

Table 2.21 Chemical interaction and/or compatibility of tungsten carbide phases (and/or their compositions) with elements (metals, non-metals), including solid matters and molten media, in the wide range of temperatures (reaction/design systems are given mainly in alphabetical order)a System

Atmo- Temperature sphere range, °C

δ-WC1±x – Ag

–

–

–

–

Interaction character, products and/or compatibility

References

The effect of substitutional Ag impurities [1256, 1433, on the properties of δ-WC1±x was simulated 1585, 1765, on the basis of first principles calculations 1984, 2001Ag metal monolayer supported by both W- 2020, 2037, and C-terminated δ-WC1±x (0001) was si- 4071] mulated on the basis of DFT calculations

–

150-200

Electrocatalytic materials based on nanocrystalline δ-WC1±x (mean size – 50 nm) – 10 % Ag composition were prepared in the glycerol medium

Vacuum 600

The addition of 2 % δ-WC1±x particles to the sintered metallic Ag significantly suppresses the growth of microporosity

Ar

970-1050

Ag – 8-31 vol.% δ-WC1±x nanocomposites were prepared by the δ-WC1±x nanoparticle (mean size – 0.15 μm) incorporation to metallic Ag through stir-casting assisted by molten salts (NaCl – KalF4 equal volume mixture) followed by melt-pressing processes

H2

~1000

Contact materials were prepared from the δ-WC1±x (mean grain size – ~ 0.8-4 μm) – 40-75 vol.% metallic Ag (mean grain size – ~5 μm) powdered mixtures by press-sintering infiltration and liquid-phase sintering methods and tested for the operation in air and vacuum

See also Table 2.26 δ-WC1±x – Ag – Be – Cd – Co – Cu – Ni – Zn

–

600-750

δ-WC1±x – 15 % Co hard metals were join- [2254] ed to Cu – 2 % Be – 0.5 % Co – 0.5 % Ni bronze foils with the usage of Ag – 15 % Cu – 24 % Cd – 16 % Zn filler alloy with the usage of hybrid ultrasonic resistance brazing method

δ-WC1±x – Ag – C

–

20-160

δ-WC1±x – 17 mol.% Ag – 78 mol.% C [1571, 2021nanometer powdered hybrid electrocatalyst 2023] was synthesized by hydrothermal method

–

25-30

δ-WC1±x – Ag – α-C (graphene) nanocomposite coatings were prepared by electroless co-deposition in the aqueous solution (pH 11-12) plating bath (exposure – 2 h)

(continued)

2.6 Chemical Properties and Materials Design

133

Table 2.21 (continued) α/β/ε/γ-W2±xC – Ag – C

–

–

α/ε-W2+xC – 10 mol.% Ag – 88 mol.% C nanocrystalline composite electrocatalyst was prepared by intermittent microwave heating (IMH) method

[1392]

δ-WC1±x – Ag – C – Co – Cr – Cu – Fe – Mn – Mo – Ni – Zn

See sections δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – Zn and δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn

δ-WC1±x – Ag – C – Co – Cr – Cu – Fe – Mo – Ti

See section δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti

δ-WC1±x – Ag – C – Co – Cu – Fe – Mn

See section δ-WC1±x – Ag – Co – Cu – (Fe – C – Mn)

δ-WC1±x – Ag – High 830 C – Co – Cu – Ti purity Ar flow

Eutectic Ag – 27.5-28.0 % Cu alloy with [2422] additions of 0.3-2.8 % Ti was used as a filler metal (thickness – 0.1 mm) for dissimilar laser-brazed joining of α-C (graphite, quasi-isotropic) and δ-WC1±x – Co cermets

δ-WC1±x – Ag – Cd – Co – Cu – Ni – Zn

Ag – 16 % Cd – 15.5 % Cu – 15.5 % Zn – [10, 1992, 3 % Ni alloy is employed as a filler metal 2024] for brazing δ-WC1±x – Co hard metals (the addition of Ni improves wetting on hard metals)

–

660

Ar

–

δ-WC1±x – Co hard metals were furnacebrazed by a Ni-electroplated Ag – Cu – Zn – Cd filler alloy

δ-WC1±x – Ag – Ar Cd – Co – Cu – Zn

–

δ-WC1±x – Co hard metals were furnacebrazed by an Ag – Cu – Zn – Cd filler alloy

–

δ-WC1±x (mean grain size – 1-6 μm) – 20- [2006, 2009] 38 % Ag – 0.5-8.0 % Co contact materials for the vacuum operation were manufactured by the infiltration methods

[2024]

δ-WC1±x – Ag – Co

–

δ-WC1±x – Ag – Co – Cu

–

1110

The interaction of δ-WC1±x – 20 % Co ce- [2177] mented carbide with molten Cu – 10 % Ag alloy showed that the addition of Ag to Cu melt has no detectable effect on its interaction with the cemented carbide

δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – Zn

–

710-810

δ-WC1±x – 20 % Co hard alloys were join- [2859] ed by the high-frequency induction brazing to the Fe – 0.35 % C – 1 % Cr – 0.5 % Mn – 0.2 % Mo steels with the usage of Ag – 16 % Cu – 23 % Zn – 7.5 % Mn – 4.5 % Ni alloys as the filler metals (interlayer thickness – 120 μm); island-like α-(Cu,Mn,Zn,Ni) solid solution grains formed in the interlayer were transforming further to the α-(Cu,Mn,Zn,Ni) layers

(continued)

134

2 Tungsten Carbides

Table 2.21 (continued) when Ni diffused to the interface δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn

–

710-770

δ-WC1±x – 15 % Co hard alloys were join- [2026-2027, ed by the brazing (including ultrasonic-as- 2029] sociated method) to steel (C – 0.33 %, Cr – 1 %, Mo – 0.2 %) parts with the usage of Ag – 16 % Cu – 23-24 % Zn – 4-8 % Mn – 5 % Ni and Cu – 38 % Zn – 4 % Mn alloyed solders; the formation of a δ-WC1±x particulate reinforced joint was achieved

δ-WC1±x – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti

–

780-800

δ-WC1±x – Co hard metals were brazed to [2030] the cold work steels by the Ag – 28 % Cu – 2 % Ti alloys as filler metals

δ-WC1±x – Ag – Vacuum 800-850 Co – Cu – (Fe – C – Mn)

δ-WC1±x – 8 % Co hard metals were bra- [2025] zed to Fe – 0.45 % C – 0.75 % Mn steels by the Ag – 28 % Cu alloys as filler metals

δ-WC1±x – Ag – Co – Cu – Mn – Ni – Zn

Ag – 16-38 % Cu – 20-23 % Zn – 2.5-9.5 [10, 1992, % Mn – 0.5-5.5 % Ni alloys are employed 2028] as filler metals for brazing δ-WC1±x – Co hard metals

–

690-840

High730 purity Ar

δ-WC1±x – 9 % Co hard metals were furnace-brazed by Ag – 16 % Cu – 23 % Zn – 7.5 % Mn – 4.5 % Ni filler alloy

δ-WC1±x – Ag – Co – Cu – Ni – Si – Zn

–

910

Ag – 50.0 % Cu – 39.7 % Zn – 9.0 % Ni – [1992] 0.3 % Si alloy is employed as a filler metal for brazing δ-WC1±x – Co hard metals

δ-WC1±x – Ag – Co – Cu – Ni – Zn

–

780-860

Ag – 30 % Cu – 25-28 % Zn – 2-5 % Ni alloys are employed as filler metals for brazing δ-WC1±x – Co hard metals

δ-WC1±x – Ag – Cu

–

850-950

10-22 vol.% δ-WC1±x nanoparticle (0.1-0.2 [10, 2019, μm) reinforced Ag – 40 % Cu alloy nano- 2034-2036] composite materials were prepared by a molten salt assisted incorporation method, including the preparation of micro- and nanowire structures

Pure Ar 950-1100

[1992]

The contact interaction and solidification of Ag – 0.2-1.0 % Cu alloys with/on highly dense δ-WC1±x ceramics were studied

See also Table 2.26 δ-WC1±x – Ag – Pure Ar 960-1100 Cu – Ni

The contact interaction and solidification [2019] of Ag – 0.2 % Cu – 0.15 % Ni alloys with/on highly dense δ-WC1±x ceramics were studied; compared to Cu, Ni displays a stronger influence on wetting as a result of the adsorption of Ni at the δ-WC1±x – Ag interface, which was also supported by the preferential segregation of Ni at the interface during cooling in contrast to Cu

(continued)

2.6 Chemical Properties and Materials Design

135

Table 2.21 (continued) See also Table 2.26 δ-WC1±x – Ag – Pure Ar, 970-1100 Ni H2, N2, or H2-N2 mixtures

The uniaxially pressed δ-WC1±x (0.8-4 μm) [2015-2016, – 40-45 % Ag (5 μm) – 0.1-6.0 % Ni 2019, 2038(7 μm) powdered mixtures (mean particle 2039] sizes are given in brackets) were subjected to liquid-phase sintering (exposure – 0.5 h), followed by infiltration of molten Ag, to prepare highly dense materials; similar composite materials were also prepared by spark-plasma sintering (with and without additional heat treatment) processes

δ-WC1±x – Ag – Pb

–

Composite Pb – 0.3 % Ag alloy – δ-WC1±x [1863] inert anodes were prepared by doublepulse electrodeposition (DPE) from an aqueous solution plating bath containing δ-WC1±x particles

δ-WC1±x – Ag – Zr

–

δ-WC1±x – α/β-BN – Ag – Co – Cu – In – Ti

–

See also Table 2.26 20-30

–

850-1050

–

δ-WC1±x – α/β-BN – Ag – Co – Cu – Ti

δ-WC1±x – α/β-SiC – Ag – Co – Cu – Ti

–

δ-WC1±x – 39.5 % Ag – 0.5 % Zr contact materials for the vacuum operation were designed and manufactured

[2006]

δ-WC1±x – 4.5 % Co hard metals were bra- [2040, 4158] zed to β-BN (cubic) materials by the usage of Ag – 0-27.5 % Cu – 0-5 % In alloys (activated by Ti) employing electron beam welding techniques (exposure – 2-5 min) δ-WC1±x – 6 % Co hard metals were brazed to β-BN (cubic) – 10 % Co materials by the usage of Ag – 27.25 % Cu – 12.5 % In – 1.25 % Ti alloys employing microwave hybrid heating (exposure ≥ 12 min)

High ≤ 800 purity Ar flow

δ-WC1±x – 6 % Co hard metals were bra- [2041-2042] zed to high purity hot-pressed α-BN (hexagonal) materials by the usage of Ag – 27.728.1 % Cu – 1.3-1.7 % Ti alloys, employing laser beam (diameter – 0.5 mm) indirect heating

High ≤ 850 purity Ar flow

δ-WC1±x – 6 % Co hard metals were brazed to pure polycrystalline β-BN (cubic) materials by the usage of Ag – 27.8-28.2 % Cu – 0.3-1.7 % Ti alloys, employing laser beam (diameter – 0.5 mm) indirect heating

High 830 purity Ar flow

Eutectic Ag – 27.5-28.0 % Cu alloy with [2423] additions of 0.3-2.8 % Ti was used as a filler metal (thickness – 0.1 mm) for dissimilar laser-brazed joining of SiC (> 99 % purity, recrystallized, porosity – 17 %) and δ-WC1±x – Co hard alloys

(continued)

136

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – α/β/γ/δ-ZrO2–x – Ag – Pb δ-WC1±x – Al

20-40

Composite Pb – 0.8 % Ag – 10 % δ-WC1±x [1501] – 3.6 % ZrO2 inert anodes were prepared by the electrodeposition from a fluoroboric bath

Air

250

1-3 vol.% δ-WC1±x particulate (< 0.8 μm) reinforced 99.6 % purity Al metal matrix composites were prepared by warm accumulative (multiple cycled) roll bonding

Air

350

Air

400-500

–

Vacuum ~400-600

–

~600

Vacuum, 640 ~0.5 mPa

[1, 33, 83, 579, 768, 940, 1885, 1941-1942, 10 vol. % δ-WC1±x particulate reinforced 2043-2092, 99.5 % purity Al metal matrix composites 2098, 2101, were prepared by continual annealing and 2132, 21392141, 2166, press bonding (CAPB) technique 2175, 2183, Al (mean particle size – 44 μm) – 0.2-2 3893, 4066, vol.% δ-WC1±x (mean particle sizes – ~0.2 4142-4148] μm and ~20 μm) powdered mixtures were treated by spark-plasma sintering (exposure – 5 min) to prepare nano-, micro- and bimodal particulate reinforced highly dense metal matrix composites; no new phases were formed in the materials 1-8 vol.% δ-WC1±x – Al materials were prepared from powders by thermal cycled sintering and hot deformation 0.5 vol.% δ-WC1±x particulate reinforced Al metal matrix composites were prepared by the sintering of powdered mixtures (exposure – 1 h) with followed compressive deformation Cold-compacted preliminarily, powdered pure Al (mean particle size – 10 μm, specific surface area – ~0.7 m2 g–1) – 1 vol.% δ-WC1±x (mean particle size – ~0.3 μm, specific surface area – ~20 m2 g–1) mixture was sintered (exposure – 2 h) to prepare a highly dense metal matrix composite; the formation of γ-WAl12 aluminide due to the interfacial reactions was detected in the composites

–

≥ 700

0.5-2.0 vol.% δ-WC1±x particulate (0.10.15 μm) reinforced Al metal matrix composites were prepared by the stir casting technique of molten metal

–

750

0.03 % (out of the total mass) δ-WC1±x nanoparticle (size – 40-70 nm) reinforced pure Al metal matrix composites were prepared by the stir casting technique

(continued)

2.6 Chemical Properties and Materials Design

137

Table 2.21 (continued) –

800-830

0.5-2.5 vol. δ-WC1±x particulate (0.2-0.4 μm) reinforced 99.5 % purity Al metal matrix composites were prepared by fluxing (with KBF4 and K2TiF6 salts) and mechanical stirring technique; the formation of different W aluminides, such as γ-WAl12, δ-WAl5–x, ε-WAl4±x and ζ-WAl3±x, was observed in the materials, depending on the volume fraction of δ-WC1±x particles containing there

–

≤ 1000

No chemical interaction and/or mutual solubilities between the components

Vacuum, 1000 1.3 Pa –

≥ 1250

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Al (exposure – 5 min) Formation of solid solutions due to the dissolution of Al in carbide crystal lattice

Vacuum, 1400-1700 The solid solution system of (W1–xAlx)C1–y or higher (0.10 ≤ x ≤ 0.86, 0.50 ≤ y ≤ 0.90) was synpressure thesized through special mechanical alloy(4.5-5.0 ing followed by solid-state reactions, or by GPa) some kind of high-pressure technique (exposure – 5-30 min); although, its formation, at least at the ambient pressures, contradicts with some other experimental data obtained, but also with the results of DFT calculations Vacuum, 1450 10 Pa

99.8 % purity δ-WC1±x (mean particle size – 15-20 nm) – 5-15 vol.% 99.99 % purity Al powdered mixtures were consolidated by the pulsed current activated sintering (PCAS) method (exposure – 3 min) to fabricate highly dense cermet materials (with mean matrix grain size – 70-400 nm)

Vacuum, ≤ 1600 15 Pa

99.8 % purity δ-WC1±x (mean particle size – 15-20 nm) – 5-15 vol.% 99.99 % purity Al powdered mixtures were consolidated by the high-frequency induction-heated sintering (HFIHS) method (heating rate – ~20 K s–1, without a holding time at the final stage of heating) to fabricate highly dense cermet materials (with mean matrix grain size – 80-200 nm)

Vacuum 1700

Vapour of Al penetrates into the porous structure of carbide materials without the formation of new phases there

(continued)

138

2 Tungsten Carbides

Table 2.21 (continued) –

–

The adhesion of Al (111, 110) – δ-WC1±x (0001, 1120) interfaces was examined using DFT calculations, taking into account both W- and C-terminations: the clean surface and optimal interface geometry are W-terminated, but the largest adhesion energies are obtained with the Ctermination

–

–

Quantum-chemical studies (calculations) of the electronic structure and some properties of probable aluminocarbide (W1–xAlx)C1–y phases have been undertaken

–

–

The properties of WAlC2–x (x = 0), W2AlC1–x (x = 0) and W3AlC2–x (x = 0) aluminocarbide (hypothetical) phases were simulated on the basis of first principles calculations The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors Some data on the system reported by various authors differ markedly

See also section δ-WC1±x – Al – C See also Table 2.26 See also section C – Al – W in Table I2.14 δ-WC1±x – α/β/ε/γ-W2±xC – Al

–

700-900

Two-phase δ-WC1±x – α/ε-W2+xC diffusion [2174] coatings on W metallic substrate are durable to molten Al (exposure – 5 h), as neither reactions nor appreciable changes were observed on its surface

See also section δ-WC1±x – Al – C See also section C – Al – W in Table I2.14 δ-WC1±x – Al – Ar B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn

–

Powdered 80 % Ni-based alloy (size dis- [4187] tribution – 47-100 μm; contents: Ni – 58.2 %, Cr – 15.5 %, Fe – 15.0 %, Si – 4.0 %, B – 3.5 %, W – 3.0 %, C – 0.8 %) – 20 % hard alloy (size distribution – 36-44 μm; contents: δ-WC1±x – 88 %, Co – 12 %) mixtures were employed as feedstocks for the fabrication of composite coating on Albased alloy (contents: Zn – 4.0-5.0 %, Mg – 1.0-1.8 %, Fe – 0.4 %, Si – 0.35 %) by laser surface alloying; the produced coatings contained the phases of aluminides NiAl1±x (major phase of the coatings) and Ni2Al3±x, carbides δ-WC1±x, γ-W2±xC and Cr23C6±x, boride CrB and γ-(Fe,Ni) metallic

(continued)

2.6 Chemical Properties and Materials Design

139

Table 2.21 (continued) solid solution δ-WC1±x – Al – B – Co – Cr – Ni – Si

–

~600-1000 To prepare the joints between δ-WC1±x – [2103] Co hardmetal and metallic Al, a Ni – 7 % Cr – 4.5 % Si – 3 % B brazing filler alloy was applied; the formed microstructure of interface consisted of the following main layers: Al / NiAl3 + Ni2Al3±x + Co2Al5±x / (Co,Ni) solid solution / (W,Co,Ni)Cx / δ-WC1±x + Co

δ-WC1±x – Al – B – Co – Cr – Ti –V

–

–

Micro- and nano-structured δ-WC1±x rein- [2938] forced Co-based alloy cladding layers on Ti – 6 % Al – 4 % V alloy substrates with good bonding with the layers and were prepared by laser cladding; the layers were composed of η2-W3Co3Cy, (Ti,W)C1–x, VC1–x, TiB2±x, Ti2±xCo, α(α′)-Ti, β-Ti and W phases, forming several eutectics

δ-WC1±x – Al – B – Cr – Cu – Fe – Ni – Si

–

–

Powdered Ni – 20 % δ-WC1±x – 10.5 % Cr [2144] – 10 % Fe – 1.5 % Si – 1.2 % B mixtures thermally sprayed on the Al – 8 % Si – 1.4 % Cu alloy substrates were applied for laser surface cladding to produce cermet layers composed of δ-WC1±x, Cr23C6±x and complex (Cr,W,Ni,Fe,Al)Cx carbides, γ′-Ni3±xAl, NiAl1±x, NiAl3, Fe3±xAl, FeAl1±x and complex (Ni,Fe,Cr,W)2(Al,Si,B)3±x (needle-like phase) aluminides and metallic γ-(Fe,Ni,Cr,Al,Cu) alloy phase

δ-WC1±x – Al – Vacuum, 1300-1400 Powdered δ-WC1±x (≥ 99.9 %, 0.6 μm) – [4313, 4318B – Cr – Fe – Ni < 6 Pa 10 % high-energy ball-milled (mechanical- 4319] – Zr ly alloyed) blend (contents: Fe (≥ 99.5 %, 6 μm) – 10.9 %, Al (≥ 99.5 %, 90 μm) – 10.5 %, Cr (≥ 99.0 %, 75 μm) – 8.1 %, Zr (≥ 99.9 %, 75 μm) – 0.9 %, B (≥ 99.0 %, 75 μm) – 0.2 %, Ni (≥ 99.5 %, 2.6 μm) – remainder) mixtures (initial purities and mean particle sizes of all the components are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to fabricate dense δ-WC1±x – γ′-(Ni,Fe,Cr,Zr,W)3±x(Al,B) cemented carbides with oriented plate-like triangular prismatic grains (a large number of the δ-WC1±x (0001) triangular plains of grains were fairly vertical to the direction of sintering pressure)

(continued)

140

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Al – B – Cr – Mo – Ni – Zr

Vacuum, 1450 0.1 mPa

δ-WC1±x – Al – B – Fe

Ar

Powdered δ-WC1±x (mean particle size – 2- [4212] 3 μm) with 30 vol.% Ni-based alloy (contents, at.%: Ni – 73.88, Al – 15.9, Cr – 8.0, Mo – 1.7, Zr – 0.5, B – 0.02) was used to prepare dense composites (porosity – 0.3 %) by melt infiltration procedure

1450-1550 Preliminarily milled/mixed powders of [2000, 2093, δ-WC1±x (initial mean particle size – 0.7 2238, 4214, μm) with ~40 vol.% (Fe – 40 at.% Al – 0.2 4217, 4245] at.% B) alloy (particle size < 45 μm) were uniaxially hot-pressed in the liquid-phase sintering mode to prepare δ-WC1±x – FeAl1±x – FeAl3±x composite materials; no interaction of δ-WC1±x with other components was detected, the presence of B modifies the δ-WC1±x/ FeAl1±x interface –

–

The preliminarily ball-milled mixtures of δ-WC1±x – 11.5 % FeAl0.67 (500 ppm B doped, prepared by mechanical alloying) powders were employed for the deposition of laser-cladded composite coatings (with minor phases: γ-W2±xC and η2-W3Fe3Cy) on stainless steel substrates

See also section δ-WC1±x – FeAl1±x – β-B δ-WC1±x – Al – B – Ni

δ-WC1±x – Al – B – Ni – Zr

δ-WC1±x – Al – α/β-C

–

1450-1550 δ-WC1±x – 40 vol.% B (500 ppm) doped [2239-2240, γ′-Ni3±xAl dense composites were prepared 2244, 4217, using liquid-phase sintering of ultra-fine 4321] powders via hot-pressing procedures Powdered δ-WC1±x (mean particle size – [4212] 2-3 μm) with 20-30 vol.% Ni-based alloy (contents, at.%: Ni – 76.9, Al – 22.5, Zr – 0.5, B – 0.1) was used to prepare dense composites (porosity – 0.3-0.5 %) by melt infiltration procedure

Vacuum, 1450 0.1 mPa

–

Vacuum, 1 mPa

δ-WC1±x is in equilibrium with aluminide ε-WAl4±x, carbide Al4C3, metallic W and α-C (graphite) phases

900

–

[2094-2096, 2183]

Nanocrystalline γ-WC1–x (metastable) – Al doped amorphous C coatings (C – 74.5 at.%, W – 17 at.%, Al – 8.5 at.%, thickness – ~2 μm) were prepared by magnetron sputtering process See also section δ-WC1±x – Al See also section C – Al – W in Table I2.14

δ-WC1±x – Al – C – Co – Cu – Fe – Mn – Ni

See section δ-WC1±x – Al – Co – Cu – (Fe – C – Mn) – Ni

(continued)

2.6 Chemical Properties and Materials Design

141

Table 2.21 (continued) δ-WC1±x – Al – C – Co – Fe – Mn – Ni – Si – Ti

See section δ-WC1±x – Co – (Fe – C – Mn – Si) – (Ni – C – Al – Ti)

δ-WC1±x – Al – C – Cr – Fe – Mn – Ni

See section δ-WC1±x – Al – (Fe – C – Cr – Mn – Ni) – Ni

δ-WC1±x – Al – C – Cr – Fe – Mn – Ni – Si – Ti

See section δ-WC1±x – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti Powdered δ-WC1±x (1-10 μm) – 56 % Ni [3859] (75-150 μm) – 5-15 % α-C (graphite) (100150 μm) mixtures (all the components – with 99 % purities, their size distributions are given in brackets) were employed as raw materials for the fabrication of hybrid metal matrix composite (HMMC) coatings on Al-based alloy (contents: Cu – 1.6 %, Si – 18 %) substrates using laser composite surfacing (LCS) techniques (with maximum power density – ~6.1 MW cm–2); the prepared coatings were composed of δ-WC1±x grains embedded in the polyaluminide matrix (NiAl3, Ni2Al3±x, NiAl1±x and Ni3–xAl phases were detected)

δ-WC1±x – Al – C – Cu – Ni – Si

–

δ-WC1±x – Al – C – Mg

–

605

Al – 2.8 % Mg alloys were reinforced by [10, 2096, 1-2 vol.% δ-WC1±x and 5 vol.% α-C (gra- 2376] phite, particle sizes – 60-90 μm) powders through melt-stir casting procedures to prepare hybrid metal matrix composites

δ-WC1±x – Al – C – Mg – Si

–

720

Al – 0.8 % Mg – 0.6 % Si alloys were rein- [2095] forced by 0.2-0.5 vol.% δ-WC1±x (5 μm) and 5 vol.% α-C (graphite, 15 μm) powders (mean particle sizes are given in brackets) through stir casting procedures to prepare hybrid metal matrix composites

δ-WC1±x – Al – Co

–

650-950

The powdered Al – 10-20 % δ-WC1±x [2097-2105, (99.5 % purity, mean particle size – 1 μm) 2166, 2424, – 1-2 % Co (99.8 % purity, mean particle 4129] size – 5 μm) mixtures were subjected to conventional sintering (holding time – 1 h) and microwave sintering (without holding) procedures to prepare highly dense metal matrix composites; the partial decomposition of δ-WC1±x and formation of small amounts of ε-WAl4±x, δ-WAl5–x and γ/β-WAl12 aluminide phases as interfacial products were detected in the sintered materials

–

(continued)

142

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1250-1400 (W0.4Al0.6)C0.5 – 13 vol.% Co two-phase 1 mPa highly dense cemented carbides (with mean grain sizes – 1-3 μm) were prepared by sintering (exposure – 0.5-2.0 h) of mechanically alloyed W, Al and C powders, mixed with 99.6 % purity Co powder (initial particle sizes of powdered mixtures – (19÷31)±(1÷3) nm) –

~1300-1450 During the liquid-phase sintering process, the behaviour of element Al impurities in δ-WC1±x – Co compositions concludes to the formation of Al4C3 particles between δ-WC1±x grains, hindering small δ-WC1±x particles to grow via grain boundary migration, and the dissolution of Al in the Co metallic binder

Vacuum, 1350-1500 Powdered δ-WC1±x (~0.6 μm) – 12 vol.% 1.3 Pa Co (~2 μm) – 10 vol.% Al (5 μm) mixtures (mean particle sizes are given in brackets) were sintered (exposure – 1 h) to prepare hardmetals; the formation of Co2Al5±x aluminide was detected in the materials Vacuum, 1400-1500 (W0.40÷0.67Al0.33÷0.60)C0.50÷0.67 (mean grain Ar size – 0.2-0.3 μm) – 5-16 vol.% Co twophase highly dense cemented carbides were prepared by the hot-pressing (exposure – 10-20 min) of mechanically alloyed W, Al and C powders, mixed with 99.099.7 % purity Co powder (initial mean particle size – 4.5 μm) –

–

Al – δ-WC1±x – Co hybrid metal matrix composites with the various contents of δ-WC1±x and Co were produced by powder metallurgy (PM) processes

–

–

Nanocrystalline δ-WC1±x – 17.5 vol.% Co – 9.5 vol.% Al coatings (grain sizes < 30 nm) were sprayed on steel substrates by the high-velocity oxy-fuel (HVOF) spraying techniques The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

δ-WC1±x – Al – Co – Cr

See section δ-WC1±x – Cr3C2–x – Al – Co

(continued)

2.6 Chemical Properties and Materials Design

143

Table 2.21 (continued) δ-WC1±x – Al – Co – Cr – Cu – Fe – Ni

Vacuum, 1100-1350 δ-WC1±x – 5-20 % high-entropy (multi-ele- [2106-2109, < 8 Pa ment) Al0.5÷1.5CoCrCuFeNi alloy (prelimi- 3080] narily subjected to the mechanical alloying via high-energy ball-milling) highly dense three-phase cermet materials (mean grain size – 0.2-0.3 μm) were prepared from the powdered mixtures (initial mean particle size of δ-WC1±x was ~50 nm) by the spark-plasma sintering (exposure – 3-6 min) techniques; before sintering the alloy binder is composed of the bcc structural major phase and the fcc structural minor phase (at the maximum Al content – only bcc phase was detected), while in the sintered materials the ratio between the bcc and fcc phases in the binder is reversed Vacuum 1250-1500 δ-WC1±x – 32-37 vol.% high-entropy Al0.5÷2.0CoCrCuFeNi alloy (preliminarily subjected to the mechanical alloying via high-energy ball-milling) multi-phase cermet materials were prepared by liquidphase sintering (exposure – 2 h); jointly with main δ-WC1±x phase – mixed Cr-rich carbide (Cr,W,Fe,Co)7C3, intermetallide (Ni,Co,Fe,Cu)Al1±x (with increased Ni and Al and decreased Cu contents), metallic (Co,Cu,Fe,Ni) binder (with slightly increased Cu content) and some other phases with the compositions, strongly depending on total C content, were detected in the materials Vacuum, 1375-1450 δ-WC1±x – 10-35 % multi-element alloy < 1.3 Pa Al0.5CrCoCuFeNi (preliminarily subjected to the mechanical alloying through highenergy ball-milling) two-phase cermets (with grain sizes divided into two distributive ranges – ~0.65 μm and ~0.15 μm) were prepared from the powdered mixtures by liquid-phase sintering Vacuum, 1420 < 1 Pa

Hard alloys (with low C content), liquidphase sintered (soak time – 1 h) from powdered δ-WC1±x (mean particle size – ~7 μm) – 20 % high-entropy (multi-element) Al0.5CoCrCuFeNi alloy mixtures, were composed of four phases: δ-WC1±x, (Fe0.24Ni0.24Co0.22Cu0.18Cr0.06Al0.05W0.01) fcc metallic solid solution (binder), (W0.54Cr0.46)2Cy semicarbide solid solution and complex carbide η2-(W0.38Co0.19Cr0.19Fe0.16Ni0.08)6Cy

(continued)

144

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1420 < 1 Pa

δ-WC1±x – Al – Co – Cr – Fe – Ni

Hard alloys (with high C content), liquidphase sintered (soak time – 1 h) from powdered δ-WC1±x (mean particle size – ~7 μm) – 20 % high-entropy (multi-element) Al0.5CoCrCuFeNi alloy mixtures, were composed of four phases: δ-WC1±x, (Ni0.25Co0.228Fe0.19Cu0.20Al0.11Cr0.02W0.002) fcc metallic solid solution (binder), carbide solid solution (Cr0.66Fe0.20Co0.10W0.02Ni0.02)7C2.8 and α-C (graphite)

Ar, 1300-1450 δ-WC1±x – 10-20 % high-entropy (multi- [2110] 10 MPa element) equiatomic AlFeCoCrNi alloy (atomized in high-purity Ar) four- or threephase cermet materials were prepared from the powdered mixtures by liquid-phase sintering; jointly with main δ-WC1±x phase (mean grain size – ~0.25 μm) – η2-W3(Co,Cr,Fe,Ni)3Cy or/and κ-W3(Co,Cr,Fe,Ni)C1+x compounds and metallic binder (Al,Cr,Fe,Co,Ni) phase, transformed from bcc- to fcc-structure during the sintering process due to the precipitation of Al, were detected in the materials

δ-WC1±x – Al – Co – Cr – Fe – Ni – Ti

–

600-1000

In the presence of δ-WC1±x, as a minor [2111-2112] phase, high-entropy (multi-element) equiatomic AlCoCrFeNiTi alloy (prepared by 25-40 h ball-milling) undergoes the phase transformation from bcc to ordered intermetallide-like structure

δ-WC1±x – α/β/ε/γ-W2±xC – Al – Co – Cr – Fe – Ni – V

–

1000-1400 Powdered δ-WC1±x – γ-W2±xC (eutectic [4664] spherical particles prepared by rotary cathode sputtering with semicarbide matrix with elongated monocarbide grains) – 10 % AlCrFeCoNiV (high-entropy equiatomic alloy, prepared by high-energy ballmilling, > 99.95 % purity, contents: C – 1.6%, O – 0.9%) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to prepare metal matrix composites (MMC) with the phase constituents, depending on SPS temperature: δ-WC1±x, γ-W2±xC, η2-W3(Fe,Co,Ni)3Cy and metastable bcc α-Fe based metallic solid solution (at 1000 °C), δ-WC1±x, η2-W3(Fe,Co,Ni)3Cy, bcc α-Fe based and fcc γ-Fe based solid solutions (at 1100 °C) and δ-WC1±x, bcc and fcc solid solutions (at 1200-1400 °C)

(continued)

2.6 Chemical Properties and Materials Design

145

Table 2.21 (continued) δ-WC1±x – Al – Co – Cr – Ni

δ-WC1±x – Al – Co – Cu

–

–

Cermet δ-WC1±x – Co – (Ni,Cr,Al) coa[2113-2114] tings were produced on steel substrates by the different approaches: plasma spraying method and plasma spraying followed by laser remelting technique; the formation of both metallic W and semicarbide W2±xC phases was detected at both technological approaches

–

–

Laser surface alloying of pure metallic Al substrate, using operating in continuous wave mode by the simultaneous feeding of δ-WC1±x – 15 % Co – 15% (Ni,Cr) powdered mixture prepared by high-energy ballmilling, leads to the formation of dispersion of δ-WC1±x, W2±xC, Al4C3, Co2Al9, NiAl3, Cr23C6±x and η1-W6Co6Cy phases in the fine-grained metal Al matrix

–

The interaction of δ-WC1±x – 20 % Co ce- [2177] mented carbide with molten Cu – 4 % Al alloy showed that the addition of Al to Cu melt has the pronounced effect on the yielding an additional carbide-free layer in the cemented carbide

1080

δ-WC1±x – Al – Vacuum, 1200-1230 δ-WC1±x – 8 % Co hard metals were brazed [2116] Co – Cu – (Fe – ~7 mPa to Fe – 0.4-0.5 % C – 0.6-0.9 % Mn steels C – Mn) – Ni by the Cu – 18.0-19.5 % Ni – 2.5-10.0 % Al alloys as brazing filler metals (exposure – 2.5-10 min) δ-WC1±x – Al – Co – Cu – Mg – Zn

δ-WC1±x – Al – Co – Ni

–

δ-WC1±x and Co particulate reinforced Al – [2105] 1.6 % Cu – 2.5 % Mg – 1.5 % Zn alloy metal matrix composites were prepared by stir casting technique; the formation of aluminide δ-WAl5–x as a minor phase due to the interfacial reactions was detected

750

[2000, 2103, Vacuum 1350-1450 δ-WC1±x – 24-50 % (Co + Ni + Al) hard alloys were prepared by the liquid-phase 2117-2119, sintering (exposure – 1-20 h) of powdered 3358] mixtures (through the prealloying stage of δ-WC1±x + Ni + Al mixed powders) with 3.5-24.0 % contents of intermetallide γ′-Ni3±xAl in the materials; the presence of γ′-Ni3±xAl inhibites the grain growth of δ-WC1±x phase –

–

Cermet coatings were prepared on steel substrates by atmospheric plasma spraying technique using δ-WC1±x – 17 % Co and Ni-coated Al powdered mixtures

(continued)

146

2 Tungsten Carbides

Table 2.21 (continued) –

δ-WC1±x – Al – Co – Zn

δ-WC1±x – Al – Cr – Fe

N2

–

Functionally graded coatings (FGC) composed of 100 vol.% (δ-WC1±x – 12 % Co hard alloy) in top layer and 60 vol.% (Ni – 5 % alloy) + 40 vol.% (δ-WC1±x – 12 % Co hard alloy) in bottom layer (with gradually changing component concentrations, total thickness – ~0.8 mm) were prepared on stainless steel substrates using high-velocity oxy-fuel (HVOF) spraying techniques; jointly with the major phases such as δ-WC1±x and Ni based solid solution, the presence of smaller amounts of metallic W, γ-W2±xC and η2-W3Co3Cy phases was detected in the coatings δ-WC1±x – Co cermet coatings (with the [2558] binder mainly consisted of η-phases), deposited on steel substrates by the high-velocity oxy-fuel (HVOF) spraying techniques, were resistant to the molten Zn – 0.33 % Al alloys, due to the formation of the Al-rich phases at the coating-melt interface, which act as a diffusion barrier against Zn and Co atoms

480

–

–

δ-WC1±x (mean particle size – 0.5 μm) – [2120-2121, 11 % Fe – 3 % Cr – 1 % Al powdered mix- 2943, 3025] tures (15-45 μm in size, agglomerated and sintered spheroids) were sprayed on steel substrates by the high-velocity oxy-fuel (HVOF) spraying techniques to produce two-phase cermet coatings (thickness – ~0.4 mm, porosity – 5 %, carbide phase contents – 58 vol.%); due to the partial decarburization (16 % C loss, relatively) of δ-WC1±x during spraying process, the formation of semicarbide W2±xC and metallic W phases was detected

–

–

δ-WC1±x – (10.8÷11.7)±(0.1÷0.5) % Fe – (2.6÷2.9)±(0.1÷0.3) % Cr – (0.6÷0.9)±0.1 % Al cermet coatings (thickness – (130÷220)±(6÷10) μm, content O – (5.0÷6.9)±(0.1÷0.4) %, index of carbide retention – 0.75-0.89, with the presence of (W,Cr)2±xC minor phase) were sprayed on steel substrates by the high-velocity oxyfuel (HVOF) spraying techniques using δ-WC1±x – 11 % Fe – 3 % Cr – 1 % Al feedstock powders (particle size range – 15-45 μm, main metallic phase constituent – α-Fe, with the presence of η2-W3Co3Cy); deposition mechanisms involve in-flight melting and homogenization of the metal

(continued)

2.6 Chemical Properties and Materials Design

147

Table 2.21 (continued) matrix, in-flight and post-deposition interaction with O, as well as some decarburization and dissolution of δ-WC1±x phase – δ-WC1±x – Ar α/β/ε/γ-W2±xC – Al – Cr – Fe – Mo – Nb – Ni – Ti

–

–

The properties of Fe – Al – Cr binder as functions of alloying content are evaluated

–

Powdered δ-WC1±x – γ-W2±xC (spherical, [3842-3843, size distribution – 25-45 μm) – 75 % Ni- 3858] based alloy (gas atomized, spherical; size distribution – 15-45 μm; contents: Cr – 1821 %, Fe – 18-20 %, Nb – 5 %, Mo – 3-4 %, Al – 1 %, Ti – 1 %) mixtures (preliminarily high-energy ball-milled) were subjected to selective laser melting (SLM) additive manufacturing (AM) to produce metal matrix composite (MMC) graded interface layers

–

Powdered δ-WC1±x – γ-W2±xC (plasmaspheroidized, size distribution – 15-53 μm) – 85-95 % Ni-based alloy (spherical, mean particle size – ~30 μm; contents: Cr – 19 %, Fe – 18 %, Mo – 3 %, Nb – 5 %, Al – 1 %, Ti – 1 %) mixtures were employed as raw materials for selective laser melting (SLM) technology to prepare composites (porosity – 0.5-0.7 %) with δ-WC1±x, γ-W2±xC, γ′-Ni3±x(Al,Ti) and γ′′-Ni3±xNb main phase constituents; the following chemical reaction: 3WC + 3Fe + 3Cr = Fe3C + Cr3C2 + 3W, was presumed to take place at the ceramicmetallic interfaces and form intermediate layers with the thicknesses of ~0.1-1.0 μm

δ-WC1±x – Al – Cr – Mo – Ni

Vacuum 1425

In the δ-WC1±x based hard alloys with Ni – [2122] 6-18 % Mo – 2-6 % Cr – 2-5 % Al metallic binder, prepared by liquid-phase sintering, the formation of γ′-Ni3±xAl phase precipitates was detected

δ-WC1±x – Al – Cu

N2

580

4 vol.% δ-WC1±x dispersoid reinforced Al [2123-2124] – 4 % Cu alloy metal matrix composites were prepared via powder metallurgy methods followed by the solution treatment and ageing procedures

Ar

650

Mechanically alloyed Al – 7 % δ-WC1±x – 2 % Cu powdered mixtures (all the components – 99.5 % purity) were sintered (exposure – 4 h) to prepare highly dense Al – Cu alloy metal matrix composites; due to the interfacial reactions the formation of aluminides γ-WAl12 and CuAl2±x was detected

(continued)

148

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Al – Cu – Fe δ-WC1±x – Al – Cu – Mg

δ-WC1±x – Al – Cu – Mg – Mn

– Ar

–

–

The properties of Fe – Al – Cu binder as [2943] functions of alloying content are evaluated

450-550

Mechanically alloyed Al – 4 % Cu – 1.5 % [2125] Mg – 1 % δ-WC1±x powdered mixtures (all the components with purity ≥ 99.5 %) were sintered (exposure – 3 h) to prepare highly dense metal matrix composites; the only new phase detected in the materials after the procedures was CuAl2±x

510-720

[2056, 2059, In 12 vol.% δ-WC1±x particulate (mean size – 2-8 μm) reinforced Al – 4-5 % Cu – 2064, 2088] 1.5-2.0 % Mg – 0.5-1.0 % Mn (initial mean powder size – 50 μm) alloy metal matrix composites, fabricated by hot-pressing method, the multiple layer interface structure, which is composed of Al / W aluminides (γ-WAl12, δ-WAl5–x) / Al4C3 / δ-WC1±x, is formed due to the interfacial reactions; the Al4C3 layer, formed along with a given crystal orientation of δ-WC1±x phase, might retard the interfacial processes

Ar, or N2 ~700-900

δ-WC1±x reinforced Al – 4-5 % Cu – 1.52.0 % Mg – 0.5-1.0 % Mn alloy metal matrix composites were prepared by lowcost stir casting with followed friction stir processing (FSP) treatment

δ-WC1±x – Al – Cu – Mg – Si

N2

580

Powdered Al – 4.5 % Cu – 0.7 % Si – 0.5 [2072] % Mg alloys (mean particle size – 24 μm) with additions of 5-15 % δ-WC1±x powders (mean particle size – 1 μm) were sintered (exposure – 20 min) to prepare metal matrix composites; intermetallide γ-WAl12 was identified as a product of the interfacial reactions (Al4C3 was not detected) in the materials

δ-WC1±x – Al – Cu – Mg – Zn

–

~500-700

Powdered Al – 1.5 % Cu – 2.0-2.5 % Mg [2069] – 5.5-6.0 % Zn alloys with the additions of 5-30 % δ-WC1±x powders were hot-pressed to prepare metal matrix nanocomposites

δ-WC1±x – Al – Cu – Mn – Si

Vacuum 560

–

~700-900

0.1-0.4 vol.% δ-WC1±x (mean particle size [10, 2083, – 0.15-0.20 μm) reinforced Al – 4-6 % Si 2092] – 2-4 % Cu – 0.2-0.6 % Mn alloy metal matrix composites were prepared by sintering (exposure – 1.5 h) of preliminarily compacted powdered mixtures 1-3 vol.% δ-WC1±x reinforced Al – 5 % Si – 3 % Cu – 0.5 % Mn alloy metal matrix composites were prepared by the stir casting technique

(continued)

2.6 Chemical Properties and Materials Design

149

Table 2.21 (continued) δ-WC1±x – Al – Cu – Nb – Ni – Ti

–

~1300-1500 Nanocrystalline 4.5 vol.% δ-WC1±x rein- [2126, 3980] forced Ti – 13 % Nb – 8 % Cu – 7 % Ni – 6 % Al alloy intermetallic matrix composites were fabricated by spark-plasma sintering and crystallization of amorphous phase; δ-WC1±x nanoparticles were stable in the ultra-fine grained crystallized matrix, including β-Ti based solid solution, (Cu,Ni)Ti2±x, TiC1–x and remaining amorphous phase

–

–

δ-WC1±x – Al – Cu – Nb – Ni – Zr

Ar (Tigetter), 80 kPa

δ-WC1±x – Al – Cu – Ni – Zr

Vacuum, 860-980 0.5 mPa

δ-WC1±x – Al – Cu – Si

δ-WC1±x – Al – Fe

850-1100

–

Vacuum, 1150 1.3 Pa

–

Amorphous (glassy) Ti66Nb13Cu8Ni6.8Al6.2 alloy powders with different nanocrystalline δ-WC1±x contents (in the presence of the ductile β-Ti phase) were prepared by mechanical alloying procedure 5-20 vol.% δ-WC1±x (particle size – 12-50 [2127, 4031] μm) reinforced Zr57Nb5Al10Cu15.4Ni12.6 alloy (purity ≥ 99.7 %) bulk metallic glass matrix composites were fabricated; at the matrix-particle interface the formation of ZrC1–x layer was occurred The interaction (exposure – 20 min) of [4030] molten Zr55Cu30Al10Ni5 bulk metallic glass with highly dense (hot-pressed) polycrystalline δ-WC1±x substrates led to the formation of intermetallide ZrW2–x (or Zr3W5), monocarbide ZrC1–x and metallic W phases in the contact zone due to the interfacial reactions (CuZr2 and Cu10Zr7 intermetallides appeared during the solidification and subsequent cooling of the melt in the contact with δ-WC1±x); the primary driving force for the good wettability in the system is the adsorption of Zr atoms at the interface, forming a precursor film, rather than the interfacial reactions During the preparation of reinforced sur- [2128] face layer by laser melting technique, the interaction between δ-WC1±x particles and Al – 4.5 % Cu – 1 % Si molten alloy was observed The mixtures of δ-WC1±x (99.8 %, 20 μm) and Fe (99 %, 150 μm) treated using mechanical alloying (MA) with Al (99 %, 100 μm) powders (preliminarily highenergy ball-milled, initial purities and mean particle sizes of the components are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 3 min) to fabricate highly dense δ-WC1±x – 25 vol.% FeAl0.67 car-

[10, 1985, 2129-2131, 2176, 2725, 2892, 2943, 3593, 42104245]

(continued)

150

2 Tungsten Carbides

Table 2.21 (continued) bide-intermetallide composites The infiltration of cold-pressed δ-WC1±x powder (mean particle size – 2.8 μm) by Fe – 40 at.% Al alloy was carried out to prepare two-phase cermets containing 70 vol.% δ-WC1±x; in equilibrium with α-C (graphite) molten Fe – 40 at.% Al alloy dissolved ~5 at.% C and ~1 at.% W

Vacuum, 1450 0.1 mPa

–

–

δ-WC1±x reinforced Fe – Al alloy composite coatings on steel substrates were fabricated by high-velocity arc spraying

–

–

The properties of Fe – Al binder as functions of alloying content are evaluated

See also sections δ-WC1±x – FeAl1±x and δ-WC1±x – Fe3±xAl in Table 2.22 δ-WC1±x – Al – Fe – Mn

–

–

The properties of Fe – Al – Mn binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – Mo

–

–

The properties of Fe – Al – Mo binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – Nb

–

–

The properties of Fe – Al – Nb binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – Ni

Vacuum 1450

(W0.5Al0.5)C0.5 – 10-16 vol.% Fe – 25-75 [10, 2132, at.% Ni alloy two-phase highly dense ce- 2943, 4308] mented carbides (with carbide mean grain size – 0.8-1.0 μm) were prepared by sintering (exposure – 1 h) of mechanically alloyed W, Al and C powders mixed with 99.5-99.6 % purity Fe and Ni powders

–

–

Powdered Ni + Al (Ni/Al atomic ratio = 3, preliminarily mixed, size distribution – 45106 μm) – 40 % δ-WC1±x (sintered, size distribution – 22-106 μm) mixtures were employed to fabricate δ-WC1±x particulate reinforced γ′-Ni3±xAl intermetallic matrix composite coatings on steel substrates using laser powder deposition method; matrix of the coatings consisted of equiaxed crystal grains (10-30 μm in size) of the ~γ′-(Ni0.84Fe0.13W0.03)3±xAl composition, enriched with Fe transferred into the coatings from the substrates

–

–

The properties of Fe – Al – Ni binder as functions of alloying content are evaluated The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

(continued)

2.6 Chemical Properties and Materials Design

151

Table 2.21 (continued) δ-WC1±x – Al – (Fe – C – Cr – Mn – Ni) – Ni

–

–

The ultra-fine grained δ-WC1±x – Ni – Al [2142] layers with interlocking bonding, fabricated on austenitic steel (C – 0.06 %, Cr – 18.5 %, Ni – 8.3 %, Mn – 1.5 %) by the combination of laser cladding and friction stir processing, compose of monocarbide δ-WC1±x, intermetallides γ′-Ni3±xAl and NiAl1±x (Ni1.1Al0.9) and γ-(Fe,Ni) metallic alloy phases

δ-WC1±x – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti

–

–

Powdered Al – 20 % Si – 20 % Ti – 10 % [2145] Ni mixtures with the additions of 10-30 % δ-WC1±x powder thermally sprayed on the stainless steel (C ≤ 0.08 %, Cr – 18-20 %, Ni – 8-10 %, Mn ≤ 2 %, Si ≤ 1 %) substrates were subjected to laser surface alloying (melting) to produce cermet layers composed of δ-WC1±x, (Ti,W,Cr)C1–x, γ-Cr2Al11±x (or CrAl5±x), FeAl1±x and metallic γ-(Fe,Ni,Cr) alloy phase

δ-WC1±x – Al – Fe – Ta

–

–

The properties of Fe – Al – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – Ti

–

–

The properties of Fe – Al – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – V

–

–

The properties of Fe – Al – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Fe – Zr

–

–

The properties of Fe – Al – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Al – Mg – Mn – Si

–

~400-600

4.8-11.6 vol.% δ-WC1±x (mean particle size – 3.7-4.1 μm) reinforced Al – 4.5 % Mg – 0.5 % Mn – 0.4 % Si alloy metal matrix composites were prepared by friction stir processing (FSP) technique

–

800-850

0.4-2.0 vol.% δ-WC1±x powder (initial mean particle size – ~ 50-75 μm) reinforced Al – 1.1 % Si – 0.9-2.0 % Mg – 0.9 % Mn alloy metal matrix composites were prepared by the stir casting technique

δ-WC1±x – Al – Mg – Si

–

–

–

800

[10, 2081, 2086-2087, 2090]

δ-WC1±x reinforced Al – 0.8-1.2 % Mg – [2073, 2077, 0.4-0.8 % Si alloy metal matrix composites 2082, 2089, were prepared by the stir casting technique 2091, 2134, 3 vol.% δ-WC1±x reinforced Al – 6.5-7.5 % 2147] Si – 0.2-0.6 % Mg alloy metal matrix composites were prepared by the squeeze casting technique

(continued)

152

2 Tungsten Carbides

Table 2.21 (continued) Ar flow, 10-15 dm3 s–1

–

1-3 vol.% 99.9 % purity δ-WC1±x powder (initial mean particle size – 20 μm) reinforced Al – 0.8-1.2 % Mg – 0.4-0.8 % Si alloy composite layer was produced using gas tungsten arc welding (GTAW) technique (welding speed – 0.25-1.0 cm s–1)

–

–

Powdered δ-WC1±x (size distribution – 45100 μm) and Al – 11.5 % Si alloy wire were employed in the coincident wirepowder laser alloying deposition on the surface of Al – 0.8-1.2 % Mg – 0.4-0.8 % Si alloy to produce cermet layers composed of δ-WC1±x, γ-W2±xC, ε-WAl4±x (rodlike structured) and Al4C3 (randomly distributed) phases dispersed in Al matrix

–

–

1 vol.% δ-WC1±x reinforced Al – 9-11 % Si – 0.25-0.45 % Mg alloy metal matrix composites were prepared via additive manufacturing, providing geometric freedom for the composite design; the crystallographic coherence (lattice matching) of δ-WC1±x phase allows to promote wetting and increase dislocation interaction in the materials

δ-WC1±x – Al – Mg – Si – Ti

–

–

δ-WC1±x (size distribution – 45-100 μm) [2147] and Ti metal powders jointly with Al – 11.5 % Si alloy wire were employed in the coincident wire-powder laser alloying deposition on the surface of Al – 0.8-1.2 % Mg – 0.4-0.8 % Si alloy to produce cermet layers composed of δ-WC1±x, ε-WAl4±x, γ-WAl12, TiC1–x, Ti3±xAl, TiAl1±x, TiAl3 and β-Ti phases dispersed in Al matrix; TiC1–x and Ti3±xAl phases formed at the δ-WC1±x – Al interface contribute as barriers to inhibit the formation of Al4C3 and some other contact reactions between the reinforcement and the matrix

δ-WC1±x – Al – Mg – Zn

–

–

δ-WC1±x reinforced Al – Mg – Zn alloy composite coatings were fabricated from mechanically alloyed powdered mixtures

δ-WC1±x – Al – Nb

–

–

Hypothetic solid solutions of M2AX phase [4143] (Nb2–xWx)AlC and their possible physical properties were studied using ab initio total energy calculations

[2133]

(continued)

2.6 Chemical Properties and Materials Design

153

Table 2.21 (continued) δ-WC1±x – Al – Ni

Ar

500-900

600-700

Microwave sintering of uniformly coated [10, 275, (via electroless plating) by Ni metal 2122, 2135δ-WC1±x and Al powders was employed to 2140, 2142fabricate δ-WC1±x reinforced intermetallide 2143, 2239, γ′-Ni3±xAl – NiAl1±x matrix composites 2245, 3764, 3893, 4217, Interaction in the powdered δ-WC1±x 4298-4322, (99.5 %, 10 μm) – 46.8 mol.% carbonyl Ni (99.8 %, 3 μm) – 15.6 mol.% Al (99.3 4669] %, 15 μm) mixtures (purity and mean particle size are given in brackets, respectively) leads to the formation of Ni2Al3±x, NiAl1±x and γ′-Ni3±xAl phases (all of them are inert chemically in respect to δ-WC1±x)

700-1100

Interaction in the same mixtures leads to the formation of NiAl1±x and γ′-Ni3±xAl phases (both of them are inert chemically in respect to δ-WC1±x)

1100-1200 Interaction in the same mixtures leads to the formation of γ′-Ni3±xAl phase (inert chemically in respect to δ-WC1±x) Vacuum 1370-1430 (W0.5Al0.5)C0.5 – 13 vol.% Ni two-phase highly dense cemented carbides (with mean grain sizes – 2-4 μm) were prepared by reactive sintering (exposure – 1-3 h) of mechanically alloyed W and Al powders, mixed with 99 % purity C and 99.6 % purity Ni powders; at the lower temperatures and shorter exposure times the presence of small amounts of semicarbide (W0.5Al0.5)2C0.5 phase was detected –

1400-1650 Powdered δ-WC1±x – 48.1-49.6 mol.% Al – 48.1-49.6 mol.% Ni mixtures (atomic ratio Al/Ni = 1) were subjected to the self-propagating high-temperature synthesis (SHS) treatment to prepare δ-WC1±x reinforced intermetallide NiAl1±x (or NiAl1±x with the presence of Ni2Al3±x as a minor phase at the highest content of δ-WC1±x in the mixture) matrix composites

Vacuum 1425

In the δ-WC1±x based hard alloys with Nibased Ni – Al metallic binder, prepared by liquid-phase sintering, the formation of γ′-Ni3±xAl phase precipitates was detected

Vacuum 1450-1700 The impregnation of powdered δ-WC1±x (exposure – 5 min) by the molten Ni – 37 at.% Al alloy results in the formation of δ-(W0.97Ni0.03)C1±x – (Ni0.605Al0.392W0.003) cermet materials (the compositions of the only main phases are given); with rising impregnation temperature the amounts of

(continued)

154

2 Tungsten Carbides

Table 2.21 (continued) minor phase η2-W3Ni3Cy and porosity in the materials increase noticeably –

–

The ultra-fine grained δ-WC1±x – Ni – Al layers, fabricated by the combination of laser cladding and friction stir processing, contain δ-WC1±x jointly with γ′-Ni3±xAl and NiAl1±x (NiAl0.82) intermetallides

–

–

During laser cladding and followed aging process of δ-WC1±x – 60 mol.% Ni – 19.5 mol.% Al coatings, δ-WC1±x dissolved and reprecipitated in the forms of α/ε-W2+xC and δ-WC1±x phases, while intermetallide γ′-Ni3±xAl orderly precipitated from metastable supersaturated Ni matrix solid solution The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

See also section δ-WC1±x – Al4C3 – Ni See also sections δ-WC1±x – NiAl3, δ-WC1±x – NiAl1±x, δ-WC1±x – NiAl1±x – γ′-Ni3±xAl and δ-WC1±x – γ′-Ni3±xAl in Table 2.22 δ-WC1±x – α/β/ε/γ-W2±xC – Al – Ni

See section δ-WC1±x – α/β/ε/γ-W2±xC – γ′-Ni3±xAl in Table 2.22

δ-WC1±x – Al – Si

–

N2

δ-WC1±x – Al – Ti – V

Ar

δ-WC1±x nanoparticle (size – 40-70 nm) [2073, 2146] reinforced Al – 7 % Si alloy metal matrix composites were prepared by the stir casting technique

760

–

~ 20-200

Powdered δ-WC1±x (mean particle size – ~10 μm) was employed in the laser surface alloying process (with melt cooling rate > 104 K s–1) of Al – 7 % Si alloy to produce cermet layers composed of δ-WC1±x (uniformly distributed, rounded in shape, mean grain size – ~1 μm) and γ-W2±xC (product of the partial decomposition of δ-WC1±x), which are dispersed in metallic Al matrix (with a braid-like structure) jointly with the products of interfacial reactions, such as W(Si,Al)2±x, Al4C3, α-Al4SiC4, β-Al4SiC4 and Al4Si2C5 phases 160 keV Ar+-implantation (Φ = 1×1016[2148-2161] 2×1017 cm–2) on the interface between δ-WC1±x magnetron sputtered films (thickness – ~50 nm) and Ti – 6 % Al – 4 % V alloy substrate induced the formation of a new phase with identified compositions as (Ti,W)C1–x, or (W,Ti)2±x(C,O)

(continued)

2.6 Chemical Properties and Materials Design

155

Table 2.21 (continued) N2

160 keV N+-implantation (Φ = 5×10152×1017 cm–2) on the interface between δ-WC1±x magnetron sputtered films (thickness – ~0.1 μm) and Ti – 6 % Al – 4 % V alloy substrate induced the formation of TiC1–x and δ-TiN1±x phases

150

Vacuum

–

δ-WC1±x particle reinforced Ti – 6 % Al – 4 % V alloy functionally graded metal matrix composite layers (coatings) were fabricated through laser melt injection (LMI), vacuum arc melting (VAM), laser metal deposition (LMD) and combined wire-powder deposition by laser (WPDL) processing; new TiC1–x and/or (Ti,W)C1–x (major) and W2±xC and/or metal W (minor) phases were formed in the layers due to the α-Ti – δ-WC1±x interfacial reactions

Ar

–

The pre-blended δ-WC1±x – 24-27 % Ti based alloy (Al – 6 %, V – 4 %) powder (particle size distribution – 40-270 μm, average size – 130 μm) or 1.2 mm diameter wire of the same Ti based alloy were employed for the laser cladding procedure; jointly with a uniform distribution of δ-WC1±x grains, the emergence of new W2±xC, metal W, TiC1–x and β-Ti solid solution phases was observed in the formed cermet clad

Ar

–

δ-WC1±x particle reinforced composite coatings on the surface of Ti – 6 % Al – 4 % V alloy, jointly with a uniform distribution of δ-WC1±x grains composed of W2±xC, metal W, TiC1–x, α- and β-Ti phases (products of interfacial reactions), were produced by the plasma transferred arc (PTA) method

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Al

–

–

3 vol.% δ-WC1±x and Al2O3 particles (mean size – 100 μm) reinforced metallic Al was prepared by the accumulative roll bonding (ARB) process

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Al – Co

–

–

δ-WC1±x – Al – Co coatings with in situ [4129] synthesized α-Al2O3 phase were deposited using high-velocity oxy-fuel (HVOF) thermal spraying technique

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Al – Ni – Zn

–

–

Cold gas dynamic sprayed δ-WC1±x based [2163] coatings with the addition of 10 % (Ni + Al + Al2O3 + Zn) composition were applied for the surface repairs of some steel substrates

[2162]

(continued)

156

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – B4±xC Vacuum 480-600 – Al – Cu – Mg

Powdered Al – 3.5 % Cu – 1.5 % Mg alloy [2164] (13 μm) – 20 vol.% 10B4±xC (7 μm) – 12 vol.% δ-WC1±x (2 μm) mixtures (initial particle sizes are given in brackets) were subjected to hot-pressing with followed hot-forging treatment to fabricate hybrid reinforced metal matrix composite plates with combined neutron and gamma radiation shielding; besides γ-WAl12, no other interface reaction product was observed in the materials

δ-WC1±x – B4±xC – Al – Mg – Si

–

1.5-4.5 % B4±xC and 1.5 % δ-WC1±x parti- [2165] cles hybrid reinforced Al – 6.5-7.5 % Si – 0.25-0.65 % Mg alloy metal matrix composites were fabricated using stir casting technique

–

Powdered Ni – 45 % δ-WC1±x – 5 % Co – [2168] 5 % α-BN (hexagonal) – 1.25 % Al mixtures, prepared from Ni – Al (particle size – 16-45 μm), δ-WC1±x – Co (particle size – 10-44 μm) and α-BN (lamellar structured) powders by blending or mechanical alloying processes, were employed to produce atmospheric plasma sprayed coatings

δ-WC1±x – α/β-BN – Al – Co – Ni

–

Ar, H2

δ-WC1±x – (BaF2, Vacuum 1400 CaF2) – Al – Co

(W0.67Al0.33)C0.67 (prepared by mechanical [2166-2167] alloying and solid state reactions, plate shape grains with ~5 μm in length and ~1 μm in thickness) – 10 % BaF2 (or CaF2, or BaF2 – CaF2 eutectic composition) – 9 % Co highly dense composite materials were prepared by hot-pressing procedure (exposure – 10 min) of powdered mixtures The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

δ-WC1±x – Air (C6H4CH2C6H4O CH2CHOH CH2O)n – Al – Co

120-180

δ-WC1±x particle reinforced – epoxy [2169] (C6H4CH2C6H4OCH2CHOHCH2O)n resin (epoxy value – ~0.41-0.47) – Co (particle size of δ-WC1±x/Co – 5-25 μm) – Al (particle size – 10-44 μm) sprayed composite coatings were prepared on steel substrates

δ-WC1±x – Air [C6H4(NH)]n – Al – Pb

35

δ-WC1±x particle modified – polyaniline [1840] [C6H4(NH)]n (PANI) – Al – Pb composite inert anodes were prepared on Al substrates by double pulse electrodeposition (DPE) from a plating aqueous solution bath containing the component particles

(continued)

2.6 Chemical Properties and Materials Design

157

Table 2.21 (continued) δ-WC1±x – [(CkHl)(CpHq) Si(CH2)]n – α/β-SiC – Al – α/ε-Co

–

δ-WC1±x – Ar CeO2–x – Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn

Powdered α-SiC – 20 % polycarbosilane [2236] [(CkHl)(CpHq)Si(CH2)]n (PCS) – 4.7 % δ-WC1±x – 0.3 % Co – 1 % Al mixtures were hot-pressed to prepare modified ceramic materials

1950

–

Powdered 78 % Ni-based alloy (size dis- [4187] tribution – 47-100 μm; contents: Ni – 58.2 %, Cr – 15.5 %, Fe – 15.0 %, Si – 4.0 %, B – 3.5 %, W – 3.0 %, C – 0.8 %) – 20 % hard alloy (size distribution – 36-44 μm; contents: δ-WC1±x – 88 %, Co – 12 %) – 2 % CeO2–x (99.9 % purity, size distribution – 8-12 μm) mixtures were employed as feedstocks for the fabrication of composite coating on Al-based alloy (contents: Zn – 4.0-5.0 %, Mg – 1.0-1.8 %, Fe – 0.4 %, Si – 0.35 %) by laser surface alloying; the produced coatings contained the phases of aluminides NiAl1±x (major phase of the coatings) and Ni2Al3±x, carbides δ-WC1±x, γ-W2±xC and Cr23C6±x, boride CrB, intermetallide CeNi5 and γ-(Fe,Ni) metallic solid solution

δ-WC1±x – Vacuum 1240-1300 Powdered (W0.6Al0.4)C0.8 (prepared by [2170] Cr3C2–x – Al – Co mechanical alloying and solid state reactions) – 0.3-0.9 % Cr3C2–x – 8 % Co mixtures were subjected to hot-pressing to prepare highly dense cermets with the mean grain size of (W0.6Al0.4)C0.8 phase in the range from 0.4 to 2.1 μm depending on treatment temperature and Cr3C2–x content The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors δ-WC1±x – FeAl1±x – Fe3±xAl – Al – Fe

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – Al – Mo – Ni

–

–

δ-WC1±x reinforced Fe – Al (with the pre- [4223] sence of FeAl1±x and Fe3±xAl aluminides) lamellar-structured metal matrix composite (MMC) coatings (thickness – 0.2-0.4 mm) on low alloyed steel substrates were deposited by high-velocity oxy-fuel (HVOF) thermal spraying technique using FeAl0.67 – 10-15 % δ-WC1±x powdered mixtures (size distribution < 60 μm) as feedstocks

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – δ-WC1±x – Al – Mo – Ni in Table III-2.22

(continued)

158

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – MoS2+x – Al – Mg – Zn

–

δ-WC1±x – α-PbO2–x – Al – Pb

–

δ-WC1±x – H2 α/β-SiC – Al – C – Si

800-850

–

2-10 % δ-WC1±x – 4 % MoS2+x particulate [2171] reinforced Al – 5.8 % Zn – 2.4 % Mg alloy metal matrix composites with the uniform distribution of components were prepared by stir casting process δ-WC1±x particle modified – α-PbO2–x – Al [1844] – Pb composite inert anodes were prepared on Al substrates by pulse electrodeposition (PE) from a plating aqueous solution bath

1750-1900 Powdered α-SiC (size distribution – 2.55.0 μm) – 25 vol.% Si (size distribution < 74 μm) – 10 vol.% δ-WC1±x (mean particle size – 2-4 μm) mixtures with the small amounts of Al and C sintering aids (preliminarily high-energy ball-milled) were subjected to hot-pressing procedure (exposure – 15 min) to fabricate dense materials (porosity – 0.2-4.1 %)

[3968]

δ-WC1±x – α/β-SiC – Al – Co – Cr – Ni

–

δ-WC1±x – α/β-SiC – Al – Mg – Si

–

~800

5-10 % δ-WC1±x – 5-10 % SiC particulate [2173] reinforced Al – 0.9 % Mg – 0.75 % Si alloy metal matrix composites were prepared by stir casting process

δ-WC1±x – α/β-SiC – Al – Si

–

~800

4-7 % δ-WC1±x – 4-7 % SiC particulate [2172] reinforced Al – 10-13 % Si alloy metal matrix composites were prepared by lowcost stir casting process

–

Modified by nanocrystalline SiC powders [2113] cermet δ-WC1±x – Co – (Ni,Cr,Al) coatings were produced on steel substrates through plasma spraying technique followed by a laser remelting treatment; the formation of metallic W and silicide WSi2 phases was detected in the coatings

δ-WC1±x – TiC1–x – δ-TiN1±x – Al – Fe

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Al – Fe in Table III-2.22

δ-WC1±x – VC1–x – Al – Co

See section VC1–x – δ-WC1±x – Al – Co in Table III-3.16

δ-WC1±x – α/β-Y2O3–x – Al – Fe

–

δ-WC1±x – α/β/γ/δ-ZrO2–x – Al – Pb

–

–

20

Highly dense FeAl1±x (x = 0.33) – 10-20 % [2176] δ-WC1±x – 1 % α-Y2O3–x composite coatings were deposited by high-velocity oxyfuel (HVOF) spraying of the mixtures of Fe, Al, α-Y2O3–x and δ-WC1±x powders 10 % δ-WC1±x particle – 3.6 % ZrO2–x par- [1827] ticle – Al – Pb composite electrode coatings were prepared in plating aqueous solution baths (exposure – 2 h)

(continued)

2.6 Chemical Properties and Materials Design

159

Table 2.21 (continued) δ-WC1±x – As

H2

1300-1600 While heating 1 % As modified δ-WC1±x [2178] powders (mean particle size – 0.1-1.2 μm), attached to their grain boundaries nanoparticles of WAs2 phase hindered the growth of δ-WC1±x grains

δ-WC1±x – Au

Vacuum, < 1000 0.1 mPa

W-C thin films with Au contents – up to [1533, 1585, 32 at.% were deposited by sputtering; in 1686, 1729, the films with high C contents the presence 1981, 4563] of γ-WC1–x phase was detected

–

–

Au metal monolayer supported by both Wand C-terminated δ-WC1±x (0001) was simulated on the basis of DFT calculations

δ-WC1±x – Au – C – Pd

–

–

Au – Pd bimetallic nanoparticles supported [1418-1419] on nanocrystalline δ-WC1±x and dispersed on C as composite electrocatalysts were designed and prepared by the intermittent microwave heating (IMH) method

δ-WC1±x – Au – C – Pd – Pt

–

–

δ-WC1±x nanoparticle promoted composite [1670, 1672, electrocatalysts Au – Pd – Pt – C were de- 1729] signed and prepared by the intermittent microwave heating (IMH) and direct chemical reduction method

δ-WC1±x – Au – Pd

–

–

Co-deposited nanosized Pd and Au loaded [1535] on single-phase δ-WC1±x form the electrocatalytic AuPd3 – δ-WC1±x system

δ-WC1±x – Au – Pd – Pt

–

–

Au – Pd – Pt alloy nanoparticles supported [1614] on nanocrystalline δ-WC1±x as composite electrocatalysts were designed and prepared by the intermittent microwave heating (IMH) method

α/β/ε/γ-W2±xC – Au – Pt – Sn

–

–

α-W2±xC nanoparticle supported 3 % Pt – 3 [1777] % Au – 10 % Sn nanocomposite electrocatalysts were designed, fabricated and tested

δ-WC1±x – Au – Sn

–

δ-WC1±x – Air α/β-SiC – α/β/γ-Si3N4 – Au – Cu – Pt – Ti

> 300

Au – Sn alloy was applied for the solid[2179] liquid interdiffusion bonding (SLID) of δ-WC1±x and standard piezoelectric materials; the bond-lines consisted of layered Au / ζ-Au6±xSn / Au structures were observed

400

The metallization stack of Si3N4 / Cu / [2180] δ-WC1±x / Ti / Pt / Ti / Au type employed for packaging (bonding) of α/β-SiC power devices remained stable in the exploitation conditions (exposure – 100 h)

(continued)

160

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – β-B

Hot-pressed δ-WC0.98 materials (porosity – 4-5 %, content non-combined C – 0.15 %) in the contact with amorphous powdered B (exposure – 3 h) were being boronized slowly, as the thickness of α-WB1±x layer has achieved only 1.2 μm (not detectable metallographically)

Vacuum 900

[1, 3, 13, 26, 53, 83, 626, 919, 1923, 2181-2182, 2184-2187, 4059, 4541]

Vacuum 1000-1100 At the similar conditions and exposure, the thickness of grown α-WB1±x layers have achieved 5.8-18.3 μm on the same materials Vacuum 1200-1300 At the similar conditions and exposure, the thickness of grown α-WB1±x layers have achieved 50-125 μm on the same materials At the similar conditions and exposure, the thickness of grown boronized layer has achieved ~280 μm (consists of α-WB1±x and β-W2B5–x layers) on the same materials

Vacuum 1400

Vacuum, 1550-1650 During the spark-plasma sintering of pow< 4 Pa dered δ-WC1±x (mean particle size – ~70 nm) – 15 mol.% B mixtures, the full conversion of B and formation of the only α-WB1±x boride phase were observed –

2300-2450 The interaction between the components results in the formation of β-W2B5–x and α-C (graphite) phases

–

~2570-2590 The maximum solid solubility of B in δ-WC1±x is ≤ 0.5 at.%

–

–

The properties of hypothetical W borocarbide phases were simulated on the basis of first principles calculations

–

–

The adsorption of B atoms on the δ-WC1±x (100) surface with 4 possible high symmetry sites on top of the W-terminated surface was studied using first principles density functional theory (DFT); the overlapping and hybridization between 2p and 2s orbits of B and 5d of surface W atoms play a major role in the bonding

See also section δ-WC1±x – B – C See also section C – B – W in Table I-2.14 α/β/ε/γ-W2±xC – β-B

–

~ 50-500

W44÷48B26÷28C26÷28-stoichiometry coatings [3, 13, 53, (thickness – 1.75-2.25 μm) with the amor- 1927, 2184phous to nanocrystalline nature were pre- 2188] pared by mid-frequency pulsed-DC magnetron sputtering deposition method

(continued)

2.6 Chemical Properties and Materials Design

161

Table 2.21 (continued) –

> 2000

The interaction between the components results in the formation of β-W2B5–x, α/β-WB1±x and α-C (graphite) phases

–

~2570-2590 The maximum solid solubility of B in γ-W2±xC phase is corresponding approximately to γ-W1.94÷2.09(C0.97B0.03) composition

See also section α/β/ε/γ-W2±xC – B – C See also section C – B – W in Table I-2.14 δ-WC1±x – β-B – α/β-C

–

1500-2100 δ-WC1±x is in equilibrium with α/β/ε-W2+xC, W2±xB, α-WB1±x, and α-C (graphite) phases

–

2150-2320 δ-WC1±x is in equilibrium with β-WB1±x, β/ε-W2+xC and α-C (graphite) phases

–

2350

–

~2350-2360 The invariant equilibrium with the participation of the liquid phase L (liquid:W0.50÷0.53B0.29÷0.33C0.17÷0.18) + α-C (graphite, 0.1 at.% B) ↔ δ-WC1.00 + β-W(B0.93C0.07)0.96 realizes in the system with the approximate compositions of phases indicated in the reaction

–

~2570-2590 The invariant equilibrium with the participation of the liquid phase L (liquid:W0.59÷0.60C0.29÷0.37B0.04÷0.11) + γ-W(C0.99÷1.00B0.00÷0.01)0.61÷0.62 ↔ δ-W(C0.99÷1.00B0.00÷0.01)0.96÷1.00 + γ-W1.94÷2.09(C0.97B0.03) realizes in the system with the approximate compositions of phases indicated in the reaction

[13, 53, 1151, 21842187]

δ-WC1±x is in equilibrium with β/ε-W2+xC, α-C (graphite) and liquid phases

See also section δ-WC1±x – β-B See also section C – B – W in Table I-2.14 α/β/ε/γ-W2±xC – Vacuum 600-750 β-B – α/β-C

Vacuum 950-1200

In the powdered W2±xC – C nanoparticles [13, 53, (mean particle size – 10-15 nm, contents: 2184-2188, total C – 2.3-8.6 %, O – 1.1-1.3 %) – 18- 2253] 38 % B (98.7 % purity, amorphous) mixed compositions, processed by spark-plasma sintering, no emergence of new phases was detected The formation of α-WB1±x and β-W2B5–x (or ε-WB2–x) boride phases was revealed in the same compositions treated similarly

(continued)

162

2 Tungsten Carbides

Table 2.21 (continued) Vacuum 1450-1600 The formation of β-W2B5–x (or ε-WB2–x) boride and B4±xC carbide phases was revealed in the same compositions treated similarly –

1500-2100 α/β/ε-W2+xC is in equilibrium with W2±xB and metallic W phases

Vacuum 1800

The dense bulk materials, prepared from the powdered W2±xC – C nanoparticles (mean particle size – 10-15 nm, contents: total C – 2.3-8.6 %, O – 1.1-1.3 %) – 1838 % B (98.7 % purity, amorphous) mixed compositions, processed by spark-plasma sintering, were containing only crystalline β-W2B5–x (or ε-WB2–x) boride with a small amount of B4±xC carbide phase

–

2150-2320 β/ε-W2+xC is in equilibrium with W2±xB, β-WB1±x and metallic W phases

–

2350

–

~2570-2590 The invariant equilibrium with the participation of the liquid phase L (liquid:W0.59÷0.60C0.29÷0.37B0.04÷0.11) + γ-W(C0.99÷1.00B0.00÷0.01)0.61÷0.62 ↔ γ-W1.94÷2.09(C0.97B0.03) + δ-W(C0.99÷1.00B0.00÷0.01)0.96÷1.00 realizes in the system with the approximate compositions of phases indicated in the reaction

β/ε-W2+xC is in equilibrium with W2±xB, metallic W and liquid phases

See also section α/β/ε/γ-W2±xC – β-B See also section C – B – W in Table I-2.14 δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Co – Cr – Fe – Mn – Ni – Si – W δ-WC1±x – B – C – Co – Cr – Fe – Mo

See section δ-WC1±x – α/β/ε/γ-W2±xC – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W

–

–

Powdered δ-WC1±x – 10 % Co – 4 % Cr [3586] hard alloys (size distribution – 5-25 μm) modified by 25 % addition of atomized Fe0.43Cr0.16Mo0.16B0.09C0.16 powder (spherical in shape, size distribution – 20-50 μm) were employed as feedstocks to deposit hard coatings on steel substrates using high-velocity oxy-fuel (HVOF) spraying techniques; the prepared coatings were composed of δ-WC1±x and Fe-based amorphous phases

(continued)

2.6 Chemical Properties and Materials Design

163

Table 2.21 (continued) δ-WC1±x – B – C – Co – Cr – Fe – Ni – Si

–

–

Powdered δ-WC1±x – 12 % Co hard alloy [2189-2190] and Ni – 15 % Cr – 4 % Fe – 4 % Si – 3 % B – 0.75 % α-C (graphite) alloy (for both mean particle size – 20-53 μm) mixtures (in mass proportion from 7/3 to 3/7) were applied for the preparation of three-phase cermet coatings (porosity – 0.5-4.0 %, thickness – 0.5 mm) by high-velocity oxyfuel (HVOF) and powder flame (PF) spraying techniques; depending on the component contents and chosen technique δ-WC1±x, γ-W2±xC or γ-(Ni,Cr,Co,Fe,Si,B) alloy were detected as the main phases in the prepared coatings

–

–

Self-fluxing Ni – 14 % Cr – 12 % Co – 8 % (Si + B) – 4 % Fe –0.4 % α-C (graphite) atomized alloy – 40 % δ-WC1±x powdered mixtures (particle size distribution – 38-125 μm) were applied for the preparation of low-porous multi-phase cermet coatings (thickness – 1.2-1.3 mm) on steel substrates using the oxy-fuel flame spraying method followed by different heating and re-melting techniques; depending on the chosen technique δ-WC1±x, γ-W2±xC, η1-W6Fe6Cy, WCoBy, W2CoB2±y and some other phases were detected in the fabricated coatings

α/β/ε/γ-W2±xC – B – C – Co – Cr – Ni – Si – W

–

–

Powdered γ-W2±xC – 50 % Co-based self- [3000] fluxing alloy (Ni – 27.8 %, Cr – 22.6 %, W – 3.9 %, B – 2.0 %, C – 1.6 %, Si – 1.4 %) mixtures were employed for thermal spraying on steel substrates to fabricate protective coatings (total thickness – 1.6-1.7 mm, thickness of deposit/substrate interface/intermediate layer – 30-40 μm)

δ-WC1±x – B – C – Cr – Cu – Fe – Mo – Ni – Si

–

–

Powdered δ-WC1±x – 11 % Ni and Ni – 16 [2207] % Cr – 4 % Si – 4 % B – 3 % Mo – 3 % Cu – 2.5 % Fe – 0.5 % α-C (graphite) alloys mixtures were used for the preparation of laser cladded multi-phase coatings with δ-WC1±x contents – up to 50 %

δ-WC1±x – B – C – Cr – Fe – Mn – Mo – Si – W

–

–

Powdered δ-WC1±x (size distribution – 15- [3608] 25 μm) – 90 % Fe0.50Cr0.18Mo0.07Mn0.02W0.02B0.15C0.04Si0.02 amorphous alloy (size distribution – 15-50 μm) mixtures were employed as the laser cladding materials to prepared composite cladding and remelting coatings on steel substrates

(continued)

164

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – B – C – Cr – Fe – Mn – Ni – Si δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Cr – Fe – Mn – Ni – Si

See section δ-WC1±x – B – Cr – Fe – (Fe – C – Mn – Si) – Ni – Si Ar/CO2 (82/18) mixture

–

δ-WC1±x – β-B – Vacuum, 1010-1050 α/β-C (graphite / < 50 mPa diamond) – Cr – Fe – Ni – Si

Powdered W carbides (size distribution – [3623] 1-2 mm) – Fe-based alloy (martensitic structured, contents: C – 0.43 %, Si – 0.3 %, Mn -1.1 %, Cr – 0.3 %, Ni – 1.6 %, B – 4.6 %) compositions were used for welding deposition of hard layers on steel substrates; the layers were composed of δ-WC1±x, γ-W2±xC, η2-W3Fe3Cy and FeB phases, dispersed in α-Fe-based matrix Brazing active filler Ni – 12 % Cr – 4 % Fe – 3 % Si – 2.5 % B alloy was employed to join δ-WC1±x (particle size distribution – 350-400 μm) and β-C (diamond, nonplated, size – 300-450 μm) with steel substrates (operation dwelling time – 10-30 min) for the preparation of abrasive tools; due to the interfacial δ-WC1±x – filler reactions, the formation of η2-W4Ni2Cy, δ-NiW1–x and Cr7C3±x phases was detected

[2191-2193, 2206, 22182220, 22252227, 2252, 2649, 3426, 3457, 3576, 3779, 3787, 3800, 3814, 3817-3818, 3832-3834, Vacuum, 1200-1275 Self-fluxing Ni – 21-23 % Fe – 9-12 % Cr 3838, 3840, 10 mPa – 3-5 % Si – 2.5-3.5 % B– 0.6-1.0 % α-C 3846, 3850(graphite) alloy (particle size – 75-150 μm) 3851, 3856, 3862, 3868, – 10-40 % δ-WC1±x (irregular in shape, particle size – 20-70 μm) powdered mix- 3870-3872, tures were subjected to cladding on steel 3928] substrates to fabricate multi-phase coatings consisted of γ-(Fe,Ni,Cr) austenite solid solution matrix (bonding phase) containing δ-WC1±x grains (rounded block-shaped after partial dissolution) jointly with various carbide, boride and silicide phases –

–

During the preparation of δ-WC1±x reinforced Ni-based alloys (C – 0.5-1.0 %, B – 3.0-4.5 %, Si – 3.5-5.0 %, Cr – 14-19 %, Fe ≤ 5 %) metal matrix composite (MMC) coatings, the dissolution process occurred at the rim of δ-WC1±x grains with the subsequent precipitation of η1-W6Fe6Cy phase

–

–

Self-fluxing Ni – 16.0-16.3 % Cr – 4.3-4.6 % Si – 3.3-3.5 % B – 1.0-4.3 % Fe – 0.80.9 % α-C (graphite) alloy (spherical in shape, particle size < 104 μm) – 30 vol.% δ-WC1±x (99.5 % purity, particle size distribution – 50-80 μm) powdered mixtures were applied for the preparation of multiphase cermet coatings (thickness – ~1 mm) on steel substrates using the laser cladding technique; in the fabricated coatings,

(continued)

2.6 Chemical Properties and Materials Design

165

Table 2.21 (continued) δ-WC1±x, γ-W2±xC, β-W2+xC and η2-W3(Ni,Cr)3C carbide phases were dispersed in γ-(Ni,Cr,Fe,Si,B) – Ni3B lamellar eutectics –

–

Laser cladding technique, employing δ-WC1±x – 15 % Ni clad with Ni – 14 % Fe – 10 % Cr – 3 % Si – 2 % B – 0.1 % α-C (graphite) alloy powdered mixtures (particle size distribution – 60-100 μm), was applied for the preparation of cermet coatings on steel substrates with the content of δ-WC1±x phase gradually increased from 20 vol.% to 80 vol.%; besides δ-WC1±x and γ-(Ni,Cr,Fe,Si,B) matrix alloy phases, the presence of η2-W4Ni2Cy was detected in the coatings

H2 / Ar / N2

–

Powdered δ-WC1±x – 5 % Ni (irregular in shape, particle size – 40-100 μm) and Ni – 16 % Cr – 4.5 % Fe – 5 % Si – 7.5 % B – 0.9 % C (globular in shape, particle size – 40-80 μm) alloys mixtures were deposited by plasma spraying to produce multi-phase coatings with γ-(Ni,Fe,Cr) metallic matrix containing jointly to δ-WC1±x and W2±xC several carbide, boride, silicide and intermetallide phases

–

–

Powdered Ni – 7.5-17.0 % Cr – 2.0-4.0 % Fe – 2.5-4.0 % Si – 1.5-3.6 % B – 0.3-1.0 % C alloys (particle size distribution – 45105 μm) – 25-75 % δ-WC1±x (spherical in shape) mixtures were employed for the preparation of laser cladded δ-WC1±x – γ-(Ni,Cr,Fe,Si,B,C) coatings on steel substrates; the amount of dissolved δ-WC1±x were increased with increasing heat input and both Fe dilution (occurring from the substrate) and δ-WC1±x dissolution were affecting the coating composition

–

–

Self-fluxing Ni –16 % Cr – 5 % Fe – 4 % Si – 4 % B– 0.8 % α-C (graphite) alloy – 15-80 % δ-WC1±x powdered mixtures (size distribution – 22-35 μm) were employed for the preparation of multi-phase cermet coatings (thickness – 0.8-1.0 mm, porosity – 2.5-7.0 %) on steel substrates using highvelocity O2-C2H2 thermal spraying techniques; in the prepared δ-WC1±x – γ-(Ni,Cr,Fe,Si,B) coatings, γ-W2±xC, Cr7C3±x and Cr23C6±x carbide and CrB2±x, Ni2B and Ni3B boride minor phases were also present

(continued)

166

2 Tungsten Carbides

Table 2.21 (continued) –

–

Powdered Ni –15.9 % Cr – 4.3 % Fe – 4.6 % Si – 3.4 % B – 0.8 % C alloy – 5-50 % δ-WC1±x (coated with 15 % Ni) mixtures (size distribution – 45-105 μm) were employed for the preparation of laser cladded coatings on stainless steel substrates with δ-WC1±x, γ-W2±xC, η2-W4Ni2Cy and Cr23C6±x carbide, Ni3B and CrB boride, β-Ni4+xW and Ni17W3 (metastable) intermetallide and metallic γ-(Ni,Cr,Fe,Si,B) solid solution phase substituents

–

–

Powdered ~50 vol.% monophase δ-WC1±x (size distribution – 50-180 μm, mean particle size – 100 μm) – ~50 vol.% Ni-based alloy (contents: B – 1.9 %, C – 0.7 %, Cr – 8.4 %, Fe – 5.2 %, Si – 4.0 %) mixtures were applied for the deposition of metal matrix composite (MMC) overlays (thickness – 4-6 mm) using plasma transferred arc welding (PTAW) on steel substrates; the formation of ~(Cr0.70W0.30)3C1.80 secondary carbide phase (precipitated after the δ-WC1±x dissolution) was observed

–

–

Powdered ~50 vol.% monophase δ-WC1±x (size distribution – 50-180 μm, mean particle size – 100 μm) – ~50 vol.% Ni-based (Cr-rich) alloy (contents: B – 2.7 %, C – 0.9 %, Cr – 13.8 %, Fe – 5.5 %, Si – 5.8 %) mixtures were applied for the deposition of metal matrix composite (MMC) overlays (thickness – 4-6 mm) using plasma transferred arc welding (PTAW) on steel substrates; the formation of ~(W0.27Cr0.33Ni0.27Si0.13)6C1.80 secondary carbide phase (precipitated after the δ-WC1±x dissolution) was observed

–

–

Powdered δ-WC1±x – Ni based alloy (contents: C – 0.5-1.2 %, B – 2.8-3.5 %, Cr – 15-17 %, Fe – 5-15 %, Si – 3.5-4.5 %) mixtures were applied as feedstock materials for the preparation of hard coatings on stainless steel substrates using high-frequency induction-heated sintering (HFIHS) techniques; the produced coatings had homogeneous microstructures, consisting of δ-WC1±x, γ-W2±xC, (Cr,W)7C3±x and (Cr,W)23C6±x carbide, FeNi1±x and FeNi3±x intermetallide and γ-(Ni,Fe,Cr) metallic solid solutions phases, formed due to the interdiffusion of elements from the coatings and substrates during the manufacturing

(continued)

2.6 Chemical Properties and Materials Design

167

Table 2.21 (continued) procedure –

–

Powdered δ-WC1±x (size distribution – 0.10.2 mm) – 80 % Ni-based self-fluxing alloy (size distribution – 0.10-0.15 mm, contents: C – 0.8-1.2 %, B – 3.0-3.5 %, Si – 3.5-4.0 %, Cr – 14-16 %, Fe – 14-15 %) mixtures were employed as feedstock materials for the fabrication of hard coatings on steel substrates via wide-band laser cladding techniques; the produced coatings were composed mainly of γ-(Ni,Fe,Cr) metallic solid solutions, residual δ-WC1±x (partly dissolved) and γ′-Ni2±xCr phases and newly formed in the molten pool by complex chemical reactions, such as γ-W2±xC, (Cr,W)3C2–x, (Cr,W)23C6±x and metastable NixC carbide and β-(W,Cr)2B5–x and Cr5B3 boride phases

Vacuum

–

Powdered δ-WC1±x (irregular, polyhedral shape; size distribution ≤ 18 μm) –Ni-based alloy (spherical; size distribution – 48106 μm; contents: C – 0.9 %, B – 3.5 %, Si – 4.2 %, Cr – 16 %, Fe – 5 %) mixtures were employed as feedstock materials for the fabrication of hard coatings on steel substrates via cladding techniques; the prepared coatings (in whole) were composed of γ-(Ni,Fe,Cr,W) metallic solid solutions (matrix), δ-WC1±x, (Cr,W)7C3±x and (Cr,W)23C6±x carbide, Ni3B and CrB boride and β-Ni3±xSi silicide phases

–

–

Powdered δ-WC1±x – self-fluxing Ni-based alloy mixtures were employed as feedstock materials for the deposition of hard coatings using O2-C2H2 flame spray-welding technique; the prepared hard coatings were composed of δ-WC1±x, (Cr,W)7C3±x and (Cr,W)23C6±x carbide and Cr2±xB and CrB2±x boride particles dispersed in γ-Nibased metallic solid solution matrix

–

–

Functionally graded (FG) coatings with the content of δ-WC1±x varying from 5 vol.% to 15 vol.% in γ-(Ni,Fe,Cr) metallic matrix were prepared by selective laser melting process using Ni – 12-18 % Cr – 4 % Fe – 2.0-4.5 % Si – 1.5-4.0 % B – 0.5-1.0 % C self-fluxing alloy (gas-atomized, particle size distribution – 40-60 μm) – δ-WC1±x (> 99 % purity) powdered mixtures

(continued)

168

2 Tungsten Carbides

Table 2.21 (continued) –

–

δ-WC1±x – Vacuum 960 α/β/ε/γ-W2±xC – B – C – Cr – Fe – Ni – Si

4-layered δ-WC1±x – Ni alloy (containing C, B, Si, Cr and Fe) functionally graded (FG) composite clads (total thickness – ~1.8 mm) on stainless steel substrates were fabricated via microwave (frequency – 2.45 GHz, power – 0.9 kW) heating route (exposure – 5-6 min); the formation of new carbide, silicide and intermetallide phases was observed in the prepared clads Powdered self-melt Ni-based alloy (size [10, 1864, distribution – 50-100 μm; contents: B – 2213-2214, 2.5-4.0 %, C – 0.5-0.9 %, Cr -14-17 %, Fe 2222-2224, – 12 %) – 30 vol.% δ-WC1±x – γ-W2±xC 2247, 2252, (size distribution – 180-250 μm; contents: 2649, 3576, total C – 3.9-4.0 %, W – 95-96 %, Fe ≤ 0.5 3832-3834, %, Cr ≤ 0.2 %) mixtures were subjected to 3838, 3840, liquid-phase sintering (exposure – 40 min) 3850-3851, procedure to fabricate materials composed 3862, 3868, of γ-(Ni,Fe,Cr) metallic solid solution, 3870-3872, δ-WC1±x and γ-W2±xC major phases with 3876-3877] the presence of (Cr,W)7C3±x, (Cr,W)23C6±x and η2-W3÷4(Ni,Fe)2÷3Cy minor phases; the grain edges of W carbides dissolved partially with the subsequent formation of core-rim microstructure and metallurgical interface with strong bonding between carbide grains and metallic matrix, the stable size (width) of rim had no obvious correspondence with the original size of carbide grains and was dependent on the sintering time (exposure), minor hard phases were precipitated at the interface

H2

1075-1125 The particles of fused δ-WC1±x – γ-W2±xC materials (initial size distribution – 0.250.4 mm) embedded in Ni – 6.5 % Cr – 2.5 % Fe – 2.75 % Si – 2.5 % B – 0.2 % C alloy matrix were subjected to liquid-phase sintering (exposure – 20-60 min) to prepare hardfacing composite layers on steel substrates; the formation of mixed Ni-W car-bides on the matrix-carbide interface and Ni3B within the matrix was detected

H2

1100

Powdered fused δ-WC1±x – γ-W2±xC (size distribution – 0.35-0.50 mm) – Ni-based alloy (contents: C – 0.2-0.5 %, B – 2.5 %, Si – 2.5 %, Cr – 6.5-12.7 %, Fe – 2.5-3.0 %) mixtures were subjected to liquid-phase sintering (exposure – 0.33-2.0 h) to prepare metal matrix composites (MMC); the presence of Ni3B in the interfacial regions among the mean phases of the γ-Ni

(continued)

2.6 Chemical Properties and Materials Design

169

Table 2.21 (continued) solid solutions (matrix) and primary W carbides was detected, the internal intermediate layer formation, close to the original primary carbides exhibited diffusion-controlled kinetics (~ τ0.5), whereas the outside layer thickness formation, proportional to the processing time (~ τ), was formed by the subsequent eutectic reaction of the matrix with carbide components Ar, 1200-1260 Powdered δ-WC1±x – γ-W2±xC (fused, poly0.1 MPa crystalline; size distribution – 60-100 μm) – 60-75 % self-fluxing Ni-based alloy (size distribution – 48-74 μm; contents: C – 0.30.5 %, Si – 3.4-4.5 %, B – 2.5-3.0 %, Cr – 9-12 %, Fe – 21-23 %) mixtures (preliminarily ball-milled) were employed for the fabrication of hard coatings on steel substrates using liquid-phase sintering (dwell time – 10 min) procedure; the coatings were homogeneously structured and composed of δ-WC1±x, γ-W2±xC, (Cr,Fe,W,Ni)7(C,B)3±x and (Cr,Fe,W,Ni)23(C,B)6±x hard phases dispersed in γ-(Fe,Ni,Cr) austenite metallic solid solutions (matrix) –

–

Powdered δ-WC1±x – W2±xC – W2±x(C,O) and Ni – 15 % Cr – 4 % Fe – 4 % Si – 3 % B – 0.7 % C mixed compositions were applied for the laser cladding preparation of coatings containing 10-30 vol.% δ-WC1±x; the formation of mixed carbide (W,Cr)xCy and borides (W,Cr)xBy phases, resulting from a partial dissolution of the δ-WC1±x and W2±xC particles within the metallic matrix, was observed

–

–

Powdered δ-WC1±x – W2±xC and Ni – 1518 % Cr – 14 % Fe – 3.5-5.5 % Si – 3.04.5 % B – 0.5-0.9 % C mixed compositions were applied for the laser cladding preparation of coatings on steel substrates; depending on the processing parameters, γ-(Ni,Fe,Cr) alloy matrix of coatings jointly to δ-WC1±x and W2±xC contained phases of complex carbides and Ni borides

–

–

Powdered δ-WC1±x – γ-W2±xC lamellar eutectics (size distribution – 0-40 μm) – 50 % Ni-based alloy (contents: C – 0.4-0.8 %, Cr – 14-19 %, Fe – 12-15 %, Si – 3-6 %, B – 3-5 %) mixtures were employed to fabricate coatings on steel substrates by laser induction hybrid rapid cladding (LIHRC)

(continued)

170

2 Tungsten Carbides

Table 2.21 (continued) techniques; δ-WC1±x grains with relatively small size were completely dissolved and fine dendritic and blocky carbides were precipitated during the procedure, the major phase constituents of the coatings were metallic γ-(Ni,Fe,Cr) solid solutions (matrix), Ni4B3±x boride and (Cr,Fe,W,Ni)23C6±x carbide, accompanied by such minor phases as δ-WC1±x, γ-W2±xC and η2-(W,Ni,Cr,Fe)6Cy carbides and Ni2B boride –

–

δ-WC1±x – 4 % γ-W2±xC (80-160 μm; total C – 3.99 %, Fe – 0.16%, Co – 0.008 %, Ni – 0.004 %) powders (spheroidal morphology) with the addition of 3-10 % δ-WC1±x (< 0.1 μm; non-combined C – 0.06 %, Si – 0.002 %, Fe – 0.0001 %) and/or 40 % Nibased alloy (1-60 μm; C – 0.2 %, B – 1.6 %, Cr – 7.5 %, Fe – 2.6 %, Si – 3.4 %, O – 0.03 %) powders (size distributions and contents of ingredients are given in brackets) were employed for the preparation of coatings using laser cladding assisted with an induction heater (LCAIH) techniques

α/β/ε/γ-W2±xC – B – C – Cr – Fe – Ni – Si

–

–

Powdered γ-W2±xC – 40 % Ni-based self- [10, 3000, fluxing alloy (Cr – 7.4 %, Fe – 6.2 %, B – 3876-3877] 3.2 %, C ≤ 0.1 %, Si – 4.5 %) mixtures were employed for thermal spraying on steel substrates to fabricate protective coatings (total thickness – 1.8-1.9 mm, thickness of deposit/substrate interface/intermediate layer – 30-40 μm)

δ-WC1±x – B – C – Cr – Fe – Ni – Si – W

–

–

Powdered Ni-based alloy (size distribution [10, 3825, – 44-100 μm; contents: B – 3.5 %, C – 0.8 3850-3851, %, Cr – 15.5 %, Fe – 15 %, Si – 4 %, W – 3870] 3 %) – 3-15 vol.% δ-WC1±x (size distribution – 75-100 μm) mixtures were employed as feedstock materials for the laser cladding of coatings (thickness – 0.55-0.65 mm) on steel substrates

δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Cr – Fe – Ni – Si – W

–

–

Powdered δ-WC1±x – γ-W2±xC – W (spheri- [3870] cal in shape, size distribution – 45-180 μm) – 60 % Ni-based alloy (size distribution – 20-200 μm; contents: C – 0.1-0.2 %, Cr – 7.0-8.0 %, Fe – 3.5-4.0 %, Si – 3.0-4.0 %, B – 3.0-3.5 %) mixtures were employed for the deposition of cohesive hardfacings (maximum thickness – 3-4 mm) with ceramics reinforced γ-(Ni,Fe,Cr) matrix on stainless steel substrates using plasma transferred arc welding (PTAW) technique

(continued)

2.6 Chemical Properties and Materials Design

171

Table 2.21 (continued) δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Cr – Ni – Si

–

–

Powdered δ-WC1±x – 78-80 % W2±xC [10, 2212, (particle size distribution – 60-140 μm) 2249] and Ni – 10-12 % Cr – 4-5 % Si – 2 % B – 0.4 % C alloys mixtures were employed to prepare multi-phase composite coatings, containing 24 vol.% W carbide phases, via electric arc-spraying (EAS) from coredwires; during the arc-spraying process W carbides were decarburized and a large amount of W was dissolved into γ-(Ni,Cr,W) solid solution, finally due to the precipitation from γ-(Ni,Cr,W) the formation of minor phases, such as β-Ni4+xW, δ-NiW1–x and metal W, jointly with Cr carbides and intermetallides, was occurred

δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Fe – Ni – Si

–

–

Powdered δ-WC1±x – γ-W2±xC (size distri- [10, 3813, bution – 63-180 μm) – 40 % Ni-based al- 3868-3869] loy (contents: C – 0.2 %, Fe – 3 %, Si – 3.5 %, B – 2.3 %) mixtures were employed for the deposition of hard coatings on steel substrates using plasma transferred arc (PTA) welding procedure

δ-WC1±x – α/β/ε/γ-W2±xC – B – C – Fe – Ni – Si – W

–

–

Powdered δ-WC1±x – γ-W2±xC – W (fused [3869] and crushed, size distribution – 65-250 μm; molecular ratio W : W2C : WC = 1.5 : 46 : 52.5) – 40 % Ni-based alloy (contents: C – 0.1 %, Fe – 1.2 %, Si – 3.3 %, B – 2.5 %) mixtures were employed for the deposition of hardfacings on steel substrates using plasma transferred arc (PTA) welding procedure

–

Ultra-incompressible and superhard phase [2194] (Mo1–yWy)2BC1–x (y = 0.55, x = 0), predicted on the basis of quantum-mechanical calculations in the combination with advanced machine-learning technique, was synthesized through an arc-melting route

δ-WC1±x – B – C Ar – Mo

δ-WC1±x – H2 α/β/ε/γ-W2±xC – B – C – Ni – Si

1075-1125 Powdered fused δ-WC1±x – γ-W2±xC (size distribution – 0.35-0.50 mm) – Ni-based alloy (contents: C < 0.1 %, B – 2.5 %, Si – 2.5 %) mixtures were subjected to liquidphase sintering (exposure – 0.33-2.0 h) to prepare metal matrix composites (MMC); the presence of Ni3B in the interfacial regions among the mean phases of the γ-Ni solid solutions (matrix) and primary W carbides was detected, the internal intermediate layer formation, close to the original primary carbides exhibited diffusioncontrolled kinetics (~ τ0.5), whereas the

[2212, 2249, 2252, 3810, 3868, 38733874]

(continued)

172

2 Tungsten Carbides

Table 2.21 (continued) outside layer thickness formation, proportional to the processing time (~ τ), was formed by the subsequent eutectic reaction of the matrix with carbide components –

–

Powdered δ-WC1±x – 78-80 % W2±xC (particle size distribution – 60-140 μm) and Ni – 4-5 % Si – 2 % B – 0.4 % C alloys mixtures were employed to prepare multi-phase composite coatings, containing ~17 vol.% W carbide phases, via electric arc-spraying (EAS) from coredwires; during the arc-spraying process W carbides were decarburized and a large amount of W were dissolved into γ-(Ni,W) solid solution, finally due to the precipitation from the solid solution β-Ni4+xW and metal W minor phases were formed

–

–

Fused δ-WC1±x – γ-W2±xC carbides – 44 % Ni-based alloy (contents: C – 0.9 %, B – 4.6 %, Si – 2.7 %) mixtures were used in hot flux-cored wires to prepare hardfacings on steel substrates via gas metal arc welding techniques; the selective dissolution of γ-W2±xC followed by the precipitation of δ-WC1±x phase in the matrix alloy led to the formation of the degradation seam, the dilution rate dominated the degradation behaviour rather than the dwell time of carbides in the melt pool

–

–

Angular cast δ-WC1±x – γ-W2±xC carbides – 50-55 vol.% Ni-based matrix alloy (contents: C – 0.15 %, B – 3 %, Si – 3 %) overlays were fabricated using plasma transfer arc welding (PTAW) techniques; modified overlays contained δ-WC1±x outer shells in the cast carbides

δ-WC1±x – β-B – High 700-1100 α/ε-Co purity H2 (with 0.6 % B2H6)

–

900

During the microwave plasma-enhanced [2181, 2195, chemical vapour deposition (PECVD) 2425, 3338boronizing process (exposure – 1 h), the 3339] following binary and ternary borides: α/β-W2B5–x, Co3B, CoB, WCoBy and W2CoB2±y – were formed on the surface of medium grain-sized δ-WC1±x – 6 % Co hard alloy due to the chemical interaction of B with W and Co Boronizing thermochemical treatment (exposure – 4 h) of δ-WC1±x – Co hard alloys resulted in the formation of boronized layer (thickness – ~28 μm) containing Co2B and W2CoB2±y phases

(continued)

2.6 Chemical Properties and Materials Design

173

Table 2.21 (continued) Vacuum ≥ 1100

–

δ-WC1±x – B – Co – Cr – Fe

Contact reactions between δ-WC1±x – Co hard alloys and amorphous powdered B leads to the emergence of a liquid phase (eutectics Co – Co3B, or Co – Co2B)

1350-1400 The introduction of 0.2-9.0 vol.% amorphous B into the δ-WC1±x – 6 % Co hard alloys leads to the formation of β-W2B5–x, W2±xB and Co2B boride phases and increasing of non-combined C contents up to 2.3 % in the materials prepared by liquidphase sintering process –

Co-coated δ-WC1±x particle reinforced Fe [2279] – Cr – B alloy composite coatings were deposited on steel substrates by arc spraying

–

Powdered δ-WC1±x – 12 % Co (mean particle size – ~35 μm) and Ni – 7 % Cr – 3 % Fe – 4.5 % Si – 3 % B alloy mixtures were used to prepare δ-WC1±x – γ-(Ni,Fe,Cr) composite coatings (with η2-W4Ni2Cy, δ-NiW1–x and Cr3NiB6 as minor phases) by the powder cloth and brazing technology

–

–

Powdered δ-WC1±x – 12 % Co and Ni – Cr – Fe – B – Si alloys mixtures were used to prepare plasma-sprayed welded biomimetic δ-WC1±x – γ-(Ni,Fe,Cr) multi-phase coatings (on steel substrates), containing several carbide, boride, silicide and intermetallide minor phases

–

–

δ-WC1±x – 4 % Co – 46-48 % Ni – 9-10 % Cr – 3 % Fe – 3 % Si – 2 % B powdered compositions were employed to deposit cermet laminar structured coatings (thickness – 0.3 mm, porosity – 0.5 %) on steel substrates using high-velocity oxy-fuel (HVOF) spraying technique; in the fabricated coatings higher amount of δ-WC1±x with a minor amount of γ-W2±xC phase were distributed in γ-(Ni,Fe,Cr,Co) matrix alloy

–

–

Powdered δ-WC1±x – 2.8 % Fe – 9.4 % Cr – 4.2 % Co – 45.0 % Ni – 3.5 % B – 4.3 % Si mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials to deposit hard coatings (porosity – ~1 %) on steel substrates; δ-WC1±x, Cr23C6±x, η2-W3Co3Cy (or η-W4–xCo2+xC) and Ni3C (metastable) carbide, W5Si3+x silicide and β-Ni4+xW intermetallide phases were detected in the prepared coatings

–

δ-WC1±x – B – Vacuum Co – Cr – Fe – Ni – Si

[2197-2198, 2204, 2209, 2215, 3448, 3715, 3902]

(continued)

174

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – α/β/ε/γ-W2±xC – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W

–

–

δ-WC1±x – B – Vacuum ~1200 Co – Cr – Ni – Si

Plasma transferred arc welding technique [2967] was employed to spray/deposit the various mixtures of carbide W (contents: total C – 3.7-4.0 %, non-combined C ≤ 0.08 %, O ≤ 0.20 %) and self-fluxed alloy (Co – 2832 % Cr – 10-12 % Ni – 5-6 % W – 3.54.5 % Si – 2.5-3.5 % B) powders on steel (contents: C – 0.14-0.22 %, Mn – 0.300.65 %, Si ≤ 0.30 %) substrates; depending on the accepted proportions between the mixtures applied, the deposited δ-WC1±x – Co based coatings were also containing η1-W6(Co,Fe)6Cy, (Cr,Fe)23(C,B)6±x, γ-W2±xC, W5Si3+x, Fe2±xSi, CrSi2, CrSi, Cr3±xSi, FeCo1±x, FeNi1±x and γ-(Ni,Fe,Cr) minor phases Brazed δ-WC1±x – Co – Ni – Cr – B – Si cermet coatings were deposited on steel substrates

[10, 2199, 3093]

–

–

Powdered δ-WC1±x – 29 % Ni – 7 % Co – 3 % Cr – 0.75 % Si – 0.25 % B mixtures were applied for the preparation of coatings on steel substrates using multilayer laser cladding (MLC) techniques

δ-WC1±x – α/β/ε/γ-W2±xC – B – Co – Cr – Ni – Si

–

–

Co-covered δ-WC1±x – γ-W2±xC powders [3373] in the mixtures with Ni – B – Cr – Si alloy were used for the preparation of composite coatings via laser cladding technology; the typical microstructures of coatings were composed of η-phase grains distributed in the multi-component pseudoeutectic matrix, which predominantly consisted of Cr carbide based phases, Ni borides and Ni based metallic solid solutions

δ-WC1±x – B – Co – Cu – Ni

–

–

For sintered coarse- and medium-grained δ-WC1±x – Co hardmetals, the alloy composed of Cu – 3 % Ni – 0.05 % B was applied as a brazing agent

δ-WC1±x – B – Co – Fe – Mo – Ni

–

–

δ-WC1±x – Co – Fe – Ni – Mo – B hard [2200-2201] alloys with the binder containing martensitic phase were prepared using conventional powder metallurgy methods

δ-WC1±x – B – Co – Fe – Si

–

–

0.1-2.0 vol.% δ-WC1±x (mean particle size [2202] – 2-3 μm) dispersed ductile amorphous Co70.5Fe4.5Si10B15 alloys were prepared via a single roller method followed by annealing and water-quenching procedures

δ-WC1±x – B – Cr – Fe

–

–

Amorphous Fe0.69Cr0.15÷0.16B0.15÷0.16 alloys [2196] strengthened by δ-WC1±x particles were designed and prepared

[10, 1992, 3104]

(continued)

2.6 Chemical Properties and Materials Design

175

Table 2.21 (continued) δ-WC1±x – B – Cr Vacuum 1280 – Fe – (Fe – C – Mn – Si) – Ni – Si

Powdered Ni-based alloy (contents: Cr – [3815] 15 %, Fe ≤ 5 %, B – 3.5 %, Si – 4.5 %) – 20-40 % δ-WC1±x mixtures were employed for the preparation of surface infiltrated composite layers on gray iron (C – 3.2-3.5 %, Si – 1.8-2.4 %, Mn – 0.5-0.9 %, Fe – remainder) using vacuum infiltration casting techniques (VICT); the surface layers were mainly composed of δ-WC1±x and W2±xC carbide, FeB and NiB boride and γ-(Ni,Cr,Fe,Si) solid solution phases

δ-WC1±x – B – Cr – Fe – Mo – Ni – Si

–

–

Pre-alloyed δ-WC1±x – 57 % Ni – 15 % Cr [3437] – 5 % Mo – 4 % Si – 3.5 % Fe – 3 % B powders were employed for the preparation of laser cladded coatings on stainless steel substrates; depending on the character of laser spot, different microstructures were formed in the fabricated coatings: δ-WC1±x particles (partially dissolved) were uniformly distributed (jointly with (Cr,Ni,Fe,W,Mo)23C6±x, Ni2+x(Cr,Fe) and γ-Ni31Si12 phases) in γ-(Ni,Fe) solid solution matrix, or core-structured δ-WC1±x particles were embedded in the lamellar eutectic matrix

δ-WC1±x – B – Cr – Fe – Mo – Si

–

–

δ-WC1±x – α-Fe based solid solution cer- [3605-3606] met coatings were deposited on steel substrates using plasma cladding technique with Fe – 13 % Cr – 0.8 % Mo – 1.6 % B – 1.2 % Si alloy powders; during the cooling process of the molten pool, δ-WC1±x grains experienced a transformation into blocky (Cr,Fe,W)7C3±x generated around the edges of δ-WC1±x, the subsequent decomposition of (Cr,Fe,W)7C3±x led to the occurrence of the eutectic net-like structures composed of (Cr,Fe,W)23C6±x and α-Fe and formation of coarse herringbone-shaped η2-(W,Fe,Cr)6Cy phase due to the dissolution reaction at the α-Fe/(Cr,Fe,W)23C6±x interfaces

δ-WC1±x – B – Cr – Fe – Ni

–

–

Ni-coated δ-WC1±x particle reinforced Fe – [2279] Cr – B alloy composite coatings were deposited on steel substrates by arc spraying

δ-WC1±x – B – Cr – Fe – Ni – Si

Vacuum, 1100 0.13 Pa

Powdered δ-WC1±x (mean particle size – 1 μm) – Ni-based alloy (mean particle size – 5 μm; contents: B – 3.0 %, Si – 4.5 %, Cr – 8 %, Fe – 3 %) mixtures were employed to fabricate brazed coatings on stainless steel substrates

[2205, 3438, 3443-3444, 3451, 3815, 3817, 3855]

(continued)

176

2 Tungsten Carbides

Table 2.21 (continued)

δ-WC1±x – B – Cr – Ni – Si

–

–

Metallized δ-WC1±x – 6-70 % Ni – 0.815.7 % Cr – 1.5-3.0 % Si – 0.8-3.5 % Fe – 0.4-2.8 % B powders were employed for the fabrication of thermally sprayed coatings

–

–

Powdered Ni – Cr – B – Si – Fe alloy – 35 % δ-WC1±x mixtures were subjected to plasma surfacing on steel substrates to fabricate three-phase coatings composed of ~10 vol.% δ-WC1±x (mean grain size – 5-7 μm), ~ 5-70 vol.% α-(Fe,Cr,Ni) solid solution (disordered) and ~ 20-85 vol.% γ-(Fe,Ni) solid solution (with short- or long-range order) phases; on moving away from the substrate interface, the main matrix phase switches from α- to γ-phase with δ-WC1±x phase contents remaining constant

Ar

Powdered 15-50 vol.% δ-WC1±x (99.5 % [10, 2208, purity, particle size distribution – 45-150 2210-2211, μm) – Ni – 10.5-15.0 % Cr – 2 % Si – 1.5 2221, 2233, % B alloy (spherical in shape, mean 3441-3442, particle size – 45 μm) mixtures were sub- 3826] jected to the liquid-phase sintering (exposure – 1 h) or thermal spraying to prepare multi-phase composites or coatings; at higher Cr content, complex boride W2CrB2 (or W3.2Cr1.8B3), jointly with various Cr carbides and Ni borides/silicoborides, was detected in the materials, which were mainly containing δ-WC1±x (reinforcement) and γ-Ni solid solution (matrix) phases

1100

Vacuum

–

δ-WC1±x reinforced Ni –Cr – Si – B alloy metal matrix composite hardfacing coatings were produced by brazing process

–

–

Powdered δ-WC1±x – 12 % Ni and Ni – Cr – Si – B alloys mixtures were used for the preparation of plasma sprayed multi-phase coatings containing, besides main δ-WC1±x (hard) and γ-Ni (metallic matrix) phases, various carbides and borides, including W2±xC as a minor phase

–

The particles of cast WC1±x – W2±xC ma- [2248, 2250terials embedded in Ni – Cr – B – Si alloy 2251] matrix were subjected to liquid-phase sintering to prepare hardfacing composite layers on steel substrates

δ-WC1±x – Vacuum α/β/ε/γ-W2±xC – B – Cr – Ni – Si

(continued)

2.6 Chemical Properties and Materials Design

177

Table 2.21 (continued) –

–

In the cast δ-WC1±x – γ-W2±xC materials, the grains of δ-WC1±x have a higher chemical resistance in respect of molten Ni – Cr – B – Si alloy than γ-W2±xC; during the preparation of WC1±x/W2±xC particle reinforced γ-(Ni,Cr) metal matrix composites by liquid-phase sintering, the interdiffusion of elements occurs between the molten matrix and the particles that leads to the reaction of W2±xC with Ni, Cr and other elements diffusing from molten matrix, while δ-WC1±x in WC1±x/W2±xC remains mostly intact, finally – the elements such as Ni and Cr in the matrix react with W and C, diffusing from the particles, to form the W-Ni-Cr rich complex carbides, which are precipitated from the melt during the cooling period

δ-WC1±x – B – Cr – Ni – Si – Ti

–

–

Powdered 30 % δ-WC1±x (≥ 99.5 % purity, [2216] irregular in shape, particle size – 0.5-7 μm) – 0-70 % Ni (≥ 99.5 % purity) – 0-70 % Ni – 16 % Cr – 4 % Si – 4 % B alloy (particle size – 40-120 μm) mixtures were applied to fabricate laser cladded coatings on Ti based alloy substrate; depending on pure Ni content in the mixtures, the composition of the coatings changed considerably: due to the partial dissolution of δ-WC1±x and intensive interaction with the substrate, mixed (Ti,W)C1–x carbide phase was formed and matrix was transformed from mainly metallic (α-Ti) to mainly intermetallide (Ti2±xNi, TiNi1±x and TiNi3)

δ-WC1±x – B – Cr – Ni – W

–

–

Hybrid cermet coatings with δ-WC1±x – W [2228] top layer and Ni – W – Cr – B interlayer (high-velocity oxy-fuel (HVOF) sprayand-fused) were applied to Ni-based alloy substrates

δ-WC1±x – B – Cu – Fe – Ni – Si

–

–

Cermet coatings composed of ~45 vol.% ~W(C0.79B0.23) hard phase and ~55 vol.% ~(Ni0.660Fe0.005Cu0.009B0.224Si0.040C0.062) metallic binder (with given approximate compositions) were prepared via laser deposition (LD) of δ-WC1±x – Ni-based alloy powdered mixtures (particle size distribution – 50-150 μm) on Cu-based alloy substrates

[2203]

(continued)

178

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – B – Fe – Ni – Si

He

–

δ-WC1±x – B – Mo – Ni – Si

Reinforced by δ-WC1±x particles (size dis- [10, 2246, tribution – 10-50 μm) Fe0.40Ni0.40Si0.06B0.14 3818, 3869] amorphous alloy metal matrix composites were prepared by the melt spinning method

1300

–

–

Powdered ~50 vol.% monophase δ-WC1±x (size distribution – 50-180 μm, mean particle size – 100 μm) – ~50 vol.% Ni-based (Cr-free) alloy (contents: B – 3.45 %, Fe – 0.65 %, Si – 3.1 %) mixtures were applied for the deposition of metal matrix composite (MMC) overlays (thickness – 4-6 mm) using plasma transferred arc welding (PTAW) on steel substrates; due to the alloy composition, only little dissolution of δ-WC1±x grains occurred, and no formation of secondary carbide phases was observed

1040-1180 During the liquid-phase sintering process [2229] of Ni – 15 % Mo – 1.6-6.4 % Si – 2.2 % B – 30 % δ-WC1±x alloy, ω-(Mo,W)2NiB2 complex boride (jointly with β-Ni3±xSi and γ-Ni5Si2–x silicide phases) was formed

δ-WC1±x – B – Ni

Ar

400-1200

During the heat treatment of 10-30% Ni – [10, 2211, B coated δ-WC1±x (≥ 99.5 % purity) pow- 2230] ders (mean particle size – 1 μm, specific surface area – 0.38 m2 g–1), the formation of new phases such as Ni3B (at lower temperatures) and η2-W4Ni2Cy (at higher temperatures) was detected

δ-WC1±x – B – Ni – Si

Ar

1100

Powdered 15-50 vol.% δ-WC1±x (99.5 % [2231-2233, purity, particle size distribution – 45-150 2235, 2252, μm) – Ni – 2 % Si – 1.5 % B alloy (spheri- 3868, 3885] cal in shape, mean particle size – 45 μm) mixtures were subjected to the liquidphase sintering (exposure – 0.25 h) to prepare composites with a B-rich net

He

–

–

1-10 vol.% δ-WC1±x particle reinforced metallic glassy Ni0.73÷0.75Si0.08÷0.10B0.17 matrix composites were prepared via the treatment of melts with particle blasting pneumatic gun or induction stirring techniques followed by rapid solidification

–

δ-WC1±x powder (mean particle size – 4-5 μm) was added with the fraction varied from 2 vol.% to 20 vol.% to the charge of amorphous Ni0.78Si0.10B0.12 alloy prior to its casting to prepare particle-dispersed twophase materials; no interfacial interaction between matrix and δ-WC1±x particles and nucleation sites at the interface for matrix

(continued)

2.6 Chemical Properties and Materials Design

179

Table 2.21 (continued) crystallization were detected

See also section δ-WC1±x – B4±xC – Ni – Si δ-WC1±x – H2 α/β/ε/γ-W2±xC – B – Ni – Si

1075-1125 The particles of fused WC1±x – W2±xC ma- [2234-2235, terials (initial size distribution – 0.25-0.4 2247, 3868] mm) embedded in Ni – 2.5 % B – 2.5 % Si alloy matrix were subjected to liquid-phase sintering (exposure – 20-60 min) to prepare hardfacing composite layers on steel substrates; the formation of mixed Ni-W carbides on the matrix-carbide interface and Ni3B within the matrix was detected –

–

The addition of 0.6-1.5 % B and Si to the δ-WC1±x – Ni powdered mixtures leads to the formation of Ni3B and β-Ni3±xSi phases, which restrains the growth of δ-WC1±x grains in the sintered hard alloys

–

–

Ni – B – Si alloy matrix composite coatings with up to 40 vol.% (WC1±x + W2±xC in total) were prepared by laser powder cladding techniques

α/β/ε/γ-W2±xC – B – Pt – Si

–

–

Pt nanoparticles and W2±xC thin films (thickness – 2.5-14.8 nm) were deposited on p-type B-doped Si (111) substrates to prepare photocathode systems

[1597]

δ-WC1±x – AlN – [(CkHl)(CpHq) Si(CH2)]n – α/β-SiC – B – α/ε-Co

–

1950

Powdered α-SiC – 20 % polycarbosilane [(CkHl)(CpHq)Si(CH2)]n (PCS) – 4.7 % δ-WC1±x – 0.3 % Co – 1 % AlN – 1 % B mixtures were hot-pressed to prepare strengthened ceramics with surface compressive layer

[2236]

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – B – Cr – Fe – Ni – Si

–

–

δ-WC1±x – [(CkHl)(CpHq) Si(CH2)]n – α/β-SiC – B – α/ε-Co

–

δ-WC1±x – CaF2 – B – Cr – Fe – Ni – Si

–

The addition of Al2O3 nanopowders to the [2205] powdered Ni – Cr – B – Si – Fe alloy – 35 % δ-WC1±x mixtures, subjected to plasma surfacing on steel substrates, resulted in the formation of coatings containing ~1025 vol.% β-W2+xC (mean grain size – 0.5 μm) and ~ 75-90 vol.% γ-(Fe,Ni) solid solution (with short-range order) phases Powdered α-SiC – 20 % polycarbosilane [2236] [(CkHl)(CpHq)Si(CH2)]n (PCS) – 4.7 % δ-WC1±x – 0.3 % Co – 1 % B mixtures were hot-pressed to prepare modified ceramic materials

1950

–

Powdered δ-WC1±x – 5 % CaF2 – 16 % Ni [3457] – 5 % Cr – 5 % Fe – 0.9 % Si – 0.7 % B mixtures were employed to deposit hard coatings, composed of δ-WC1±x, CaF2 and γ-(Fe,Ni) solid solution phases, on steel substrates using laser cladding techniques; the assistance by ultrasonic vibration pro-

(continued)

180

2 Tungsten Carbides

Table 2.21 (continued) cessing to the cladding resulted in the changes of microstructure and additional formation of W2±xC and Cr23C6±x carbide phases in the prepared coatings δ-WC1±x – CeO2–x – B – Co – Cr – Fe – Ni – Si

–

–

Modified by adding 0.4 % CeO2–x (99.95 [3902] % purity, size distribution – 5-15 μm), powdered δ-WC1±x – 2.8 % Fe – 9.4 % Cr – 4.2 % Co – 45.0 % Ni – 3.5 % B – 4.3 % Si mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials to deposit hard coatings (porosity – ~1 %) on steel substrates; δ-WC1±x, Cr7C3±x, κ-W3CoC1+x, (or W9÷10Co3C4) and Ce2Ni22C3–x carbide, Ni3B boride, NiSi, Cr3±xSi and WSi2 silicide and Ce24Co11 and λ-Fe2W intermetallide phases were detected in the prepared coatings

δ-WC1±x – Cr3C2–x – B – C – Co – Cr – Cu – Fe – Ni – Si – Zn

See section δ-WC1±x – Cr3C2–x – B – Co – Cr – Cu – (Fe – C) – Ni – Si – Zn

δ-WC1±x – Vacuum, 1050 Cr3C2–x – B – Co ~70 mPa – Cr – Cu – (Fe – C) – Ni – Si – Zn

To prepare the brazed joints (exposure – [3273] 10-60 min) between δ-WC1±x – 0.5-1.0 % Cr3C2–x – 4-13 % Co hard alloys and tool steel (C – 0.45 %) parts, the following stacking sequence for filler metals was applied: steel / Cu – 1 % Zn – 0.7 % Si alloy (100 μm) / amorphous Ni – 3.7 % B – 15.5 % Cr alloy (40 μm) / hard alloy (thicknesses are given in brackets); the presence of Cr3C2–x in the hard alloys inhibits the formation of η2-W3Co3Cy and coarsening of δ-WC1±x; at longer exposures and smaller amounts of Cr3C2–x in the alloys, the precipitation of Cr7C3±x phase in the interfacial layer was observed

δ-WC1±x – Cr3C2–x – B – Cr – Fe – Ni – Si

–

–

Powdered Ni – Cr – Fe – B – Si alloy – 10- [2217] 40 % δ-WC1±x – 10-40 % Cr3C2–x (particle size distribution of hard phases – 50-150 μm) mixtures were employed to deposit coatings by plasma transferred arc welding technique on steel substrates; besides W2±xC and δ-WC1±x, (Ni,Cr,W)3C (metastable) and (Cr,Fe,Ni,W)7C3±x carbide phases were detected in the coatings

(continued)

2.6 Chemical Properties and Materials Design

181

Table 2.21 (continued) δ-WC1±x – FeAl1±x – β-B

–

1100-1200 Materials containing 15-65 vol.% δ-WC1±x [2238-2244, with intermetallide FeAl0.67 – 8 mol.% 4214, 4217] Fe2B binder were prepared from powders by pulse current sintering (PCS) process

High 1450-1550 Powdered δ-WC1±x (mean particle size – purity Ar, 0.7-0.8 μm) – 40 vol.% FeAl0.67 (doped 10 kPa with 0.025-0.1 % B) mixtures were hotpressed (exposure – 4 min) to fabricate highly dense composite materials

See also section δ-WC1±x – Al – B – Fe δ-WC1±x – Fe3±xAl – β-B

–

δ-WC1±x – NiAl1±x – β-B – Ni

Vacuum, 1375-1450 Powdered δ-WC1±x – Ni – NiAl~1.0 – B [4321] 7-9 mPa mixtures (mean particle size (after wetmilling) – 1.2-1.7 μm) were subjected to liquid-phase sintering (exposure – 1 h) procedure to fabricate dense δ-WC1±x – 25 vol.% γ′-Ni3.08(Al0.98B0.02) hard composite materials (porosity – 1-2 %, with the presence of small amounts of η2-W4Ni2Cy phase)

1150

δ-WC1±x – 9.7 % Fe3±xAl – 0.3 % B hard [2237] alloys were prepared by spark-plasma sintering (exposure – 8 min) procedure

See also section δ-WC1±x – Al – B – Fe

δ-WC1±x – Ar, 1150-1450 Powdered δ-WC1±x (mean particle size – γ′-Ni3±xAl – β-B 0.1 MPa 2.5 μm) – 17-68 vol.% γ′-Ni3±xAl (several kinds of inert gas atomized powders, 0.020.05 % B-doped, size distribution ≤ 44 μm,) mixtures (preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 0.25-2.0 h) to prepare dense ceramic composites

[2239-2240, 2243-2245, 4212, 4217, 4304]

High 1450-1550 Powdered δ-WC1±x (mean particle size – purity Ar, 0.7-0.8 μm) – 40 vol.% γ′-Ni3.00Al (doped 10 kPa with 0.025-0.10 % B) mixtures were hotpressed (exposure – 4 min) to fabricate highly dense composite materials Vacuum 1450-1550 Ultra-fine powdered δ-WC1±x – 40 vol.% B (500 ppm) doped γ′-Ni3±xAl mixtures were subjected to liquid-phase sintering using hot-pressing procedure to prepare fully dense composites δ-WC1±x – Vacuum, 1450 γ′-Ni3±xAl – B – 0.1 mPa Cr – Mo – Zr

Powdered δ-WC1±x (mean particle size – 2- [4212] 3 μm) with 30 vol.% pre-alloyed ~γ′-(Ni,Cr,Mo,Zr)3±x(Al,B) was used to prepare dense composites (porosity – 0.3 %) by melt infiltration procedure

(continued)

182

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Ar, 1150-1450 Powdered δ-WC1±x (mean particle size – [4212, 4304] γ′-Ni3±xAl – B – 0.1 MPa 2.5 μm) – 17-68 vol.% γ′-Ni3±xAl (several kinds of inert gas atomized powders, 7.8 % Cr – Zr Cr-alloyed, 0.02 % B- and 0.6-0.8 % Zrdoped, size distribution ≤ 44 μm) mixtures (preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 0.25-2.0 h) to prepare dense ceramic composites δ-WC1±x – Vacuum, 1450 γ′-Ni3±xAl – B – 0.1 mPa Zr

Powdered δ-WC1±x (mean particle size – [4212] 2-3 μm) with 20-30 vol.% pre-alloyed ~γ′-(Ni0.99Zr0.01)3.42(Al0.955B0.005) was used to prepare dense composites (porosity – 0.3-0.5 %) by melt infiltration procedure

δ-WC1±x – TiB2±x Vacuum, 1000-1900 Sintered dense materials composed of [4383] – B – Co – Ni 40 mPa (Ti0.86÷0.97W0.03÷0.14)B2±x, φ-(W,Ti)(Co,Ni)B, ω-(W,Ti)2(Co,Ni)B2, γ-(W,Ti)3(Co,Ni)B3, (Ni,Co)3B, (Ni,Co)2B and α/β-(Ni,Co)4B3±x mixed and complex boride phases were prepared from 80-90 vol.% TiB2±x – 2-6 vol.% Ni – 1-2 vol.% Co – 3 vol.% B powdered mixtures, containing 8-14 vol.% δ-WC1±x, by liquidphase sintering (exposure – up to 4 h) procedure δ-WC1±x – Bi

–

No wettability by molten Bi, no chemical [13, 579, interaction 1941]

500

Vacuum, 800 1.3 Pa –

Sintered WC0.98 materials (content noncombined C – 0.10%) does not interact with pure molten Bi (exposure – 10 h) The surface of δ-WC1±x is perfectly wetted by molten Bi

1200

See also Table 2.26 δ-WC1±x – α/β-C (graphite / diamond and other allotropes)

–

–

–

–

–

–

Prism shaped δ-WC1±x nanocrystals (mean size – 5 nm, dominated by (0110), (1010) and (1100) facets with a preferred orientation of ) were synthesized on α-C (graphene) surface using intermittent microwave heating (IMH) techniques

[1, 53, 74, 99, 175, 270, 282, 284, 314, 354, 357, 375, 377, δ-WC1±x (mean particle size – ~30 nm) – C 385, 390, nanocomposites were synthesized by ion- 396, 412, 441, 444, exchange (with strongly basic ion-exchange resins employed as C frameworks 449-450, in aqueous solutions and C sources in the 458, 480, 522, 526further operations) method followed by heat treatment to provide carbothermal re- 529, 540, 546-547, duction reactions in the materials 626, 858, δ-WC1±x nanoparticles were pasted onto C 1172, 1175, clothes to prepare δ-WC1±x-decorated sur-

(continued)

2.6 Chemical Properties and Materials Design

183

Table 2.21 (continued) faces for electrochemical applications –

–

Coated with well-crystallized α-C (graphite) nanoparticles γ-WC1–x@C (mean size – 30 nm) were synthesized by pulsed plasma in liquid

–

–

δ-WC1±x nanoparticles (characteristic size – from several to tens nm) surrounded by the amorphous C and closed onion-like curved C structures (consisting of few layers) were synthesized using C60 (fullerene) as a C source

–

–

δ-WC1±x nanoparticles (mean size – ~1.5 nm) were anchoring on few-layer C (reduced graphene oxide) sheets, based on a controllable assembly, to construct a kind of intercalation compound

–

–

δ-WC1±x nanoparticles supported on multiwalled C nanotubes or graphite-like mesoporous C were synthesized by microwaveassisted solid-state carburization method

–

–

The properties of multi-walled C nanotube – δ-WC1±x interfaces (junctions) were studied in detail

–

–

Bio-based porous C – δ-WC1±x hybrid materials were prepared by a microwave-assisted method

–

–

2D arrays of nanodots constituted of amorphous WC1±x clusters embedded in the matrix with the structure intermediate between nanocrystalline α-C (graphite) and amorphous C were prepared by means of focused-electron-beam induced deposition using the W carbonyl precursor

Pure Ar

–

δ-WC1±x – α-C (amorphous, predominantly containing sp2-hybridized bonds) multilayers (nanometers in period, total thickness – 0.21 μm) were deposited on Si substrates using magnetron sputtering method with the presence of crystalline γ-WC1–x (x ≈ 0.36) phase, having (200) preferred orientation (a sharp interface of 1-2 atomic layers in thickness was observed between γ-WC1–x and α-C layers)

CH4, 10 kPa

–

δ-WC1±x nanoparticles (mean particle size – 1.9±0.9 nm), comprising a high density of single W atoms, sub-nanometer and nanometer W-C clusters, completely encapsulated in high-defective α-C (graphite) layers to form δ-WC1±x@C nanostructures (with the presence of W2±xC phase), have

1347, 1355, 1386, 14121413, 1454, 1467, 1472, 1488, 1499, 1521, 1524, 1526, 1550, 1559, 1562, 1569, 1592, 1618, 1621, 1630, 16321633, 1635, 1639, 1658, 1674, 1690, 1702, 1705, 1710, 17181719, 1750, 1826, 1943, 1978-1979, 2094, 22552278, 22802315, 2382, 3996-3997, 4059, 40704071, 4541]

(continued)

184

2 Tungsten Carbides

Table 2.21 (continued) been prepared by modified arc-discharge process (exposure – 6 h) techniques Ar/C2H2

–

Nanosized γ-WC1–x – amorphous C (matrix) composite coatings (thickness – 2.0±0.2 μm) were prepared on the cemented carbide substrates by d.c. magnetron sputtering deposition (exposure – 2 h)

Vacuum, Ar

–

γ-WC1–x – C nanocomposite coatings (thickness – 0.3-0.8 μm) were deposited on various substrates using different variants of reactive magnetron sputtering technique

Ar flow

–

Nanocomposite “superlattice coatings” (thickness – 4-6 μm) with alternating amorphous C / nanocrystalline metastable γ-WC1–x layers were prepared by magnetron sputtering techniques; the structure of coatings changed from clearly columnar to glassy-like or fine-grained once the contents of W in them excessed 5.4 at.%

Ar flow

–

Nanomultilayered γ-WC1–x – amorphous C coatings with modulation period ranging from 1.3 to 11.5 nm were designed and fabricated via unbalanced magnetron sputtering processing techniques

CH4

–

Modified β-C (diamond) thin films, containing δ-WC1±x nanophase, were designed and fabricated by chemical vapour deposition (CVD) method

Vacuum

–

δ-WC1±x – β-C (diamond) and δ-WC1±x – C (nanotubes) – β-C (diamond) composites with β-C (diamond) matrix were fabricated by hot-pressing

Vacuum, 1 mPa

–

Nanocrystalline γ-WC1–x (metastable) – amorphous C coatings (C – 76 at.%, W – 24 at.%, thickness – ~2 μm) were prepared by magnetron sputtering process

Ar/N2

20-350

Vacuum ~ 50-300

20-40 % γ-WC1–x (0.34 < x < 0.43, mean size – ~2 nm, metastable) nanoparticles – C (black) composites were prepared via thermal decomposition process of W carbonyl followed by stirring and anchoring the carbide on C using a mixture of organic liquids (solvents)

Nanocrystalline (or near-amorphous) γ-WC1–x (mean grain size – from 1-3 nm for near-amorphous to 5-10 nm for nanocrystalline, depending on the degree of its crystallinity) embedded amorphous diamond-like C composite coatings were produced from intersected plasma fluxes; an

(continued)

2.6 Chemical Properties and Materials Design

185

Table 2.21 (continued) increase in total C content induced the amorphization of γ-WC1–x phase Vacuum, ~100 1 mPa

Composite coatings (thickness – ~0.3 μm) composed of nanosized γ-WC1–x, dispersed in continuous amorphous C matrix, were prepared by using a hybrid deposition system of r.f. plasma assisted chemical vapour deposition (PACVD) and d.c. magnetron sputtering techniques

Ar, CH4, 150-500 4-8 Pa

γ-WC1–x – β-C (diamond-like) multilayers were prepared by reactive r.f. magnetron sputtering technique

N2

200

δ-WC1±x nanoparticles on platelet type – α-C (nanofibers) were synthesized using W carbonyl as a precursor

200-650

Annealed nanocrystalline γ-WC1–x (with a small amount of α-W2+xC phase, mean size – 12-140 nm) particles, initially synthesized by the ion arc method, were encapsulated within crystalline α-C (graphite shell, thickness – 4-30 nm)

–

Vacuum 300

Hybrid materials composed of C (multiwalled nanotubes) decorated with γ-WC1–x nanocoatings of various morphologies, ranging from spatially separated nanoparticles (size distribution – 10-50 nm) to uniform coatings (thickness – ~0.3 μm) with granular structures, were prepared by metal-organic chemical vapour deposition (MOCVD) technique (exposure – 1-1.5 h)

High 400 purity H2 flow

Heterostructures of amorphous WC1±x nanoparticles decorated uniformly onto the disordered and mesoporous walls of C (amorphous nanotubes) were set up via vapour deposition process

Ar/C2H2 500 mixture

Thin films of WC1±x – C compositions were deposited on steel substrates by r.f. reactive magnetron sputtering in the differrent modes of gas introducing; γ-WC1–x, δ-WC1±x, W3+xC, α-C (graphite) and β-C (diamond) phases were detected in the films, depending on a mode employed

–

500-800

Nanostructures of C encapsulated (or dispersed on activated C) carbide δ-WC1±x@C (mean size – 15-35 nm) were prepared using autoclave (exposure – 10 h) techniques

(continued)

186

2 Tungsten Carbides

Table 2.21 (continued) H2

600

δ-WC1±x nanowall structures were synthesized on nanocrystalline β-C (diamond) by d.c. plasma chemical vapour deposition techniques using pre-carburized W cathode

H2/CH4 600-850

Composite films δ-WC1±x (with the presence of W2±xC) – β-C (diamond) (thickness – ~1.5 μm) on Si (100) substrates were prepared by microwave plasmaassisted chemical vapour deposition (PACVD) technique

H2/CH4 700-800 mixture

Nanostructured δ-WC1±x (grain size – 5-6 nm) – amorphous C composite thin films (thickness – 0.20-0.45 μm) were fabricated on Si (100) substrates using a hot filament chemical vapour deposition (HFCVD) method; the amount of C in the films depends on gas mixture composition and substrate temperature

CO

3D network-like single-phase δ-WC1±x particles (standing as a joint, size distribution – around tens nanometers) – C (nanotubes, bamboo shaped) composites (specific surface area – 18-33 m2 g–1) were prepared through the heat treatment (exposure – 3 h) of W oxide precursor; the δ-WC1±x particles were cracked due to mechanical stress during the growth of C (nanotubes), but the fragments were still connected to them

700-1000

C2H2/H2 > 750 mixture

The mixtures of nanocrystalline δ-WC1±x powders (mean particle size – 20-30 nm) with C (nanotubes, or nanorods) were synthesized in the presence of metallic catalysts via carburization of W oxide nanoparticles

H2

800

Nanostructured δ-WC1±x continuous polycrystalline films were synthesized on nanocrystalline β-C (diamond) by d.c. plasma chemical vapour deposition techniques using pre-carburized W cathode

CH4/H2 800 mixture

Polyporous α-C (amorphous) – nanocrystalline γ-WC1–x composites (specific surface area (without contribution from micropores) – ~75 m2 g–1) were fabricated via simultaneous reduction and carbonization (exposure – 2 h) followed by treatment in etching aqueous solution (exposure – 12 h)

Ar

Coated by porous C δ-WC1±x powdered electrode compositions were prepared by the chemical heat treatment

800-1050

(continued)

2.6 Chemical Properties and Materials Design

187

Table 2.21 (continued) CH4/H2 800-1100 (10/1) mixture

δ-WC1±x surface-decorated C (single and multi-walled nanotubes) compositions were prepared by in situ reduction-carbonization process through chemical heat treatment (exposure – 4-20 h)

He

δ-WC1±x (single phase, mean grain size – 5-60 nm) – C (cellular matrix, agglomeration of nanoonions of spherical or multilayered tubular shapes) nanocomposites were synthesized by the precursor method

800-1100

Ar/H2 850 mixture

Modified by δ-WC1±x multi-walled C (nanotubes) were prepared by carbothermal carbonization technique

CH4/H2 850 (50/50) mixture

20-40 % δ-WC1±x nanoparticles (mean size – ~10 nm) – C (black) compositions were synthesized via an impregnation method followed by heat treatment (duration – 4 h)

N2/H2 900 mixture flow

δ-WC1±x nanoparticles (mean size – ~40 nm) – C wormhole-like mesoporous composites (specific surface area – up to 315 cm2 g–1) were synthesized by carbothermal reduction (exposure – 3 h) techniques

High 900 purity H2 flow

Heterostructures of δ-WC1±x nanoparticles decorated uniformly onto the disordered and mesoporous walls of C (amorphous nanotubes) were set up via vapour deposition process (exposure – 1 h)

Ar

900

δ-WC1±x – C (nanofibers) were synthesized using the electrospinning process followed a heat treatment of the as-spun nanofibers

CO

900

20-30 % δ-WC1±x nanoparticles – α-C (reduced graphene oxide) nanosheets compositions were prepared by program-controlled reduction-carburization (duration – few hours) technique

900-1400

Containing C (amorphous/nanostructured) δ-WC1±x with higher specific surface area was prepared by combustion synthesis techniques

920-950

δ-WC1±x nanowires covered by the fewlayered α-C (graphene) nanosheets were prepared by a hot wall chemical vapour deposition method (exposure – 0.5-4.0 h); the growth of these layers on the nanowires followed an in situ growth of α-C (graphene) layers along the faceted δ-WC1±x nanowires

–

C2H4 flow

(continued)

188

2 Tungsten Carbides

Table 2.21 (continued) CH4/H2 975 mixture

Pure single-phase δ-WC1±x nanoparticles (size < 30 nm) were synthesized with relatively high coverage on the surface of C (black, specific surface area – ~800 m2 g–1) by a temperature programmed reaction (TPR) method procedure (exposure – 8 h)

H2/Ar 980-1020 mixture flow

Highly uniform 2D in-plane δ-WC1±x – α-C (graphene) heterostructures were prepared by the liquid metal solvent based cosegregation (LMSCS) procedure followed by chemical vapour deposition (CVD)

H2/Ar 1000 mixture

Pure single-phase δ-WC1±x nanoparticles (mean size – ~5 nm) distributed over nanostructured C (nanotubes and/or nanosheets as polymer carbonization products) were synthesized by solid state reduction processing (exposure – 4 h)

High 1000 purity N2

Ultra-thin and coiled C (nanosheets, 10-16 atomic layers, specific surface area – ~550 m2 g–1) with high grade of graphitization were synthesized on δ-WC1±x surface by chemical vapour deposition (CVD) method

Vacuum 1200

δ-WC1±x (mean grain size – 22-34 nm) – C nanocomposites were prepared from hybrid precursor via the annealing process; with the amount of carbide volume fraction in the materials increasing, a higher degree of crystallization of δ-WC1±x was observed

–

1350-1650 Powdered δ-WC1±x (mean particle size – ~0.1 μm, specific surface area – ~5 m2 g–1) – 22 vol.% β-C (diamond) compositions were spark-plasma sintered operating in current-control mode (the combination of the ultra-fast heating rate and short holding time) to fabricate highly dense composites

N2 flow 1400

–

1500

Cham- > 1500 ber of (6 GPa) anvil type

Nanocomposites composed of spherical α-C (graphite) encased δ-WC1±x (mean particle size – ~15 nm) were prepared via solid state reaction initiated by heat treatment (exposure – 3 h) Dense δ-WC1±x – C (onion) composite materials were prepared by electrical current activated sintering δ-WC1±x (matrix, grain size 50-200 nm) – β-C (diamond dispersion, grain size – 3-8 μm) highly dense nanocomposites were prepared by reactive sintering techniques at higher pressure and temperatures

(continued)

2.6 Chemical Properties and Materials Design

189

Table 2.21 (continued) Cham- 1500-2000 Highly dense β-C (diamond) – 10-30 % ber of (8 GPa) δ-WC1±x composites were fabricated by anvil type sintering at higher pressures and temperatures; the grains of both phases were regularly placed and uniform in size over the whole volume of the materials Vacuum, 1550-1800 Powdered δ-WC1±x (mean particle size – 1 Pa 0.6-4.1 μm) – 0.1-0.5 % α-C (graphite) mixtures were spark-plasma sintered (without a holding time) to prepare binderless carbide ceramics (sometimes with the presence of W2±xC) or δ-WC1±x – C materials (when the amount of C additive ≥ 0.3 %) Ar, N2

~1600

The accelerated graphitization of amorphous C by the catalytic action of δ-WC1±x phase was observed in solar furnace conditions

Vacuum, 1700-1900 Preliminarily milled and mixed powdered ≤ 6 Pa δ-WC1±x (mean particle size – ~0.2 μm) – 1 % C (multi-walled nanotubes, outer diameter – ~ 60-100 nm, length – ~ 5-15 μm) compositions were subjected to the sparkplasma sintering procedure to prepare poreless materials; at the highest temperature in the studied interval the destruction of C (nanotubes) and formation of α-C (graphene/graphite) were observed 1750

Spark-plasma sintering of δ-WC1±x-coated α-C (graphite) flakes (with average diameter – 800 μm and thickness – 50 μm) led to the formation of 3D δ-WC1±x (4-60 vol.% skeleton) reinforced α-C highly textured (oriented) composites; due to the contact interaction between the phases, an amorphous layer with a thickness of ~1 nm was formed on the interface, the presence of the Mrozowski cracks (shuttle-like structured with the length in the range of 15-100 nm and width in 5-15 nm, parallel to flake basic planes), which were bridged by α-C crystallites in the matrix, was also observed

Ar flow 1850

Powdered δ-WC1±x (mean particle size – ~1 μm) – 0.5-6.0 % α-C (graphene) platelets (or flakes, mean thickness – 12 nm (30-50 monolayers), mean particle (lateral) size – 4.5 μm) mixtures were hot-pressed to prepare highly dense nanocomposites (with the orientation of α-C platelet basic planes in the direction perpendicular to the

–

(continued)

190

2 Tungsten Carbides

Table 2.21 (continued) load applied during a hot-pressing process and high level of platelet agglomeration) Ar flow 1900-2000 Powdered δ-WC1±x (size distribution – 0.50.7 μm) – 0.2-0.4 % α-C (amorphous, after the pyrolysis of polymer resin) mixtures were subjected to sintering to prepare dense single-phase materials (porosity – 1.5-4.0 %, mean grain size – 2-8 μm) H2/CH4 2000

Pure single-phase nanocrystalline δ-WC1±x (particle size – 4.5-21.5 nm) uniformly distributed on the tips of vertically aligned C (nanotubes) was synthesized by hot filament chemical vapour deposition (HFCVD) techniques

Ar, N2

2100

Employing powdered compositions of selfsintering microspheres of carbonaceous mesophases, 5 mol.% δ-WC1±x doped α-C (graphite) composite materials were prepared through the operations used for production of pure α-C materials

–

2300

Fine weaved preforms with δ-WC1±x filaments (carburized from initial W metallic filaments during the treatment, diameter – 100 μm) in the pierced C fiber bundles (distance between each pierced C fiber bundles – 1.54 mm) were used as the additional reinforcements of C/C composites prepared/treated by the conventional route

–

≤ 2500

No contact interaction with bulk α-C (graphite) materials

–

~2600-2900 Fine grain powdered δ-WC1±x acts as a catalyst (4 at.% W in the composition) decreasing the graphitization (ordering) temperature of carbonaceous materials

–

–

Synthesis of nanoparticles of W carbide on C nanotube supports and related composite materials was realized via sonochemical decomposition of W carbonyls followed by heat treatments under various conditions

–

–

δ-WC1±x – β-C (diamond) composites were designed and fabricated by tape casting followed by high temperature and pressure consolidation; a δ-WC1±x / β-C (diamond) (111) interface was studied for the nanotribological viewpoint

(continued)

2.6 Chemical Properties and Materials Design

191

Table 2.21 (continued) –

–

The adsorption of C atoms on the δ-WC1±x (100) surface with 4 possible high symmetry sites on top of the W-terminated surface was studied using first principles density functional theory (DFT); the overlapping and hybridization between 2p and 2s orbits of C and 5d of surface W atoms play a major role in the bonding

–

δ-WC1±x – W2±xC nanoparticles (mean [125, 212, particle size – 1.9±0.9 nm), comprising a 314, 377, high density of single W atoms, sub-nano- 390, 441, meter and nanometer W-C clusters, com- 523, 526pletely encapsulated in high-defective α-C 529, 531, (graphite) layers to form complex nano541, 554, structures, have been prepared by modified 1442, 1453, arc-discharge process (exposure – 6 h) 1466, 1480, techniques 1500, 1503, 1521, 1593, Nanocomposite coatings (thickness – ~0.3 1657, 1675, μm) with H-free amorphous C matrix, con1687, 1709taining δ-WC1±x, α/ε-W2+xC and γ-WC1–x 1710, 1730, nanocrystalline embedded particles (mean 1740, 1768, size – ~6 nm), were deposited on Ti-based 2277, 2282, alloy substrate by means of reactive mag2296, 2303, netron sputtering technique 2311, 2415] γ-WC1–x – γ-W2±xC – diamond-like β-C (with the presence of graphite-like α-C) coatings were deposited onto cemented carbide substrates by high power impulse magnetron sputtering (HiPIMS) technique

See also section C – W in Table I-2.13 δ-WC1±x – CH4, α/β/ε/γ-W2±xC – 10 kPa α/β-C (graphite / diamond)

Ar flow

–

C2H2/Ar mixture, 1 Pa

–

Ar, 0.4-0.8 Pa

–

Vacuum, 150-200 0.3-600 mPa

γ-WC1–x (major phase, particle size distribution – 5-150 nm) – γ-W2±xC (minor phase, particle size – 2-4 nm) – diamondlike C (with presence of amorphous C) coatings (W/C atomic ratio – 0.24-0.30) were deposited on Si (100) substrates through the gas injection magnetron sputtering (GIMS) technique Thin films (thickness – 0.4-2.5 μm) composed of γ-WC1–x and γ-W2±xC phases (with crystallite sizes of 2-5 nm and 7-9 nm, respectively) embedded in amorphous C matrix were deposited by dual magnetron sputtering (exposure – 4 h) from individual δ-WC1±x and α-C (graphite) targets connected to r.f. and d.c. power sources

(continued)

192

2 Tungsten Carbides

Table 2.21 (continued) –

500-800

Core-shell nanostructured (encapsulated by in situ produced outer C layer) carbide δ-WC1±x/W2±xC@C particles (mean size – 50 nm) were prepared using autoclave (duration – 10 h) technique

H2/CH4 600-850

Composite films δ-WC1±x – W2±xC – β-C (diamond) (thickness – ~1.5 μm) on Si (100) substrates were prepared by microwave plasma-assisted chemical vapour deposition (PACVD)

H2/CH4 700-800 mixture

Nanostructured δ-WC1±x – α/ε-W2+xC – amorphous C composite thin films (thickness – 0.20-0.45 μm) were fabricated on Si (100) substrates using a hot filament chemical vapour deposition (HFCVD) method

Ar

Eutectoid-structured α/ε-W2+xC – 20-37 mol.% δ-WC1±x crystal heterostructures were synthesized during heat treatment (exposure – 3-5 h) on α-C (nanosheets)

750

H2/Ar 800-1200 mixture

Modified by δ-WC1±x/W2±xC compositions (with W2±xC-dominated phase at lower temperatures and δ-WC1±x-dominated phase at higher temperatures) 3D mesoporous C (specific surface area – 380-520 m2 g–1) was prepared by the carbothermal reduction carburization route

H2/CH4 850 (80/20) mixture

~17 % δ-WC1±x + W2±xC nanoparticles (size distribution – 4-8 nm) dispersion on C (activated, specific surface area – 1280 m2 g–1) support was prepared by carbothermal reduction treatment (duration – 1 h)

Ar

850

C covered δ-WC1±x – W2±xC nanoparticles (size distribution – 0.5-1.0 μm) were prepared by solid-state reaction using W carbonyl as a precursor

N2

850

Highly dispersed δ-WC1±x – W2±xC – C composite powders (content W – 10-30 %) with the uniform distribution of carbide crystalline phases in C were prepared by the heat treatment (exposure – 5 h) of functionalized C preliminarily used for the adsorption of W from organic solutions

Ar/H2 900 (95/5) mixture

Ultra-high specific surface area (22002600 m2 g–1) C materials with 5-20 % dispersed on its surface δ-WC1±x – 82-83 mol.% α-W2+xC nanoparticles (size distribution – 5-12 nm) were prepared via carbothermal reduction processing

(continued)

2.6 Chemical Properties and Materials Design

193

Table 2.21 (continued) H2 900 (or N2), flow

δ-WC1±x – W2±xC – C (activated) compositions (contents W (total) – 10-30 %, fraction of δ-WC1±x increased with increasing total W contents) were prepared by carbothermal reduction processing of preliminarily impregnated C materials

Ar flow 950

Monodispersed δ-WC1±x – W2±xC nanoparticles (size – ~5 nm) were in situ formed and anchored on the surface of nanosized C (black) and C (nanotubes) via molten salt synthesis technique

Pure Ar 1100-1450 δ-WC1±x – W2±xC – C composites (with flow contents of amorphous C – up to 50 %) were prepared during heat treatment (exposure – 8-24 h) by combustion-carbothermal reduction method Ar

Heterostructures of δ-WC1±x/γ-W2±xC nanoparticles (size distribution from 10 to 50 nm, mean particle size – ~20 nm) decorated uniformly onto the walls of C (nanotubes) were set up via vapour deposition process followed by special annealing (exposure – 0.5 h)

2200

Ar

–

δ-WC1±x – γ-W2±xC fused materials with the presence of non-combined C, both α-C (graphite) and β-C (diamond-like), as minor phases were fabricated using arc plasma melting procedure

Ar

–

Nearly-monodispersed δ-WC1±x/γ-W2±xC (particle size – 2-5 nm) surface-decorated C (nanotubes) compositions were synthesized by microwave-assisted metal-organic chemical vapour deposition (MOCVD) method in a fluidized bed reactor (exposure – several minutes)

–

Ultra-fine W2±xC nanodots homogeneously decorated on C (nanotubes) 3D-skeleton (network) W2±xC@CNT was synthesized via a spray drying method followed by a carbonization process

See also section C – W in Table I-2.13 α/β/ε/γ-W2±xC – α/β-C (graphite / diamond)

–

Ar, 2 MPa

–

H2/CH4 600-850

[212, 277, 314, 377, 390-391, 451, 526, 541, 1453, 40 % γ-W2±xC – C compositions (specific 1466, 1480, surface area – 55 m2 g–1) were prepared by 1527, 1593, modified self-propagating high-tempera- 1657, 1687, 1695, 1740, ture synthesis (SHS) technique 1753, 1865, Composite films W2±xC – β-C (diamond) 2277, 2282, (thickness – ~1.5 μm) on Si (100) sub2303, 2316] strates were prepared by microwave plasma-assisted chemical vapour deposition

(continued)

194

2 Tungsten Carbides

Table 2.21 (continued) (PACVD) H2

800-850

W2±xC (with various grades of crystallinity) dispersions on the activated C were prepared by the carbothermal reduction carburization route, including supported carbide catalysts containing up to 30 % W2±xC phase and having the value of specific surface area – up to 450 m2 g–1

H2, flow 800-900

10-30 % W2±xC nanoparticles (mean size – ~20 nm, with the presence of small amounts of W metallic phase) – C (activated) compositions (specific surface area – 350470 m2 g–1, total pore volume – 0.24-0.31 cm3 g–1, average pore size – 2.5-2.7 nm) were prepared by carbothermal reduction processing of preliminarily impregnated C materials

Ar/H2 850 (95/5) mixture

Ultra-high surface area (2200-2600 m2 g–1) C materials with 5-20 % dispersed on its surface α-W2+xC nanoparticles (size distribution – 5-12 nm) were prepared via carbothermal reduction processing

H2

850

~17 % W2±xC nanoparticles (size distribution – from several nanometers to tens of nanometers) dispersion on C (activated, specific surface area – 1280 m2 g–1) support was prepared by carbothermal reduction treatment (exposure – 1 h)

High 900 purity H2 flow

Heterostructures of W2±xC nanoparticles (size distribution from 2 to 10 nm, mean particle size – ~5 nm) decorated uniformly onto the disordered and mesoporous walls of C (amorphous nanotubes) were set up via vapour deposition process (exposure – 1 h)

N2 flow 1000

15 % W2±xC nanoparticles (mean size – 4-5 nm) – C (nanofiber) compositions (specific surface area – ~110 m2 g–1, pore volume – 0.30 cm3 g–1) were prepared by heat treatment of preliminarily impregnated nanofibers (exposure – 3 h)

See also section C – W in Table I-2.13 δ-WC1±x – α/β-C (graphite / diamond) – α/ε-Co

–

–

Full-dense three-phase δ-WC1±x – Co – [2, 10, 53, β-C (diamond) nanocomposites were pre- 62, 976, pared via the chemical vapour infiltration 1118, 1387, (CVI) of porous, partially sintered δ-WC1±x 1562, 1594, – Co preforms with α-C (graphite) or 1638, 1666, amorphous C, followed by the high-pres- 1893, 1896sure – high-temperature consolidation 1898, 1900treatment 1903, 1937,

(continued)

2.6 Chemical Properties and Materials Design

195

Table 2.21 (continued) –

–

Polycrystalline β-C (diamond) – δ-WC1±x – 1943, 231711-20 % Co honeycomb structured compo- 2356, 2411, sites were prepared via co-extruding pow- 2416, 2426, der-polymer mixtures (similarly to fibrous 2564, 2709, monolith ceramics fabrication) to form a 2783, 2786, green compact followed by the high-pres- 2986, 3017, 3026, 3119, sure – high-temperature consolidation 4672] treatment

–

–

The nucleation of β-C (diamond) during the chemical vapour deposition (CVD) process on δ-WC1±x – Co alloys substrates initiates at the grain boundaries of them

–

–

C (nanotubes) strengthened δ-WC1±x – Co hard alloys (mean grain size < 100 nm) were prepared by hot-pressing of nanophase powdered compositions with a fraction of in situ synthesized 1D nanostructures of C

–

–

Reinforced cermets of the δ-WC1±x – 10 % Co – 0.5 % C (nanotubes) compositions were fabricated by spark-plasma sintering procedure

–

–

40-47 vol.% β-C (diamond, synthetic, size distribution – 20-28 μm) containing, dense δ-WC1±x – 6 % Co hard alloys were prepared by shock-wave sintering technique

–

–

The surface layers (depth – ~20 μm) of δ-WC1±x – 6 % Co hard alloys were modified by C using ion implantation to dose levels of 1×1016 cm–2 to 7×1018 cm–2

–

–

0.35 % C (multi-walled nanotubes, > 95 % purity, outer diameter – 20-40 nm, length – 5-15 μm) strengthened δ-WC1±x (with various particle size distributions) – 12 % Co hard alloy coatings were sprayed on steel substrates using a high-velocity oxyfuel (HVOF) thermal spraying process

–

–

δ-WC1±x – Co cermet coatings modified by α-C (graphene oxide) were prepared via detonation gun spraying techniques

–

–

δ-WC1±x – 12 % Co cermet coatings, modified by C (nanotubes, 98 % purity, diameter – 10-20 nm, length – 10-20 μm), were high-velocity oxy-fuel (HVOF) sprayed on Ti based alloy substrates

–

–

C (glassy) materials were modified by flake-like structured δ-WC1±x (mean particle size – 0.5 μm) with Co nanoparticles embedded on the δ-WC1±x surface

(continued)

196

2 Tungsten Carbides

Table 2.21 (continued) H2/CO mixture

Air

–

120

CO2/CO 700-850 mixture flow

–

It was experimentally proved that finegrained δ-WC1±x – 4-7 % Co hard alloys as substrates are suited for preparation of the uniform, tough and adherent, chemical vapour deposited (CVD) β-C (diamond) coatings (mean grain size – 3-4 μm) C coated δ-WC1±x particles (atomic ratio C/W = 1.3) were modified with 0.8 % Co through the aqueous solution impregnation / drying procedure to prepare a supported catalyst (specific surface area – 6 m2 g–1) The preparation of adjusted compositions in the δ-WC1±x – C – Co system was realized by the control of CO2/CO ratio in the reactive gas phase flow due to conjugated equilibria of the reactions: CO2 + C ↔ 2CO and η1-W6Co6C + 5C ↔ 6WC + 6Co; at the ratio CO2/CO < 0.75 in the contact with C component the decomposition of η1-phase was occurred

730

The causes of emergence of turbostratic (imperfect) α-C (graphite) crystals, dispersed intragranularly in the Co phase (metallic binder) of the quenched hard alloys, are considered

CH4 flow

800

C-encapsulated W-Co carbides CoWC@C particles (size – 0.1-0.2 μm, irregular in shape, total contents: C – from 2 to 70 %, Co – from 9 to 40 %), consisted of the outer layer of C and η2-W3Co3Cy – δ-WC1±x – Co internal core, were synthesized by reduction carbonization method (duration – 0.5-4.0 h)

–

1000-1150 δ-WC1±x is in equilibrium with metallic W, η1-W6Co6Cy, η2-W3Co3Cy, κ-W3CoC1+x (?), α-(Co,W,C) solid solution and α-C (graphite) phases

Vacuum, 1050 ~ 3-4 Pa

Containing 2-10 vol.% β-C (nanodiamond, 98 % purity, mean particle size – ~10 nm, specific surface area – ~280 m2 g–1), dense δ-WC1±x (mean particle size – 0.6-0.7 μm) – 12 % Co based hard alloys were fabricated by spark-plasma sintering (SPS) procedure (exposure – 5 min)

(continued)

2.6 Chemical Properties and Materials Design

197

Table 2.21 (continued) Vacuum, 1100 5 mPa

Containing 30 vol.% β-C (diamond, size distribution – 40-60 μm), dense δ-WC1±x (initial particle size – 0.8 μm) – 6 % Co based hard alloys were produced under the conditions of thermodynamic instability by pulse-plasma sintering (PPS) technique (exposure – 5 min); in the sintered materials β-C grains were bound with the matrix by a transition layer composed of (Co,C,W) solid solution, no α-C (graphite) precipitates were detected in the materials

Ar flow 1100

δ-WC1±x and Co nanoparticles were synthesized simultaneously with mesoporous C (black) using solution plasma processing (SPP) technique (duration – 0.5 h)

Cham- > 1100 ber of (5 GPa) anvil type

Powdered δ-WC1±x – 6 % Co (size distribution – 63-100 μm) compositions with addition of β-C (diamond, size distribution – 315-400 μm) were subjected to highpressure sintering to prepare dense composites

Ar

1200

Highly dense δ-WC1±x – 10 % Co – 0.4-1.6 % C (multi-walled nanotubes, average inner/outer diameters – 60/100 nm) nanocomposites (mean grain size – 0.4-0.5 μm) were prepared via spark-plasma sintering (exposure – 10 min) technique

Vacuum, 1200 1 Pa

Powdered δ-WC1±x (≥ 99.5 % purity, mean particle size – ~0.2 μm, contents: noncombined C – 0.11%, O – 0.38 %) – 11 % Co (≥ 99.6 % purity, mean particle size – ~60 nm, content O – 0.32 %) – 1.0-2.5 % α-C (graphite) mixtures were spark-plasma sintered (exposure – 5 min) to fabricate dense hard alloys (mean grain size < 2 μm)

Vacuum 1200-1400 Doped with 0.05-0.20 % α-C (graphene, multilayered, thickness – 1-10 nm, diameter – 1-5 μm), powdered δ-WC1±x (99.9 % purity, mean particle size – ~0.4 μm) – 515 % Co (99.9 % purity, mean particle size – ~0.5 μm) mixtures were subjected to two-step sintering (TSS) hot-pressing procedure to produce functionally graded (nanolaminated) hard alloys with the pre-designed Co gradient

(continued)

198

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x is in equilibrium with η1-W6Co6Cy (η-W4–xCo2+xC), α/ε-W2+xC, metallic W, α-C (graphite) and α-(Co,W,C) solid solution phases, while α-(Co,W,C) – with η1-W6Co6Cy, η-W4–xCo2+xC, μ-Co7W6±x and α-C (graphite); the maximum solid solubility of δ-WC1±x in α-(Co,W,C) is ~14.5 mol.%, the solubilities of elemental W and C in α-Co are ~10 % and ~0.1 %, respectively; in practice, the solubilities also depend on environmental conditions: gas media and contacting materials

–

1250

–

~1260-1300 Eutectic ternary (invariant equilibrium) δ-WC1±x – α-Co – α-C (graphite): L (liquid:Co0.84W0.05C0.11) ↔ δ-WC1.0 + α-(Co0.93W0.03C0.04) + α-C (graphite), realizes in the system with the compositions of phases indicated in the reaction

–

1290-1400 Powdered δ-WC1±x (99 % purity, mean particle size – 0.95 μm) – 5-15 % Co (99.9 % purity, mean particle size – 1-2 μm) – 0.1-0.3 % α-C (graphene, thickness – 2-10 nm, diameter – 5 μm, specific surface area – 20-40 m2 g–1) compositions were applied to fabricate pre-designed functionally graded composites (with Co gradient) using the hot isostatic pressing (HIP) techniques

–

1300

δ-WC1±x is in equilibrium with α/ε-W2+xC, η2-W3Co3Cy, κ-W3CoC1+x (?), α-(Co,W,C) solid solution, α-C (graphite) and liquid phases

–

~1370

The invariant equilibrium with the participation of the liquid phase L (liquid:Co0.81W0.12C0.07) + η-W2.9Co3.1C1.0 ↔ δ-WC1.0 + α-(Co0.89W0.09C0.02) realizes in the system with the compositions of phases indicated in the reaction

–

1380-1530 Various compositions of δ-WC1±x – Co – β-C (diamond) materials were fabricated by hot-pressing techniques under the conditions of thermodynamic instability; the formation of α-C (graphite) is occurred at first as clusters on the surface of β-C crystals, then an α-C layers (thickness – up to ~3 μm) form and dissolve in the Co based melts (while cooling after heat treatment, the equilibrium content of C in the Co based phase decreases from 2.1-2.3 % to 0.06 % that causes to the formation of secondary α-C segregates)

(continued)

2.6 Chemical Properties and Materials Design

199

Table 2.21 (continued) –

1400

The contact interaction between sintered δ-WC1±x – 5 % Co hard alloy and β-C (diamond, natural, size – 2.5 mm, free from any visible internal defects) during induction heating hot-pressing procedures depends on the C content in carbide phase of the alloys: higher deviation from the stoichiometry in a carbide – more intensive dissolution of β-C into the interfacial transition zone was observed; for the optimal production of β-C-containing hard alloys only carbides with ratios C/W ≥ 0.97÷0.98 were recommended for the alloys

–

1400-1500 Superhard composites based on δ-WC1±x (mean grain size – 0.5-3.0 μm) – 6-8 % Co hard alloys, containing 25 vol.% uniformly distributed addition of β-C (diamonds, natural, size distribution – from 200 μm to 630 μm), were fabricated by induction heating hot-pressing process

–

1400-1500 δ-WC1±x is in equilibrium with α/ε-W2+xC, η2-W3Co3Cy, κ-W3CoC1+x (metastable, ?), α-C (graphite) and liquid phases

–

1450

Powdered β-C (diamond, natural, size distribution – 630-800 μm) – 70 % δ-WC1±x – 4.5 % Co (size distribution – 5-20 μm, irregular in shape) mixtures were subjected to hot-pressing procedure to prepare β-C containing composite materials with twophase hard alloy matrix

Vacuum 1480

The carburization of δ-WC1±x – 20 % Co hard alloys, containing large amounts of η2-W3Co3Cy phase after sintering, with α-C (graphite) powders leads to the full decomposition of η-phase and formation of δ-WC1±x and α-Co phases, according to the following reaction: W3Co3C + 2C = 3WC + 3Co

High1500 pressure chamber, 8 GPa

α-C (graphite) – chemical vapour infiltrated porous δ-WC1±x – 15 % Co (electrochemically etched) performs were treated to transform α-C into β-C (diamond) and complete the densification of functionally graded (FG) δ-WC1±x – Co – β-C nanocomposite materials

(continued)

200

2 Tungsten Carbides

Table 2.21 (continued) –

~1870

The invariant equilibrium with the participation of the liquid phase L (liquid:Co0.53W0.33C0.14) + γ-W2.23C ↔ δ-WC1.0 + η-W3.9Co2.1C1.0 realizes in the system with the compositions of phases indicated in the reaction

–

≥ 2535

The invariant equilibrium (?) with the participation of the liquid phase L (liquid:W0.53C0.32Co0.15) + γ-WC0.61 ↔ δ-WC1.0 + γ-W2.23C realizes in the system with the compositions of phases indicated in the reaction Some data on the system reported by various authors differ markedly

See also section δ-WC1±x – Co See also section C – Co – W in Table I2.14 δ-WC1±x – Vacuum, 800 α/β/ε/γ-W2±xC – 10 mPa α/β-C (graphite / diamond) – α/ε-Co

Vacuum, 900 10 mPa

In the powdered δ-WC1±x – 7 % γ-W2±xC – [10, 53, 62, 7 % ε-Co – 0.3 % C mixtures (mean par- 2416] ticle size – ~ 1-2 μm, amounts of particles (< 0.5 μm) – 10-15 vol.%, content total C – 5.6 %) subjected to heat treatment (holding time – 10 min) the composition converts to the mixture of δ-WC1±x, γ-W2±xC, α-Co and κ-Co3±xW phases In the powdered mixtures (see above) subjected to heat treatment (holding time – 10 min), the composition converts to the mixture of δ-WC1±x, γ-W2±xC, α-Co, κ-Co3±xW and η1-W6Co6Cy phases

Vacuum, 1000-1200 In the powdered mixtures (see above) subjected to heat treatment (holding time – 10 10 mPa min) the composition converts to the mixture of δ-WC1±x, α-(Co,W,C) solid solution and η1-W6Co6Cy phases Vacuum, 1300-1600 In the powdered mixtures (see above) subjected to heat treatment (holding time – 10 10 mPa min), the composition converts to the mixture of δ-WC1±x, α-(Co,W,C) solid solution and η2-W3Co3Cy phases

See also section C – Co – W in Table I2.14 α/β/ε/γ-W2±xC – Ar/H2 650-750 α/β-C (graphite / (95/5) diamond) – mixture α/ε-Co

Ultra-high surface area C materials with 5- [10, 53, 62, 20 % dispersed on its surface Co-promoted 212, 976, (atomic ratio Co/W = 0.2) α/ε-W2+xC nano- 1892-1893, particles (mean size distribution – ~10 nm) 1895-1898, were prepared via carbothermal reduction 1900-1903] processing

(continued)

2.6 Chemical Properties and Materials Design

201

Table 2.21 (continued) –

1300-1500 α/ε-W2+xC is in equilibrium with δ-WC1±x, η2-W3Co3Cy and metallic W phases; semicarbide and η-phases can be stable only at much lower C contents or at an exceptionnally low Co contents compared to the monocarbide phases

–

~1870

The invariant equilibrium with the participation of the liquid phase L (liquid:Co0.53W0.33C0.14) + α/ε-W2.23C ↔ δ-WC1.0 + η2-W3.9Co2.1C1.0 realizes in the system with the compositions of phases indicated in the reaction

–

~1965

The invariant equilibrium with the participation of the liquid phase L (liquid:W0.45Co0.44C0.11) + α/ε-W2.23C + (W~1.0) ↔ η2-W~4.0Co~2.0C1.0 realizes in the system with the compositions of phases indicated in the reaction

–

≥ 2535

The invariant equilibrium (?) with the participation of the liquid phase L (liquid:W0.53C0.32Co0.15) + γ-WC0.61 ↔ δ-WC1.0 + γ-W2.23C realizes in the system with the compositions of phases indicated in the reaction Some data on the system reported by various authors differ markedly

See also section α/β/ε/γ-W2±xC – α/ε-Co See also section C – Co – W in Table I2.14 δ-WC1±x – α/β/ε/γ-W2±xC – C – Co – Cr

–

–

δ-WC1±x – γ-W2±xC – Co – Cr – C compo- [2234] site coatings were fabricated on steel substrates using laser cladding techniques

δ-WC1±x – C – Co – Cr – Cu – Fe – Mn – Ni – Zn

See section δ-WC1±x – Co – Cu – (Fe – C – Cr – Mn) – Ni – Zn

δ-WC1±x – C – Co – Cr – Cu – Fe – Mo – V – W

See section δ-WC1±x – Cu – (Fe – C – Co – Cr – Mo – V – W)

δ-WC1±x – C – Vacuum 1470 Co – Cr – Cu – Fe – N – Nb – Ni – Ta – Ti

Powdered mixtures with the compositions: [2429-2430] δ-WC1±x – 1.46 % Fe – 1.54 % Co – 1.54 % Ni – 1.36 % Cr – 1.67 % Cu – 1.80 % Ti – 2.72 % Ta – 0.44 % Nb – 0.17 % N – 0.15-35 % C – were subjected to liquidphase sintering procedure to fabricate functionally graded multicomponent hard alloys with high-entropy metallic binders

(continued)

202

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – C – Co – Cr – Cu – Fe – Ni – Si – Zn

See section δ-WC1±x – Co – Cu – (Fe – C – Cr – Si) – Ni – Zn

δ-WC1±x – C – Co – Cr – Fe

See section δ-WC1±x – Co – (Fe – C – Cr)

δ-WC1±x – α/β/ε/γ-W2±xC – C – Co – Cr – Fe – Mn

See section δ-WC1±x – α/β/ε/γ-W2±xC – Co – (Fe – C – Cr – Mn)

δ-WC1±x – C – Co – Cr – Fe – Mn – Mo – Nb – Ni – Si

See section δ-WC1±x – Co – (Fe – C – Cr – Mn – Mo – Ni – Si) – (Fe – C – Mn – Nb – Ni)

δ-WC1±x – C – Co – Cr – Fe – Mn – Ni

See section δ-WC1±x – Co – (Fe – C – Cr – Mn) – Ni

δ-WC1±x – C – Co – Cr – Fe – Mn – Ni – Ti

See section δ-WC1±x – Co – (Fe – C – Cr – Mn) – Ni – Ti

δ-WC1±x – C – Co – Cr – Fe – Mn – Si

See section δ-WC1±x – Co – (Fe – C – Cr – Mn – Si)

δ-WC1±x – C – Co – Cr – Fe – Mo – Ni – V – W

See section δ-WC1±x – Co – (Fe – C – Cr – Mo – Ni – V – W)

δ-WC1±x – C – Co – Cr – Fe – Mo – Si – V

–

–

General considerations of the system con- [3990] taining various carbide phases

See also section δ-WC1±x – Co – (Fe – C – Cr – Mo – Si – V) δ-WC1±x – C – Co – Cr – Fe – Mo – V

See sections δ-WC1±x – Co – (Fe – C – Cr – Mo – V) and δ-WC1±x – (Fe – C – Co – Cr – Mo – V)

δ-WC1±x – C – Co – Cr – Fe – Mo – V – W

See section δ-WC1±x – Co – (Fe – C – Cr – Mo – V – W)

δ-WC1±x – C – Co – Cr – Mn – Mo – Ni – Si

See section δ-WC1±x – Co – (Co – C – Cr – Mn – Mo – Ni – Si)

δ-WC1±x – C – Co – Cu – Fe

See section δ-WC1±x – Co – Cu – (Fe – C)

δ-WC1±x – C – Co – Cu – Fe – Mn

See section δ-WC1±x – Co – Cu – (Fe – C – Mn)

(continued)

2.6 Chemical Properties and Materials Design

203

Table 2.21 (continued) Vacuum, 850 δ-WC1±x – α/β-C (graphite / 1-103 diamond) – Co – mPa Cu – Fe – Ni

The powdered mixtures of β-C (diamond, [2348] synthetic, size distribution – 300-500 μm) with the addition of Cu – 28-29 % Ni – 1617 % Fe – 16-17 % Co – 1.7-6.4 % nanosized δ-WC1±x (initial mean particle size – 70 nm, specific surface area – 6.5 m2 g–1) compositions were hot-pressed (exposure – 3 min) and annealed (exposure – 5-30 min) to prepare special materials; the spontaneous formation of δ-WC1±x layer on a β-C surface was revealed during the treatment

δ-WC1±x – Vacuum, 850 α/β-C (graphite / 0.06 mPa diamond) – Co – Cu – Fe – Sn

The addition of nanosized δ-WC1±x (size [2336] distribution – 20-100 nm, specific surface area – 6-9 m2 g–1) to the powdered mixtures of β-C (diamond, synthetic, size distribution – 40-50 μm) with metallic binder Fe – 21 % Cu – 12 % Co – 3 % Sn was found to suppress the β-C → α-C transformation (graphitization) by 25-30 % during the sintering (exposure – 30 min) process of the mixtures

δ-WC1±x – C – Co – Fe

See section δ-WC1±x – Co – (Fe – C)

δ-WC1±x – C – Co – Fe – Mn – Nb – Ni

See section δ-WC1±x – Co – (Fe – C – Mn – Nb – Ni)

δ-WC1±x – C – Co – Fe – Mn – Si

See section δ-WC1±x – Co – (Fe – C – Mn – Si)

δ-WC1±x – C – Co – Fe – Mn – Nb – Ni – Si – Y

See section δ-WC1±x – Co – (Fe – C – Mn – Si) – (Ni – C – Fe – Nb – Y)

δ-WC1±x – C – Co – Fe – Mo – Ni

See section δ-WC1±x – (Fe – C – Co – Mo – Ni)

δ-WC1±x – C – Co – Fe – N

Pure Ar 700-900

Surface N-doped α-C (graphite) – uniform- [2358] ly encapsulated θ-Fe3C and Co3C metastable carbides, closely wrapped around a δ-WC1±x platelet, Fe/Co/WC@N-C hybrid nanoparticles were one-pot-synthesized via tailored composition pyrolysis method

δ-WC1±x – C – Co – N

Ar

Hybrid materials CoWC@N-CNFs, com- [397, 1712, posed of stacked η1-W6Co6Cy nanocrystals 1764, 1769] anchored on N-doped C (nanofibers), were designed and produced via chemical vapour deposition (CVD) processing

700-1000

(continued)

204

2 Tungsten Carbides

Table 2.21 (continued) Ar

800-1100

The multi-component nanocomposites consisting of dispersion of δ-WC1±x nanoparticles on Co-embedded, C (bamboo-like nanotubes) with high-level N doping (WC/Co@N-CNTs) were designed (DFTcalculated) and fabricated by the pyrolysis of precursors (duration – 2 h)

–

–

Nanocomposites consisting of δ-WC1±x – Co nanoparticles encapsulated in an Ndoped porous C framework were synthesized via a multi-component co-assembly pathway

δ-WC1±x – C – Co – Pd

–

–

δ-WC1±x-doped C supports for Pd – Co ca- [1562] talysts were designed and fabricated; the synergistic effect of joint usage of δ-WC1±x – C supports and Pd – Co alloy nanoparticles for electrocatalysis was confirmed

δ-WC1±x – C – Cr

–

1300-1400 δ-WC1±x phase is in equilibrium with α/ε-(W,Cr)2+xC, (Cr,W)3C2–x and α-C (graphite) phases

–

~1505-1510 The invariant equilibrium δ-(W,Cr)C1±x + (Cr,W)3C2–x ↔ α/ε-(W,Cr)2+xC + α-C (graphite) realizes in the system

–

~1605-1645 The invariant equilibrium γ-(W,Cr)C1–x ↔ α/ε-(W,Cr)2+xC + (Cr,W)3C2–x + α-C (graphite) realizes in the system

–

1800

–

~1820-1860 The invariant equilibrium with the participation of the liquid phase L (liquid:Cr0.54C0.375W0.085) + γ-(W0.32Cr0.68)C0.59 + α-C (graphite) ↔ (Cr0.83W0.17)3.00C2.00 realizes in the system with the compositions of phases indicated in the reaction

–

~1830-1865 The invariant equilibrium γ-(W,Cr)C1–x + δ-(W,Cr)C1±x ↔ α/ε-(W,Cr)2+xC + α-C (graphite) realizes in the system

[47, 53, 193, 794, 23872393, 33933404, 3724, 4044]

δ-WC1±x is in equilibrium with α/ε-(W,Cr)2+xC and α-C (graphite) phases; the maximum solid solubility of Cr in the δ-WC1±x phase is corresponding approximately to the δ-(W0.97Cr0.03)C1.00 composition

(continued)

2.6 Chemical Properties and Materials Design

205

Table 2.21 (continued) –

~2650

The invariant equilibrium with the participation of the liquid phase L (liquid:W0.515C0.405Cr0.08) + δ-(W0.95Cr0.05)C1.00 ↔ γ-(W0.90Cr0.10)C0.65 + α-C (graphite) realizes in the system with the compositions of phases indicated in the reaction Some data on the system reported by various authors differ markedly

See also section δ-WC1±x – Cr See also section C – Cr – W in Table I2.14 α/β/ε/γ-W2±xC – C – Cr

–

~1505-1510 The invariant equilibrium α/ε-(W,Cr)2+xC + α-C (graphite) ↔ δ-(W,Cr)C1±x + (Cr,W)3C2–x realizes in the system

–

~1605-1645 The invariant equilibrium α/ε-(W,Cr)2+xC + (Cr,W)3C2–x + α-C (graphite) ↔ γ-(W,Cr)C1–x realizes in the system

–

~1625-1635 The invariant equilibrium with the participation of the liquid phase L (liquid:Cr0.70C0.18W0.12) + α/ε-(W0.41Cr0.59)2.28C ↔ (W0.81Cr0.18C0.01) + (Cr0.87W0.13)23C~6.0 realizes in the system with the compositions of phases indicated in the reaction

–

~1635-1650 The invariant equilibrium with the participation of the liquid phase L (liquid:Cr0.695C0.195W0.11) + α/ε-(W0.27Cr0.73)2.28C + (Cr0.93W0.07)7C2.93 ↔ (Cr0.87W0.13)23C~6.0 realizes in the system with the compositions of phases indicated in the reaction

–

~1785-1835 The invariant equilibrium with the participation of the liquid phase L (liquid:Cr0.54C0.345W0.115) + γ-(W0.31Cr0.69)C0.57 ↔ α/ε-(W0.22Cr0.78)2.03C + (Cr0.85W0.15)3C~2.0 realizes in the system with the compositions of phases indicated in the reaction

–

~1830-1865 The invariant equilibrium α/ε-(W,Cr)2+xC + α-C (graphite) ↔ γ-(W,Cr)C1–x + δ-(W,Cr)C1±x realizes in the system

[53, 193, 2387-2393, 3724]

See also section α/β/ε/γ-W2±xC – Cr See also section C – Cr – W in Table I2.14

(continued)

206

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – C – Cr – Cu – Fe – Ni

See section δ-WC1±x – Cu – (Fe – C – Cr – Ni)

δ-WC1±x – C – Cr – Fe

See section δ-WC1±x – Cr – (Fe – C)

δ-WC1±x – C – Cr – Fe – La – Ni – Si

–

Powdered δ-WC1±x (size distribution – 45- [3845] 100 μm) – 40 % self-fluxing Ni-based alloy (size distribution – 80-100 μm; contents: C – 0.3 %, Cr – 4.0 %, Fe – 6.6 %, Si – 3.2 %) – 0.4 % La mixtures were subjected to laser cladding procedure to fabricate poreless hard coatings on steel substrates; the prepared coatings were composed of γ-(Ni,Fe,Cr,W) metallic solid solutions, δ-WC1±x, γ-W2±xC, Cr7C3±x, Cr23C6±x and metastable θ-Fe3C carbide and β-Ni4+xW intermetallide phases

δ-WC1±x – C – Cr – Fe – Mn – Mo – Ni – Si

See sections δ-WC1±x – (Fe – C – Cr – Mn – Mo – Ni – Si) and δ-WC1±x – (Fe – C – Cr – Mn – Mo – Ni – Si) – Ni – Si

δ-WC1±x – C – Cr – Fe – Mn – Nb

See sections δ-WC1±x – C – (Fe – C – Cr – Mn – Nb) and δ-WC1±x – (Fe – C – Cr – Mn – Nb)

δ-WC1±x – C – Cr – Fe – Mn – Ni

See section δ-WC1±x – (Fe – C – Cr – Mn – Ni)

δ-WC1±x – C – Cr – Fe – Mn – Ni – Si

See section δ-WC1±x – (Fe – C – Cr – Mn – Ni – Si)

δ-WC1±x – α/β/ε/γ-W2±xC – C – Cr – Fe – Mn – Ni – Si

See section δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mn – Ni – Si)

δ-WC1±x – α/β/ε/γ-W2±xC – C – Cr – Fe – Mn – Ni – Si – Ti

See section δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mn – Ni – Si – Ti)

δ-WC1±x – C – Cr – Fe – Mn – W

See section δ-WC1±x – (Fe – C – Cr – Mn – W)

δ-WC1±x – C – Cr – Fe – Mo – Nb – Ti – V

See section δ-WC1±x – (Fe – C – Cr – Mo – Nb – Ti – V)

δ-WC1±x – C – Cr – Fe – Mo – Ni

See section δ-WC1±x – (Fe – C – Cr – Mo – Ni)

δ-WC1±x – C – Cr – Fe – Mo – Si – V

See section δ-WC1±x – (Fe – C – Cr – Mo – Si – V)

(continued)

2.6 Chemical Properties and Materials Design

207

Table 2.21 (continued) δ-WC1±x – α/β/ε/γ-W2±xC – C – Cr – Fe – Mo –V δ-WC1±x – C – Cr – Fe – Ni

See section δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mo – V)

Vacuum, 1400 20 Pa

The sintering procedure (exposure – 1 h) [1982] of δ-WC0.99 (< 10 μm) – 3 mol.% Cr (< 38 μm) – 11 mol.% Fe (< 60 μm) – 12 mol.% Ni (3-7 μm) – 1-1.5 mol.% C (carbon black) powdered compositions (particle sizes are given in brackets) leads to the formation of δ-WC1±x – γ-(Fe,Ni,Cr,W,C) two-phase cermets

See also sections δ-WC1±x – (Fe – C – Cr – Ni) and δ-WC1±x – (Fe – C – Cr) – Ni δ-WC1±x – C – Cr – Fe – Ni – Si

–

–

Powdered δ-WC1±x (size distribution – 45- [3845] 100 μm) – 40-80 % self-fluxing Ni-based alloy (size distribution – 80-100 μm; contents: C – 0.3 %, Cr – 4.0 %, Fe – 6.6 %, Si – 3.2 %) mixtures were subjected to laser cladding procedure to fabricate hard coatings on steel substrates; the prepared coatings were composed of γ-(Ni,Fe,Cr,W) metallic solid solutions, δ-WC1±x, γ-W2±xC, Cr7C3±x, Cr23C6±x and metastable θ-Fe3C carbide and β-Ni4+xW intermetallide phases

δ-WC1±x – α/β/ε/γ-W2±xC – C – Cr – Fe – Ni – Si

–

–

Powdered δ-WC1±x – γ-W2±xC lamellar eu- [3576] tectics (size distribution – 0-40 μm) – 50 % Fe-based alloy (contents: C – 0.2-0.4 %, Cr – 2-5 %, Ni – 4-8 %, Si – 1-3 %) mixtures were employed to fabricate coatings on steel substrates by laser induction hybrid rapid cladding (LIHRC) techniques; δ-WC1±x grains were dissolved almost completely and coarse eutectic complex carbides were precipitated during the procedure, the major phase constituents of the coatings were metallic α-(Fe,Ni,Cr,W,C) solid solutions and metastable χ-Fe5C2, accompanied by such minor phases as γ-(Fe,Ni,Cr,W,C) retained austenite solid solutions, η2-(W,Fe,Cr,Ni)6Cy and γ-W2.38C carbides

δ-WC1±x – C – Cr – Fe – V – W

See section δ-WC1±x – (Fe – C – Cr – V – W)

δ-WC1±x – C – Cr – Fe – W

See section δ-WC1±x – (Fe – C – Cr) – W

(continued)

208

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Vacuum, 850 α/β-C (graphite / 1 mPa diamond) – Cu

The interfacial interaction of β-C (dia[2360] mond, synthetic, size distribution – 35-40 μm) with Cu – 5 % δ-WC1±x (mean particle size – 0.1-0.12 μm) composite binder during the sintering process (exposure – 0.5 h) resulted in the formation of δ-WC1±x layers on β-C grains

δ-WC1±x – C – Cu – Fe – Mo – Ni

–

δ-WC1±x – α/β-C (graphite / diamond) – Cu – Mn – Ni – Pb – Sn – Zn

–

δ-WC1±x – C – Cu – Pt

–

δ-WC1±x – α/β-C – α/γ/δ-Fe

–

500

δ-WC1±x is in equilibrium with η2-W3Fe3Cy and κ-W3FeCy ternary compounds, W-based and α-(Fe,W,C) metallic solid solutions and α-C (graphite) phases

–

~740

The invariant equilibrium δ-WC1±x + α-(Fe0.999C0.001W0.000) + α-C (graphite) ↔ γ-(Fe0.969C0.031W0.000) realizes in the system with the compositions of phases indicated in the reaction

–

~850

The invariant equilibrium δ-WC1±x + α-(Fe0.993C0.001W0.006) ↔ γ-(Fe0.986C0.009W0.005) + η2-(W2.70Fe3.30)C1.00 realizes in the system with the compositions of phases indicated in the reaction

–

10 % δ-WC1±x particle reinforced [1990] α-(Fe,Cu,Ni,Mo,C) – highly dense sintered metal matrix composites, mainly consisted of spheroidal pearlite (with some residual austenite and cementite), were prepared from the powdered mixture of Fe, Cu, Ni, Mo, C and δ-WC1±x by ball-milling (mechanical alloying, exposure – 40 h) and subsequent spark-plasma sintering 20 vol.% β-C (diamond, synthetic, size dis- [3732] tribution – 270-325 μm) and 0-3 % nanocrystalline δ-WC1±x (mean particle size – 80 nm) added to powdered 55 % δ-WC1±x (99.9 %, 10 μm) – 35 % bronze (99.9 %, 50 μm, contents: Sn – 6 %, Zn – 6 %, Pb – 3 %, Cu – remainder) – 5 % Ni (99.9 %, 75 μm) – 5 % Mn (99.9 %, 60 μm) mixtures (purities and mean particle sizes are given in brackets, preliminarily ball-milled) were subjected to hot-pressing (exposure – 5 min) procedure to fabricate dense composite materials (porosity – 3.9-6.9 %)

980

–

Nanostructured δ-WC1±x (size distribution [1620] – 10-20 nm) highly dispersed both on the edge and between the layers of α-C (reduced graphene oxide) were used as a support to load different contents (up to 0.4 %) of Pt via sacrificial Cu adlayers [10, 53, 1887-1894, 1937, 1966, 2709, 3005, 3119, 3549, 3602, 3724, 3986]

(continued)

2.6 Chemical Properties and Materials Design

209

Table 2.21 (continued) δ-WC1±x is in equilibrium with η2-W3Fe3Cy and κ-W3FeCy ternary compounds, W-based, γ-(Fe,C,W) and α-(Fe,C,W) metallic solid solutions and α-C (graphite) phases; the presence of metastable θ-Fe3C phase in the alloys containing δ-WC1±x and γ-(Fe,C,W) solid solutions was observed experimentally

–

1000

–

~1050-1120 Eutectic ternary (metastable) η2-W3Fe3Cy – γ-Fe – θ-Fe3C

–

~1085-1125 Eutectic ternary (metastable) η2-W3Fe3Cy – γ-Fe – α-C (graphite)

–

~1085-1140 Eutectic ternary (metastable) δ-WC1±x – γ-Fe – θ-Fe3C

–

~1140-1145 Eutectic ternary δ-WC1±x – γ-Fe – α-C (graphite): L (liquid:Fe0.81C0.18W0.01) ↔ δ-WC1±x + γ-(Fe0.91C0.08W0.01) + α-C (graphite)

–

1250

–

1250-1300 The effects of sintering temperature and C variation on the densification and interfacial bond strength of bilayer δ-WC1±x – Fe cermet – steel processed by powder metallurgy methods were studied

–

1255

–

~1270-1290 The invariant equilibrium with the participation of the liquid phase L (liquid:Fe0.81C0.12W0.07) + η2-(W2.81Fe3.19)C1.00 ↔ γ-(Fe0.93C0.04W0.03) + δ-WC1±x realizes in the system with the compositions of phases indicated in the reaction

–

1320-1500 δ-WC1±x is in equilibrium with α/ε-W2+xC semicarbide, η2-W3Fe3Cy ternary compound, α-C (graphite) and Fe-based liquid phases

δ-WC1±x is in equilibrium with α/ε-W2+xC semicarbide, η2-W3Fe3Cy and κ-W3FeCy ternary compounds, W-based and γ-(Fe,W,C) metallic solid solutions, α-C (graphite), θ-Fe3C (metastable) and liquid phases

The invariant equilibrium δ-WC1±x + (W0.994Fe0.006C0.000) ↔ α/ε-(W0.999Fe0.001)2.12C + κ-(W3.00Fe1.00)C1.00 realizes in the system with the compositions of phases indicated in the reaction

(continued)

210

2 Tungsten Carbides

Table 2.21 (continued) –

~1370

The invariant equilibrium δ-WC1±x + κ-(W3.00Fe1.00)C1.00 ↔ α/ε-(W0.999Fe0.001)2.11C + η2-(W3.21Fe2.79)C1.00 realizes in the system with the compositions of phases indicated in the reaction

–

~1530

The invariant equilibrium with the participation of the liquid phase L (liquid:Fe0.64W0.22C0.14) + α/ε-(W0.999Fe0.001)2.10C ↔ δ-WC1±x + η2-(W3.10Fe2.90)C1.00 realizes in the system with the compositions of phases indicated in the reaction

–

~1670

The invariant equilibrium with the participation of the liquid phase L (liquid:Fe0.57W0.27C0.16) + (W~1.0) + δ-WC1±x ↔ η2-W3Fe3Cy realizes in the system with the composition of liquid phase indicated in the reaction

–

2525

The invariant equilibrium with the participation of the liquid phase L (liquid:W0.55C0.34Fe0.11) + δ-WC1±x + γ-(W>0.999Fe0.999Fe0.999Fe0.999Fe 95 % purity) reinforced δ-WC1±x – 40 vol.% Al2O3 – highly dense composites were prepared by hot-pressing process (holding time – 1.5 h); the addition of C (nanotubes) suppressed the carbide-oxide interaction and decarburization process (formation of W2±xC) in the composites

Vacuum, 1100 δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 10 mPa – C – Cr – Ni

Modified by the addition of 1-4 % α-C [3453] (graphene) oxide, powdered δ-WC1±x (75 μm) – α-Al2O3 (30 nm) – Cr (45 μm) – Ni (60 μm) mixtures (initial mean particle sizes are given in brackets, preliminarily high-energy ball-milled) were subjected to hot-pressing (exposure – 0.5 h) procedure to fabricate the dense materials composed of Ni-based metallic solid solution, δ-WC1±x, α-Al2O3, Cr2O3 and Cr carbides phases

δ-WC1±x – Al2O3 – Cr3C2–x – TiC1–x – VC1–x – C

See section TiC1–x – Al2O3 – Cr3C2–x – VC1–x – δ-WC1±x – C in Table III-2.22

Vacuum, 1540-1640 Powdered δ-WC1±x (size distribution δ-WC1±x – [4137] α/γ/δ/κ/θ/χ-Al2O3 ~0.13 Pa < 74 μm) – 30 vol.% Al2O3 (amorphous, – TiO2–x – α/β-C mean particle size – 75 μm) mixtures with 2-6 % TiO2–x (nanosized) and 0.5 % C (multi-walled nanotubes, > 95 % purity, mean diameter – 10-20 nm, length – ~30 μm) additives (preliminarily ball-milled in two steps) were subjected to hotpressed procedure (exposure – 1.5 h) to prepare dense composite materials (porosity – 0.5-2.0 %, δ-WC1±x mean grain size – 1.8-2.6 μm); during the heat treatment of materials the transformation of amorphous Al2O3 to γ-Al2O3, then to δ-Al2O3 and finally to α-Al2O3 modification was observed, at the higher contents of the TiO2–x the appearance of Al2TiO5–x phase was marked δ-WC1±x – B4±xC –C

– Ar

2100-2200 The formation of β-W2B5–x and β-WB1±x phases in the mixtures of components 2150

1.5-6.0 % C (pyrolytic, ~50 % yielded from a phenolic resin binder) doped B4±xC (> 90 % purity, mean particle size < 1 μm) – 10 vol.% δ-WC1±x (> 99.5 % purity, mean particle size < 1 μm) powdered mixtures (total C content – 5.6-10.1 %) were sintered (exposure – 2 h) to prepare dense

[3, 151, 1926, 24002401]

(continued)

244

2 Tungsten Carbides

Table 2.21 (continued) ceramics; the complete conversion of δ-WC1±x into α/β-W2B5–x phase was observed in the sintered materials

See also section C – B – W in Table I-2.14 δ-WC1±x – B4±xC – C – Fe– Mn – Mo – Ni – Zr

See section δ-WC1±x – B4±xC – (Fe – C – Mn) – Mo – Ni – Zr

δ-WC1±x– B4±xC – (C6H4COC6H4O)n –C

–

δ-WC1±x – α/β/ε/γ-W2±xC – B4±xC – Cr7C3±x – Cr23C6±x – C – Cr – Fe – Ni

–

δ-WC1±x – α/β-BN – C – Cu – Ni

–

δ-WC1±x – (C2F4)n – C

–

–

88 % δ-WC1±x – 5 % C (activated) – polytetrafluoroethylene (C2F4)n (PTFE) electrodes were designed and fabricated

δ-WC1±x – [C6H3(CN)2OC6 H4C(CH3)2C6H4 OC6H3(CN)2]n – C

–

–

Phthalonitrile [C6H3(CN)2OC6H4C(CH3)2 [2403, 4183] C6H4OC6H3(CN)2]n (PN) resin based polymer matrix composites (PMC), containing 10-20 % δ-WC1±x nanoparticles (mean size – 50 nm) and ~50 % C (fiber, silane surface modified, diameter – 10 μm, density –

350-400

–

Polyaryletherketone (C6H4COC6H4O)n [1075, 2402] (PAEK) – 0.375-1.5 % δ-WC1±x powder (size distribution – 0.1-0.2 μm) – 0.75-1.0 % B4±xC nanopowder (size distribution – 30-60 nm) – 0.375-1.5 % C (functionalized (modified with –COOH group) multiwalled nanotubes, > 97 % purity, inner diameter – 16 nm, outer diameter – 20 nm, length – 20 μm) nanocomposites were fabricated via melt-mixing process by twin screw extrusion techniques Coatings with fine and uniform micro[2414] structures composed of δ-WC1±x (up to 30 %), γ-W2±xC, Cr7C3±x, Cr23C6±x, B4±xC and γ-(Ni,Cr,Fe) solid solution (metallic matrix) phases and modified by 0.1-0.5 % α-C (graphene) were fabricated by laser cladding on steel substrates Powdered Cu (size distribution ≤ 60 μm) – [3518] 20 % Ni (micrometre-sized) – 0.1 % C (multi-walled nanotubes, diameter – 3-5 nm, length – 70-90 nm) – 0.1 % α-BN (hexagonal, 98 % purity, mean particle size – 10 μm) – 0.7 % δ-WC1±x (95 % purity, size distribution – 50-80 nm) mixtures (preliminarily high-energy ball-milled with the formation of α-BN nanoplatelets (diameter – 70-80 nm, height – 15-20 nm)) were subjected to hot-pressing (exposure – 0.5 h) procedure to prepare dense materials (porosity – 7.5 %, mean grain size – 1.6±0.4 μm, ~50 % δ-WC1±x were located in the intergranular layers, while C nanotubes were distributed homogeneously)

850

[1242]

(continued)

2.6 Chemical Properties and Materials Design

245

Table 2.21 (continued) 1.76 g cm–3), were designed and fabricated δ-WC1±x – (C6H4COC6H4O)n –C

–

δ-WC1±x – Co3O4 Ar –C–N

δ-WC1±x – Co3O4 – α/β/γ/ε-Fe2O3 – α/β-NiO1±x – C

350-400

Polyaryletherketone (C6H4COC6H4O)n [1075, 2402] (PAEK) – 0.375-1.5 % δ-WC1±x powder (size distribution – 0.1-0.2 μm) – 0.375-1.5 % C (functionalized (modified with –COOH group) multi-walled nanotubes, > 97 % purity, inner diameter – 16 nm, outer diameter – 20 nm, length – 20 μm) nanocomposites were fabricated via meltmixing process by twin screw extrusion techniques

800

δ-WC1±x – Co3O4 – α-C (reduced graphene [1720] oxide) – N-doped C nanocomposites were prepared by the heat treatment of precursors

Vacuum, 1140-1400 The chemical interaction in the powdered [4189] or Ar δ-WC1±x (2-5 μm) – 3-13 % Co3O4 (~40 nm, 23.3 m2 g–1) – 10-23 % α-Fe2O3 (~0.1 μm, 11.8 m2 g–1) – 7-9 % β-NiO1±x (~0.13 μm, 6.1 m2 g–1) mixtures (mean particle sizes and specific surface areas of the components are given in brackets) with the addition of C (soot, highly dispersed) subjected to heat treatment (exposure – 1 h) led to the reduction of metal oxides (formation of fcc γ-Fe based or bcc α-Fe based metallic solid solutions) and partial or complete retaining of δ-WC1±x; in the case of a lack of C, the formation of complex carbides such as η1-(W,Fe,Co,Ni)12C and/or η1-(W,Fe,Co,Ni)6C was observed

δ-WC1±x – CrB2±x Cham– α/β-C (graphite ber of / diamond) – Co anvil type

> 1100 (5 GPa)

2 % CrB2±x doped powdered δ-WC1±x – 6 % Co (size distribution – 63-100 μm) compositions with addition of β-C (diamond, size distribution – 315-400 μm) were subjected to high-pressure sintering to prepare dense composites

[2331, 2338]

δ-WC1±x – CrB2±x – α/β-W2B5–x – α/β-C (graphite / diamond) – Co

–

–

Doped by CrB2±x and β-W2B5–x composi- [2337-2338] tions of δ-WC1±x – Co – β-C (diamond) materials were fabricated by hot-pressing technique; the addition of these borides suppresses the formation of non-diamond C layers at the β-C interfaces

δ-WC1±x – Cr3C2–x – C – Co – Cr – Mn – Si – W

–

–

Powdered δ-WC1±x – 10-20 % Cr3C2–x – [3294] 60-70 % Co-based alloy (C – 3.0-3.5 %, Cr – 28-30 %, W – 5-6 %, Mn – 0.5-0.7 %, Si – 0.2-0.5 %) mixtures were employed as feedstock powders to deposit hard coatings on steel substrates using flame spraying process

(continued)

246

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cr3C2–x – C – Cr – Fe – Mn – Mo – Ni – Si

See section δ-WC1±x – Cr3C2–x – (Fe – C – Cr – Mn – Ni – Si) – Mo

δ-WC1±x – Cr3C2–x – C – Cr – Fe – Ni

See section δ-WC1±x – Cr3C2–x – (Fe – C – Cr – Ni)

δ-WC1±x – Cr3C2–x – C – Fe – Mn

See section δ-WC1±x – Cr3C2–x – (Fe – C – Mn)

δ-WC1±x – Vacuum 1300-1400 Powdered δ-WC1±x – 1.5-42 % Cr3C2–x – [3908] Cr3C2–x – C – Ni 20 % Ni – 2-6 % α-C (graphite) mixtures were subjected to liquid-phase sintering to prepare dense two- and three-phase hard alloys δ-WC1±x – Cr3C2–x – TiC1–x – δ-TiN1±x – C – Co – Mo – Ni

See section TiC1–x – δ-TiN1±x – Cr3C2–x – δ-WC1±x – C – Co – Mo – Ni in Table III2.22

δ-WC1±x – Cr3C2–x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/β-C – Ni

–

δ-WC1±x – Cr7C3±x – C – Co – Cr – Fe – Mn

Ar

1400-1500 Powdered δ-WC1±x (high purity, mean par- [3890, 3945] ticle size – ~0.9 μm) – 8 % Ni – 6 % β/γ-ZrO2–x (mean particle size – ~30 nm, 3 mol.% α-Y2O3–x partially stabilized) – 0.4 % Cr3C2–x (mean particle size – 2-3 μm) – 0.4-0.7 % α-C (graphite, mean particle size – ~6 μm) mixtures (preliminarily ball-milled) were subjected to vacuum sintering and hot isostatic pressing (HIP) procedures (dwell time – from 0.5 h to 1 h) to prepare highly dense, fine-grained hard alloys with Ni metallic binder 1150

δ-WC1±x – Cr7C3±x – TiC1–x – C – Co δ-WC1±x – CrN1±x – α/β-C (graphite / diamond)

Powdered Co – 20 % Cr – 15 % W – 10 % [3026] Ni – 3% Fe – 1.5 % Mn – 0.1 % C alloy (mean particle size – 34 μm, containing 3.8-6.4 vol.% Cr7C3±x + δ-WC1±x) – 1-20 vol.% C (chopped fibre, length – 3 mm, diameter – 7 μm) mixtures were subjected to hot isostatic pressing (HIP) procedure (exposure – 2.5 h) to fabricate highly dense composite materials

See section TiC1–x – Cr7C3±x – δ-WC1±x – C – Co in Table III-2.22 –

–

Coatings composed of δ-WC1±x, CrN1±x [2305] and β-C (diamond-like) were produced by physical vapour deposition (PVD) methods

(continued)

2.6 Chemical Properties and Materials Design

247

Table 2.21 (continued) δ-WC1±x – CrSi2 – α/β-C (graphite / diamond) – Co

–

–

δ-WC1±x – Cu2O –C

δ-WC1±x – θ-Fe3C – C

–

25 vol.% β-C (diamond) particles (size distribution – 0.3-0.4 mm) were introduced into 0.5-3.0 % CrSi2 (mean particle size – 10-40 μm) doped δ-WC1±x – 6 % Co hard alloy powdered mixtures to fabricate dense composites by hot-pressing (exposure – 8 min) procedure; the CrSi2 phase does not interact with β-C (diamond) and δ-WC1±x, it dissolves in Co-based metallic binder to form (Co,W,C,Cr,Si) solid solutions, decreasing the energy of the stacking fault, which contributes to α-Co (cubic) → ε-Co (hexagonal) polymorphic transformation, Cr and Si atoms from the binder interact with the surface of β-C that leads to the disappearance of α-C (graphite) layer at the β-C/Co interface, formation of η2-W3Co3Cy phase in the hard alloy matrix and increasing the adhesion between β-C particles and matrix

1500

–

Doping with CrSi2 for the compositions of [2337, 2344, δ-WC1±x – Co – β-C (diamond) materials 3340] was recommended on the basis of thermodynamic calculations; the addition of Cr silicide can suppress the formation of nondiamond C layers at the β-C interfaces

–

Highly 600-1100 pure N2 flow

Hybrid materials, composed of hierarchi- [2404] cally deposited Cu2O (inner layer) and robust C (carbide derived) structure with 70 % δ-WC1±x, were fabricated using electrochemical methods δ-WC1±x – θ-Fe3C – α-C (graphite) nano- [2407] composites (mass ratio WC/Fe3C = 1) were synthesized by using the in situ carbothermal reduction method with spongelike (highly porous) waste biomass, serving as the C source, preliminarily immersed into the W-Fe mixed precursor aqueous solutions

See also section C – Fe – W in Table I2.14 δ-WC1±x – Fe2+xN N2 – FeWO4 – C

δ-WC1±x – FeNi1±x – C – Co – Fe –Mn – Si

700

δ-WC1±x – C (ordered mesoporous) nano- [1680] composites modified by FeWO4 and Fe2+xN were designed and prepared by the calcination (duration – 3 h) process

See section δ-WC1±x – FeNi1±x – Co – (Fe – C – Mn – Si)

(continued)

248

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – α/β/γ/ε-Fe2O3 – C

Vacuum, 1200-1300 The interaction in the powdered δ-WC1±x [2405] Ar (mean particle size – 2-5 μm) – 17 mol.% α-Fe2O3 (pure, mean particle size – ~0.1 μm, specific surface area – ~12 m2 g–1) – 55 mol.% C (black, super-fine in particle size) mixtures (exposure – 1 h) leads to the formation of η2-W3Fe3Cy, θ-Fe3C and metallic α-Fe phases (the composition of products are depending on the gas atmosphere employed during the heat treatment)

δ-WC1±x – α/β/γ/ε-Fe2O3 – α/β-NiO1±x – C

Vacuum, 1150-1300 The interaction in the powdered δ-WC1±x [2406] Ar (mean particle size – 2-5 μm) – 15 mol.% α-Fe2O3 (pure, mean particle size – ~0.1 μm, specific surface area – ~12 m2 g–1) – 8 mol. % β-NiO1±x (pure, specific surface area – ~6 m2 g–1) – 46 mol.% C (black, super-fine in particle size) mixture (exposure – 1 h) leads to the formation of μ-(Fe,Ni)7W6–x, η2-W3(Fe,Ni)3C and metallic W and α-(Fe,Ni) and γ-(Fe,Ni) solid solutions phases, depending on the gas media employed during the heat treatment

δ-WC1±x – FePt1±x – FeS1+x – C – N

–

–

δ-WC1±x – La2O3–x – C – Co – Cr – Cu – Fe – Mn – Ni – Si

See section δ-WC1±x – La2O3–x – Co – Cu – (Fe – C – Cr – Mn – Ni – Si)

δ-WC1±x – La2O3–x – α/β-C (graphite / diamond) – Fe δ-WC1±x – γ-MoC – α/β-C

Hybrid materials with nanoarchitecture [1640] consisting of δ-WC1±x, FeS1+x, FePt1±x and N-doped C were designed and fabricated

–

CO

–

Mixed δ/γ-(W,Mo)C1±x monocarbide (he- [369, 1258, xagonal) layers on C (fiber) substrates 1271, 1285, were prepared by the carburization reac- 2821] tion of metallic chemical vapour deposited (CVD) films

820

–

0.5 % La2O3–x-doped, β-C (diamond) en- [2408, 3716] hanced and Fe-rich composites based on δ-WC1±x were designed and fabricated via activated low-temperature high-pressure hot-pressing procedure

–

δ-WC1±x – H2/CH4 ~ 900-1000 α/β-Mo2±xC – α/β-C (graphite / diamond)

δ/γ-(Mo0.02÷0.54W0.46÷0.98)C1±x monocarbide (hexagonal) nanoparticles (mean size – 1-4 nm) on high surface area C (black) support were synthesized for catalysis purposes by removable ceramic coating method Microwave plasma-enhanced chemical vapour deposition (CVD) method was employed to grow β-C (diamond) films (thickness – 2.0-2.5 μm) on δ-WC1±x – β-Mo2±xC composite materials; the film/substrate adhesions were estimated

[1464, 1500, 2409-2410, 2821, 4280]

(continued)

2.6 Chemical Properties and Materials Design

249

Table 2.21 (continued) 1700-2000 Powdered δ-WC1.00 (mean particle size – ~0.7 μm, contents: non-combined C – 0.02%, Fe – 0.05%, Mo – 0.02%) – β-Mo2.01C (mean particle size – 1.6 μm, contents: non-combined C – 0.11%, Co – 0.08%) – C (black) mixtures, taken in the proportions x = 0.05÷0.40, according to the solid state reaction: (1 – x)WC + x/2Mo2C + x/2C = (W1–xMox)C), were subjected to reaction sintering by the hot-pressing followed with annealing procedures to prepare dense ceramics; the materials with x < 0.2 were composed of the δ-(W1–xMox)C1±x solid solution phase, which in each grain was not compositionally homogeneous due to a two-phase separation during cooling process into two different phases of a W-rich core phase (~δ-(W0.92÷0.98Mo0.02÷0.08)C~1.0) and W-deficient peripheral phase (~δ-(W0.52÷0.56Mo0.44÷0.48)C~1.0)

See also section C – Mo – W in Table I2.14 δ-WC1±x – CH4/H2 700-800 α/β/ε/γ-W2±xC – (20/80) α/β-Mo2±xC – flow α/β-C

N2

[1464, 1500, In the powdered equimolar α-W2+xC – β-Mo2±xC mixtures with the presence of 2821, 4280] C (black) excess, α/ε-W2+xC phase was carburized to δ-WC1±x, but the structure of β-Mo2±xC phase remained the same δ-WC1±x, α/ε-W2+xC and β-Mo2±xC carbides imbedded ordered mesoporous C materials were synthesized by direct carbonization (duration – 3 h) method

800

See also section C – Mo – W in Table I2.14 δ-WC1±x – α/β-Mo2±xC – C – N

–

–

Well-defined 0D/2D heterojunctions of uniform n(β-Mo2±xC) – (1 – n)(δ-WC1±x) (0 < n < 1) quantum dots (mean particle size – ~ 3-5 nm) on N-doped α-C (graphene) nanosheets were obtained via a nanocasting method using graphene as a template

δ-WC1±x – α/β-Mo2±xC – C – Pd

–

–

20 % Pd nanoparticles supported on nano- [1592] sized δ-WC1±x – β-Mo2±xC carbides and C (aerogel) composites were prepared

δ-WC1±x – α/β-Mo2±xC – C – Pt

–

–

β-Mo2±xC – δ-WC1±x – C composite supports for Pt catalysts were designed and fabricated by the co-impregnation of Mo and W precursors

[1697]

[1493]

(continued)

250

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – α/β-Mo2±xC – α/β-SiC – α/β-C

–

δ-WC1±x – MoS2+x – α/β-C

–

δ-WC1±x – δ-NbN1–x – α/β-C (graphite / diamond) – Co

–

1600-1800 Powdered δ-WC1.00 (mean particle size – [4280] 0.73 μm, contents: non-combined C – 0.02%, Fe – 0.05%, Mo – 0.02%) – 8-24 mol.% β-Mo2.01C (mean particle size – 1.57 μm, contents: non-combined C – 0.11%, Co – 0.08%) – 5-30 mol.% β-SiC (mean particle size – 0.60 μm, contents: non-combined C – 0.85%, Fe – 0.015%, Al – 0.012%, SiO2 – 0.30%) – 8-24 mol.% C (black) mixtures (preliminarily ball-milled) were subjected to hot-pressing procedure to fabricate dense ceramics; the following solid state reaction: (1 – x)WC + x/2Mo2C + x/2C = (W1–xMox)C resulted in the formation of monocarbide solid solution (mixed carbide) matrix with the grains composed of a W-rich core phase (~δ-(W0.92÷0.98Mo0.02÷0.08)C~1.0) and W-deficient peripheral phase (~δ-(W0.52÷0.56Mo0.44÷0.48)C~1.0) due to a two-phase separation during cooling process; addition of β-SiC promoted the reaction marked above, so two-phase materials were obtained for β-SiC content ≥ 5 mol.% and (W≥0.8Mo≤0.2)C~1.0 mixed carbide compositions (the presence of small amounts of (Mo,W)5Si3Cy compound (Nowotny phase) as a product of interaction with β-SiC was detected) –

1450

Materials composed of layered MoS2+x [1589] supported on α-C (reduced graphene oxide) decorated with nanosized δ-WC1±x were designed and produced Powdered β-C (diamond, natural, size dis- [2411] tribution – 630-800 μm) – 70 % δ-WC1±x – 2 % δ-NbN~1.0 (size distribution – 25-40 μm, with the presence of ε-NbN1±x and γ-Nb4N3+x phases) – 4.5 % Co (size distribution – 5-20 μm, irregular in shape) mixtures were subjected to hot-pressing procedure to prepare β-C containing composite materials with two-phase hard alloy (mean grain size ≤ 1 μm) matrix

Vacuum, 1400-1450 Powdered δ-WC1±x (2.5 μm) – β-NiO1±x δ-WC1±x – [3886] α/β-NiO1±x – 2-6 Pa (4 μm) – SiC (99 % purity; 2 μm) – C α/β-SiC – α/β-C (black, pure; 2 μm) mixtures (mean particle sizes of the components are given in brackets; preliminarily ball-milled, reduced in H2, cold-pressed, pre-sintered and machined) were subjected to transient liquid-

(continued)

2.6 Chemical Properties and Materials Design

251

Table 2.21 (continued) phase (TLP) sintering (exposure – ~1 h) procedure to fabricate two-phase hard alloys (mean δ-WC1±x grain size – 2.5 μm) with Ni-based metallic binder (contents: C – 1.8 %, Si – 4.1 %); no SiC and/or C phases were detected in the sintered materials δ-WC1±x – NiPx (Ni3P, Ni2–xP) – C

–

–

δ-WC1±x – NiPx – α-C (graphite) composite [2412] materials were designed and manufactured

δ-WC1±x – Vacuum 1200-1600 Powdered δ-WC1±x (mean particle size – [2413, 4280] α/β-SiC – 0.6 μm) – 20 vol.% SiC-coated β-C (diaα/β-C (graphite / mond, mean particle size – 7 μm, average diamond) thickness of SiC layer – 80 nm) mixtures were spark-plasma sintered (holding time – 5 min) to fabricate dense β-C containing composite materials; no β-C (diamond) → α-C (graphite) phase transition was observed in the materials

See also section δ-WC1±x – C – Si See also section δ-WC1±x – Si See also section C – Si – W in Table I-2.14 δ-WC1±x – H2/N2/ α/β-SiC – /CO α/β-C (graphite / diamond) – Fe

1100

Powdered Fe (atomized, size distribution [3599] < 200 μm) – 0.33-1.0 % δ-WC1±x (size distribution – 2-6 μm) – 0.33-1.0 % SiC (mean particle size – ~2 μm) – 1.0-1.67 % α-C (graphite, particulates, mean particle size – ~3 μm) mixtures were subjected to sintering (exposure – 1 h) procedure to fabricate metal matrix composites (MMC) with porosity – 13-16%; with the additions of δ-WC1±x and SiC in the mixtures, the increase of α-Fe (ferrite) contents in the pearlite (α-Fe – θ-Fe3C) structure of the sintered materials was observed

δ-WC1±x – TiC1–x –C

See section TiC1–x – δ-WC1±x – C in Table III-2.22

δ-WC1±x – TiC1–x – C – Co

See section TiC1–x – δ-WC1±x – C – Co in Table III-2.22

δ-WC1±x – TiC1–x – C – Co – Cu

See section TiC1–x – δ-WC1±x – C – Co – Cu in Table III-2.22

δ-WC1±x – TiC1–x – C – Co – Ni

See section TiC1–x – δ-WC1±x – C – Co – Ni in Table III-2.22

δ-WC1±x – TiC1–x – C – Pt

See section TiC1–x – δ-WC1±x – C – Pt in Table III-2.22

δ-WC1±x – TiC1–x – ZrC1–x – C

See section ZrC1–x – TiC1–x – δ-WC1±x – C in Table II-5.24

(continued)

252

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – TiO2–x CO – C – Pt

900

Pt nanoparticles (mean size – 3.75 nm) [1584] dispersed homogeneously on the α-C (bamboo charcoals) supported TiO2–x – δ-WC1±x system with a well-defined structure were prepared using carbonization and microwave-assisted processes

δ-WC1±x – VC1–x – ZrC1–x – C δ-WC1±x – α/β-W2B5–x – α/β-C (graphite / diamond) – Co

See section ZrC1–x – VC1–x – δ-WC1±x – C in Table II-5.24 –

δ-WC1±x – NH3 δ-WN1±x – α/β-C

–

–

α/β-W2B5–x doped compositions of [2337-2338] δ-WC1±x – Co – β-C (diamond) materials were fabricated by hot-pressing technique; the addition of W borides suppresses the formation of α-C (graphite) and/or nondiamond C at the β-C interfaces

700-800

5-17 % monocarbonitride (hexagonal) [1175, 1678] δ-W(C,N)1±x nanoparticles (mean size < 2 nm) uniformly dispersed on α-C (activated, specific surface area – 1280 m2 g–1) were synthesized by carbothermal reduction (duration – 1 h) method

750-950

Monocarbonitride (hexagonal) δ-W(C,N)1±x nanoarray structures on α-C (fibre) papers (with atomic ratio C/N ≈ 8.6) composed of thin belts (length – 5 μm, width – 0.4 μm, thickness – 7-8 nm) were synthesized using reduction-carbonization (exposure – 3 h) reactions

–

δ-WC1±x, α/ε-W2+xC and δ-WN1±x nanopar- [1641] ticles decorated on α-C (graphene) nanoplatelets were synthesized

See also section C – N – W in Table I-2.14 δ-WC1±x – – α/β/ε/γ-W2±xC – δ-WN1±x – α/β-C

See also section C – N – W in Table I-2.14 α/β/ε/γ-W2±xC – Ar δ-WN1±x – α/β-C –N

700-900

α/ε-W2+xC – δ-WN1±x – N-doped α-C fra- [1719] mework nanocrystalline complex (with nanosheet (mean size – ~ 0.1-0.2 μm) like morphology) was synthesized by in situ carbonization method for electrocatalysis purposes

See also section C – N – W in Table I-2.14 δ-WC1±x – Ar, or 20-200 δ-WN1±x – α/β-C Ar/N2 –W (50/50), 0.3 kPa

W – δ-W(C,N)1±x bilayered coatings (with [4021-4023] the presence of α-C (graphite) and amorphous C, thickness – 0.65-1.3 μm, mean grain size – 0.65-1.2 μm) were produced on stainless steel substrates using a repetitive pulsed vacuum arc discharge techniques; chemical compositions of the coatings were determined by the C and N atoms competition

See also section C – N – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

253

Table 2.21 (continued) N2 δ-WC1±x – W24O68 – C – N – Pt

700-900

5 % Pt nanoparticles (mean size – 3-4 nm) [1773] loaded microsized δ-WC1±x – W24O68 – Ndoped zeolitic imidazole framework derived α-C (graphite-like, sp2- and sp3-hybridized) composite rods (specific surface area – 74-84 m2 g–1, mean pore size – 5-6 nm, pore volume – ~0.02 cm3 g–1) were fabricated for catalysis purposes using heat treatment in the special gas atmosphere followed by modified reduction method

α/β/ε/γ-W2±xC – N2/H2 800-900 WP – C – N (95/5) mixture

Dispersion of small-size WP-doped W2±xC [2421] nanoparticles on N-doped C materials were prepared by one-step pyrolysis process

δ-WC1±x – Ar, α/β-WS2–x – 0.2 Pa α/β-C (graphite / diamond)

–

Exhibiting self-adaptation to operating [2417-2420] conditions nanocomposite coatings (thickness – ~0.5 μm, contents: W – 20-30 at.%, C – 40-50 at.%, S – 20-30 at.%), composed of γ-WC1–x (mean grain size – 1-2 nm) and WS2–x (mean grain size – 5-10 nm) embedded in amorphous β-C (diamondlike) matrix were fabricated on stainless steel substrates using hybrid magnetron sputtering – pulsed laser deposition or laser ablation deposition methods

–

–

3D nanostructures composed of δ-WC1±x and WS2–x directly grown on vertically aligned free-standing C (nanotubes) forests were designed and fabricated

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/β-C – Co

–

1400-1500 Powdered δ-WC1±x (high purity, mean [3945] particle size – ~0.9 μm) – 6 % Co – 6 % β/γ-ZrO2–x (mean particle size – ~30 nm, 3 mol.% α-Y2O3–x partially stabilized) – 0.25 % α-C (graphite) mixtures (preliminarily ball-milled) were subjected to vacuum sintering and hot isostatic pressing (HIP) procedures (dwell time – from 0.5 h to 1 h) to prepare dense hard alloy with Co metallic binder

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/β-C – Ni

–

~1300-1500 Powdered δ-WC1±x (99 % purity, mean [10, 3890, particle size – ~0.9 μm) – 8 % Ni (99.7 % 3945-3947] purity, mean particle size – 7 μm) – 6 % β/γ-ZrO2–x (mean particle size – 30-100 nm, 3 mol.% α-Y2O3–x stabilized) – 0.2-0.7 % α-C (graphite) mixtures (preliminarily ball-milled) were subjected to vacuum sintering, hot isostatic pressing (HIP) and spark-plasma sintering (SPS) procedures (dwell time – from 1 min to 1 h) to prepare dense hard alloy with Ni metallic binder

(continued)

254

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – ZrB2±x – α/β-C

–

~2000-2200 In the presence of α-C (graphite), the inter- [4346] action in the δ-WC1±x – ZrB2±x powdered mixtures leads to the appearance of (Zr,W)C1–x and β-(W,Zr)2B5–x solid solution (mixed) phases, formed in accordance to the following reaction 4WC + 5ZrB2 + C = 5ZrC + 2W2B5

δ-WC1±x – α/β/γ/δ-ZrO2–x – α/β-C – Ni

–

1400-1500 Powdered δ-WC1±x (mean particle size – [3944] ~0.9 μm) – 8 % Ni (99.7 % purity, mean particle size – ~20 μm) – 6 % α-ZrO2–x (monoclinic, mean particle size – ~10 μm) – 0.2-1.0 % α-C (graphite) mixtures (preliminarily ball-milled) were subjected to vacuum sintering, spark-plasma sintering (SPS) and hot isostatic pressing (HIP) procedures to prepare highly dense hard alloys with Ni metallic binder

See also section δ-WC1±x – α/β/γ/δ-ZrO2–x – Ni δ-WC1±x – Cd

δ-WC1±x – Ce – Co

Vacuum, 550 1.3 Pa –

Sintered WC0.98 materials (content noncombined C – 0.10%) does not interact with pure molten Cd (exposure – 10 h) –

The addition of 0.1 % Ce to δ-WC1±x – 6 % [3174] Co hard alloy leads to the stabilization of α-Co (cubic) phase due to restraining the martensitic α-Co → ε-Co transformation

δ-WC1±x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Ce – Co – Ni

See section TaC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Ce – Co – Ni in Table II-2.21

δ-WC1±x – Ce – Ni

See section δ-WC1±x – CeO2–x – Ni

δ-WC1±x – α/ε-Co

–

–

–

–

[579, 1941]

The formation of η1-W6Co6Cy (or η1-W6+xCo6–xC, 0 ≤ x ≤ 3), η2-W3Co3Cy (or η-W4–xCo2+xC, 0 ≤ x ≤ 1.2; or θ-W4Co2C, or (W,Co)6C), η3-W6Co3C2 (?) and κ-W3CoC1+x, (or W9÷10Co3C4, metastable, ?) ternary phases; WCo3C phase was predicted theoretically by DFT calculations

[1-5, 8-10, 13, 39-40, 43, 53, 6263, 68-69, 83, 87, 97, 108, 111, 118, 130, 151, 158, The solubilities of W and C in metallic Co 166, 236, phase freeze-in upon the solidification and 240, 294, thus diverge from the equilibrium values; 320, 374, the low C content in the Co-based binder 438, 464, can be explained by the growth of δ-WC1±x 490-491, grains upon cooling, which consumes the 562, 578W and C from the binder resulting in a W- 579, 626, 655-656, depleted gradient close to the δ-WC1±x grains, so the low C content in the binder 660-665,

(continued)

2.6 Chemical Properties and Materials Design

255

Table 2.21 (continued) is not caused by the decarburization

–

–

–

–

Vacuum, 8 mPa

–

N2

(–196)

N2

(–196)

671, 679, 792, 798, 817, 824827, 833, 851, 862863, 872, 879, 893, 908, 914, 916, 920In δ-WC1±x – 6 % Co hard alloy (with low 924, 927, C content) the particles of η-phase were 941, 946found to be associated with microscopic 947, 972, steps in δ-WC1±x grains and with Co-defi- 976, 986, cient interfaces 1001, 1005, The surface microstructure of δ-WC1±x – 6 1013, 1020, % Co hard alloy irradiated by high current 1035-1043, pulsed electron beam (HCPEB) with 1077-1078, energy density of 3 J cm–2 (20 pulses) 1080, 1113composed of γ-WC1–x (size distribution – 1139, 114220-100 nm) and κ-W3CoC1+x phases 1143, 1156, 1159, 1163, The slow cooling (2 K min–1), soaking 1171, 1261(for 180 min) and slow bringing back 1262, 1374, (2 K min–1) to ambient temperatures of sintered δ-WC1±x – 11 % α/ε-Co two-phase 1464, 1783, hard alloys lead to the formation of small 1789, 1791, amounts of η1-W6Co6Cy and η2-W3Co3Cy 1799, 1805, phases due to the recrystallization of me- 1808, 1811tallic binder and dissolution of carbide in 1825, 1831, it, whereas the content of α-Co phase in the 1854, 1856, binder decreases from 50.2 % to 40.7 %; 1860, 1862, (the analysis results of the W content in the 1864, 1867binder support the content changing trend 1868, 18701871, 1886, of α-Co phase there before and after the treatment, but there is no accurate linear 1893, 1895relationship between the W concentration 1903, 1924, and α-Co content in the binder); after the 1928-1945, treatment δ-WC1±x grains were refined into 1973-1977, 1980-1981, their most stable form, triangular prism, 1983, 1985via the phenomenon of spheroidization 1989, 1991, –1 The slow cooling (3 K min ) and soaking 1993-2000, (for 72 h) of sintered δ-WC1±x – 12-80 % 2093, 2108, α/ε-Co two-phase hard alloys showed that 2111, 2118, there is no significant change in their mic2120-2122, romorphology after deep cryogenic treat2325-2337, ment (DCT); the amount of ε-Co and the 2337, 2411, ε-Co to Co ratio both in low-Co alloys are 2416, 2431lower than that in high-Co alloys at room 2999, 3002, temperature, DCT could increase the amo3007-3008, unt of ε-Co, and the ε-Co in low-Co alloys 3013-3017, shows a bigger increase than that in high3036, 3055, Co alloys after DCT 3060, 3102In the sintered (deposited) δ-WC1±x – Co hard alloys (coatings) the presence of α/β/ε/γ-W2±xC phases due to the decarburization processes can be detected even after slow cooling, while γ-WC1–x is only found when the alloys (coatings) has been quenched rapidly

(continued)

256

2 Tungsten Carbides

Table 2.21 (continued) N2

(–196)(–110)

N2

(–193)

–

20-1000

–

~440-820

Vacuum 600-800

3109, 3119, 3122-3127, 3133-3136, 3146, 3148, 3158, 3160, 3175-3177, 3182-3186, 3204, 32063207, 3210, 3213, 3221, 3239, 32423247, 3261, The deep cryogenic treatment (slow cool- 3266, 3274, –1 ing (0.25 K min ), soaking (for 27 h) and 3284, 3287, slow bringing back (0.15 K min–1) to am- 3304-3320, bient temperatures) of sintered δ-WC1±x – 3349, 33539-25 % α/ε-Co two-phase hard alloys led 3356, 3372, to the slight increase of ε-Co (hexagonal) 3377, 3385modification content in the alloys 3386, 3389With temperature increasing within the 3392, 3470, ranges, the maximum equilibrium solid 3583, 3631, solubility of δ-WC1±x in α-Co (cubic) in- 3712, 3753creases from 0.3 mol.% to 1.2 mol.%, the 3755, 3759, dissolution of δ-WC1±x in the metal phase 3773-3774, stabilizes α-Co, making it difficult to trans- 3909, 3925, form to ε-Co (hexagonal), the decomposi- 3936-3939, tion of the α-(Co,W,C) solid solution under 3966, 3982, slow cooling conditions occurs with dif- 4065, 4067ficulty, but annealing at 700-900 °C (expo- 4068, 4071, sure – 1-2 h) leads to the decline of W and 4159, 4281, C contents in α-(Co,W,C); an increase in 4291-4295, the C content of δ-WC1±x phase results in 4386, 4488decreasing its solubility in the metallic 4490, 4492, α-(Co,W,C) solid solution, the minimum 4495, 4502, of solubility corresponds to δ-WC1.01 com- 4504-4505, position 4522, 4543, ε-Co (hexagonal) → α-Co (cubic) allotro- 4590-4592, pic transformations were observed in the 4616] binder of δ-WC1±x – Co hard alloys at various temperatures, mainly depending on W contents in it – more the W content in Cobased phase, the higher its transformation temperature was observed (the transformation could be reversed by mechanical strain at room temperature) The cryogenic treatment (soaking time – up to 72 h) of δ-WC1±x – 6-8 % Co hard alloys results in the change of residual stresses and martensitic α-Co (cubic) → ε-Co (hexagonal) phase transformation; δ-WC1±x particles refined into their most stable forms (stress-free crystallographic configuration) via the phenomenon of spheroidization along with the precipitation of η-phases in the alloys are observed after this treatment

The cracks in δ-WC1±x – 6-10 % Co hard alloys were healed partially by annealing (exposure ≥ 2 min), the amount of healing increases with increasing annealing temperature and time; healing does not occur in δ-WC1±x grains but is due only the partial resintering of Co-based binder phase

(continued)

2.6 Chemical Properties and Materials Design

257

Table 2.21 (continued) N2/H2 600-800 (50/50) mixture + CH4

–

H2

–

Powdered δ-WC1±x (mean particle size – 3.5 μm, contents: total C – 6.12-6.16 %, non-combined C – 0.02 %) – 10 % Co (mean particle size – 1.2 μm, content C – 0.013 %) mixtures were heat-treated in chemically active gas atmosphere to eliminate η-phases (without causing carbon precipitation) in the materials being subjected to liquid-phase sintering at the next stages of production

740-1100

The controlled heat treatment (ageing) procedures of δ-WC1±x – 25 % Co hard alloys lead to the α-Co (cubic) → ε-Co (hexagonal) martensitic transformation and essential change in grain size of the metallic Co binder

780-1030

The formation of only η1-W6Co6Cy phase on the δ-WC1±x – 6 % Co hard alloys exposed to a concentrated solar radiation source was detected in this temperature interval

780-1130

The individual δ-WC1±x grains in the powdered δ-WC1±x – Co mixtures subjected to heat treatments are welded together in their contact points

Vacuum, 800-900 10 mPa

The heat treatment (exposure – 10 min) of cold-pressed δ-WC1±x – 8 % ε-Co (hexagonal) nanocrystalline powdered mixtures (mean particle size – ~60 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 52 %) composed of δ-WC1±x, α-Co (cubic) and minor (κ-Co3±xW, η1-W6Co6Cy) phases

Ar

Metallic Co can spread on the surface of δ-WC1±x phase in solid state as a thin layer with high values of spreading velocities due to the favourable energies of the carbide, vapour and metal interfaces; there is a relation between the solubilities of W and C in Co, defect concentrations in Co and viscosity of layers formed near the contact between Co and δ-WC1±x

800-1050

Vacuum 800-1190

The sintering process (initial solid state densification) of δ-WC1±x (mean particle size – ~80 nm, specific surface area – 4 m2 g–1) – 2.5-10 % Co powdered mixtures attributes mainly to grain growth – densification indicated by acceptable fittings to a modified Coble intermediate stage model

(continued)

258

2 Tungsten Carbides

Table 2.21 (continued) High 900-1100 vacuum

Highly dense δ-WC1±x – 3 % Co hard alloys were fabricated by spark-plasma sintering (SPS) process (exposure – 5 min)

Vacuum, 900-1250 0.67 Pa

The relationship between the width of diffusion zone (δ), produced by the solidphase interaction of hot-pressed δ-WC0.96 (> 99.4 % purity, content non-combined C – 0.14 %) with pure metallic Co (exposure – 1-16 h), and time (τ) is described by the equation δ n = K0 exp(–E/RT) τ, where the reactive diffusion parameters: exponent constant n (declines from 6.2 to 4.7 with temperature increasing) and apparent activation energy E ≈ 250±30 kJ mol–1

Vacuum 950-1000

Fully densified δ-WC1±x – 10 % Co hard alloys (mean carbide grain size – 0.3 μm) were prepared by solid-phase sintering process using spark-plasma sintering (exposure 10 min) techniques

Vacuum, 950-1250 0.13 Pa

Ultra-fine δ-WC1±x – 40 % Co hard alloys were fabricated via solid-phase sintering by hot-pressing under high pressures

Vacuum 950-1350

Highly dense δ-WC1±x – 16 % Co fine-grained hard alloys were fabricated by solidphase sintering of high-energy compacted powdered mixtures

Vacuum, < 1000 0.1 mPa

W-C thin films with Co contents – up to 22 at.% were deposited by sputtering; in the films with high C contents the presence of γ-WC1–x phase was detected

N2

1000

The heat treatment (exposure – 4 h) of synthesized via cryogenic mechanical milling nanostructured δ-WC1±x – 18 % Co powder (as-synthesized mean carbide particle size – 25nm) led to the rather small growth of δ-WC1±x grains (final mean size < 0.1 μm) and formation of minor (η1-W6Co6Cy, W2±xC and W3+xC) phases

Vacuum, 1000 10 mPa

The heat treatment (exposure – 10 min) of cold-pressed δ-WC1±x – 8 % ε-Co (hexagonal) nanocrystalline powdered mixtures (mean particle size – ~60 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 46 %) composed of δ-WC1±x, α-Co (cubic) and minor (η1-W6Co6Cy, η2-W3Co3Cy) phases

(continued)

2.6 Chemical Properties and Materials Design

259

Table 2.21 (continued)

H2

–

1000-1100 In the sintered δ-WC1±x – 16 vol.% Co hard alloys (mean grain size – ~2 μm), subjected to the compressive creep testing, δ-WC1±x grain growth takes place preferentially in the plane perpendicular to the load axis and formation of Co phase lamellae at δ-WC1±x/δ-WC1±x grain boundaries suggests that accommodated grain boundary sliding contributes to the deformation

–

1000-1150 δ-WC1±x is in equilibrium with metallic W, η1-W6Co6Cy, η2-W3Co3Cy, κ-W3CoC1+x (?), α-(Co,W,C) solid solution and α-C (graphite) phases

–

1000-1200 Powdered δ-WC1±x (different mean grain sizes – from 0.1 μm to 1-3 μm, contents: C – 6.10-6.18 %, non-combined C – ~0.06 %, total O – ~0.10 %) – 7.5 % Co mixtures were subjected to pulse plasma compaction (PPC) procedures (holding time – 5 min) to prepare highly dense two-phase hard alloys

–

1000-1300 In powdered δ-WC1±x – α/ε-Co mixtures, the grains of δ-WC1±x phase grow intensively according to a mechanism of solidstate sintering 1030-1420 The formation of only η2-W3Co3Cy phase on the δ-WC1±x – 6 % Co hard alloy exposed to a concentrated solar radiation source was detected in this temperature interval

Vacuum 1040

Mechanically alloyed (milling time – 100 h) δ-WC1±x – 6 % Co mixtures (mean particle size – ~10 nm) were subjected to sintering procedure (holding time – 1 h) to prepare hard alloys (porosity – 20 %, mean grain size < 0.2 μm)

H2

The annealing (exposure – 1 h) of electrodispersed of δ-WC1±x – 8-20 % Co powder, containing non-combined C (2.6-4.1 %) and γ-WC1–x phase, leads to the formation of needle-like δ-WC1±x crystals through the reactions γ-WC1–x + C → δ-WC1±x + α-W2+xC + C → δ-WC1±x and decrease of the content of non-combined C up to 0.2 %, the growth of δ-WC1±x crystals occurs in the certain crystallographic directions with the preferred one, which is the dihedral angle 90°

1040

(continued)

260

2 Tungsten Carbides

Table 2.21 (continued) –

1050

In δ-WC1±x – 12 % Co hard alloys (homogeneously microstructured, mean grain size – 85 nm), solid-state sintered by using spark-plasma sintering (exposure – 5 min) techniques, the δ-WC1±x (0001) // α-Co (110) orientation relationship at the phase boundary and the coherent correspondence of δ-WC1±x (1010) and α-Co (110) in the bulk materials were consistent with those in the particles of starting powdered materials; consequently, the orientation relationship and coherence state at the phase boundaries in the initial composite particles were retained in the sintering process and existed in the prepared hard alloys

Vacuum, 1050-1100 δ-WC1±x – 12 % Co hard alloys (porosity – 4 Pa 0.10÷0.65 %, mean carbide grain size – (0.70÷0.80)±(0.04÷0.07) μm, carbide grain contiguity – (0.40÷0.42)±(0.10÷0.14), mean binder intercept length – (0.25÷0.29)±(0.05÷0.06) μm) were fabricated by spark-plasma sintering (exposure – 10 min) techniques from high-energy ball-milled powders (carbide size distribution – 40-250 nm, contents: total C – 5.325.36 %, O – 0.23 %) Vacuum 1050-1250 Hardening operation (holding time – 1 h) of δ-WC1±x – 6-25 % α-Co (cubic) sintered (two-phase) hard alloys led to the additional solution of carbide phase and increase of W contents in Co-based metallic binder from 7.1-11.6 % up to 11.8-16.3 %; at lower holding times (5-15 min) in the alloys with higher Co contents the emergence of ε-Co (hexagonal) phase was observed, at higher holding times in all the studied alloys decarburization of δ-WC1±x and formation of metallic W phase were detected –

1100

δ-WC1±x – 6.3 % Co hard alloys (with the presence of certain amounts of α/ε-W2+xC, η1-W6Co6Cy and η2-W3Co3Cy phases, porosity – 0.9 %, mean grain size – 0.35 μm) were prepared by spark-plasma sintering (exposure – 10 min) from nanocrystalline ball-milled powders (mean particle size – 30 nm, specific surface area – 13.4 m2 g–1, contents: total C – 6.12 %, non-combined C – 0.33 %, O – 0.23 %)

(continued)

2.6 Chemical Properties and Materials Design

261

Table 2.21 (continued) Vacuum, 1100 2-10 Pa

Powdered δ-WC1±x (99.95 % purity, content O – 0.52 %, mean particle size – 0.9 μm) – 12 % α/ε-Co (99.95 % purity, mean particle size – 1.5 μm) mixture was subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare highly dense hard alloys; the composition of prepared materials was evaluated to be 81 % δ-WC1±x, 11 % α-Co, 3 % ε-Co, 3 % Co (metastable) and 2 % η-W4Co2Cy

Vacuum, 1100-1200 Highly dense δ-WC1±x – 12 % Co hard 50 mPa alloys (mean carbide crystallite size – 50110 nm) were fabricated using ultra-fine powders (99.9 % purity, size distribution – 40-80 nm) by the pulse-plasma sintering (PPS) techniques (exposure – 5 min) 1100-1200 During the heat treatment (exposure – 2 h), interaction in powdered δ-WC1±x (size distribution – 0.1-0.7 μm, mean particle size – 0.2-0.3 μm, content non-combined C – 0.2 %) – 17 mol.% Co mixtures leads to the formation of η1-W6Co6Cy phase

Ar

Vacuum, 1100-1300 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 8 % ε-Co (hexagonal) nanocrystalline powdered mixtures (mean particle size – ~60 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 10-35 %) composed of δ-WC1±x and α-(Co,W,C) cubic metallic solid solution (with the presence of η1-W6Co6Cy and η2-W3Co3Cy phases) –

1130

In the spark-plasma sintered (exposure – 5 min) highly dense nanocrystalline δ-WC1±x – 10 % α/ε-Co hard alloys (mean grain size – ~80 nm), γ-WC1–x phase coexists with the main carbide phase at the δ-WC1±x / δ-WC1±x or δ-WC1±x / Co interfaces, the formation of layer-like γ-WC1–x at the δ-WC1±x (0001) / γ-WC1–x (111) interface results from the low surface energy and the coherent relationship between the two phases, which are both favourable for overcoming the phase transformation barrier; moreover, due to the higher solubility of C in the binder than that of W, the atomic C/W ratio in the vicinity of the nanoscale δ-WC1±x/Co phase boundaries is likely to be < 1, leading to a composition of γ-WC1–x

(continued)

262

2 Tungsten Carbides

Table 2.21 (continued) –

1130-1300 The solid solutions of WC1±x in metallic Co are formed in the powdered δ-WC1±x – Co mixtures subjected to heat treatments; the powdered mixtures shrink, and all Co passes to the liquid phase

Vacuum 1150-1230 The sintering process (softening solid state stage or eventually liquid formation) of δ-WC1±x (mean particle size – ~80 nm, specific surface area – 4 m2 g–1) – 2.5-10 % Co powdered mixtures attributes mainly to viscous flow densification behaviour operating prior to apparently the solutionprecipitation liquid-phase sintering; the presence of Co has a very strong catalytic effect in the δ-WC1±x – Co system, increasing apparently the diffusivity of W and C in δ-WC1±x Vacuum 1150-1350 During the sintering of δ-WC1±x (size distribution – 0.1-0.5 μm) – Co powdered mixtures significant local grain growth already occurs on heating to the isothermal hold in both isotropic and anisotropic modes with the formation of large trigonal δ-WC1±x plates containing growth twins Vacuum, 1170-1300 δ-WC1±x – 0.3-1.0 % α/ε-Co hard alloys 5 Pa (porosity – 2.1-5.6 %, with the presence of κ-W3CoC1+x, η1-W6Co6Cy and η2-W3Co3Cy phases) were fabricated from various types of plasma-chemical nanopowders (contents: total C – 6.10-7.19 %, non-combined C – 0-0.5 %, O – 0.47-0.75 %) using spark-plasma sintering (SPS) processes; a sequence of the following stages (with different mechanisms, apparent activation energies Ei are given in brackets) of SPS processes: sintering by the grain boundary diffusion (E1 ≈ 180-280 kJ mol–1), sintering by the volume diffusion in Co binder (E2 ≈ 400-1000 kJ mol–1) and sintering in the conditions of intensive δ-WC1±x grain growth (E3 ≈ 100-200 kJ mol–1) – was identified by the kinetics studies carried out –

1200

The dissolution of δ-WC1±x in α-(Co,W,C) solid solutions is limited by diffusion and depending on intermediate phase layers; the calculated coefficients for the W diffusion in α-(Co,W,C), η1-W6Co6Cy and η2-W3Co3Cy phases are 3×10–11, 6.5×10–11 and 2×10–11 cm2 s–1, respectively

(continued)

2.6 Chemical Properties and Materials Design

263

Table 2.21 (continued) Vacuum, ~1200 ~5 Pa

Highly dense δ-WC1±x – 15 vol.% Co hard alloys (mean carbide grain size – 0.26 μm, mean thickness of the binder phase – ~12 nm) were fabricated using ultra-fine powders (mean particle size < 0.2 μm) by highfrequency induction-heated sintering (HFIHS) process (exposure – ~1 min)

Vacuum, ~1200 ~5.3 Pa

Powdered δ-WC1±x (99.5 %, 0.4 μm) – 10 % Co (99.7 %, ~3 μm) mixtures (purities and mean particle sizes are given in brackets; preliminarily ball-milled) were subjected to high-frequency induction-heating sintering (HFIHS) procedure (exposure – ~40 s) to fabricate dense two-phase hard alloys (porosity – 1.8 %, mean grain size – 0.45 μm); the densification temperature of δ-WC1±x powder was reduced remarkably by the addition of Co

–

1200

Vacuum 1200

Powdered δ-WC1±x (99.95 % purity, mean particle size – 0.5 μm) – 3 % Co (99.5 % purity, mean particle size – ~10 μm) mixtures were subjected to spark-plasma sintering (exposure – ~4 min) procedure to fabricate hard alloys (porosity – ~1 %, mean grain size – ~0.3 μm); the presence of γ-W2±xC and γ-WC1–x phases in the alloys was detected Powdered δ-WC1±x – 6 % Co mixture (mean particles size – 0.8 μm) was subjectted to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense two-phase hard alloys (porosity – ~0.15 %)

–

≥ 1200

In the powdered δ-WC1±x – 16 % Co mixtures subjected to sintering procedures, the growth of δ-WC1±x particles occurred considerably faster (by a factor of 4 or more)

–

1200

The maximum solid solubility of δ-WC1±x in the metallic Co phase is ~7 mol.%

H2

1200-1300 Functionally graded δ-WC1±x – Co hard alloys with Co content ranging from 10 to 30 % were prepared from powdered mixtures using either solid-state or liquid-phase sintering followed by hot isostatic pressing procedure

H2

1200-1400 The examination of coalescence process of δ-WC1.0 crystals during the liquid-phase sintering of powdered δ-WC1.0 (content non-combined C – 0.03 %) – 15-50 % Co (99.9% purity) mixtures showed that the recrystallization by coalescence took place

(continued)

264

2 Tungsten Carbides

Table 2.21 (continued) at grain boundaries of small angle misorientation, the crystals were bounded by the habit planes such as (0001), (1010) and (1012), in some cases the growth occurred by the agglomeration of crystals with the relation of twins on the crystal planes of (1012) Vacuum 1200-1400 The dual-grain structured (fine grains showed a round granular shape, whereas coarse grains exhibited two different shapes: rectangle and truncated triangle) δ-WC1±x – Co hard alloys were fabricated through an in situ reaction followed by sintering (holding time – 1 h) procedure; the δ-WC1±x/γ-WC1–x/Co sandwich structures (5-6 atomic layers of γ-WC1–x phase between the fine δ-WC1±x grains and metallic Co phase) were observed in the alloys 1220-1320 Powdered δ-WC1±x (size distribution – 4080 nm) – 12 % Co mixtures (99.9 % purity) were subjected to pressure assisted fast electric sintering (PAFES) process to fabricate highly dense two-phase hard alloys with α-Co-based solid solution metallic binder

Ar

–

1250

The maximum solid solubility of δ-WC1±x in α-(Co,W,C) is ~14.5 mol.%, the solubilities of elemental W and C in α-Co are ~10 % and ~0.1 %, respectively; in practice the solubilities also depend on environmental conditions: gas media and contacting materials

Pure H2, 1250 5.3-8.0 kPa

In the conditions (pressure – 9.8 MPa, exposure – 5 min) of ion-beam heated diffusion bonding (welding) of δ-WC1±x and Co dense bulk materials, due to the diffusional dissolution of δ-WC1±x in Co the formation of 40 μm thickness hard alloy layer with variable Co content (ranging from 0 to 100 %) is occurred in the transition zone between the bulk materials

Ar

The annealing (exposure – 1 h) of sintered δ-WC1±x – α/ε-11 % Co two-phase hard alloys, followed by oil-quenched treatment has little influence on the phase composition of the materials, whereas the content of α-Co in the metallic binder increases from 50.2 % to 87.2 % (the analysis results of the W content in the binder support the content changing trend of α-Co phase there before and after the treatment, but there is

1250

(continued)

2.6 Chemical Properties and Materials Design

265

Table 2.21 (continued) no accurate linear relationship between the W concentration and α-Co content in the binder); in contrary to the starting alloys, the δ-WC1±x grains with rounded facets could be observed in the treated materials 1250-1350 δ-WC1±x – 5 % Co two-phase hard alloys were prepared by sintering (holding time – 1-4 h) using nanostructured powders (mean particle size – ~70 nm)

Ar

Vacuum 1250-1400 Various δ-WC1±x – 20-45 % Co two-phase hard alloys (with high and low C content, fine-grained, mean grain size – ~1.6 μm and coarse-grained, mean grain size – ~50 μm) were sintered (holding time – 1-2 h); near the ground surface layer in the alloys, the formation of ε-Co (hexagonal) phase due to the strain-induced transformation of binder was revealed, the depth of layer of this phase was affected with composition and mean carbide grain size in the alloys, it was formed in a plate shape along slip bands in the binder with the habit plane – α-Co (111), the precipitate of κ-Co3±xW appearing by annealing low C alloys at high temperatures was usually observed along the pre-existed ε-Co phase Vacuum 1260-1400 The sintering process (diffusional liquidphase sintering) of δ-WC1±x (mean particle size – ~80 nm, specific surface area – 4 m2 g–1) – 2.5-10 % Co powdered mixtures is characterized by activation energy E = 440-630 kJ mol–1 depending on Co content (standard rearrangement stage is also valid partially in these conditions at temperatures ≥ 1320 °C) Ar, 1270-1330 Powdered nanosized δ-WC1±x – 15 % Co 10 MPa mixtures were subjected to hot isostatic pressing (HIP) procedure to fabricate dense hard alloys –

~1275

The generation of a liquid phase and formation of the eutectics, which melt ~10 % of δ-WC1±x, occur in the δ-WC1±x – 5-15 % Co powdered mixtures during heating; in the subsequent resolidification during cooling, the dissolved δ-WC1±x precipitates

–

< 1280

Preliminarily cold pressed and pre-sintered fully dense δ-WC1±x – 6 % Co granules (> 99 % purity, size distribution – 40-300 μm) with the addition of 23-38 vol.% Co (fine powders) were consolidated via rapid omnidirectional compaction (ROC) pro-

(continued)

266

2 Tungsten Carbides

Table 2.21 (continued) cess under solid-state sintering conditions (duration < 2 min) to produce fully dense dual (or double cemented) δ-WC1±x – Co hybrid particulate metal matrix composites –

~1280-1380 Eutectic (pseudobinary) δ-WC1±x – α-Co with needle-like microstructure is formed; the maximum solid solubility of δ-WC1±x in α-Co is 4-10 mol.% and that of Co in δ-WC1±x is practically negligible

–

1280-1400 In the powdered δ-WC1±x – Co mixtures subjected to heat treatments, due to the migration of δ-WC1±x grains in the liquid phase, the materials acquire their final compact shape

CH4/H2 1300 mixtures

Functionally graded δ-WC1±x – Co hard alloys were prepared by heat treatment of sintered fully dense alloys in carburizing atmospheres at the temperature within the δ-WC1±x – Co (solid) – Co (liquid) triple field of the phase diagram, during the carburization process, the C gradient induces Co migration, thus creating the Co gradient in the final product

Ar

1300

During the heat treatment (exposure – 2 h), interaction in powdered δ-WC1±x (size distribution – 0.1-0.7 μm, mean particle size – 0.2-0.3 μm, content non-combined C – 0.2 %) – 17 mol.% Co mixtures leads to the formation of η2-W4Co2Cy phase

–

1300

Highly dense δ-WC1±x – 4-14 % Co twophase hard alloys (mean grain size – 0.220.38 μm) were prepared from ultra-fine powders (99.9% purity, mean particle sizes – 60 nm and 600 nm, respectively) using spark-plasma sintering (exposure – 5 min) techniques

–

1300

Powdered δ-WC1±x (99.5 %, < 1 μm) – 10 % Co (99.9 %, 44 μm) mixtures (preliminarily ball-milled, purity and initial mean particle size, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5-10 min) to fabricate dense hard alloys (porosity – 1-1.5 %)

H2 flow 1300-1450 The two-phase δ-WC1±x – α-(Co,W,C) cermets can be prepared only with the deviations of C content from those corresponding to the WC1.00 – Co cross-section – not more than 0.04-0.07 % (for Co content – 4 %), 0.18 % (for Co content – 10 %) and

(continued)

2.6 Chemical Properties and Materials Design

267

Table 2.21 (continued) 0.52 % (for Co content – 25 %), otherwise with lower C content the formation of three-phase δ-WC1±x – α-(Co,W,C) – η2-W3Co3Cy cermet materials is occurred; the C content in the hard alloys grows, when the rate of H2 flow is decreased and α-C (graphite) content in the furnace environment (packing materials) is raised Ar, 1320 120 MPa

Spark-plasma sintered δ-WC1±x – 6.3 % Co hard alloys (with the presence of certain amounts of α/ε-W2+xC, η1-W6Co6Cy and η2-W3Co3Cy phases, porosity – 0.9 %, mean grain size – 0.35 μm) were subjected to hot isostatic pressing (exposure – 60 min) to modify the alloys (no presence of minor phases in the final products)

Ar, 1320 120 MPa

Conventionally sintered (from nanopowders) δ-WC1±x – 6.3 % Co hard alloys (with the presence of certain amounts of η2-W3Co3Cy phase, porosity – 2.3 %, mean grain size – 0.7 μm) were subjected to hot isostatic pressing (exposure – 60 min) to modify the alloys (in the final products: no presence of η-phase, porosity – 1.2 %)

> 1320

The emergence of a liquid phase in powdered δ-WC1±x – Co mixtures subjected to sintering leads to the conditions when a small change in heating rate can drastically change the densification rate of the materials

H2 flow 1320-1340 Powdered Co (99.5 % purity) – 0.25-7.5 mol.% δ-WC1.0 mixtures were treated by conventional powder metallurgy methods (cooling rate down to 700 °C – 1.67 K s–1) to prepare sintered bodies; the maximum solid solubility of δ-WC1.0 in Co was estimated to be ~6 mol.%, α-Co (cubic) modification was stabilized in the materials at carbide content ≥ 1 mol.% Vacuum 1320-1400 The sintering process (particle rearrangement stage during diffusional liquid-phase sintering) of δ-WC1±x (mean particle size – ~80 nm, specific surface area – 4 m2 g–1) – 2.5-10 % Co powdered mixtures is characterized by activation energy E = 25-150 kJ mol–1 depending on Co content

(continued)

268

2 Tungsten Carbides

Table 2.21 (continued) –

1350

Nanostructured δ-WC1±x – 12-24 vol.% Co hard alloys (mean carbide grain size – 70 nm) were prepared by liquid-phase sintering (holding time – 1 h), higher contents of W and higher α/ε ratio of Co phases in the metallic binder compared with those in the conventional δ-WC1±x – 10-16 vol.% Co (carbide grain size distribution – 0.72.5 μm) hard alloys were detected; amorphous phases with much higher W contents, than in the crystalline binder phase, were observed in the metallic binder of the nanostructured hard alloys

N2/H2 flow

1350

Multilayer functionally graded δ-WC1±x – (from 10 % to 20%) Co two-phase hard alloys with both Co content and δ-WC1±x grain size gradients were designed and fabricated by lamination pressing of powdered mixtures (mean particle size – 0.8 μm) and microwave sintering (exposure – 20 min) of the layered compacts

Ar, 5 MPa

1350-1430 Powdered δ-WC1±x (coarse-grained) – 1030 % (0-20 % fine-grained δ-WC1±x + 10 % Co) mixtures were subjected to hot isostatic pressing (HIP) procedure (exposure – 40 min) to prepare highly dense hard alloys with inhomogeneous microstructure composed of coarsened δ-WC1±x grains and δ-WC1±x – Co microregions consisting of δ-WC1±x dispersoids and metallic Co binder phase

–

1350-1700 In the δ-WC1±x – 17-37 vol.% Co hard alloys the growth of mean carbide grain size follows a law of cubic root and is independent on the content of Co in the materials, it is thermally activated; the kinetics of growth is controlled by a second-order reaction (activation energy E ≈ 360 kJ mol–1) at the solid-liquid interface

Vacuum, 1360 < 2 Pa

Articles made from δ-WC1±x – 20 % Co hard alloys were fabricated by sintering (exposure – 1 h) of 3D gel-printed green bodies, prepared using hydroxyethyl methacrylate (HEMA) based slurries with 4756 vol.% solid loading

Vacuum 1370

The surface interaction of polycrystalline (hot-pressed) δ-WC1±x materials (porosity – 0.9 %, mean grain size – 20 μm), immersed into Co melt saturated with C (2.14 %) and W (32.9 %), occurs through the penetration process of liquid Co alloy into the

(continued)

2.6 Chemical Properties and Materials Design

269

Table 2.21 (continued) solid δ-WC1±x along its grain boundaries, the rate of the penetration (accumulation) of the melt in δ-WC1±x is determined by the recrystallization of δ-WC1±x, at which the grains tend to acquire the equilibrium shape, the value of penetration rate was estimated to be 0.25 mm min–1 Vacuum 1380

δ-WC1±x – 6.3 % Co hard alloys (with the presence of certain amounts of η2-W3Co3Cy phase, porosity – 2.3 %, mean grain size – 0.7 μm) were prepared by liquid-phase sintering (exposure – 60 min) from nanocrystalline ball-milled powder (mean particle size – 30 nm, specific surface area – 13.4 m2 g–1, contents: total C – 6.12 %, non-combined C – 0.33 %, O – 0.23 %)

Ar, 4 MPa

In ultra-coarse δ-WC1±x – 10 % Co hard alloys, liquid-phase sintered by using of hot isostatic pressing (exposure – 0.5 h) from coarse δ-WC1±x powder (size distribution – 3-10 μm), only the minority of δ-WC1±x/δ-WC1±x grain boundaries were completely wetted by thick Co layers, whereas other δ-WC1±x/δ-WC1±x grain boundaries were pseudopartially wetted, namely they had the high contact angle with Co phase and, nevertheless, contain a 2-3 nm thin uniform Co-rich layer

1380

Vacuum, 1380 Ar

In sintered (exposure – 45 min) and further hot-isostatic-pressed (exposure – 30 min) δ-WC1±x – 10 % Co hard alloys with various C contents, the wettability of δ-WC1±x/δ-WC1±x grain boundaries by the liquid metallic Co-based binder in the high-C hard alloys was noticeably worse than that in the low-C alloys

–

1390-1420 Coarse-grained δ-WC1±x – 10 % Co hard alloys, sintered from narrow-fraction δ-WC1±x powder (size distribution – 5-15 μm), had no porosity at the stoichiometric content of C, but the alloys had considerable porosity at its lowered content

–

~1400

The experimentally measured solubility of Co in the δ-WC1±x phase of cemented carbides is < 9×10–4 at.%; the DFT-calculated value is 3.5×10–5 at.%

(continued)

270

2 Tungsten Carbides

Table 2.21 (continued) –

1400

The observation of δ-WC1±x – 25 % Co hard alloy liquid-phase sintering process (holding time – 100 h) showed that the δ-WC1±x crystals form the triangular prisms with a base to height ratio of 2.0±0.1, which are slightly truncated along the edges parallel to the prism axis

Belt-type 1400 apparatus (~6 GPa)

δ-WC1±x – 4.3 % Co hard alloys were prepared by liquid-phase sintering process; the main mechanisms of sintering were plastic deformation and solution-precipitation through the liquid binder phase

Ar

1400

During the heat treatment (exposure – 2 h), interaction in powdered δ-WC1±x (size distribution – 0.1-0.7 μm, mean particle size – 0.2-0.3 μm, content non-combined C – 0.2 %) – 17 mol.% Co mixtures leads to the formation of η2-W3Co3Cy phase

Ar, 5 MPa

1400

The liquid-phase sintering (exposure – 1 h) of powdered δ-WC0.99 (size distribution ≤ 1 μm, specific surface area – 2.8 m2 g–1, contents: non-combined C – 0.04%, O – 0.28%) – 10 % Co mixtures leads to the formation of highly dense hard alloys (with the presence of η2-W3Co3Cy minor phase, mean carbide grain size – ~0.4 μm)

Ar, 2 MPa

1400

Highly dense δ-WC1±x – 12 % Co hard alloys, fabricated by hot isostatic pressing (exposure – 40 min) techniques, had the mean grain sizes of 0.45 μm (microstructure with well-preserved Co layers) and 0.76 μm (micro-structure with broken Co layers) in the cases of using powders prepared by solution method and by ballmilling method, respectively

–

1400

Powdered δ-WC1±x – 6 % Co mixtures (99.9 % purity, mean particle size – 0.1-0.2 μm) were subjected to spark-plasma sintering procedure to fabricate highly dense hard alloys; during the procedure, the decarburization of δ-WC1±x phase occurred and W2±xC, η1-W6Co6Cy and η2-W3Co3Cy secondary minor phases were formed in the sintered alloys (porosity – 0.7-1.6 %)

Vacuum 1400

δ-WC1±x – Co powders with different Co contents (6 %, 10 % and 16 %) and mean particle sizes (1 μm and 5 μm) were subjected to liquid-phase sintering procedure (exposure – 1 h) to produce functionally graded (FG) hard alloys (with the gradients

(continued)

2.6 Chemical Properties and Materials Design

271

Table 2.21 (continued) of Co and C contents and presence of η2-W3Co3Cy); initial particle size differences could induce a step-wise profile of Co content while an initial difference in C content could be used to obtain a Co gradient within the δ-WC1±x – Co sintered body, final Co distribution in the sintered FG materials was the result of combined effect on capillary forces and phase equilibria H2, > 0.1 MPa

1400-1450 δ-WC1±x – 12 % Co hard alloys (porosity – 0.15÷1.40 %, mean carbide grain size – (0.78÷1.06)±(0.09÷0.14) μm, carbide grain contiguity – (0.39÷0.46)±(0.08÷0.14), mean binder intercept length – (0.26÷0.34)±(0.07÷0.11) μm) were fabricated by liquid-phase sintering (exposure – 30-45 min) from high-energy ball-milled powders (carbide size distribution – 40250 nm, contents: total C – 5.32-5.36 %, O – 0.23 %)

Vacuum, 1400-1450 Quasi-nanosized δ-WC1±x – 5-10 % Co 0.13 Pa hard alloys with δ-WC1±x-core – Co-shell structure were prepared by spark-plasma sintering (exposure – 10 min) from the fine powders (mean particle size – 0.16-0.30 μm) Ar, 3 MPa

1400-1500 δ-WC1±x – 18 vol.% Co two-phase hard alloys (mean δ-WC1±x grain size – 1 μm) were prepared through 12-hour-sintering cycle of industrial sinter-HIPing process with 1.5-hour-exposure at maximum temperature

–

1400-1500 δ-WC1±x is in equilibrium with α/ε-W2+xC, η2-W3Co3Cy, κ-W3CoC1+x (metastable, ?), α-C (graphite) and liquid phases, while α/ε-W2+xC – with η2-W3Co3Cy and metallic W phases

–

1400-1500 From the computation analysis it was concluded that during the liquid-phase sintering of δ-WC1±x – Co hard alloys the dissolution of δ-WC1±x grains is controlled by the diffusion of W in the Co-based melt; the diffusion coefficient of W in the stirred liquid Co is ~2×10–5 cm2 s–1 at 1450 °C

Vacuum 1400-1500 The wettability of δ-WC1±x by a liquid metallic Co-based binder is complete at low C contents and becomes incomplete when the C content increases that can lead to the migration of Co-based binder from δ-WC1±x regions with high C content into the regions with low C content, the regions with

(continued)

272

2 Tungsten Carbides

Table 2.21 (continued) low C contents attract the liquid binder from those with high C contents due to their better wetting by the liquid binder and consequently higher capillary forces; δ-WC1±x/δ-WC1±x interfaces in the δ-WC1±x – Co hard alloys with high C content do not comprise Co interlayers, whereas the majority of such interfaces in the alloys with low C content comprise Co interlayers of the order of several nanometres or thicker Vacuum, 1400-1600 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 8 % ε-Co (hexagonal) nanocrystalline powdered mixtures (mean particle size – ~60 nm, total content of combined C – ~5.50 %) led to the formation of sintered hard alloys (porosity – 3-9 %) composed of δ-WC1±x and α-(Co,W,C) cubic metallic solid solution (with the presence of η2-W3Co3Cy phases) Vacuum 1410

Powdered δ-WC1±x (mean grain size – from 0.8 to 6.0 μm, total C content – from 6.11 % to 6.18 %) – 10 % Co mixtures were subjected to liquid-phase sintering (exposure – 1 h) to prepare highly dense two-phase hard alloys; the effect of dissolved W in the binder had a more significant effect on the binder phase morphology and polymorphism than the value of δ-WC1±x grain size

Ar, 2 MPa

Highly dense δ-WC1±x – 10 % Co hard alloys with plate-like δ-WC1±x grains were fabricated via hot isostatic pressing (exposure – 1 h) procedure using the addition of ultra-fine δ-WC1±x powders

1410

Vacuum 1410

The following minor phases were detected in sintered δ-WC1±x – 20 % Co hard alloys, depending on total C content: η-phases – at 4.51 %, none (two-phase structure) – at 4.71-4.93 % and α-C (graphite) – 5.09 %

Ar, 1410 10 MPa

The following minor phases were detected in gas pressure sintered δ-WC1±x – 20 % Co hard alloys, depending on total C content: η-phases – at 4.47 %, none (twophase structure) – at 4.72-4.96 % and α-C (graphite) – 5.09 %

(continued)

2.6 Chemical Properties and Materials Design

273

Table 2.21 (continued) –

1420

Due to the specific wetting and capillarity phenomena in δ-WC1±x – 5-10 % Co hard alloys, the sintered parts at slow cooling (< 0.5 K min–1) are completely covered with Co films after sintering procedures; in the case of difference in δ-WC1±x grain size in the local regions of these alloys, considerable drifts of metallic binder occur from coarse-grain into fine-grain regions due to different capillary forces

Vacuum 1420

Highly dense δ-WC1±x – 6 % Co hard alloy was obtained from a preliminary milled powder by liquid-phase sintering (dwelling time – 0.5 h) procedure; some Co was present on the δ-WC1±x grain surface after breaking the specially prepared thin foils (thickness – 10-20 nm) of this alloy by applying tensile loads at the δ-WC1±x – Co interfaces, so that the crack propagation path presumably lied not directly at the interface, but in the metallic binder region adjacent to it

Vacuum, 1420 0.1 Pa

Powdered δ-WC1±x (> 99 %, 10-12 μm) – 8 % Co (> 99.5 %, 5 μm) mixtures (initial purities and mean particle sizes are given in brackets, total content of non-combined C – 0.04 %, preliminarily ball-milled to δ-WC1±x mean size < 0.6 μm) were subjected to high-speed electron beam sintering procedure (exposure – 1.0-2.5 min) to fabricate poreless hard alloys (mean grain size ≤ 1 μm, content of non-combined C – 0.05 %)

Vacuum 1420-1460 Gradient δ-WC1±x – Co hard alloys, comprising no η-phases and having various combinations of δ-WC1±x mean grain size, were produced by obtaining various C contents in the alloy near-surface layer and core; alloys with low Co contents in the surface region were fabricated by carburization of green articles with the original low C content followed by the liquid-phase sintering, and alloys with high Co contents in the surface region were obtained by decarburization of green articles with the original high C content followed by the liquid-phase sintering

(continued)

274

2 Tungsten Carbides

Table 2.21 (continued) H2

1420-2030 In this interval of temperatures, no other phases, except those in the starting materials, were detected on the surface of δ-WC1±x – 6 % Co hard alloys exposed to a concentrated solar radiation source, the surface film of hard alloys was enriched with Co, at the highest temperatures Co due to the sublimation vanished from the surface but remained in crystalline form in the bulk materials

Vacuum > 1440

δ-WC1±x – 15 % Co hard alloys were prepared by the infiltration of pre-sintered δ-WC1±x – 3 % Co skeleton composition by the infiltrant with δ-WC1±x – 75 % Co composition; during the infiltration, the skeleton composition varies continuously from δ-WC1±x – η2-W3Co3Cy – κ-W3CoC1+x region to the δ-WC1±x – η2-W3Co3Cy – L (liquid) due to the reaction: κ-W3CoCy + 2Co = η2-W3Co3Cy, which might be a clue to understanding the cause for the abnormal grain growth in the δ-WC1±x – Co system

Ar, 5 MPa

1450

Medium-sized δ-WC1±x (mean particle size – ~4 μm), prepared by H2-reduction, can be directly used for the preparation of twophase coarse-grained δ-WC1±x – 8 % Co hard alloys by hot isostatic pressing (HIP)

1450

With increasing C content in the liquidphase sintered δ-WC1±x – 20 % Co hard alloys (with the contents of total C from 4.45 % to 5.25 %, the compositions with minimal and maximal C contents were three-phase alloys, containing either η2-W3Co3Cy, or α-C (graphite) phases, respectively; the change in δ-WC1±x mean grain size, corresponding to the C contents, was from 2.5 μm to 3.1 μm), δ-WC1±x grains have coarsened, and their morphology characteristic tends to show truncated trigonal prism shape (grain growth mechanism of δ-WC1±x cannot be explained by the Ostwald ripening and Lifshitz-Slyozov-Wagner theory); in addition, increasing C content results in the decrease of W amounts dissolved in the metallic Cobased binder, in the C-rich alloys the binder dissolves – ~4 % W and in the C-deficient alloys – up to 20 % W

–

(continued)

2.6 Chemical Properties and Materials Design

275

Table 2.21 (continued) The dissolution of δ-WC1±x in the stirred Co-based liquid is limited by diffusion of W in it, this diffusion coefficient was evaluated to be ~2×10–5 cm2 s–1

–

1450

–

1450-1475 Coarse-grained δ-WC1±x – 10 % Co hard alloys, sintered from narrow-fraction δ-WC1±x powder (size distribution – 5-15 μm), had porosity < 0.02 %, irrespectively of C content; the alloys with a C deficit of 0.1-0.9 % had a two-phase structure, while the alloys with a C deficit of 1.3 % were containing inclusions of the η-phases in the addition to δ-WC1±x and Co phases, the contents of dissolved W was 10 %, 12 %, 15 % and 19 % for the carbides without deficit and with low, middle and high C deficits, respectively

–

1450-1500 In general, the sintered δ-WC1±x – Co hard alloys can be two-phase materials, containing δ-WC1±x grains and metallic Co-based binder between them, only at the certain conditions to the contents of C; at a deficit or an excess of C, the alloys become threephase and contain additionally either η2-W3Co3Cy or α-C (graphite), respectively

Vacuum 1480

The additional carburization of δ-WC1±x – 20 % Co hard alloys, containing large amounts of η2-W3Co3Cy phase after sintering, leads to the full decomposition of η-phase and formation of δ-WC1±x + α-Co, according to the following reaction: W3Co3C + 2C = 3WC + 3Co

Ar

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Co (exposure – 5 min)

1500

Vacuum 1500

Preliminarily mechanical alloyed δ-WC1±x – 1-2 % Co mixtures were sintered (exposure – 20 min) to prepare two-phase hard alloys; increasing in Co content in the mixtures resulted in the formation of η2-W3Co3Cy phase

Ar

Liquid-phase sintered (holding time – 1 h) δ-WC1±x – 10 % Co two-phase hard alloys, prepared from the preliminarily heat-treated powders containing less crystal defects, had a significantly smaller δ-WC1±x grain size, compared with the alloys prepared from non-treated powders

1500

(continued)

276

2 Tungsten Carbides

Table 2.21 (continued) –

1500

The melt composition of metallic binder in δ-WC1±x – 10 % Co alloy varies in ranges from (Co0.775W0.075C0.15) to (Co0.68W0.21C0.11), depending on total C contents in the alloy

–

1500

Powdered (purity level and initial mean particle size, respectively, are given in the brackets) δ-WC1±x (99 %, 0.2 μm) – 0.5 % Co (99 %, ~75 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (exposure – 5 min) procedures to prepare dense hard alloys (porosity – 2.4 %)

–

1500-1530 In the powdered and pre-sintered δ-WC1±x – Co mixtures subjected to heat treatments, the additional dissolution of the δ-WC1±x grains in metallic Co and growth of δ-WC1±x grains due to the recrystallization via the liquid phase occur simultaneously; further during the cooling process after the holding time of sintering, the dissolved δ-WC1±x deposits from the liquid phase onto the surface of carbide grains, which results in their growth

High 1700-1900 Powdered δ-WC1±x (~13 μm) – 10 % Co pressure (~11.5 μm) mixtures (mean grain sizes are machine, given in brackets) were subjected to high7.7 GPa pressure high-temperature (HPHT) treatment (exposure – 2 min) to prepare completely densified hard alloys –

~1870

The invariant equilibrium with the participation of the liquid phase L (liquid:Co0.53W0.33C0.14) + γ-W2.23C ↔ δ-WC1.0 + η-W3.9Co2.1C1.0 realizes in the system with the compositions of phases indicated in the reaction

–

> 2535

The invariant equilibrium (?) with the participation of the liquid phase L (liquid:W0.53C0.32Co0.15) + γ-WC0.61 ↔ δ-WC1.0 + γ-W2.23C realizes in the system with the compositions of phases indicated in the reaction

Vacuum, ~2800 8 mPa

The surface treatment of δ-WC1±x (grain size – 1.25-5.0 μm) – 6 % Co hard alloys under the non-equilibrium conditions by high current pulsed electron beam (HCPEB) irradiation (pulse duration – 2.5 μs, energy density – 3.0 J cm–2) led to the formation of nanograined γ-WC1–x, ternary κ-W3CoC1+x and η2-W3Co3Cy phases

(continued)

2.6 Chemical Properties and Materials Design

277

Table 2.21 (continued) and α-C (graphite) precipitate domains (mean size – ~50 nm) –

~4200

The surface ablation under the UV pulse laser shots with fluence – 2.5 J cm–2 (irradiance – 125 MW cm–2) of sintered δ-WC1±x – 6 % Co hard alloys (mean carbide grain size – 3 μm) led in the laser irradiated areas to the fast evaporation (selective removal) of Co binder and partial transformation of initial δ-WC1±x phase to γ-WC1–x, then to α-W2+xC and W3+xC, and finally to metallic W phase (escape of elemental C due to the accumulated heating of the surface)

C2H2/Ar

–

Powdered δ-WC1±x – 8-20 % Co mixtures were employed to deposit hard alloy coatings (thickness – 0.25-0.75 mm) on steel and Ti-based alloy substrates by detonation techniques; the deposited coatings were containing ~ 40-50 % of the δ-WC1±x presented in the starting mixtures, W2±xC phase, metallic W and Co, μ-Co7W6±x and κ-Co3±xW intermetallide phases and small amounts of η2-W3Co3Cy and κ-W3CoC1+x complex carbide phases

–

–

δ-WC1±x – Co hard alloys with η2-W3Co3Cy (or θ-W4Co2C) nanoparticles reinforced (nano-strengthened) Co-based binder were designed and fabricated

–

–

In the δ-WC1±x – Co hard alloys the content of W dissolved in the Co-based metallic binder (Cw) varies from 1.2 % up to 28 % in the accordance to total C content in the materials (CC), as a reciprocal relationship exists between these parameters: Cw CC = const; the total C content also affects the grain size distribution and mean grain size of δ-WC1±x phase

–

–

The δ-WC1±x grains in δ-WC1±x – 6-20 % α/ε-Co hard alloys (mean grain size – 0.330.49 μm) have both faceted and rounded surfaces, which is a consequence of the relatively low amount of liquid phase during sintering, making impingements significant

–

–

The formation of graded structures in δ-WC1±x – Co hard alloys can be achieved through the liquid phase migration, which is induced by different techniques

(continued)

278

2 Tungsten Carbides

Table 2.21 (continued) –

–

The microstructural parameters of twophase sintered δ-WC1±x – 5-35 vol.% Co hard alloys such as the Co intercept length, lCo, the δ-WC1±x intercept length, lWC, and phase volume fractions of Co and δ-WC1±x, respectively, VCo and VWC (VCo + VWC = 1), are empirically related by the equation: lCo = lWC (0.1 + 2VCo); more accurate value for lCo can be obtained by measurement of contiguity, C, using the following relationship: lCo = lWC VCo / (1 – VCo) (1 – C)

–

–

Nanocomposite δ-WC1±x – Co powders consisting of grains with a Co-core / δ-WC1±x-rim structure were prepared by precipitation covering – continuous reduction / carburization method

–

–

A model of an interpenetrating network in δ-WC1±x – Co hard alloys was examined and from the arguments based on energetics it was shown that a WC-WC network cannot exist in the presence of Co

–

–

The massive loss of C – up to 40-65 % and Co – up to 20-35 % (relative to the starting powdered materials) was observed in the high-energy plasma sprayed δ-WC1±x – 12 % Co coatings (cast and crushed powders with particle size distributions – from 5 to 100 μm, average sizes – 15-45 μm and contents total C – ~4 %); for the coatings with the same compositions prepared by high-velocity oxy-fuel (HVOF) spraying techniques from the similar starting materials the observed loss of C – up to ~40 % relative, but no Co loss was detected

–

–

The loss of C – up to ~25 % (relative to the starting powdered materials) was observed in the plasma sprayed δ-WC1±x – 17 % Co coatings (starting materials: agglomerated type powders with average particle sizes – ~ 10-45 μm, approximate compositions of the prepared coatings: δ-WC1±x – major phase, γ-W2±xC and metallic W – minor phases or traces, η1-W6Co6Cy and η2-W3Co3Cy – traces and binder – α-Co or α/ε-Co)

(continued)

2.6 Chemical Properties and Materials Design

279

Table 2.21 (continued) –

–

The comparison of high-velocity air-fuel (HVAF) and high-velocity oxy-fuel (HVOF) spraying techniques for the deposition of δ-WC1±x – Co coatings showed that substantial amounts of W2±xC phases and higher contents of W in the metallic binder phases were inherent to the produced HVOF-sprayed coatings due to the processes occurring during the spraying, in contrast to the HVAF-sprayed coatings, in which the compositions were unchanged from those of the starting powders, with a 100 % retention of δ-WC1±x and complete absence of W2±xC in the coatings

–

–

The heterogeneous melting and localized superheating of feed nanosized δ-WC1±x – Co powder during its high-velocity oxyfuel (HVOF) spraying lead to extensive dissolution of the δ-WC1±x nanoparticles in the liquid Co, accompanied by rapid reaction of the dissolved C in the environment; upon cooling down from the peak temperature, the Co-rich melt (deficient in C) forms W2±xC and metallic W phases, depending on the loss of C by gasification

–

–

Multimodal δ-WC1±x – 12 % Co powders, composed of 50 % nano- and 50 % microparticles (with size distributions – 50-90 nm and < 0.2 μm, respectively) and agglomerated to the size distribution of 10-45 μm, were employed for the deposition of coatings (porosity – ~1 %) on steel substrates via high-velocity oxy-fuel (HVOF) spraying techniques; due to the decarburization processes the deposited coatings were containing W2±xC, metallic W and η1-W6Co6Cy phases in opposite to the coatings, prepared from sintered and crushed δ-WC1±x – 12 % Co powders (particle size distribution – 10-45 μm, crystalline size – 2-3 μm), which were mainly consisting of δ-WC1±x and Co (almost the same composition as that of the starting powder for their preparation)

–

–

The coatings, deposited using powdered δ-WC1±x – 12 % α-Co mixtures (contents: total C – 6.8 %, Fe – 0.5 %) by high-velocity flame (HVF) spraying technique, were composed mainly of δ-WC1±x and γ-W2±xC phases (with small amounts of Co)

(continued)

280

2 Tungsten Carbides

Table 2.21 (continued) –

–

Nanostructured δ-WC1±x – 12 % Co hard coatings were prepared by liquid-fuel highvelocity oxy-fuel (HVOF) spraying techniques

–

–

The bimodal-grained δ-WC1±x – Co hard coatings were fabricated using the in situ synthesized nanoscale powder having a particle size of 70-200 nm and a small amount of ultra-coarse δ-WC1±x particles in the size range of 5-20 μm as raw materials for the liquid-fuel high-velocity oxy-fuel (HVOF) spray technique processing

–

–

Powdered δ-WC1±x – 12 % Co mixtures (agglomerated and sintered, mean particle size – 33 μm) were employed for the fabrication of hard coatings (porosity – 1.7±0.2 μm, mean grain size 0.6±0.2 μm) on steel substrates using liquid-fuel high-velocity oxy-fuel (HVOF) spray technique; the sprayed/deposited coatings were composed of δ-WC1±x and η1-W6Co6Cy phases in amorphous metallic Co-based matrix

–

–

Films (thickness – 2-3 μm) deposited on steel substrates by d.c. diode and r.f. magnetron sputtering techniques using the δ-WC1±x – 6-15 % Co hard alloys as targets were structured in the ranges from amorphous (with higher Co contents) to crystalline (equilibrium or metastable) and mainly composed of γ-WC1–x (with (111) or (311) preferential orientation) and γ-W2±xC (with (1100) preferential orientation) phase constituents

–

–

The coatings, prepared using a pulsed plasmatron supplied with δ-WC1±x – 12 % Co powdered mixtures (size distribution – 3556 μm), were composed of crystal δ-WC1±x grains (mean size – 0.15 μm), traces of γ-WC1–x, W2±xC, μ-Co7W6±x, κ-Co3±xW and W phases and α/ε-Co (mean size – 25 nm) grains with the grain boundaries containing η2-W3Co3Cy particles (mean size – 15 nm)

–

–

Nanostructured δ-WC1±x – Co coatings prepared via a vacuum plasma spraying process were mainly composed of δ-WC1±x phase (mean grain size – 35 nm, similar to that in the primary powders; however, in some regions it was reduced to ~10 nm, in some – it has grown to ~100 nm, in other – due to the second recrystallization it was as large as ~500 nm) with such minor phases

(continued)

2.6 Chemical Properties and Materials Design

281

Table 2.21 (continued) as α-W2+xC, γ-WC1–x and η2-W3Co3Cy –

–

Powdered δ-WC1±x (size distribution – 0.10.2 μm) – 12 % Co mixtures were applied for the fabrication of coatings on steel substrates using detonation-gun spraying technique; the decomposition of δ-WC1±x phase into γ-W2±xC, metallic W and complex amorphous phases was observed during the high-temperature detonation spraying and rapid quenching processes

–

–

Surface δ-WC1±x – Co metal matrix composites (MMC) were produced by plasma melt injection of δ-WC1±x – 17 % Co and crushed δ-WC1±x – 8 % Co particles

–

–

The effect of substitutional Co impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

–

–

For the conventional coarse-grained δ-WC1±x – Co hard alloys, the corresponddence of δ-WC1±x (0001) // α-Co (111) and δ-WC1±x (0110) // α-Co (110) at the δ-WC1±x/Co interface generally results from the dissolution-precipitation mechanism in the liquid-phase sintering process The δ-WC1±x (1010) prism facets and (0001) basal planes are the surfaces, which are most frequently in contact with metallic Co in the δ-WC1±x – Co hard alloys, the δ-WC1±x habit is an approximately equiaxed trigonal prism bound by 3 prism facets and 2 basal facets; 90°-twist boundaries about (1010) comprise 11 % of all the observed δ-WC1±x – δ-WC1±x interfaces and 2 types of boundaries (twist and an asymmetric tilt) with a 30°-rotation about (0001) – 3 % of the population

–

–

–

–

In δ-WC1±x – 8 % Co hard alloys, grain boundary plane distribution regardless of misorientation indicate that the (0001) basal and (1010) prismatic planes are the most common habit planes, and the interface area aspect ratio is determined by the ratio of the (0001) plane area to the (1010) plane area The stability of δ-WC1±x (1010) / δ-WC1±x (1010) grain boundaries and adhesion properties at the α-Co (001) / WC (1010) interface were examined using density functional theory (DFT) in the context of liquid-phase sintering process

(continued)

282

2 Tungsten Carbides

Table 2.21 (continued) –

–

The interaction of δ-WC1±x (0001), (1010) (1210) and γ-WC1–x (100) surfaces with Co atoms was studied using methods of the density functional theory (DFT) and pseudopotentials

–

–

In δ-WC1±x – 13 % α/ε-Co hard alloys (mean grain size – 0.7 μm) subjected to the grinding procedure, the following microstructural features in Co phase binder were observed at various depths: 0-1 μm – almost all the phase is ε-Co, formation of nanograins, stacking faults exist in most of nanograins; 1-3 μm – the phase mostly is ε-Co, grain subdivision, high degree of deformation; 5-8 μm – the phase is α/ε-Co, martensitic phase transformation resulted in large ε-Co platelets, which have coherent interfaces with the parent α-Co crystal, according to the ε-Co (0001) // α-Co (111) and ε-Co // α-Co orientation relationships

–

–

Powdered δ-WC1±x (50-80 nm) – 75 % Co (1-2 μm) mixtures (average particle sizes are given in brackets) were subjected to selective laser melting (SLM) procedure to prepare hard alloys with the nonuniformity scale as low as 0.5 μm

–

–

Crack-free highly dense δ-WC1±x – 20 % Co hard alloys with the variation of grain sizes from submicron to ~20 μm in either vertical or horizontal cross-sections and an apparently lamellar microstructures in the vertical cross-sections were fabricated using one-step selective laser melting (SLM) techniques without any further heat treatment

–

–

The fabrication of non-porous articles of complex geometry from δ-WC1±x – Co granules initially containing 13 % Co was carried out by a single-step process of additive manufacturing based on selective electron beam melting (SEBM) techniques

–

–

δ-WC1±x – Co nanowires (length – 3.7-4.7 μm) were fabricated by using focused ion beam (FIB) techniques and microprobe sampling technologies Some data on the system reported by various authors differ markedly

See also Table 2.26 See also section δ-WC1±x – α/β-C – α/ε-Co

(continued)

2.6 Chemical Properties and Materials Design

283

Table 2.21 (continued) See also section C – Co – W in Table I2.14 δ-WC1±x – Vacuum, 800 α/β/ε/γ-W2±xC – 10 mPa α/ε-Co

Vacuum, 800-900 10 mPa

In the powdered δ-WC1±x – 7 % γ-W2±xC – 7 % ε-Co (hexagonal) mixtures (mean particle size – ~ 1-2 μm, amounts of particles (< 0.5 μm) – 10-15 vol.%, content total C – 5.6 %) subjected to heat treatment (holding time – 10 min) the composition converts to the mixture of δ-WC1±x, γ-W2±xC, α-Co (cubic) and κ-Co3±xW phases

[158, 490491, 2093, 2416, 2473, 2542, 2569, 2602, 2668, 2710, 2728, 2819, 2880, 2895, 2907, The heat treatment (exposure – 10 min) of 2932, 2940cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC 2942, 2984, 2986, 2997, – 8 % ε-Co (hexagonal) powdered mix3372] tures (mean particle size – ~6 μm, total content of combined C – ~5.55 %) led to the formation of sintered bodies (porosity – 39 %) composed of δ-WC1±x, α-Co (cubic) and minor (γ-W2±xC, κ-Co3±xW, η1-W6Co6Cy) phases

Vacuum, 800-900 10 mPa

The heat treatment (exposure – 10 min) of cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) sub-microcrystalline powdered mixtures (mean particle size – ~0.15 μm, total content of combined C – ~5.60 %) led to the formation of sintered bodies (porosity – 50 %) composed of δ-WC1±x, α-Co (cubic) and minor (γ-W2±xC, η1-W6Co6Cy) phases

Vacuum, 800-900 10 mPa

The heat treatment (exposure – 10 min) of cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) ball-milled nanopowdered mixtures (mean particle size – ~20 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 41-43 %) composed of δ-WC1±x, α-Co (cubic) and minor (κ-Co3±xW, η1-W6Co6Cy) phases

Ar

Amorphous coatings, deposited using powdered δ-WC1±x – γ-W2±xC – 12 % Co mixtures by high-energy plasma (HEP) or high-velocity oxy-fuel (HVOF) thermal spray techniques, transform after a heat treatment to η1-W6Co6Cy and η-W4–xCo2+xC (with the latter phase becoming more predominate at the higher temperatures) and δ-WC1±x and metallic W phases (γ-W2±xC phase could not be detected at higher temperatures)

> 850

(continued)

284

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 900 10 mPa

Ar

≥ 900

Vacuum, 1000 10 mPa

In the powdered mixtures δ-WC1±x – 7 % γ-W2±xC – 7 % ε-Co (mean particle size – ~ 1-2 μm, amounts of particles (< 0.5 μm) – 10-15 vol.%, content total C – 5.6 %) subjected to heat treatment (holding time – 10 min) the composition converts to the mixture of δ-WC1±x, γ-W2±xC, α-Co, κ-Co3±xW and η1-W6Co6Cy phases Crack-free articles made from δ-WC1±x – 17 % α/ε-Co (with presence of γ-W2±xC) hard alloys were building by the additive manufacturing, in particular – using laser powder-bed fusion (LPBF) process The heat treatment (exposure – 10 min) of cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) sub-microcrystalline powdered mixtures (mean particle size – ~0.15 μm, total content of combined C – ~5.60 %) led to the formation of sintered bodies (porosity – 49 %) composed of δ-WC1±x, α-Co (cubic) and minor (η1-W6Co6Cy, η2-W3Co3Cy) phases

Vacuum, 1000-1200 In the powdered mixtures δ-WC1±x – 7 % 10 mPa γ-W2±xC – 7 % ε-Co (mean particle size – ~ 1-2 μm, amounts of particles (< 0.5 μm) – 10-15 vol.%, content total C – 5.6 %) subjected to heat treatment (holding time – 10 min) the composition converts to the mixture of δ-WC1±x, α-(Co,W,C) solid solution and η1-W6Co6Cy phases Vacuum, 1000-1200 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) powdered mixtures (mean particle size – ~6 μm, total content of combined C – ~5.55 %) led to the formation of sintered bodies (porosity – 22-37 %) composed of δ-WC1±x and α-(Co,W,C) cubic metallic solid solution (with the presence of η1-W6Co6Cy phase) Vacuum, 1000-1200 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) ball-milled nanopowdered mixtures (mean particle size – ~20 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 24-38 %) composed of δ-WC1±x, η1-W6Co6Cy and η2-W3Co3Cy phases

(continued)

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285

Table 2.21 (continued) Vacuum, 1100-1600 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) sub-microcrystalline powdered mixtures (mean particle size – ~0.15 μm, total content of combined C – ~5.60 %) led to the formation of sintered bodies (porosity – 9-48 %) composed of δ-WC1±x, α-(Co,W,C) cubic metallic solid solution and η2-W3Co3Cy phases Vacuum, 1300-1600 In the powdered mixtures δ-WC1±x – 7 % 10 mPa γ-W2±xC – 7 % ε-Co (mean particle size – ~ 1-2 μm, amounts of particles (< 0.5 μm) – 10-15 vol.%, content total C – 5.6 %) subjected to heat treatment (holding time – 10 min) the composition converts to the mixture of δ-WC1±x, α-(Co,W,C) solid solution and η2-W3Co3Cy phases Vacuum, 1300-1600 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) powdered mixtures (mean particle size – ~6 μm, total content of combined C – ~5.55 %) led to the formation of sintered hard alloys (porosity – 1-7 %) composed of δ-WC1±x and α-(Co,W,C) cubic metallic solid solution (with the presence of η2-W3Co3Cy phase) Vacuum, 1300-1600 The heat treatment (exposure – 10 min) of 10 mPa cold-pressed δ-WC1±x – 4.5-7.5 % γ-W2±xC – 8 % ε-Co (hexagonal) ball-milled nanopowdered mixtures (mean particle size – ~20 nm, total content of combined C – ~5.50 %) led to the formation of sintered bodies (porosity – 9-17 %) composed of δ-WC1±x, and η2-W3Co3Cy phases Cubic press, 4.5-5.5 GPa

1350-1500 Powdered δ-WC1±x (mean particle size – 0.5-2.0 μm) was infiltrated due to the contact interaction with a δ-WC1±x – 16 % Co hard alloy δ-WC1±x – 40 vol.% Co (with the presence γ-W2±xC) of hard alloys were prepared by uniaxial hot-pressing of powdered mixtures in the liquid-phase sintering regime

–

1500

–

~1500-3000 The coatings, deposited on polymeric substrates using powdered δ-WC1±x (with the presence of α-W2+xC) – 12 % α/ε-Co mixtures (size distribution – 15-45 μm) by high-velocity oxy-fuel (HVOF) spraying technique (modified by the addition of CO2 gas flows, velocity – 300-900 m s–1), were composed of δ-WC1±x, γ-WC1–x,

(continued)

286

2 Tungsten Carbides

Table 2.21 (continued) α/β-W2+xC, η2-W3Co3Cy and metallic α/ε-Co (binder) phases; the decomposition (interaction with Co) of δ-WC1±x and subsequent formation of other carbide phases occurred on the surface of the δ-WC1±x particles to a thickness of ~ 10-100 nm (traces of γ-WC1–x phase were also detected in the metallic Co binder) –

Dense δ-WC1±x – γ-W2±xC – 12 % Co hard coatings (thickness – (1.35÷1.80)±0.06 mm) were deposited on steel substrates using cast crushed composite powders (size distribution – 45-75 μm) by laser engineering net shaping (LENS) process (laser energy input – 365-465 J mm–3); small amounts of δ-WC1±x phase were transformed to γ-W2±xC during processing due to decarburization

–

–

Powdered δ-WC1±x – 2 % W2±xC – 12 % Co mixtures (with the presence of 1 % η1-W6Co6Cy, content total C – 5.37±0.02 %, particle size distribution – 20-70 μm) were employed to deposit various coatings on steel substrates using high-velocity oxyfuel (HVOF) thermal spraying method; the deposited coatings (index of crystallinity – 42-73 %, contents: total C – 2.9-4.3 %, W – 81.3-83.8 %, Co – 13.3-14.3 %) were composed of δ-WC1±x, W2±xC, metallic W and Co phases

–

–

Powdered δ-WC1±x – W2±xC – 11 % Co mixtures (agglomerated and sintered, size distribution – 10-45 μm, with the presence of η2-W3Co3Cy) were applied for the deposition of various coatings on steel substrates using high-velocity oxy-fuel (HVOF) thermal spraying techniques; depending on the operating conditions the deposited coatings (thickness – 0.25-0.34 mm, porosity – 0.2-0.7 %) were composed of δ-WC1±x, γ-W2±xC, W3+xC, Co3C and (Co,C) phases

–

–

The δ-WC1±x – ~12 % Co (with presence of W2±xC phase) highly dense coatings, fabricated on Al alloy substrate from nanostructured powders (particle size distribution – 0.05-0.5 μm) using high-velocity oxy-fuel (HVOF) thermal spraying techniques, were composed of nano-, submicronand micro-sized carbide grains uniformly dispersed in a nanocrystalline/amorphous (Co,W,C) matrix

Ar

(continued)

2.6 Chemical Properties and Materials Design

287

Table 2.21 (continued) –

–

The δ-WC1±x – 12 % Co (with presence of W2±xC and γ-WC1–x phases) highly dense coatings were fabricated using supersonic high-velocity oxy-fuel (HVOF) thermal spraying techniques

See also section C – Co – W in Table I2.14 α/β/ε/γ-W2±xC – α/ε-Co

–

H2

1250-1400 The products of interaction between the [13, 1930, components are η2-W3Co3Cy and δ-WC1±x 2416, 2574] phases 1430

Powdered γ-W~2.0C (mean particle size – ~1 μm, contents: non-combined C – 0.09 %, O < 0.02 %, Fe < 0.015 %, Co < 0.01 %) – 0.1-5.0 % Co (mean particle size – 1.4 μm, contents: total C – 0.022 %, H – 0.37 %, Fe < 0.02 %) mixtures were subjected to sintering to prepare highly dense materials; noticeable dissolution of carbide in the metallic Co phase was observed

See also section α/β/ε/γ-W2±xC – α/β-C – α/ε-Co See also section C – Co – W in Table I2.14 δ-WC1±x – Co – Ar (Co – C – Cr – Mn – Mo – Ni – Si)

δ-WC1±x – Co – Cr

–

1150

Powdered δ-WC1±x – 12 % Co alloy (mean [3001] particle size < 105 μm) in the mixture with 50 % Co-based alloy (C – 0.25 %, Cr – 28 %, Mo – 5 %, Ni – 2.5 %, Si ≤ 2 %, Mn ≤ 1 %; atomized spherical particles with size < 105 μm) was subjected to hot isostatic pressing (HIP) procedure (holding time – 3 h) to fabricate metal matrix composites; the formation of γ-W2±xC and η-(W,Co,Cr,Mo)6Cy phases was detected in the prepared materials

~650

The heat-treatment of coatings (average [10, 1821, porosity – 0.85 %) deposited on steel sub- 1989, 1998, strates by means of high-velocity oxy-fuel 2333, 2578, (HVOF) thermal spraying, using powdered 2593, 2612, δ-WC1±x – 10 % Co – 4 % Cr mixtures 2615, 2652, (particle size range – 5-45 μm), resulted in 2656, 2942, the transformation of as-sprayed coating 2966, 3007matrix, composed of a mixture of amor3056, 3067phous and nanocluster phases, into the 3083, 3158, nanocrystalline structure; apart of major 3186, 3208, δ-WC1±x, such minor phases as (W,Cr)2±xC 3328, 3435, and η1-W6Co6Cy were detected in the coa- 4068] tings

(continued)

288

2 Tungsten Carbides

Table 2.21 (continued) –

700-1000

In the alloys Co – 24-32 % W – 3-5 % Cr – 1.9 % C produced by melting procedures, the decomposition of η-(W,Co,Cr)6Cy phases occur, so the formation of δ-WC1±x can be controlled within a wide range by proper heat treatment, including the possibility to fabricate directionally solidified materials

–

700-1050

In the Co-rich alloys (C – 0.6-2.0 %, W ≤ 50 %, Cr ≤ 50 %), δ-WC1±x phase can be in the equilibrium with α-(Co,Cr,W,C) metallic solid solution and (Cr,W)7C3±x, η-(W,Co,Cr)6Cy and η-(W,Co,Cr)12Cy carbide phases; the η-(W,Co,Cr)6Cy becomes unstable under the certain conditions – it will transform into δ-WC1±x in a Co-Cr metallic matrix, if the Cr content in it is < 5 % and decarburization does not occur

–

1200

The solubility of δ-WC1±x in α-(Co,W,C) solid solutions, measurable only on the Wrich side of the δ-WC1±x – Co line, is not changed significantly by the Cr addition; Cr replaces partly W, as it decreases slightly the limit W contents in α-(Co,W,C), corresponding to the fields α-Co – η2-W3Co3Cy – δ-WC1±x and α-Co – η1-W6Co6Cy – η2-W3Co3Cy in the phase diagram, hence for a defined W content, the Co for Cr substitution promotes the formation of η1-W6Co6Cy and η2-W3Co3Cy phases

–

~1350-1450 The addition of Cr significantly affects the melting temperature of Co-based binder in the δ-WC1±x – Co compositions, decreasing it by over 100 °C but also broadening the melting range (in particular, at low C contents) due to the high solubility of Cr in molten Co, which was determined by both experiments and calculations

–

~1400

The experimentally measured solubility of Cr in the δ-WC1±x phase of cemented carbides is 0.184±0.009 at.%

Ar

1400

Powdered δ-WC1±x (0.9 μm) – 24.5-25.0 mol.% Co (0.9 μm) – 1.5 mol.% Cr (0.9 μm) mixtures (mean particles sizes are given in brackets; with the small amounts of W and C added in order to fix atomic ratios C/W = 0.96 and 1.04 in the different three-phase fields δ-WC1±x + (Co,Cr) + C and δ-WC1±x + (Co,Cr) + η-(W,Cr,Co)6C) were subjected to solid state sintering pro-

(continued)

2.6 Chemical Properties and Materials Design

289

Table 2.21 (continued) cedure (exposure – 0.5 h) to prepare dense hard alloys; it was found that Cr addition has no significant effect on the solubility of W in the metallic Co-based binder Vacuum 1410

–

In sintered δ-WC0.99 – 9.9 % Co – 0.3 % Cr hard alloys (total content C– 5.45 %), Cr was observed to segregate to some carbidebinder phase boundaries, the amount of Cr at the interface corresponded to 17 % of the metal atoms assuming a 1.0 layer thick cubic (Cr,W)C1–x carbide (the rest should therefore be W atoms); at the carbide-carbide grain boundary segregations, 33 % of segregated Co were replaced by Cr atoms

1410-1450 Powdered δ-WC1±x (mean particle size – 0.2-0.9 μm) – 22-26 mol.% Co – 1-3 mol.% Cr mixtures (with various C/W and Cr/(Cr + Co) atomic ratios) were subjected to liquid-phase sintering (exposure 1-2 h) to prepare various hard alloys; metastable Cr-rich cubic (Cr,W)C1–x phase was found out at the δ-WC1±x – Co interfaces, the formed (Cr,W)C1–x – δ-WC1±x interfaces were characterized by the following epitaxial orientation relationships: δ-WC1±x (0001) // (Cr,W)C1–x (111) with δ-WC1±x // (Cr,W)C1–x and δ-WC1±x (1010>) // (Cr,W)C1–x (001) with δ-WC1±x // (Cr,W)C1–x and δ-WC1±x // (Cr,W)C1–x – with very low misfits (the high solubility of Cr in the liquid binder leads to assume that (Cr,W)C1–x precipitates on cooling)

Vacuum, 1450 < 1 Pa

Hard alloys (with low C content), liquidphase sintered (soak time – 1 h) from powdered δ-WC1±x (mean particle size – ~7 μm) – 5 % Co – 15 % Cr mixtures, were composed of three phases: δ-WC1±x, α-(Co0.85Cr0.12W0.03) metallic binder and η1-(W0.40Co0.49Cr0.11)12Cy complex carbide

Vacuum, 1450 < 1 Pa

Hard alloys (with high C content), liquidphase sintered (soak time – 1 h) from powdered δ-WC1±x (mean particle size – ~7 μm) – 5 % Co – 15 % Cr mixtures, were composed of four phases: δ-WC1±x, α-(Co0.91Cr0.08W0.01) metallic binder, (Cr0.53Co0.45W0.02)7C3.3 carbide solid solution and α-C (graphite)

(continued)

290

2 Tungsten Carbides

Table 2.21 (continued) 1450

While in the δ-WC1±x – 11 % Co – 1.1 % Cr hard alloys, the content of C increasing from 5.1 % to 5.7 %, the composition of minor phases, which are in the attendance with δ-WC1±x + Co phases, changes: η-(W,Co,Cr)6C – at ~ 5.1-5.3 %, no minor phases – at ~ 5.3-5.4 %, (Cr,Co,W)7C3±x – at ~ 5.4-5.5 % and (Cr,Co,W)7C3±x + α-C (graphite) – at ~ 5.5-5.7 %; the precipitates of (Cr,Co,W)7C3±x phase are very small and very few in number and often can therefore not be conclusively identified as such experimentally, besides – (Cr,Co,W)3C2–x phase can sometimes precipitate in the alloys instead of (Cr,Co,W)7C3±x (or jointly with it)

Vacuum, 1450 0.5 kPa

δ-WC1±x – 10 % Co – 0.4 % Cr hard alloys (with the presence of small amounts of η2-W3Co3Cy, mean δ-WC1±x grain size – 0.71-0.85 μm, total contents of C – 5.335.62 %) were prepared using liquid-phase sintering (exposure – 1 h) procedure (losses C during the sintering – 0.09-0.11 % in absolute, or 1.6-2.0 % in relative per cents)

–

–

–

Powdered δ-WC1±x – 10 % Co – 4 % Cr mixtures were employed to deposit cermet coatings (free of significant porosity) on austenitic stainless steel substrates using high-velocity oxy-fuel (HVOF) supersonic thermal spraying techniques; during spraying a fraction of δ-WC1±x decomposes into γ-W2±xC and/or reacts to form η2-W3(Co,Cr)3Cy and a small quantity of other mixed (complex) phases, the addition of Cr inhibits the decomposition process and avoids the occurrence of metallic W, the transformation of δ-WC1±x into γ-W2±xC occurs mainly in the outer layers of δ-WC1±x grains up to a thickness of ~ 10-100 nm, these grains are dispersed in nanocrystalline Co-Cr-W-C alloy (grain size distribution – 4-8 nm) coating matrix

–

–

Powdered δ-WC1±x – 10 % Co – 4 % Cr mixtures with C content above the nominal value were characterized by the additional presence of large grains of another carbide phase, such as (Cr,Co,W)7C3±x, which was retained as well in the coatings, deposited using the high-velocity air-fuel (HVAF) thermal spray technique, due to low C loss during the processing; however, this phase

(continued)

2.6 Chemical Properties and Materials Design

291

Table 2.21 (continued) was not detected in the coatings, deposited using high-velocity oxy-fuel (HVOF) spraying technique, due to more intensive metallurgical reactions and higher C loss inherent to it; both HVOF- and HVAFspraying processes are capable of producing highly dense δ-WC1±x – 10 % Co – 4 % Cr coatings, but as the former causes higher C loss – lower δ-WC1±x content was achieved in HVOF-spraying processed coatings –

–

Some δ-WC1±x-containing Co-based alloys with small additions of Cr can be produced by melting procedure (not only by powder metallurgy techniques); the formation of δ-WC1±x can be controlled within a wide range by proper heat treatment, including the possibility of directional solidification

–

–

Powdered δ-WC1±x – 10 % Co – 4 % Cr mixtures (mean particle size – ~40 μm; with the presence of small amounts of η1-W6Co6Cy and Cr7C3±x carbide phases) were employed to deposit cermet coatings on steel substrates by thermal spraying process using multi-chamber gas-dynamic accelerator; the deposited coatings were composed of δ-WC1±x, as a major phase, and minor phases, such as γ-W2±xC, η1-W6Co6Cy and metallic W

–

–

Powdered δ-WC1±x – 10 % Co – 4 % Cr mixtures (with various mean particle size – from 0.20 μm to 0.86 μm) were applied for the deposition of hard coatings on steel substrates using high-velocity oxy-fuel (HVOF) spraying technique; the compositions of deposited three-phase coatings (porosity – from 0.4 % to 0.9 %, for δ-WC1±x (major phase): volume fraction – 53-70 % and mean grain size – from 0.18 μm to 0.81 μm) were in the ranges of δ-WC1±x – 61-91 %, γ-(W,Cr)2±xC – 3-29 % and η2-W3(Co,Cr)3Cy – 4-10 %, depending on the particle size and other characteristics of the initial powders

–

–

Sintered δ-WC1±x – 10 % Co – 4 % Cr mixed powders (particle size distribution – 16-49 μm) were employed for the purposes of additive manufacturing (AM) using selective laser melting (SLM) techniques (energy density – 12.5 J cm–2, laser power – 100 W, scan speed – 40 mm s–1) to pro-

(continued)

292

2 Tungsten Carbides

Table 2.21 (continued) duce dense (porosity – 2.5 %) hard alloy parts with complex geometry Some data on the system reported by different authors differ markedly

See also section δ-WC1±x – Cr3C2–x – α/ε-Co δ-WC1±x – Co – Vacuum 1470 Cr – Cu – Fe – Nb – Ni – Ta – Ti

δ-WC1±x – Co – Cr – Cu – Fe – Ni

Powdered mixtures with the compositions: [2430] δ-WC1±x – 2.72 % Ta – 1.80 % Ti – 1.67 % Cu – 1.54 % Co – 1.54 % Ni – 1.46 % Fe – 1.36 % Cr – 0.44 % Nb – were subjected to liquid-phase sintering to fabricate functionally graded multi-component hard alloys with high-entropy metallic binders

Vacuum, 1200-1350 δ-WC1±x – 19 vol.% high-entropy (multi- [2108-2109, element) CoCrCuFeNi alloy (preliminarily 3084] < 8 Pa subjected to the mechanical alloying via high-energy ball-milling) highly dense three-phase cermet materials (mean grain size – 0.2 μm) were prepared from the powdered mixtures (initial mean particle size of δ-WC1±x was ~50 nm) by the sparkplasma sintering (exposure – 5 min); the alloy binder is composed of the fcc structural predominant phase and the bcc structural minor phase Vacuum 1250-1500 δ-WC1±x – 32 vol.% high-entropy equiatomic CoCrCuFeNi alloy (preliminarily subjected to the mechanical alloying via high-energy ball-milling) multi-phase cermet materials were prepared by liquidphase sintering (exposure – 2 h); jointly with main δ-WC1±x phase – semicarbide α/ε-(W,Co,Cr)2+xC, mixed carbide (Cr,W)7C3 and κ-(W,Cr)3CoC1+x, metallic fcc γ-(Ni,Co,Fe,Cu) binder and some other phases with the compositions, strongly depending on total C content, were detected in the materials –

–

Powdered δ-WC1±x (mean particle size – ~75 μm) – 20-80 % high-entropy CrFeCoNiCu (> 99 % purity, mechanically alloyed) mixtures were applied for the preparation of cermet (metal matrix composite) coatings (thickness – 1.5±0.2 mm) on steel substrates using spark-plasma sintering techniques; the coatings were composed of carbide phase and fcc γ-(Fe,Ni) based multi-element metallic matrix (binder)

(continued)

2.6 Chemical Properties and Materials Design

293

Table 2.21 (continued) δ-WC1±x – Co – Ar flow 1450 Cr – Fe – Mn – Ni

–

δ-WC1±x – Co – Ar Cr – Fe – Mo – Nb – Ni

δ-WC1±x – Co – Cr – Fe – Mo – Ni

Powdered δ-WC1±x (> 98 % purity, mean [10, 2000, particle size < 0.5 μm) – 10-30 vol.% high- 3085-3086] entropy equiatomic CoCrFeNiMn (> 99 % purity, mechanically alloyed, 2050 μm aggregates formed by 0.5-5.0 μm spherical particles) mixtures were subjected to liquid-phase sintering (holding time – 1 h) procedure to produce highly dense hard alloys; depending on the preliminary milling conditions of powders, the final products were containing 48-88 % δ-WC1±x (major phase), 12-42 % η2-W3(Co,Ni,Fe,Cr)3Cy (main side phase) and such minor phases as κ-W3FeCy (≤ 17 %), (Cr,W)7C3±x (≤ 12 %) and η1-W6(Co,Ni,Fe,Cr)6Cy (≤ 8 %) –

δ-WC1±x reinforced metal matrix composites (MMC) based on Fe0.50(CoCrMnNi)0.50 medium-entropy alloy were designed and fabricated by friction stir processing (FSP)

~1650-1670 Powdered δ-WC1±x (mean particle size – 5 [3853] μm) – 90 % Ni-based alloy (mean particle size – ~0.1 mm; contents: Cr – 20-23 %, Mo – 8-10 %, Nb – 3-4 %, Fe ≤ 5 %, Co ≤ 1 %) mixtures (preliminarily ball-milled) were subjected to laser deposition to fabricate metal matrix composite (MMC) coatings (thickness – 1.0-1.2 mm); during the technological procedure δ-WC1±x grains mainly dissolved in the Ni-based matrix, and γ-(Ni,Cr,W,Fe) metallic solid solution with η1-(Mo,W)6Ni6Cy were revealed to be the major phase constituents in the prepared coatings (partial dissolution of δ-WC1±x in the matrix resulted in the appearance of topologically close-packed phases at the ceramic-metal interfaces) –

~1700

Powdered δ-WC1±x (mean particle size – [2120] 0.7 μm) – 8.5% Ni – 2.25 % Mo – 2.15 % Cr – 0.85 % Fe – 0.6 % Co mixtures (agglomerated and sintered, size distribution – 15-65 μm) were employed as feedstock powders to deposit hard coatings on steel substrates using high-velocity oxy-fuel (HVOF) thermal spraying; the formation of coatings occurs through the following stages: melting of metallic binder phase, dissolution of carbide in the metallic binder, decarburization (loss of carbon – 36 %) and solidification – the final products (porosity – 2.2 %, mean pore size – 0.3

(continued)

294

2 Tungsten Carbides

Table 2.21 (continued) μm) were containing 59 vol.% δ-WC1±x (mean grain size – 0.6 μm), dispersed in multi-element metallic binder along with some minor phases (γ-W2±xC, metallic W) formed due to the decarburization δ-WC1±x – Co – Ar Cr – Fe – Nb – Ni – Ta – Ti

δ-WC1±x – Co – Cr – Fe – Ni

δ-WC1±x – Co – Cr – Fe – Si – Ti

–

1500

Powdered δ-WC1±x – 2.7 % Ta – 2.0 % Co [3087] – 1.95 % Ni – 1.9 % Fe – 1.8 % Ti – 1.7 % Cr – 0.4 % Nb mixtures were subjected to liquid-phase sintering (exposure – 1 h) to fabricate highly dense hard alloys with high-entropy alloy binder

1100

Powdered (Fe0.25Co0.25Cr0.25Ni0.25) high[10, 2854, entropy alloy (high purity) – 3-11 mol.% 3087-3088] δ-WC1±x mixtures were subjected to sparkplasma sintering (exposure – 0.5 h) process to fabricate dense materials (porosity – ~2 %) composed of fcc metallic matrix, W-rich carbide (mean grain size – 4-5 μm) and two Cr-rich carbide solid solution phases; for the materials fabricated from the mixture, containing 9 mol.% δ-WC1±x, the following compositions of the phases were identified: fcc γ-(Fe0.25Co0.22Cr0.12Ni0.24W0.02C0.15), (W0.49Fe0.11Co0.16Cr0.10Ni0.14)2.14C, (Cr0.91Fe0.04Co0.03Ni0.015W0.05)23C6.80 and (Cr0.81Fe0.08Co0.06Ni0.04W0.01)7C2.99

–

–

Sintered δ-WC1±x (mean grain size – 4.7 μm) – 19 % Co – 9.5 % Ni – 1 % Cr – 0.5 % Fe hard alloys were produced and studied in detail

–

–

δ-WC1±x reinforced Si – Fe – Co – Cr – Ti [3089] high-entropy alloy coatings were prepared on steel substrates by laser cladding techniques; the addition of δ-WC1±x decreases the dilution rate of the substrates and leads to the formation of dendrite microstructure with the presence of large amounts of intermetallide compounds

δ-WC1±x – Co – Vacuum 1420-1425 δ-WC1±x Co – Cr – Mo – Ni hard alloys [10, 2122, Cr – Mo – Ni with various compositions were designed 3158] and prepared Ar, 3 MPa

1400-1500 δ-WC1±x – 1.5 % Co – 1.1 % Cr – 0.4 % Mo – 7 % Ni two-phase hard alloys (volume fraction of Ni-based metallic binder – 18 %, mean δ-WC1±x grain size – 0.75 μm) were prepared through 12-hour-sintering cycle of an industrial sinter-HIPing process with 1.5-hour-exposure at the maximum temperature

(continued)

2.6 Chemical Properties and Materials Design

295

Table 2.21 (continued) δ-WC1±x – Co – Cr – Ni

–

–

1250-1450 δ-WC1±x – 4.5 % Co – 2 % Cr – 5 % Ni dense hard alloys (porosity – ~0.5 %) were prepared by spark-plasma sintering (exposure – 5 min) procedure

[1812, 1815, 2245, 2553, 2714, 2750, 2918, 2902, 1300-1500 δ-WC1±x (mean grain size – 3.5-5.0 μm) – 3090-3093, 10-30 % (Co,Ni,Cr) hard alloys were pre- 3158, 3389] pared by the classic powder metallurgical route and studied in detail Powdered δ-WC1.005 (mean particle size – 3.7 μm, contents: non-combined C – 0.02 %, O – 0.06 %, Fe – 0.003 %) – 9-16 % Ni – 5-8 % Co – 1.0-1.5 % Cr mixtures (nominal composition of the binder phase: Ni – 60-63 %, Co – 31-33 %, Cr – 6-7 %) were subjected to hot isostatic pressing (exposure – 0.75 h + 0.25 h under low and high gas pressures, respectively) procedure to produce dense hard alloys (porosity – 0.02-0.06 %, total C content – (4.60÷5.11)±(0.01÷0.05) %) composed of three phases: δ-WC1±x (mean grain size – (1.8÷2.3)±(0.8÷0.9) μm), metallic binder (41-54 % Ni, 27-30 % Co, 12-28 % W, 3-4 % Cr) and complex carbide η2-(W0.62Co0.15÷0.16Ni0.16÷0.20Cr0.03÷0.06)6Cy

Ar, 1400 0.01-5.0 MPa

–

–

δ-WC1±x – 11.25-16.2 vol.% Co – 11.2516.2 vol.% Ni – 2.5-3.6 vol.% Cr hard alloys with the different contents of C were fabricated; the mean carbide grain size in the alloys with high and low contents of C was in the ranges of 2.3-3.1 μm and 2.02.7 μm, respectively, increasing with an increase of content of Cr in the alloys

–

–

δ-WC1±x – 0.4-9.1 % Co – 0.1-7.4 % Ni – 0.4-0.6 % Cr hard alloys were prepared and studied in detail

δ-WC1±x – Co – Vacuum 1410 Cr – Ta

δ-WC1±x – Co – Cr – W

–

Powdered δ-WC1.005 (mean particle size – [3094] 0.9 μm, content O – 0.12 %) – 10 % Co (mean particle size – 0.8 μm, content O – 0.38 %) – 0.5 % Cr – 0.2-1.0 % Ta mixtures were subjected to liquid-phase sintering (holding time – 1 h) to produce threephase hard alloys composed of δ-WC1±x and cubic (Ta,W)C1–x carbides, uniformly dispersed in metallic Co-based binder –

Hybrid cermet coatings with δ-WC1±x – W [2228] top layer and Co – Cr interlayer (lasercladded) were applied to steel stainless substrates

(continued)

296

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Co – Cu

–

600

Powdered Cu (17 μm) – 10-20 % δ-WC1±x [10, 2177, (1-9 μm) – 5 % Co (1.5 μm) mixtures 3095-3109] (mean particle sizes are given in brackets) were subjected to hot-pressing (exposure – 0.5 h) procedure to prepare dense metal matrix composites (porosity – 1.3-3.7 %)

–

1000

At the δ-WC1±x – Co hard alloy / Cu interface, atoms of Cu diffuse much more into the hard alloy than the amounts of Co atoms diffusing into Cu, Cu-rich layer is formed at the interface between δ-WC1±x and binder phases in the diffusion area of Cu in the alloy, the thickness of diffusion area or the diffusion depth of Cu is varied according to the binder and C contents of the hard alloy applied

–

1080

Good wettability of melted Cu on the surface of δ-WC1±x – 3.5 % Co hard alloy (final contact angle – 6°) was observed; no interfacial reaction was detected, but an increased concentration of Co at the interface δ-WC1±x – Co / Cu indicates a diffusion of Co into Cu

Vacuum, ≤ 1120 0.13 Pa

–

1120

During interdiffusion in the δ-WC1±x – Co hard alloy – Cu system, a Cu-bonded δ-WC1±x layer develops with simultaneous diffusion of Co from the alloy into the bulk molten Cu, the Cu-bonded δ-WC1±x layer grows until a Co-rich layer forms at the Cu / δ-WC1±x – Co interface; further heating pushes the Cu-bonded δ-WC1±x layer deep into the bulk alloy without any significant change in layer thickness The interaction of δ-WC1±x – 20 % Co cemented carbide with molten pure Cu and Cu – 5 % Co alloy showed that the addition of Co to Cu melt checks the penetration of Cu into the cemented carbide

Vacuum 1250-1350 Powdered δ-WC1.00 (≥ 99.5 % purity, mean particle size – ~1.2 μm, contents: noncombined C – 0.31 %, O – 0.22 %) – 4.55.5 % Co (≥ 99.6 % purity, mean particle size – ~1.4 μm) – 0.5-1.5 % Cu (mean particle size – ~1.5 μm) mixtures were subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare dense twophase hard alloys (mean carbide grain size – ~ 0.8-1.0 μm)

(continued)

2.6 Chemical Properties and Materials Design

297

Table 2.21 (continued) N2/H2 flow

1350

Powdered δ-WC1±x (mean particle size – 0.8 μm) – 10 % composite α/ε-Co – Cu (granular shaped, mean particle size – 0.2 μm, content Cu – 0.5-2.0 %) mixtures were subjected to preliminarily ball-milling followed by microwave sintering (exposure – 20 min) to fabricate dense hard alloys (mean carbide grain size – ~ 0.35-0.40 μm)

Ar, 5 MPa

1400

Powdered δ-WC1±x (mean particle size – 0.7 μm) – 8.0-9.5 % Co – 0.5-2.0 % Cu mixtures (prepared by a co-precipitation method) were subjected to hot isostatic pressing (exposure – 1 h) procedure to prepare highly dense hard alloys (mean carbide grain size – 0.55-0.75 μm); the dissolution of δ-WC1±x phase and its grain growth, depending on the solution-reprecipitation mode at elevated temperatures, can be inhibited by the addition of Cu

Ar, 5 MPa

1450

Powdered δ-WC1±x (mean particle size – 4.1 μm) – 4.8 % α/ε-Co – 1.2 % Cu mixtures were subjected to hot isostatic pressing (exposure – 1 h) procedure to prepare ultra-coarse two-phase hard alloys (mean carbide grain size – 4.8 μm); the addition of Cu stabilizes α-Co (cubic) modification and retards the morphology evolution of δ-WC1±x grains from round shape to facet shape

–

–

Powdered Cu (99 % purity, mean particle size – 15 μm) – 30 % δ-WC1±x – Co composite (irregular in shape, mean equivalent spherical diameter – 0.6 μm, content Co – 10 %) mixtures were subjected to direct metal laser sintering (DMLS) or selective laser sintering (SLS) procedures to prepare metal matrix composites (MMC); besides the major phases of Cu and δ-WC1±x, the metastable carbides of Co were revealed in the prepared materials Some data on the system reported by various authors differ markedly

δ-WC1±x – Co – Cu – Fe

–

δ-WC1±x – Co – Cu – (Fe – C)

–

1120-1150 The interaction of δ-WC1±x – 20 % Co ce- [10, 1992, mented carbide with molten Cu – 5 % Fe 2177, 3111] alloy showed that the addition of Fe to Cu melt checks the penetration of Cu into the cemented carbide –

δ-WC1±x – 6 % Co hard metals were brazed [3110] to Fe – 0.11-0.85 % C steels by the pure Cu as a filler metal

(continued)

298

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Co – Vacuum Cu – (Fe – C – Mn) δ-WC1±x – Co – Cu – Fe – Ni

800-1100 δ-WC1±x – 8 % Co hard metals were brazed [2025] to Fe – 0.45 % C – 0.75 % Mn steels by the pure Cu as a filler metal

–

δ-WC1±x – Co – Vacuum, Cu – (Fe – C – 0.1 Pa Cr – Mn) – Ni – Zn

–

The small addition of Cu to δ-WC1±x – 13 [3112] % (Fe,Co,Ni) hard alloys had refining and spheridizing effects on δ-WC1±x grains

960

To join δ-WC1±x – 11 % Co hard alloys to [3117] steel (C – 0.47 %, Mn – 0.9 %, Cr – 0.9 %) parts by diffusion brazing (holding time – 2.5-12.5 min) procedure, the Cu – 40 % Zn – 9.5 % Ni alloy was applied as a filler metal; interdiffusion of Ni and Co leads to the formation of γ-(Fe,Ni,Cr,Mn) austenite solid solution phase at the steel interface and release of δ-WC1±x particles at the hard alloy interface, additionally α-(Cu,Ni,Zn) and β-ZnCu(Ni)1±x solid solutions and complex η2-W3Co3Cy carbide phase were observed in the joint (diffusion) zone at high holding times

δ-WC1±x – Co – Vacuum, 1060-1140 The brazing (holding time – 5-25 min) pro- [3124] Cu – (Fe – C – 0.05 Pa cedures of δ-WC1±x – 8 % Co hardmetals Cr – Si) – Ni – with steel (C – 0.33 %, Cr – 13.4 %, Si – 0.39 %) parts were performed using 20 μm Zn film Ni electroplated Cu – 38 % Zn alloy interlayer (thickness – 0.2 mm); the addition of Ni promoted the formation of interdiffusion zone with γ-(Fe,Ni,Cr) austenite solid solutions, presented as columnar crystals mainly on the hardmetal/interlayer interfaces than on the interlayer/steel interfaces, η2-W3Fe3Cy and η2-W3Co3Cy phases were also detected in the joints δ-WC1±x – Co – Cu – Mn

–

955-1100

The interaction of δ-WC1±x – 8 % Co hard [10, 2177, metals with molten Cu – 17.7-61.1 % Mn 3113-3115] alloy resulted in the formation of diffusion layers with different structures, depending on the temperatures and Mn contents in the melt; heating near the liquidus temperature of the Cu – Mn system yields additional carbide-free layer in the hard metal, while at the higher temperature η-phases form in it, the structures of diffusion layers are influenced markedly by carbide grain size but not significantly by the contents of C

–

980

The interaction of δ-WC1±x – 20 % Co cemented carbide with molten Cu – 18 % Mn alloy showed that the addition of Mn to Cu melt has the pronounced effect on the yielding an additional carbide-free layer in the cemented carbide

(continued)

2.6 Chemical Properties and Materials Design

299

Table 2.21 (continued) –

≥ 980

Cu – 10 % Co – 5 % Mn alloy is suitable for the brazing of δ-WC1±x – Co cemented carbides

δ-WC1±x – Co – Cu – Mn – Ni

–

≥ 970

Cu – 11 % Mn – 2.5 % Ni alloy is suitable [10, 1992, for the brazing of δ-WC1±x – Co cemented 3104, 3115] carbides, the alloy is also employed to join cemented carbides to steel parts

δ-WC1±x – Co – Cu – Mn – Ni – Sn – Zn

–

δ-WC1±x – Co – Cu – Mn – Ni – Zn

–

910

Cu – 35 % Zn – 6 % Ni – 4 % Mn alloy is [1992] employed as a filler metal for brazing δ-WC1±x – Co hard metals

δ-WC1±x – Co – Cu – Mn – Zn

–

930

Cu – 39 % Zn – 2 % Mn – 2 % Co alloys are suitable for the brazing of δ-WC1±x – Co cemented carbides

δ-WC1±x – Co – Cu – Ni

–

1120

The interaction of δ-WC1±x – 20 % Co ce- [2177, 2725, mented carbide with molten Cu – 6 % Ni 3102, 3104, alloy showed that the addition of Ni to Cu 3109] melt has the pronounced effect on the yielding an additional carbide-free layer in the cemented carbide

Ar, 5 MPa

1400

Powdered δ-WC1±x (mean particle size – 0.7 μm) – 8 % Co – 1 % Cu – 1 % Ni mixtures (prepared by a co-precipitation method) were subjected to hot isostatic pressing (exposure – 1 h) procedure to prepare highly dense hard alloys (mean carbide grain size – 0.75 μm)

Ar, 5 MPa

1450

Powdered δ-WC1±x (mean particle size – 4.1 μm) – 4.8 % α/ε-Co – 0.6 % Cu – 0.6 % Ni mixtures were subjected to hot isostatic pressing (exposure – 1 h) procedure to prepare ultra-coarse two-phase hard alloys (mean carbide grain size – 5.3 μm); the addition of Cu and Ni stabilizes α-Co (cubic) modification, Cu retards the morphology evolution of δ-WC1±x grains from round shape to facet shape, while Ni promotes carbide grains to evolve towards the plate-like shape

1100

Cu – 2.7 % Ni – 0.7 % Si alloy is employ- [1992] ed as a filler metal for brazing δ-WC1±x – Co hard metals

δ-WC1±x – Co – Cu – Ni – Si

–

–

For sintered coarse- and medium-grained [3104] δ-WC1±x – Co hardmetals, the alloy composed of Cu – 12.5 % Mn – 3.25 % Ni – 1 % Sn – 1 % Zn was applied as a brazing agent

[1992]

(continued)

300

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Co – Cu – Ni – Si – Zn

–

910

–

Cu – 39.7 % Zn – 10.0 % Ni – 0.3 % Si alloy is employed as a filler metal for brazing δ-WC1±x – Co hard metals –

[10, 1992, 3104]

For sintered coarse- and medium-grained δ-WC1±x – Co hardmetals, the alloy composed of Zn – 48 % Cu – 10 % Ni – 0.2 % Si was applied as a brazing agent

δ-WC1±x – Co – Cu – Ni – Zn

–

980

To prepare δ-WC1±x – 6 % Co hard alloy – [3116-3117] Ni (99.5 % purity) joints by brazing (exposure – 1-35 min) procedure, Cu – 30 % Zn brass was employed as a joining element

δ-WC1±x – Co – Cu – Zn

–

980-1030

Cu – 10 % Zn – 4 % Co alloy is employed [1992] as a filler metal for brazing δ-WC1±x – Co hard metals

δ-WC1±x – Co – Fe

–

Dry H2

δ-WC1±x – Co – (Fe – C)

δ-WC1±x – Co – (Fe – C – Cr)

–

Fe exhibits a high solubility in Co-based metallic binder of the δ-WC1±x – Co hard alloys but no solubility in the δ-WC1±x phase, it does not form stable carbides in the alloys; no disperse phases are observed at δ-WC1±x/Co and δ-WC1±x/δ-WC1±x interfaces, Fe stabilizes α-Co (cubic) modification in the δ-WC1±x – Co alloys

[10, 1937, 2550, 2688, 3011, 31183122, 4667]

1350-1400 Powdered δ-WC1.00 (mean particle size – ~0.8 μm, size distribution – from 0-1 to 45 μm, contents: non-combined C – 0.04 %, O – 0.10 %, Fe – 0.006 %, Ni – 0.0002 %) – 2.5-7.5 % Co (mean particle size – 2.3 μm, contents: O – 0.35 %, Ni – 0.2 %, Fe – 0.04 %) – 2.5-7.5 % Fe (mean particle size – 3-4 μm, contents: total C – 0.8 %, O – 0.3 %, N – 0.9 %) mixtures subjected to liquid-phase sintering to fabricate dense hard alloys (porosity – 0.5-10.0 %)

–

–

δ-WC1±x – Co hard coatings, modified by various amounts of Fe, were produced using electro-spark alloying (ESA) method

–

–

[1015, 1937, Steel matrix composites reinforced by δ-WC1±x – Co hard alloy particles were 2357, 2961, fabricated via hot isostatic pressing (HIP) 3119]

–

–

Functionally graded δ-WC1±x – Co – steel materials were designed and fabricated

–

–

High-Cr white cast Fe based materials ha- [3410] ving an in situ and ex situ δ-WC1±x particle reinforced composite region (depth – 5-8 mm below the working surface) were produced by double casting techniques

(continued)

2.6 Chemical Properties and Materials Design

301

Table 2.21 (continued) δ-WC1±x – Ar α/β/ε/γ-W2±xC – Co – (Fe – C – Cr – Mn)

~1800

δ-WC1±x – Co – Vacuum 1250 (Fe – C – Cr – Mn – Mo – Ni – Si) – (Fe – C – Mn – Nb – Ni)

δ-WC1±x – Co – Vacuum (Fe – C – Cr – Mn – Si)

Tool steel (C – 0.9 %, Mn – 1.2 %, Cr – [1818] 0.5 %) mixed with 15.3-16.5 % fused W carbides (99 % purity) and 1-8 % metallic Co (99.5 % purity) were subjected to W inert gas arc-melting procedure followed by solidification to prepare metal matrix composites (MMC), similar to those generated in an industrial hard-facing process, composed mainly of α-(Fe,Co) and η2-W3Fe3Cy phases During the post-welding heat-treatment [2961] (exposure – 2-16 h) performed on δ-WC1±x – 20 % Co hard alloy – stainless steel (C – 0.03 %, Cr – 16 %, Ni – 12 %, Mo – 2.5 %, Mn – 2 %, Si – 1 %) weldments with Fe-based alloy (Ni – 42 %, Mn – 3.5 %, Nb – 3 %, C – 0.6 %) as an interlayer (thickness – 1-2 mm), the dissolving behaviour of δ-WC1±x prismatic facets leads to the abnormal carbide grain growth in the metallic matrix composed of α-Co and γ-(Fe,Ni) phases; in the fusion zone, adjacent to the hard alloy interface, complex mixed carbide skeleton was formed with a microstructure of continuous rods and isolated islands

–

A part of δ-WC1±x – 30 % Co hard alloy – [3004] steel (C – 0.4 %, Cr – 0.8-1.1 %, Mn – 0.50.8 %, Si – 0.2-0.4 %) joint, formed using electron beam welding (EBW) techniques, was revealed to be composed mainly of martensite α-(Fe,C) and η2-W3Fe3Cy carbide phases (with decrease of heat input, the content of η2-W3Fe3Cy would decline)

δ-WC1±x – Co – Ar (Fe – C – Cr – Mo – Ni – V – W)

1150

Powdered δ-WC1±x – 12 % Co alloy (mean [3001] particle size < 105 μm) in the mixture with 50 % steel (C – 1.2 %, W – 6.2 %, Mo – 4.8 %, Cr – 4.0 %, V – 3.1 %, Ni – 0.9 %; atomized spherical particles with size from 106 μm to 212 μm) was subjected to hot isostatic pressing (HIP) procedure (holding time – 3 h) to fabricate metal matrix composites; the formation of η-(W,Fe,Mo)6Cy phase was detected in the composites

δ-WC1±x – Co – Ar (Fe – C – Cr – Mo – Si – V)

1150

Powdered δ-WC1±x – 12 % Co alloy (mean [3001] particle size < 105 μm) in the mixture with 50 % steel (C – 2.45 %, V – 9.75 %, Cr – 5.25 %, Mo – 1.30 %, Si – 0.90 %; atomized spherical particles with size < 105 μm) was subjected to hot isostatic pressing (HIP) procedure (holding time – 3 h) to

(continued)

302

2 Tungsten Carbides

Table 2.21 (continued) fabricate metal matrix composites; the formation of V8C7±x phase was detected in the prepared materials δ-WC1±x – Co – Vacuum, 1100 (Fe – C – Cr – 2-10 Pa Mo – V)

δ-WC1±x – Co – Ar (Fe – C – Cr – Mo – V – W)

δ-WC1±x – Co – (Fe – C – Mn – Nb – Ni)

Powdered δ-WC1±x (99.95 % purity, mean [3002] particle size – 0.9 μm, content O – 0.52 %) – 8 % α/ε-Co (99.95 % purity, mean particle size – 1.5 μm) – 35 % steel (particle size < 22 μm, contents: C – 0.4 %, Cr – 5 %, Mo – 1 %, V – 1 %, O – 0.13 %; mass ratio α-Fe/γ-Fe =8.5) mixtures were subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare highly dense cermets; the composition of as-prepared materials was evaluated to be 60 % δ-WC1±x, 34 % α-Fe, 4 % γ-Fe and 2 % η-W4Co2Cy, after the additional heat-treatment (exposure – 9 h) in Ar at the same temperature the composition changed to 32 % α-Fe, 4 % γ-Fe and 64 % η-W4Co2Cy

1300-1350 Powdered δ-WC1±x (mean particle size – [3626] from 0.1 μm to 0.5 μm) – 10 % Co (mean particle size – 25 nm) mixtures (preliminarily cold-pressed) were subjected to liquidphase sintering (exposure – 1.5 h) in the direct contact with high-speed steel (C – 0.9 %, Cr – 4.0 %, Mo – 5.0 %, V – 1.9 %, W – 6.4 %, Fe – remainder) parts; the increase of δ-WC1±x particle size led to the decrease of diffusion processes, no significant diffusion of Fe and W occurred at the steel – hard alloy interface, and only a certain degree of Co diffusion occurred at the larger δ-WC1±x particle size; when the size was smaller, Fe diffused from steel into the contacted δ-WC1±x – Co structure, which produced a certain width of the fusion (transition) layer at the hard alloy – steel interface and resulted in relatively strong metallurgical bonding –

δ-WC1±x – Co – Vacuum (Fe – C – Mn – Si)

–

The laser-TIG combination welded joints [3692] between δ-WC1±x – 30 % Co hard alloy and invar (C – 0.6 %, Ni – 42 %, Mn – 3.5 %, Nb – 3 %, Fe – remainder) alloy parts were developed and behaviour of δ-WC1±x during the processing was studied

–

A part of δ-WC1±x – 30 % Co hard alloy [3003] (thickness – 30 mm) – steel (C – 0.4-0.5 %, Mn – 0.5-0.8 %, Si – 0.2-0.4 %) joint, formed using electron beam welding (EBW) techniques, was revealed to be composed mainly of martensite α-(Fe,C),

(continued)

2.6 Chemical Properties and Materials Design

303

Table 2.21 (continued) residual austenite γ-Fe and herringbonelike structured η-(W,Fe,Co)6Cy carbide phases (η-phase was formed around the δ-WC1±x grain boundaries at the δ-WC1±x loose area by swallowing of the δ-WC1±x particles, while cracks tend to form and propagate along the interface) δ-WC1±x – Co – Vacuum, 1410 Fe – Mo – Ni < 1 Pa

δ-WC1±x – 6.5 % (Co + Fe + Ni) – 0.4 % [2546, 4293] Mo hard alloys were fabricated by liquidphase sintering (holding time – 50 min) method (metallic binders in the alloys were characterized by fcc (cubic) structures)

δ-WC1±x – Co – Fe – Ni

The two-phase region in the δ-WC1±x – 4.15 % Ni – 0.80 % Fe – 0.25 % Co hard alloys (without the presence of α-C (graphite) or η1-W6Co6Cy phases) lies approximately in the range of C contents from 5.73 % to 5.81 %

–

–

1200

[10, 1812, 1937, 1985, 1994, 2000, 2546, 2688, 2725, 2786, 2811, 2821, 2948, 31191200-1250 δ-WC1±x – 13.5 % (Co + Fe + Ni) twophase hard alloys (porosity – ~0.2 %, mean 3132, 3158, grain size – 0.35-0.43 μm) were fabricated 3583, 3700] by hot-pressing (holding time – 1 h) techniques

Ar, 1250 125 MPa

δ-WC1±x – 13.5 % (Co + Fe + Ni) twophase hard alloys (porosity – ~0.3 %, mean grain size – 0.65 μm) were fabricated by hot isostatic pressing (HIP) technique (holding time – 100 min)

Vacuum 1300

Preliminarily cold-pressed (from nanopowders) δ-WC1±x (80 nm) – 20 % Co (50 nm) and Fe (50 nm) – 36 % Ni (50 nm) compacts (mean particle sizes are given in brackets) were sinter-bonded (holding time – 2-16 h) with the formation of consolidated interface (diffusional zone) comprised of δ-WC1±x and γ-(Fe0.64Ni0.36) solid solution with the presence of complex carbide η2-W3Co3Cy phase, whose content increased as a function of holding time; the grain growth of δ-WC1±x at the interface was accompanied by abnormal grain growth, as the maximum grain size increased up to 69 μm (~ 6.5-8.5 times larger than the mean grain size in the δ-WC1±x – 20 % Co base material at the vicinity of the interface)

Vacuum, 1300-1400 δ-WC1±x – 13.5 % (Co + Fe + Ni) two1.3 mPa phase hard alloys (porosity – 0.35-1.0 %, mean grain size – 0.5-0.8 μm) were fabricated by liquid-phase sintering (soaking time – 1 h) method

(continued)

304

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1350-1400 δ-WC1±x – 11.6 % Fe – 3 % Ni – 0.4 % Co 1.3 mPa two-phase hard alloys (poreless, mean grain size – 0.8-0.9 μm) were fabricated by liquid-phase sintering (soaking time – 1 h) method Dry H2

1350-1400 Powdered δ-WC1.00 (mean particle size – ~0.8 μm, size distribution – from 0-1 to 45 μm, contents: non-combined C – 0.04 %, O – 0.10 %, Fe – 0.006 %, Ni – 0.0002 %) – Co (mean particle size – 2.3 μm, contents: O – 0.35 %, Ni – 0.2 %, Fe – 0.04 %) – Fe (mean particle size – 3-4 μm, contents: total C – 0.8 %, O – 0.3 %, N – 0.9 %) – Ni (mean particle size – 3.7 μm, specific surface area – 0.3 m2 g–1, contents: total C – 0.06 %, O – 0.05 %, N – 0.003 %, Fe – 0.005 %, Co – 0.0003 %) mixtures (in corresponding proportions) were prepared and subjected to liquid-phase sintering to fabricate δ-WC1±x – 0-10 % Co – 0-10 % Fe – 0-10 % Ni dense hard alloys (porosity – 0.5-12.0 %)

Vacuum, 1370-1450 δ-WC1±x – 7-28 % (Co + Fe + Ni) hard al< 1 Pa loys were fabricated by liquid-phase sintering (holding time – 25-60 min) method (metallic binders in all the δ-WC1±x – (Co,Fe,Ni) alloys were characterized by fcc (cubic) structures) Vacuum 1380

Highly dense δ-WC1±x – 7-14 % Fe – 2-4 % Ni – 1-2 % Co two-phase (carbide and metallic binder) and three-phase (additionally containing α-C (graphite), or η2-(W,Fe,Ni,Co)6Cy phases) hard alloys were fabricated (using high purity δ-WC1±x powder with mean particle size – 0.6 μm and varying total C contents) by liquidphase sintering (exposure – 1 h) with formed Fe based austenitic-martensitic structured binder

Vacuum, 1380-1460 Powdered δ-WC1.00 (99.9 % purity, content Ar O – 0.01 %, mean particle size – 2.3 μm) – 4 % Co (99.2 % purity, content O – 0.55 %, mean particle size – 1.1 μm) – 8-13 % Fe (98.5 % purity, content O – 0.40 %, mean particle size – 2.0 μm) – 3-8 % Ni (99.8 % purity, content O – 0.20 %, mean particle size – 2.5 μm) mixtures were subjected to preliminarily ball-milling followed by liquid-phase sintering (holding time – 1-2 h) to fabricate dense hard alloys (porosity – from 0.1 to 1.5 %, mean grain size

(continued)

2.6 Chemical Properties and Materials Design

305

Table 2.21 (continued) – 1.2-1.3 μm); depending on the Fe/Ni atomic ratio, the structure of metallic binder was mainly fcc (cubic) γ-(Fe,Ni,Co) – at Fe/Ni = 1÷1.67, hetero-phase blend consisting of fcc (cubic) γ-(Fe,Ni,Co) and bcc (cubic) α-(Fe,Ni,Co) – at Fe/Ni = 2.2 and single-phase bcc (cubic) α-(Fe,Ni,Co) – at Fe/Ni = 3÷4.3 with the amounts of W and C dissolved in the binder decreasing gradually from 6.35 % and 0.54 % (at Fe/Ni = 1) to 1.65 % and 0.12 % (at Fe/Ni = 4.3), respectively Ar, 1400-1500 δ-WC1±x – 2 % Co – 4 % Fe – 4 % Ni hard 3-5 MPa alloys (mean δ-WC1±x grain size – ~0.8 μm) were prepared through 12-hour-sintering cycle of industrial sinter-HIPing process with 1.5-hour-exposure at maximum temperature; δ-WC1±x, FeNi1±x and α-Fe solid solution phases were detected in the alloys Vacuum 1410

The following minor phases were detected in sintered δ-WC1±x – 5 % Co – 10 % Fe – 5 % Ni hard alloys, depending on total C content: η-phases – at 4.56-4.81 %, none (two-phase structure) – at 4.99-5.01 % and α-C (graphite) – 5.56 %

Ar, 1410 10 MPa

The following minor phases were detected in gas pressure sintered δ-WC1±x – 5 % Co – 10 % Fe – 5 % Ni hard alloys, depending on total C content: η-phases – at 4.54-4.83 %, none (two-phase structure) – at 5.025.00 % and α-C (graphite) – 5.54 %

Vacuum 1410

The following minor phases were detected in sintered δ-WC1±x – 5 % Co – 5 % Fe – 10 % Ni hard alloys, depending on total C content: η-phases – at 4.50-4.71 %, none (two-phase structure) – at 4.83-4.97 % and α-C (graphite) – 5.28 %

Ar, 1410 10 MPa

The following minor phases were detected in gas pressure sintered δ-WC1±x – 5 % Co – 5 % Fe – 10 % Ni hard alloys, depending on total C content: η-phases – at 4.53-4.73 %, none (two-phase structure) – at 4.914.98 % and α-C (graphite) – at 5.34 %

Vacuum 1450

Highly dense δ-WC1±x – 4.13-4.18 % Ni – 0.79-0.83 % Fe– 0.24-0.26 % Co hard alloys (with total C contents from 5.72 % to 5.83 %) were prepared using liquid-phase sintering (exposure – 1 h) procedure

(continued)

306

2 Tungsten Carbides

Table 2.21 (continued) 1450

δ-WC1±x – 3.9 % Fe – 3.7 % Ni – 1.9 % Co dense hard alloys were fabricated using hot isostatic pressing (HIP) technique

Vacuum 1450

Highly dense δ-WC1±x – 4.7 % Fe – 4.7 % Ni – 2.4 % Co two-phase (carbide and metallic binder) and three-phase (additionally containing α-C (graphite), or η2-(W,Fe,Ni,Co)6Cy phases) hard alloys were fabricated (using δ-WC1±x powder with mean particle size – 1.4 μm and varying total C contents) by liquid-phase sintering (exposure – 1 h) with formed γ-Fe (austenitic) structured binder (content W – 3 %)

Ar

δ-WC1±x – 7-28 % (Co + Fe + Ni) hard alloys were fabricated by hot isostatic pressing (HIP) technique (metallic binders in all the δ-WC1±x – (Co,Fe,Ni) alloys were characterized by fcc (cubic) structures)

Ar, 5 MPa

1700

See also section C – Co – Fe – Ni – W in Table I-2.14 δ-WC1±x – Co – Vacuum, 750 (Fe – C – Cr – 5 Pa Mn) – Ni

The rapid diffusion bonding (exposure – [3128] 13 min) of δ-WC1±x – 10 % Co hard alloy to steel (C – 0.43 %, Cr – 0.96 %, Mn – 0.57 %) parts with pure metallic Ni foils (thickness – 50-150 μm) as interlayers was carried out by utilizing plasma activated sintering (PAS) technique

δ-WC1±x – Co – Vacuum, 950-1100 (Fe – C – Cr – 0.1-1.0 Mn) – Ni – Ti mPa

δ-WC1±x – 10 % Co hard alloy – steel (C – [3161] 0.43 %, Cr – 0.96 %, Mn – 0.57 %) joints were formed with Ti (20 μm) /Ni (150 μm) / Ti (20 μm) interlayers (thicknesses of sublayers are given in the brackets) by partial transient liquid phase (PTLP) bonding procedure (holding time – 1 h); the transition layers adjacent to the hard alloy interface consisted of TiC1–x and dispersed δ-WC1±x particles (with the small amounts of η1-W6Co6Cy), the thickness of the intermediate TiNi3 layer increased linearly with the bonding temperature increase, this increase enhanced the dissolution of Co and resulted in the formation of (Ti,Co,Ni) metallic layer instead of the intermetallide TiNi1±x layer; an individual TiC1–x layer was found adjacent to the steel interface, TiNi1±x and TiNi3 layers with δ-WC1±x particles were also identified at the steel side

(continued)

2.6 Chemical Properties and Materials Design

307

Table 2.21 (continued) δ-WC1±x – Co – Ar (Fe – C – Mn – Si) – (Ni – C – Al – Ti)

–

δ-WC1±x – 30 % Co hard alloy – steel (C – [3006] 0.5 %, Mn – 0.6-0.9 %, Si – 0.15-0.35 %) joint was formed with Ni-based alloy (C – 0.03 %, Al + Ti – 1-3 %) filler metal using W – inert gas (TIG) welding techniques (no complex carbides (η-phases) were formed in it)

δ-WC1±x – Co – Vacuum (Fe – C – Mn – Si) – (Ni – C – Fe – Nb – Y)

–

A part of δ-WC1±x – 30 % Co hard alloy [3003] (thickness – 30 mm) – steel (C – 0.4-0.5 %, Mn – 0.5-0.8 %, Si – 0.2-0.4 %) crackfree joint, formed with Ni-based alloy (C – 0.5 %, Fe – 8.2 %, Y – 0.8 %, Nb – 0.5 %) filler metal (thickness – 1 mm), using electron beam welding (EBW) techniques, was revealed to be composed mainly of austenite γ-Fe solid solution and herringbonelike microstructured (with reticulate and dispersive distribution) κ-W3FeCy carbide phases

δ-WC1±x – Co – Fe – Si

–

–

Thermodynamic calculations in the system [4667] have been undertaken in order to provide guidelines for the selection of suitable binders for hard alloys

δ-WC1±x – Co – Ga

–

–

δ-WC1±x – Co hard alloys were modified by Ga+ using ion implantation to dose levels of 2×1016 cm–2 to 5×1017 cm–2

δ-WC1±x – Co – N2 Ga – Mn – Ni

δ-WC1±x – Co – In

875

–

δ-WC1±x – Co – Ar, Ln (rare earth 5 MPa elements: misch metal, La, Ce, Nd, Dy, Pr, Y)

90 vol.% hard alloy (δ-WC1±x – 12 % Co) [3134] – 10 vol.% martensite alloy (non-modulated Ni0.50Mn0.25Ga0.25Cox) and 18 vol.% hard alloy (δ-WC1±x – 12 % Co) – 82 vol.% martensite alloy (five-layered modulated Ni0.50Mn0.30Ga0.20Cox) double dispersion composites were fabricated using pulsed electric current sintering (PECS) procedure (exposure – 8 min) –

1400

[1119]

The surface of δ-WC1±x – Co hard alloys were modified by In+ using ion implantation to dose levels of 2×1016 cm–2 to 5×1017 cm–2

[1119]

The addition of 0.5-2.0 % La to δ-WC1±x – [2759, 3032, 8.0-9.5 % α-Co hard alloys (mean grain 3133, 3168size – ~ 0.3-0.4 μm), prepared by gas pres- 3174, 3200, sure sintering, suppresses the formation of 3247, 3287, binder-enrichment structure on the sintered 3950] skin and decreases the volume fraction (or eliminates the formation) of complex carbide η2-W3Co3Cy phase

(continued)

308

2 Tungsten Carbides

Table 2.21 (continued) –

–

δ-WC1±x – Co based hard alloys with the addition of 0.1-0.2 % misch metal (total Ln contents – 95 %, including Ce – 55 %, La – 25 % Nd – 15-18 %) were fabricated and studied

–

–

The metallic binder phase in Ln-doped δ-WC1±x – 8 % Co hard alloys consisted of > 90 % α-Co (cubic) and only 3-9 % ε-Co (hexagonal) modifications due to the stabilization of α-Co by Ln elements via restraining the martensitic transformation of α-Co → ε-Co, the presence of Ln also led to the increase of amounts of dissolved W in the binder

See also section δ-WC1±x – LnOy (oxides of rare earth elements: La2O3–x, CeO2–x, Y2O3–x) – Co δ-WC1±x – Co – Ar Mn

–

[2725, 3019, After the arc-melting procedure of δ-WC1±x – 40 mol.% Co – 26.7 mol.% Mn 3023, 3135composition, the phases of δ-WC1±x, 3136] μ-Co7W6±x and ~α-(Co0.55Mn0.17W0.08C0.20) metallic solid solutions (with core-rim structures) were detected in the materials

Vacuum 1000

After the annealing (exposure – 168 h) of as-cast δ-WC1±x – 40 mol.% Co – 26.7 mol.% Mn samples, the phases of γ-W2±xC and Co-based metallic solid solutions were detected in the materials

Vacuum 1000

After the annealing (exposure – 168 h) of as-cast δ-WC1±x – 16.7 mol.% Co – 50 mol.% Mn samples, the phases of γ-W2±xC and ~β-(Mn0.42Co0.33W0.01C0.24) metallic solid solutions were detected in the materials

Vacuum 1410

In liquid-phase sintered (exposure – 1 h) δ-WC1±x – 9.9 % Co – 0.2 % Mn twophase hard alloys (mean grain size – 0.70±0.01 μm, fraction of binder phase – 13.7 vol.%, contents in the binder, at.%: W – 2.95±0.10 and Mn – 1.20±0.14, only fcc (cubic) α-Co phase was detected in the binder), Mn was observed to segregate to some carbide/binder and carbide/carbide phase boundaries (interfaces) in the fractions of 7 % and 5 %, respectively

Ar

–

After the arc-melting procedure of δ-WC1±x – 16.7 mol.% Co – 50 mol.% Mn composition, the phases of δ-WC1±x, and ~β-(Mn0.50Co0.27W0.03C0.20) metallic solid solutions were detected in the materials

(continued)

2.6 Chemical Properties and Materials Design

309

Table 2.21 (continued)

δ-WC1±x – Co – Mn – Ni

–

–

δ-WC1±x – 6.4 % Co – 1.6 % Mn hard alloys were designed, fabricated and studied

–

–

δ-WC1±x – 6 % Co – 1.2 % Ni – 0.8 % Mn [3135-3136] and δ-WC1±x – 3.6 % Co – 3.6 % Ni – 0.8 % Mn hard alloys were designed, fabricated and studied

δ-WC1±x – Co – Vacuum 1250 Mo

Powdered δ-WC1±x – 6 % Co – 1-4 % Mo mixtures were subjected to spark-plasma sintering (exposure – 10 min) procedure to produce two-phase δ-WC1±x – α-Co hard alloys (porosity – 1.0-4.6 %, mean δ-WC1±x grain size – 0.7-0.9 μm); during the sintering process, Mo converted to Mo2±xC phase, and then Mo2±xC dissolved preferentially in Co-based metallic binder that can restrain the dissolution-reprecipitation of δ-WC1±x in the binder, the partial dissolution of Mo in δ-WC1±x is also possible δ-WC1±x – 9 % Co – 10 % Mo particulate composites (porosity – 3-4 %) were fabricated by hot-pressing technique using Mo powders different in particle sizes

Vacuum 1350

–

1500-1600 Powdered δ-WC1±x – 5 % Co – 5 % Mo mixtures (preliminarily high-energy ballmilled) were subjected to fast microwave sintering (without holding time) to produce cermet materials (porosity – in the range of 1.5-6.4 %); the presence of β-Mo2±xC and η2-Mo3Co3Cy phases as side products was detected in the prepared materials

–

–

δ-WC1±x – Co – Mo coatings were deposited using the atmospheric plasma spraying (APS) method with mechanically mixed powders (size distribution – 5-30 μm)

–

–

The surface layers (depth – ~20 μm) of δ-WC1±x – 6 % Co hard alloys were modified by Mo using ion implantation to dose levels of 1×1016 cm–2 to 7×1018 cm–2

δ-WC1±x – Co – Ar, Mo – Ni 5 MPa

[10, 1118, 2861, 3137, 3345, 3349, 3386, 42914295, 4497]

1450

Powdered δ-WC1±x (mean particle size – [10, 2948, ~24 μm) – 4.75-6.05 % Ni – 2.85-4.15 % 2976, 3158, Co (mean particle size – ~1.4 μm) – 0.60- 4292] 0.90 % Mo (mean particle size – ~3.7 μm) mixtures were subjected to liquid-phase sintering procedure followed by hot-isostatic pressing (HIP) to fabricate super-coarse hard alloys

(continued)

310

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Co – N

–

–

[1118, 1131, The surface layers (depth – ~20 μm) of δ-WC1±x – 6 % Co hard alloys were modi- 1146, 1656, fied by N using ion implantation to dose 3379] levels of 1×1016 cm–2 to 7×1018 cm–2; radiation stimulated diffusion of N was observed

–

–

Co- and N-co-doped δ-WC1±x was synthesized for the purpose of electrocatalysis

δ-WC1±x – Co – Vacuum 1350 Nb

δ-WC1±x – 9 % Co – 10 % Nb particulate [10, 1901, composites (porosity – 3-4 %) were fabri- 3137-3138] cated by hot-pressing technique

–

1400

After rapid cooling, the compositions of cubic carbide phase in the equilibria with η2-phase or with α-C (graphite) were (Nb0.91W0.09)C1–x or (Nb0.94W0.06)C1–x, respectively, and composition of complex carbide phase was η2-(W2.80Co3.04Nb0.16)Cy

–

1450

In the sintered δ-WC1±x – 20 vol.% Co hard alloys, the solubility of Nb in Co-based metallic binder phase (in equilibrium with C) is ~ 3.5-4.0 % (it is not affected by the initial porosity) Some data reported in literature by various authors differ markedly

See also section C – Co – Nb – W in Table I-2.14 δ-WC1±x – Co – Ar Nb – Ta – Ti

δ-WC1±x – Co – Ni

Powdered δ-WC1±x – 7.2 % Co – 2.7 % Ta [3087] – 1.8 % Ti – 0.4 % Nb mixtures were subjected to liquid-phase sintering (exposure – 1 h) to fabricate highly dense hard alloys

1500

–

–

Having large- (> 5 μm) and small- (< 2.5 μm) grain sizes, grades of δ-WC1±x – 14 % Co – 14 % Ni hard alloys were designed, fabricated and studied

[10, 685, 1812, 1988, 2122, 2524, 2567, 2786, – 1000-1225 The preparation of two-phase δ-WC1±x – 5 2919-2920, 2948, 2977, % Co – 5 % Ni hard alloys (without the presence of α-C (graphite) or η1-W6Co6Cy 3011, 3102, phases) can be realized at the total C con- 3109, 3119, 3122, 3133tent being in the range of 5.28-5.47 % 3136, 3139, Vacuum 1300 Functionally graded δ-WC1±x – Co – Ni 3141-3158, materials composed of δ-WC1±x – 8 % Co, 3435, 3760, transitional and Ni layers were designed 4505] and fabricated from the powders of components (mean carbide particle size – 3.6 μm) with 99.9 % purity by preliminarily ballmilling and pressing followed by sintering (exposure – 1 h) process

(continued)

2.6 Chemical Properties and Materials Design

311

Table 2.21 (continued) –

Dry H2

1350

The addition of Ni to liquid Co – Ni metallic binder of δ-WC1±x based hard alloys decreases the maximum solubility of α-C (graphite) in the binder from ~ 2.8-3.1 % (for pure Co melt) to ~ 1.9-2.0 % (for pure Ni melt) at the concentration of W in the melt in the range from ~5 % to ~10 %

1350-1400 Powdered δ-WC1.00 (mean particle size – ~0.8 μm, size distribution – from 0-1 to 45 μm, contents: non-combined C – 0.04 %, O – 0.10 %, Fe – 0.006 %, Ni – 0.0002 %) – 2.5-7.5 % Co (mean particle size – 2.3 μm, contents: O – 0.35 %, Ni – 0.2 %, Fe – 0.04 %) – 2.5-7.5 % Ni (mean particle size – 3.7 μm, specific surface area – 0.3 m2 g–1, contents: total C – 0.06 %, O – 0.05 %, N – 0.003 %, Fe – 0.005 %, Co – 0.0003 %) mixtures were subjected to liquid-phase sintering to fabricate dense hard alloys (porosity – 0.5-12.0 %)

Vacuum 1400

δ-WC1±x – 8 % Co – 8 % Ni hard alloys were fabricated by liquid-phase sintering

Ar, 5 MPa

Powdered δ-WC1±x (mean particle size – 0.7 μm) – 8-9 % Co – 1-2 % Ni mixtures (prepared by a co-precipitation method) were subjected to hot isostatic pressing (exposure – 1 h) procedure to prepare highly dense hard alloys (mean carbide grain size – 0.80-0.85 μm)

1400

Vacuum 1420

δ-WC1±x – 6.8 % Co – 3.2 % Ni (1.4-1.7 μm) and δ-WC1±x – 0.4 % Co – 9.6 % Ni (1.6-1.9 μm) highly dense hard alloys (mean carbide grain sizes are given in brackets) were fabricated by liquid-phase sintering process

Vacuum 1450

Powdered δ-WC1±x – 1.2-4.9 % Co – 1.24.8 % Ni mixtures (mean particle size – 2.3-2.5 μm, contents: total C – 5.73-5.75 %, O – 0.25-0.30 %, Co + Ni – 6.0 %) were subjected to liquid-phase sintering (exposure – 1 h) procedure; the contents of dissolved W in the binder phase of the prepared hard alloys (total porosity – (0.6÷0.7)±0.1 %) increased from 3.1 % to 9.0 % with the increase of Ni contents in the alloys from 1.2 % to 4.8 %, while the mean δ-WC1±x grain size increased in the alloys from ~1.5 μm to ~2.4 μm

(continued)

312

2 Tungsten Carbides

Table 2.21 (continued) Ar, 5 MPa

1450

Coarse-grained δ-WC1.00 – 4-8 % Co – 2-6 % Ni hard alloys were fabricated by sinterHIPing and cyclic sintering; the contents of dissolved W in the binder phase of the sintered alloys decreased from 10.3 % to 6.1 % with the increase of Ni contents in the alloys from 2 % to 6 %, while the mean grain size increased in the alloys from ~3.7 μm to ~4.4 μm (without cyclic sintering) or from ~4.2 μm to ~5.8 μm (after two thermal cycles)

Ar, 5 MPa

1450

Powdered δ-WC1±x (mean particle size – 4.1 μm) – 4.8 % α/ε-Co – 1.2 % Ni mixtures were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare ultra-coarse two-phase hard alloys (mean carbide grain size – 5.3 μm); the addition of Ni stabilizes α-Co (cubic) modification and promotes δ-WC1±x grains to evolve towards the plate-like shape

–

–

δ-WC1±x – 4 % Co – 4 % Ni hard alloys were designed, fabricated and studied

–

–

10 vol.% cermet (δ-WC1±x – 8 % Co) reinforced (randomly dispersed) Ni-based metal matrix composites (MMC) were fabricated via microwave energy casting process (exposure – 25 min)

–

–

Powdered δ-WC1±x (mean particle size – 1-6 μm) – 12 % Co – 5.5 % Ni mixtures (agglomerated/sintered + electroless Ni plating, size distribution – 15-45 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials to deposit hard coatings (porosity – 0.3±0.1 %, thickness – 420±15 μm, C loss – 2.6%, presence of small amounts of γ-W2±xC)

–

–

Powdered δ-WC1±x (mean particle size – 5-30 nm) – ~11 % Co – ~3 % Ni mixtures (agglomerated/sintered + mechanical milling + electroless Ni plating + spray drying, size distribution – 5-45 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials to deposit hard coatings (porosity – 0.5±0.1 %, thickness – 400±30 μm, C loss – 5.4%, presence of small amounts of γ-W2±xC)

(continued)

2.6 Chemical Properties and Materials Design

313

Table 2.21 (continued) –

–

Hardfacing nanostructured δ-WC1±x – Co – Ni coatings (poreless, thickness – ~80 μm, carbide fraction – up to 30 vol.%) were deposited on Ni-based alloy substrates by electroplating process

–

–

Nanocrystalline δ-WC1±x – Co – Ni composite electrocatalysts with mesoporosity were prepared by a spray drying gas solid reaction Some data on the system in literature reported by various authors differ markedly

See also section C – Co – Ni – W in Table I-2.14 δ-WC1±x – Co – Ni – Re

–

–

δ-WC1±x – 4.8 % Co – 1.6 % Ni – 1.6 % Re and δ-WC1±x – 3.2 % Co – 3.2 % Ni – 1.6 % Re hard alloys were designed, fabricated and studied

δ-WC1±x – Co – Os

–

–

The addition of Os, which is not a carbide [3162] forming element, to δ-WC1±x – 6 % Co hard alloys leads to its dissolution in the metallic binder of the alloys and promotion of the transformation of α-Co (cubic) to ε-Co (hexagonal) modification, resulting in the formation of a dispersed substructure in the binder phase

[3135-3136]

See also section C – Co – Os – W in Table I-2.14 δ-WC1±x – Co – P δ-WC1±x – Co – Pd

δ-WC1±x – Co – Re

See section δ-WC1±x – CoPy – Co –

–

The synergistic effect of joint usage of [10, 1562, δ-WC1±x supports and Pd – Co alloy nano- 1661] particles for electrocatalysis was confirmed

–

–

Hollow δ-WC1±x – 6 % Co spheres (diameter – 8-18 μm) were covered with δ-WC1±x – Pd microporous layer (thickness – 0.31.0 μm) via surface replacement method for electrocatalysis purposes

–

–

The addition of Re, which is not a carbide [10, 3011, forming element, to δ-WC1±x – 6 % Co 3135-3136, hard alloys leads to its dissolution in the 3162, 3166metallic binder of the alloys and promotion 3167, 3691] of the transformation of α-Co (cubic) to ε-Co (hexagonal) modification, resulting in the formation of a dispersed substructure in the binder phase

–

1350

The two-phase region in the sintered δ-WC1±x – 6 % Co – 9 % Re hard alloys (without the presence of α-C (graphite) or η1-W6Co6Cy phases) lies approximately in the range of 5.40-5.67 % C contents

(continued)

314

2 Tungsten Carbides

Table 2.21 (continued) –

Powdered δ-WC1±x (initial mean particle size – 0.8-3.0 μm) – 6-9 % Co – 9-13.5 % Re mixtures (preliminarily ball-milled) were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to fabricate fine-grained dense hard alloys with the presence of small amounts of η2-(W0.2÷0.4Re0.6÷0.8)3Co3Cy phase and hexagonal Re – Co solid solution metallic binder (the content of ε-Co (hexagonal) modification in the binder phase steadily increases when increasing the content of Re dissolved there and the binder containing ≥ 60 % Re (in the binder mass fractions) composes almost exclusively of ε-Co (hexagonal) modification)

1520

–

–

Powdered δ-WC0.99 (99.9%) – 7.5-9.0 % Re (99.99 %) – 6.0-7.5 % Co (99.3 %) mixtures (purities are given in brackets) were used to fabricate dense δ-WC1±x – α-(Co,Re) hard alloys (porosity ≤ 0.2 %) by the conventional powder metallurgy methods (0.1 vol.% α-C (graphite) phase was detected in the materials with the maximum contents of Re)

–

–

δ-WC1±x – 4.8 % Co – 3.2 % Re hard alloys were designed, fabricated and studied

–

–

Powdered 47.5-76.0 % Re (99.99 %) – 19.0-47.5 % Co (99.3 %) – 5 % δ-WC0.99 (99.9%) mixtures (purities are given in brackets) were used to fabricate dense δ-WC1±x dispersed ε-(Re,Co) sintered alloys by the conventional powder metallurgy methods (α-(Re,Co) phase was detected in the materials only with the maximum contents of Co)

See also section C – Co – Re – W in Table I-2.14 δ-WC1±x – Co – Ru

–

–

The addition of Ru, which is not a carbide [1835, 2000, forming element, to δ-WC1±x – 6 % Co 3162, 3175hard alloys leads to its dissolution in the 3178] metallic binder of the alloys and promotion of the transformation of α-Co (cubic) to ε-Co (hexagonal) modification, resulting in the formation of a dispersed substructure in the binder phase

(continued)

2.6 Chemical Properties and Materials Design

315

Table 2.21 (continued) Ar, 1350 0.1 MPa

Powdered δ-WC1±x (2.0 μm) – 10 % Co (1.3 μm) – 0.2-0.4 % Ru (50 μm) mixtures (preliminarily ball-milled, initial particle sizes are given in brackets) were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare highly dense fine-grained hard alloys

Vacuum 1410

δ-WC1±x – 5-10 % Co – 0.4-3.0 % Ru highly dense hard alloys (mean δ-WC1±x grain size – 0.65-0.75 μm) were prepared by liquid-phase sintering (exposure – 1 h) process

See also section C – Co – Ru – W in Table I-2.14 δ-WC1±x – Co – S

–

–

δ-WC1±x – 6 % Co hard alloy reacts with [1119, 3957] powdered S to form WS2–x phase surface layer within the area of friction contact under sliding friction conditions (tribosynthesis)

–

–

δ-WC1±x – Co hard alloys were modified by S+ using ion implantation to dose levels of 2×1016 cm–2 to 5×1017 cm–2

δ-WC1±x – Co – Se

–

–

δ-WC1±x – 6 % Co hard alloy reacts with [3957] powdered Se to form WSe2–x phase surface layer within the area of friction contact under sliding friction conditions (tribosynthesis)

δ-WC1±x – Co – Si

–

δ-WC1±x – Co – Sn

–

δ-WC1±x – Co – Ta

–

1500-1600 Powdered δ-WC1±x – 5 % Co – 5 % Si [4497] mixtures (preliminarily high-energy ballmilled) were subjected to fast microwave sintering (without holding time) to produce cermet materials (porosity – in the range of 0.8-14 %); the presence of η1-W6Co6Cy, SiC and CoSi2 phases as side products was detected in the prepared materials –

δ-WC1±x – Co hard alloys were modified by Sn+ using ion implantation to dose levels of 2×1016 cm–2 to 5×1017 cm–2

[1119]

[1901, 3138, 1250-1270 The three-phase region in the sintered δ-WC1±x – 10 % Co – 0.5 % Ta hard alloys 3179-3180] (without the presence of α-C (graphite) or η1-W6Co6Cy phases) lies approximately in the range of C contents from 5.35 % to 5.54 %

(continued)

316

2 Tungsten Carbides

Table 2.21 (continued) 1400

After the rapid cooling of sintered δ-WC1±x – Co – Ta hard alloys, the compositions of cubic carbide phase in the equilibria with η2-phase or with α-C (graphite) were (Ta0.95W0.05)C1–x or (Ta0.96W0.04)C1–x, respectively, and composition of complex carbide phase was η2-(W2.74Co3.04Ta0.22)Cy

Vacuum 1410

δ-WC1±x – 10 % Co – 0.5 % Ta highly dense hard alloys were prepared by liquidphase sintering process

–

–

1450

In the δ-WC1±x – 20 vol.% Co sintered hard alloys, the solubility of Ta in Co-based metallic binder phase (in equilibrium with C) is ~ 4.0-4.5 % (it is not affected by the initial porosity) Some data reported in literature by various authors differ markedly

See also section C – Co – Ta – W in Table I-2.14 δ-WC1±x – Co – Ti

–

1100

The formation of hexagonal W4Ti2C3–x (0 < x < 1) ternary compound (?) in the presence of δ-WC1±x, (Ti,W)C1–x, ε-Co, α-(Co0.981÷0.984W0.014÷0.017Ti0.002Cx) and η1-W6Co6Cy phases was revealed

–

1400

After rapid cooling, the compositions of cubic carbide phase in the equilibria with η2-phase or with α-C (graphite) were (Ti0.60W0.40)C1–x or (Ti0.65W0.35)C1–x, respectively, and composition of complex carbide phase was η2-(W2.99Co2.96Ti0.05)Cy

CO/Ar 1410 (50/50), ptot = 5 kPa

δ-WC1.02 – 10 % Co – 0.2 % Ti highly dense hard alloys were designed (for the contents of formed (Ti,W)C1–x phase to be 0.7 vol.%) and prepared by liquid-phase sintering (exposure – 1 h) procedure

–

1450

Vacuum, 1500 1 Pa

[1901, 1988, 1991, 3027, 3072, 3138, 3140, 31813185, 3982]

In the δ-WC1±x – 20 vol.% Co sintered hard alloys, the solubility of Ti in Co-based metallic binder phase (in equilibrium with C) is ~1 % (it is not affected by the initial porosity and is approximately the same for both equilibria with α-C (graphite) and η2-W3Co3Cy phases) Powdered δ-WC1±x (0.125 μm) – 1 % Co (3.6 μm) – 9 % Ti (3.6 μm) mixtures (preliminarily high-energy ball-milled, initial mean particle sizes are given in brackets) were subjected to sintering (exposure – 1 h) procedure to prepare dense hard alloys (porosity – 3.6 %, with the presence of

(continued)

2.6 Chemical Properties and Materials Design

317

Table 2.21 (continued) small amounts of α/ε-W2+xC, (Ti,W)C1–x cubic monocarbide and (Ti,W,Co) metallic solid solution phases)

See also section C – Co – Ti – W in Table I-2.14 δ-WC1±x – Co – Vacuum 1410 V

In sintered δ-WC0.99 – 9.9 % Co – 0.3 % V [1998, 2333, hard alloys (total content C– 5.44 %), V 2860, 3015, was observed to segregate to some carbide- 3017, 3019, binder phase boundaries, the amount of V 3023, 3027, at the interface corresponded to a 1.0-1.1 3032, 3072, layer thick cubic (V,W)C1–x carbide; at the 3186-3187, carbide-carbide grain boundary segrega- 3982, 4488tions, 33 % of segregated Co were re4489] placed by V atoms δ-WC1±x – 10 % Co – 0.2 % V hard alloys (with the presence of small amounts of η2-W3Co3Cy, mean δ-WC1±x grain size – 0.63-0.79 μm, total contents of C – 5.355.64 %) were prepared using liquid-phase sintering (exposure – 1 h) procedure (losses C during the sintering – 0.02-0.07 % in absolute, or 0.4-1.3 % in relative per cents)

Vacuum, 1450 0.5 kPa

–

–

The diffusion of V into δ-WC1±x – 10 % Co hard alloy is characterized by apparent activation energy of E ≈ 330 kJ mol–1 (determined experimentally)

See also section VC1–x – δ-WC1±x – Co in Table III-3.16 δ-WC1±x – Co – W

Pure H2, 1450 5.3-8.0 kPa

In the conditions (pressure – 9.8 MPa, ex- [1944-1945, posure – 5 min) of ion-beam heated diffu- 2333] sion bonding (welding) of δ-WC1±x – 3-20 % Co hard alloys and metallic W bulk materials, the phases of α/ε-W2+xC, η2-W3Co3Cy and (Co,W) solid solutions (adjoined to the hard alloy side) and the phases of γ-WC1–x, μ-Co7W6±x and (W,C) solid solutions (adjoined to the metal side) were detected in the diffusion contact zones; the presence of Co content in the hard alloys up to 6-8 % increases the amount of γ-WC1–x, further raising the Co content leads to a growth in the widths of the diffusion zones (together with an increase in porosity), though no γ-WC1–x phase was found in the contact zones with the hard alloys containing 15-20 % Co

See also section C – Co – W in Table I2.14

(continued)

318

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – H2, or He α/β/ε/γ-W2±xC – Co – W

–

–

δ-WC1±x – γ-W2±xC – W – Co coatings [3374-3375] were deposited on steel substrates using δ-WC1±x – 12 % Co powders (agglomerate sizes – from 15 μm to 45 μm) and atmospheric plasma spraying (APS) technique; the Co constituent was presented by amorphous and/or nanocrystalline phases

–

δ-WC1±x – γ-W2±xC – W – Co coatings (with the small amounts of κ-W10Co3C3.4 phase, thickness – 0.2-0.3 mm, porosity – ~ 0.5-1.2 %) were deposited on steel substrates using δ-WC1±x – ~12 % Co (with the presence of η1-W6Co6Cy and η2-W3Co3Cy) feedstock powders with total C contents from 3.6 % to 5.1 % and highvelocity oxy-fuel (HVOF) thermal spraying techniques

See also section C – Co – W in Table I2.14 δ-WC1±x – Co – Y

–

δ-WC1±x – Co – Zn

–

430-510

[2554, 2907, High-velocity flame sprayed (HVFS) δ-WC1±x – 11-12 % Co coatings (produced 3188-3194] from “sintering and crushing” processed powders, total C content – 4.2 %), mainly containing η1-W6Co6Cy and/or η2-W3Co3Cy phases in the binder, had higher durability in molten pure Zn than those (produced from “spray-drying” processed powders, total C content – 6.8 %), which mainly were composed of metallic α-Co phase in the binder (apparent activation energy for the growth of Zn-diffusion layer in the coatings of the first type E = 170 kJ mol–1)

–

480-900

The reaction zone between sintered δ-WC1±x – 6 % Co hard alloy and molten metallic Zn is characterized by a lamellar structure (Liesegang bands) in which δ-WC1±x layers and metal layers alternate; γ-CoZn4±x, γ1/δ-CoZn8–x and γ2-CoZn12±x phases jointly with elemental Zn were identified in the metal layer of the reaction zone

–

The addition of 0.1 % Y to δ-WC1±x – 6 % [3174] Co hard alloy leads to the stabilization of α-Co (cubic) modification due to restraining the martensitic α-Co → ε-Co transformation

(continued)

2.6 Chemical Properties and Materials Design

319

Table 2.21 (continued) –

500-700

Sintered δ-WC1±x – 4-20 % Co hard alloys were subjected to contact interaction with molten metallic Zn (exposure – 0.25-2.0 h) resulted in Co transfer from the surface of hard alloys into Zn melt accompanied by the migration of Zn into the alloys along channels, which had been previously filled with Co, dissolution of Co and formation of Zn-Co solution enclosed in the pores in the alloys; finally, Co was completely dissolved and the individual δ-WC1±x grains were randomly distributed in the Zn melt that led to cracking and separation of the δ-WC1±x frame from the alloys

Vacuum 1340-1440 δ-WC1±x – 5.0-9.5 % Co – 0.5-5.0 % Zn hard alloy (no presence of non-combined C or η-phases, mean δ-WC1±x grain size – 1.5-1.8 μm) were fabricated by liquidphase sintering (exposure – 1-5 h) procedure –

–

The thickness of Co – Zn – W alloy layers, formed on the surface of δ-WC1±x – Co hard alloys after treatment with excess molten metallic Zn, decreased with the binder mean free path of the δ-WC1±x – Co alloys

δ-WC1±x – Al4C3 Vacuum,1250-1400 (W0.4Al0.6)C0.5 – 13 vol.% Co two-phase [2101] – α/ε-Co 1 mPa highly dense cemented carbides (with mean grain sizes – 1-3 μm) were prepared by sintering procedure (exposure – 0.5-2 h) using 99.6 % purity Co powder The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors δ-WC1±x – AlN – Ar, α/ε-Co 5 MPa

1400

Powdered δ-WC1±x (0.2 μm) – 0.5-2.0 % [3210] AlN (0.3 μm) – 10 % Co (0.8 μm) mixtures (mean particle sizes are given in brackets, preliminarily high-energy ball-milled) were subjected to hot isostatic pressing (HIP) procedures (exposure – 1 h) to fabricate dense hard alloys (porosity – 0.82.1 %, mean δ-WC1±x grain size – 0.650.72 μm, mean free path – ~ 0.10-0.14 μm)

δ-WC1±x – AlN – [(CkHl)(CpHq) Si(CH2)]n – α/β-SiC – α/ε-Co

1950

Powdered α-SiC – 20 % polycarbosilane [2236] [(CkHl)(CpHq)Si(CH2)]n (PCS) – 4.7 % δ-WC1±x – 0.3 % Co – 2 % AlN mixtures were hot-pressed to prepare modified ceramic materials

–

(continued)

320

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Vacuum 1300 α/γ/δ/κ/θ/χ-Al2O3 – α/ε-Co

Powdered δ-WC1±x (> 99.3 %, ~1.5 μm) – [3195-3207, 0.25-1.0 % Al2O3 (> 99.9 %, 20 nm) – 4084, 4502] 8 % Co (> 99.6 %, ~1.2 μm) mixtures (preliminarily ball-milled, initial purities and mean particle sizes of the components are given in brackets,) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare dense threephase hard alloys (porosity – 0.8-1.1 %, mean grain size < 1 μm); Al2O3 nanoparticles dispersed in Co binder inhibits the α-Co (cubic) → ε-Co (hexagonal) transformation to a certain extent, no chemical reactions were detected in the prepared materials

Vacuum 1350

Powdered δ-WC1±x (1.5 μm) – 3-5 % Al2O3 (4 μm) – 1-3 % Co (30 μm) mixtures (all the ingredients of 99 % purity, mean particle size is given in brackets, preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 4 min) to prepare dense three-phase cermets (porosity – 0.41.8 %) with the uniform distribution of Al2O3 and Co in δ-WC1±x matrix (no interphase interaction was detected in the prepared materials)

Vacuum 1360

Powdered δ-WC1±x (0.9 μm) – 5.0-87.5 % α-Al2O3 (0.2 μm) – 10 % Co (0.03 μm) mixtures (mean particle sizes are given in brackets) were subjected to hot-pressing (exposure – 1 h) procedure to prepare highly dense composite materials; in the materials with α-Al2O3 matrix (porosity – from 0.5 to 3.0 %), δ-WC1±x and η2-W3Co3Cy phases with the small amounts of α-Co and α-C (graphite) were identified, while in δ-WC1±x-based materials (porosity – from 0.25 to 0.5 %) – α-Al2O3 and η2-W3Co3Cy as major phases uniformly distributed in the matrix were observed (no metal phase was detected)

Vacuum 1440

Powdered δ-WC1±x (≥ 99.5 % purity, mean particle size – ~6 μm) – 8 % Co (≥ 99.8 % purity, mean particle size – ~1 μm) – 0.31.2 % Al2O3 (≥ 99.9 purity, mean particle size – ~20 nm) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) procedure to prepare highly dense hard alloys

(continued)

2.6 Chemical Properties and Materials Design

321

Table 2.21 (continued) Ar

δ-WC1±x – 86-87 % Al2O3 – 3.0-4.5 % Co cermet composites (porosity < 5 %) were fabricated by liquid state sintering (exposure – 2 h) process

1600

–

–

δ-WC1±x – 7-8 % Co hard alloys with the addition of 0.5-3.0 % Al2O3 nanoparticles were fabricated by spark-plasma sintering techniques

–

–

δ-WC1±x – 10-15 % Al2O3 – 12-72 % α/ε-Co high-velocity oxy-fuel (HVOF) sprayed coatings were designed and deposited on stainless steel substrates; the presence of η1-W6Co6Cy phase was detected

δ-WC1±x – Al2O3 – TiC1–x – Co

See section TiC1–x – Al2O3 – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – Al2O3 – TiC1–x – Co – Ni

See section TiC1–x – Al2O3 – δ-WC1±x – Co – Ni in Table III-2.22

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/ε-Co

–

δ-WC1±x – B4±xC – α/ε-Co

–

1340

δ-WC1±x – 15 % Co – 0.1-1.0 % B4±xC [3211-3213, hard alloys were prepared by hot-pressing 4153] procedure; the formation of W-Co-B ternary compound phases was observed

–

1350

δ-WC1±x – Co hard alloys with incorporated B4±xC particles were fabricated using hot-pressing procedure

–

1500

Powdered (purity level and initial mean particle size, respectively, are given in the brackets) δ-WC1±x (99 %, 0.2 μm) – 0.5 % Co (99 %, ~75 μm) – 0.5-2.0 % B4±xC (97 %, 3.5 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (exposure – 5 min) procedures to prepare dense hard alloys (porosity – 5-9 %), containing the δ-WC1±x platelet grains with some planar defects and facet-roughening surfaces (steps / kinks), which were growing through the defect-assisted nucleation; small amounts of α/β-WB1±x and W2CoB2±y, newly formed boride phases jointly with α-C (graphite) were identified in the alloys

–

δ-WC1±x – 30 % Y2O3–x-stabilized ZrO2–x – [3209] 55 % Al2O3 – 5 % Ni – 1 % Co cermets were fabricated from nanocrystalline and submicron mixed powders using the microwave sintering (MWS) and hot isostatic pressing (HIP) procedures

(continued)

322

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1800-1900 Powdered B4±xC (> 96 % purity, mean par13 mPa ticle size – 2-6 μm) – 20-40 vol.% δ-WC1±x (mean particle size – 2-8 μm) mixtures with the addition of 6 % Co as a sintering aid (preliminarily ball-milled) were subjected to hot-pressing procedure to prepare dense materials (porosity – 2-9 %); the reaction products β-W2B5–x and α-C (graphite) were located in the materials between the B4±xC and δ-WC1±x grains in the form of mixture of layered phases δ-WC1±x – B4±xC – α/β-SiC – α/ε-Co

–

–

δ-WC1±x – B4±xC – SiC – Co hard coatings [3214] were deposited on steel substrates using laser cladding techniques

δ-WC1±x – B4±xC Vacuum, 1450 – TiB2±x – α/ε-Co Ar

B4±xC – 25 % TiB2±x – 9 % δ-WC1±x – 1 % [3215] Co fine-grained powdered composition was prepared by the chemical synthesis route

δ-WC1±x – B4±xC Vacuum < 1300 – α/β-Y2O3–x – α/ε-Co

The B4±xC + Y2O3–x coated surface of [3216] δ-WC1±x – 20 % Co hard alloy interacts with the base forming ternary compound W2Co21B6±y phase; the presence of Y2O3–x catalyzes the decomposition of B4±xC and promotes the diffusion of active B atoms from the surface into the bulk of hard alloy

δ-WC1±x – α/β-BN – α/ε-Co

–

1100-1125 Powdered δ-WC1±x-based hard alloy (mean [53, 2806, particle sizes – 0.2 μm (δ-WC1±x) and 0.8 3218-3239, μm (Co), content Co – 1-10 %) – 30-50 4051, 4071, vol.% cubic β-BN (mean particles sizes – 4158] from 0.4 μm to 4.4 μm) mixtures were subjected to glass-encapsulated hot isostatic pressing (GE-HIP) procedure (exposure – 1 h) to fabricate dense composites (porosity – 0-5 %); no phase transformation of cubic β-BN phase to hexagonal α-BN phase was detected in the materials

Vacuum, 1100-1200 Powdered δ-WC1±x-based hard alloy (mean 5 mPa particle sizes – 0.4 μm (δ-WC1±x) and 1 μm (Co), content Co – 6-12 %) – 30 vol.% cubic β-BN (mean particles sizes – from 1-3 μm to 37-44 μm) mixtures (preliminarily ball-milled) were subjected to pulse plasma sintering (PPS) procedure (exposure – 5 min) to fabricate dense composites (porosity – from 0.2 % to ~7 %) with α-(Co,W,C) solid solution metallic binder; no phase transformation of cubic β-BN phase to hexagonal α-BN phase was detected in the materials

(continued)

2.6 Chemical Properties and Materials Design

323

Table 2.21 (continued) –

1100-1400 δ-WC1±x – Co hard alloys – 10-20 vol.% β-BN dispersion highly dense composites were produced using spark-plasma sintering technique; the partial transformation of cubic β-BN to hexagonal α-BN phase, accompanied by the increase of porosity in the composites, was observed at ≥ 1400 °C

Vacuum, 1150-1300 Powdered δ-WC1±x-based hard alloy (mean 100 Pa particle sizes – 0.8 μm (δ-WC1±x) and 1.1 μm (Co), content Co – 10 %) – 30 vol.% cubic β-BN (mean particles size – 40 μm) mixtures (preliminarily high-energy ballmilled) were subjected to spark-plasma sintering (exposure – 5-8 min) procedure to fabricate dense three-phase composites (porosity – 3.5-7.5 %) with ultra-fine hard alloy matrix Vacuum 1250-1300 Powdered δ-WC1±x-based hard alloy (mean δ-WC1±x particle size – 0.8 μm, content Co – 6 %) – 25 vol.% cubic β-BN (mean particles size – 5 μm) mixtures were subjected to spark-plasma sintering (SPS) procedure (exposure – 5-7.5 min) to fabricate dense composites (porosity – 0.4-0.6 %); no phase transformation of cubic β-BN phase to hexagonal α-BN phase was detected in the materials Powdered δ-WC1±x (99.5 %, < 1 μm) – 2-4 % cubic β-BN (N/A, 0.6 μm) – 6-8 % Co (99.9 %, 44 μm) mixtures (preliminarily ball-milled; purity and initial mean particle size, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedures (exposure – 5-10 min) to fabricate composites (porosity – 3.5-8.0 %)

–

1300

–

1300-1400 δ-WC1±x – 4-10 % Co hard alloys, modified by 5-20 vol.% ultra-hard cubic β-BN phase, were prepared using hot-pressing (exposure – 1.5 h) technique

Vacuum 1330-1390 Powdered δ-WC1±x-based hard alloy (mean particle sizes – 0.8 μm (δ-WC1±x) and 3 μm (Co), content Co – 6 %) – 30 vol.% cubic β-BN (mean particles size – 40 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (exposure – 5 min) procedure to fabricate highly dense three-phase composites with ultra-fine hard alloy matrix

(continued)

324

2 Tungsten Carbides

Table 2.21 (continued) Powdered δ-WC1±x-based hard alloy (content Co – 15 %) – cubic β-BN mixtures were subjected to high-temperature – highpressure treatment (exposure – 40 s) to fabricate dense hard composites

High 1400 pressure machine, 7.0 GPa

δ-WC1±x – Vacuum 1300-1400 Powdered δ-WC1±x (99.99 %, 2.4 μm) – [3238] α/β-BN – Cr3C2–x 8 % Co (99.9 %, 0.8 μm) – 0.15-0.30 % – α/ε-Co Cr3C2–x (99.7 %, 1.35 μm) – 1.9 % (7.5 vol.%) cubic β-BN (99.9 %, 1.5 μm) mixtures (preliminarily ball-milled, purity and initial mean particle size, respectively, are given in brackets) were subjected to hotpressing (exposure – 1.5 h) procedure to fabricate dense three-phase composites (open porosity – 0.2-1.0 %) δ-WC1±x – α/β-BN – NiPx (Ni3P, Ni2–xP) – Co – Ni

Vacuum 1100-1300 Powdered δ-WC1±x-based hard alloy (mean [3225-3226] particle sizes – 0.2 μm (δ-WC1±x) and 3 μm (Co), contents: Co – 9.7 %, Ni + P – 2.9 %) – 10-30 vol.% cubic β-BN (mean particles sizes – 2-3 μm and 10-14 μm) mixtures (preliminarily ball-milled) were subjected to pulse electric current sintering (PECS) procedure (exposure – 10 min) to produce dense composites (porosity – 0-5 %) with ultra-hard β-BN phase homogeneously distributed in them; the partial transformation of cubic β-BN to hexagonal α-BN was detected only at ≥ 1300 °C

δ-WC1±x – α/β-BN – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/ε-Co

–

δ-WC1±x – BaF2 – CaF2 – Co – Cu

–

Powdered δ-WC1±x (99.5 %, < 1 μm) – 4-7 [3239] % β-(Zr,Y)O2–x (> 99.9 %, 45 μm, content Y2O3–x – 7.5 %) – 2 % cubic β-BN (N/A, 0.6 μm) – 1-4 % Co (99.9 %, 44 μm) mixtures (preliminarily ball-milled; purity and initial mean particle size, respectively, are given in brackets) were subjected to sparkplasma sintering (SPS) procedure (exposure – 5-10 min) to fabricate dense composites (porosity – 0-6 %); the partial decomposition of β-(Zr,Y)O2–x solid solution and formation of α-ZrO2–x (monoclinic) phase were observed

1300

–

δ-WC1±x – 7.2-9.6 % Co – 10-30 % Cu – [3217] 6.2 % BaF2 – 3.8 % CaF2 coatings (with the presence of small amounts of γ-W2±xC) were deposited via atmospheric plasma spraying (APS) process by using feedstock powders composed of δ-WC1±x – 12 % Co hard alloy, pure Cu and BaF2 – 38 % CaF2 (eutectic) composition

(continued)

2.6 Chemical Properties and Materials Design

325

Table 2.21 (continued) δ-WC1±x – (C8H6O2)n – Co – Fe – Ge

–

–

The flake-type powders of Fe36Co62Ge4 [3240] (mean particle size – 73 μm), mixed with 10-30 % δ-WC1±x (mean particle size – 1.4 μm) and 10 % phenol-formaldehyde (C8H6O2)n resin binder, were employed to fabricate magnetostrictive composites

δ-WC1±x – [(CkHl)ON (CpHq)O]n – α/ε-Co

–

–

Functionally graded δ-WC1±x – Co hard [3241] alloy powder (mean particle size – ~20 μm) – 46-58 vol.% thermosetting polyimide [(CkHl)ON(CpHq)O]n coatings (thickness – 0.3-0.6 mm, porosity – 16-28 %) were high-velocity oxy-fuel (HVOF) sprayed on polymer matrix com-posites (PMC) as substrates

δ-WC1±x – [(CkHl)(CpHq) Si(CH2)]n – α/β-SiC – α/ε-Co

–

1950

δ-WC1±x – CaF2 – α/ε-Co

–

1050-1100 Functionally graded δ-WC1±x (99 %) – [10, 2946, 4-5 vol.% CaF2 (95 %) – 5-12 vol.% Co 3242-3243] (99 %) materials (purity is given in brackets) were fabricated using spark-plasma sintering (SPS) procedure (exposure – 5 min) of the powdered layers with various compositions

N2

δ-WC1±x – Ar, CeB6±x – α/ε-Co 5 MPa

Powdered α-SiC – 20 % polycarbosilane [(CkHl)(CpHq)Si(CH2)]n (PCS) – 4.7 % δ-WC1±x – 0.3 % Co mixtures were hotpressed to prepare modified ceramics

[2236]

1450

Powdered δ-WC1±x (99.8 %, 15-18 μm) – 10 % Co (99.5 %, 20-30 μm) – 3-10 % CaF2 (98 %, 170-180 μm) mixtures (preliminarily high-energy ball-milled, purity and initial mean particle sizes are given in brackets) were subjected to liquid-phase sintering (exposure – 1 h) to produce dense three-phase materials (porosity – 5-20 %)

1400

Powdered δ-WC1±x (0.4 μm) – 8 % Co [3244] (3 μm) – 0.5-1.5 % CeB6±x (3 μm) mixtures (preliminarily high-energy ball-milled to ~40 nm mean size, the initial mean particle sizes are given in brackets) were subjected to vacuum sintering followed by gas pressure sintering (exposure – 1 h) procedure to fabricate dense fine-grained hard alloys (porosity – 1.0-2.5 %); the addition of CeB6±x inhibits α-Co (cubic) → ε-Co (hexagonal) polymorphic transformation, decreases the amounts of η2-W3Co3Cy phase and promotes the formation of WCoBy and W2Co21B6±y phases in the alloys

(continued)

326

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Vacuum 1400-1450 Powdered δ-WC1.00 (from 3 μm to 11 μm) [3245-3254] CeO2–x – α/ε-Co – 11 % Co (1.5-3.0 μm) – 0.05-0.5 % CeO2–x (10-50 nm) mixtures (preliminarily ball-milled, initial mean particle sizes are given in brackets) were subjected to liquidphase sintering (exposure – 1.5 h) procedure to fabricate fine-grained hard alloys (porosity – 0.35-0.65 %); nano-additives of CeO2–x inhibit α-Co (cubic) → ε-Co (hexagonal) polymorphic transformation –

δ-WC1±x – CeO2–x – MgSiN2 – α/β/γ-Si3N4 – α/β-Y2O3–x – α/ε-Co

Ar

–

1650

δ-WC1±x – CoPy Vacuum 950-1050 – α/ε-Co

–

δ-WC1±x – 12 % Co hard coatings, modified by 0.1-2.0 % CeO2–x, were deposited on various steel substrates by using several different technological approaches, such as laser cladding (LC) technique, high-velocity oxy-fuel (HVOF) spraying technology and electric contact surface strengthening (ECSS) method Powdered α-Si3N4 (0.7 μm) – 5-15 % [4332] δ-WC1±x (0.5 μm) – 5 % MgSiN2 (0.5 μm) – 1-4 % Co (0.5 μm) – 3 % α-Y2O3–x (1 μm) – 1 % CeO2–x (1 μm) mixtures (preliminarily high-energy ball-milled, initial mean particle sizes are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 6 min) to prepare dense hard materials (porosity – ~ 0.6-1.0 %); the contents of β-Si3N4, formed during the processing due to the α-Si3N4 → β-Si3N4 transformation, increased with the increase in δ-WC1±x contents, but decreased with the increase in Co contents in the processed mixtures Powdered δ-WC1±x (mean particle size – 1 [3163-3165] μm) – 7 % Co (mean particle size – 40 nm) – 0.3 % P (99 % purity, modification – red) mixture was subjected to spark-plasma sintering procedure to fabricate highly dense hard alloys (porosity – 0.1-1.8 %, mean δ-WC1±x grain size – 0.17-0.24 μm); the addition of P promotes noticeably the powder densification process

1070-1380 δ-WC1±x – CoPy – Co hard alloys (porosity – 5-8 %, total contents: Co – 6-15 %, P – 0.2-1.7 %) were designed and fabricated by hot-pressing technique

(continued)

2.6 Chemical Properties and Materials Design

327

Table 2.21 (continued) δ-WC1±x – CrB2±x – α/ε-Co

–

1350-1400 The introduction of 0.1-2.5 vol.% CrB2±x [3339, 4386] into the δ-WC1±x – 6 % Co hard alloys did not lead to the formation of any new phase constituents in the materials prepared by standard liquid-phase sintering process

Vacuum 1450

δ-WC1±x – Vacuum 900-1100 Cr3C2–x – α/ε-Co

Ar or N2, 950-1150 70 kPa

Vacuum, 1100 10 Pa

Powdered δ-WC1.00 (4-9 μm) – 0.5-10.0 % CrB2.00 (5-7 μm) – 5.4-6.0 % Co (2 μm) mixtures (size distributions / mean particle sizes of the components are given in brackets) were subjected to hot-pressing procedure (exposure – 8 min) to fabricate dense hard alloys; the introduction of CrB2±x led to the formation of thin (~0.1 μm) and extended layers of Co binder even between fine δ-WC1±x grains Powdered δ-WC1±x – 0.17 % Cr3C2–x – 10 % Co mixtures (initial mean carbide particle sizes < 1 μm, preliminarily ball-milled) were subjected to heat treatment; only slight outgassing and no shrinkage acceleration were observed in the mixture

[64, 976, 1802, 1992, 1996-1998, 2333, 2546, 2564, 2598, 2610, 2631, The diffusion parameters (activation ener- 2633, 2652, gy and pre-exponential factor) of Cr in the 2709, 2715, 2733-2734, couple of δ-WC1±x – 85 vol.% Co and δ-WC1±x – 50 vol.% Co – 40 vol.% Cr3C2–x 2786, 2801, hard alloys were experimentally determi- 2821, 28552856, 2871, ned to be E = 267±8 kJ mol–1 and D0 = 8.1±1.7 cm2 s–1, respectively, while in the 2878, 2915, 2917, 2919, couple of δ-WC1±x – 16.3 vol.% Co and 2955, 2965, Cr3C2–x – 16.3 vol.% Co hard alloys the 3015, 3032, same diffusion parameters were E = 3080, 3186, 250 kJ mol–1 and D0 = 66.9 cm2 s–1, res3247, 3255pectively 3320, 3390, Powdered δ-WC1±x (mean particle size – 4201, 4505] from 40-80 nm to 100-250 nm) – 0.5-1.0 % Cr3C2–x (mean particle size – 0.5-1.0 μm) – 12 % Co mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare dense hard alloys (without the presence of η-phases, porosity – 0.3-1.8 %, mean δ-WC1±x grain size – (0.21÷0.24)±0.01 μm)

Vacuum 1200-1250 Powdered δ-WC1±x (≥ 99.5 % purity, mean particle size – ~0.25 μm, contents: noncombined C – 0.11 %, O – 0.38 %) – 0.20.8 % Cr3C2–x (mean particle size – 3.6 μm, contents: non-combined C – 0.18 %, O – 0.22 %) – 11 % Co (≥ 99.6 % purity, mean particle size – 60 nm, content O – 0.32 %) mixtures (preliminarily ball-milled) were

(continued)

328

2 Tungsten Carbides

Table 2.21 (continued) subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare dense hard alloys (porosity – 0-3 %, mean δ-WC1±x grain size – 0.4-0.5 μm) Vacuum 1200-1300 δ-WC1±x – 0.2-0.8 % Cr3C2–x – 9-12 % Co dense hard alloys were fabricated from the nanocrystalline powders (mean particle size – ~10 nm), prepared via mechanical alloying (MA) method, using for their densification a spark-plasma sintering (SPS) technique Ar, 1200-1300 Powdered δ-WC1±x (90 nm) – 10 % Co 10 MPa (from ~0.2 μm to ~0.5 μm) – 0.9 % Cr3C2–x (~0.5 μm) mixtures (preliminarily ball-milled, initial mean particle sizes are given in brackets) were subjected to hot isostatic pressing (HIP) procedure to fabricate practically poreless two-phase hard alloys Vacuum 1200-1400 Powdered δ-WC1±x – 0.17 % Cr3C2–x – 10 % Co mixtures (initial mean carbide particle sizes < 1 μm, preliminarily ball-milled) were subjected to heat treatment; strong outgassing reaction was observed in the mixture –

1240

δ-WC1±x – 0.9 % Cr3C2–x – 12 % Co highly dense hard alloys (mean δ-WC1±x grain size – ~0.2 μm) were fabricated by pulsed electric current sintering (PECS) technique (exposure – 2 min) in the solid state mode

–

~1245

Eutectic (pseudobinary) (Cr,W)3C2–x – (Co,Cr,W)

1300

Powdered δ-WC1±x (~ 0.1-0.4 μm) – 0.9 % Cr3C2–x (~ 0.5-1.5 μm) – 10 % Co (~ 0.20.8 μm) mixtures (preliminarily high-energy ball-milled, intial mean particle sizes are given in brackets) were subjected to hot isostatic pressing (HIP) procedure to fabricate poreless two-phase hard alloys

Ar, 5 MPa

Vacuum 1300-1575 Powdered δ-WC1±x (0.9 μm) – 0.5 % Cr3C2–x (1 μm) – 6-10 % Co (1.6 μm) mixtures (with high C and low C contents, preliminarily ball-milled, intial mean particle sizes are given in brackets) were subjected to liquid-phase sintering (exposure – 2 h) to prepare dense fine-grained hard alloys

(continued)

2.6 Chemical Properties and Materials Design

329

Table 2.21 (continued) 1340-1410 Powdered δ-WC1.01 (mean particle size – 0.6 μm, content O – 0.12 %) – 0.3-0.65 % Cr3C~2.0 (mean particle size – 1.25 μm, content O – 0.55 %) – 10 % Co (mean particle size – ~0.8 μm, content O – 0.55 %) mixtures (total contents of C – ~5.46 %, preliminarily ball-milled and pressed) were subjected to sintering procedure to prepare dense hard alloys (mean δ-WC1±x grain size – ~ 0.6-0.7 μm, Cr contents in the binder phase – from 0.21 % to 0.45 %)

Ar

Ar, 1350 100 MPa

–

1360

Powdered δ-WC1±x (0.9 μm) – 1 % Cr3C2–x (1-3 μm) – 8 % Co (1.3 μm) mixtures (preliminarily ball-milled, intial mean particle sizes are given in brackets) were subjected to vacuum sintering followed by hot isostatic pressing (HIP) procedure to prepare highly dense hard alloys (mean δ-WC1±x grain size – 0.7 μm, total C content – 5.595.68 %)

Nanocrystalline δ-WC1±x – 1 % Cr3C2–x – 10 % Co hard alloys (mean grain size < 0.3 μm) were prepared by hot-pressing method

Vacuum, 1360-1400 Powdered δ-WC0.98 (mean particle size – ~1.3 mPa 0.84 μm, contents: non-combined C – 0.02 %, O – 0.16 %) – 9.0-9.75 % Co (mean particle size – 0.87 μm, contents: total C – 0.02 %, O – 0.42 %) – 0.25-1.0 % Cr3C2–x (mean particle size – ~2.8 μm, contents: non-combined C – 0.30 %, O – 0.70 %) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate dense two-phase hard alloys (porosity – 2-4 %, mean grain size – 0.5-0.8 μm) Vacuum 1380

Powdered δ-WC1±x – 1-10 % Cr3C2–x – 15 % Co mixtures (preliminarily ball-milled, intial mean particle sizes – 1.3-1.5 μm) were subjected to liquid-phase sintering (exposure – 1 h) procedure to fabricate dense hard alloys; the solid solubility limit of elemental Cr in the metallic binder phase was ~4 % and ~11 % in the alloys with high C and low C contents, respectively (it increased by rapid cooling after sintering), so when the additional amounts of Cr3C2–x was excess beyond the limits, (Cr,Co,W)7C3±x phase was observed in the alloys; total amounts of Co and W dissolved in this phase increased in the alloys with high C contents, and the amounts of

(continued)

330

2 Tungsten Carbides

Table 2.21 (continued) (Cr,Co,W)7C3±x was in the same way under a fixed amount of Cr3C2–x Ar, 1380 5.6 MPa

–

1390

Ar, 1390 10 MPa

δ-WC1±x – 10 % Co – 0.6 % Cr3C2–x highly dense hard alloys were prepared by gas pressure sintering (exposure – 40 min) procedure Dense δ-WC1±x – 10 % Co – 0.2-1.2 % Cr3C2–x hard alloys were fabricated by hot isostatic pressing (HIP) procedure (exposure – 75 min) Powdered δ-WC1±x – 12 % Co – 0.7 % Cr3C2–x mixture (preliminarily ball-milled to reach the nanoscale) was subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare dense hard alloys with the nanoscale precipitated in δ-WC1±x grains Cr3C2–x and Co nanoparticles, which mainly had a coherent or semi-coherent interface with the matrix δ-WC1±x grains, the pinning effect of the nanoparticles on the motion of dislocations within the δ-WC1±x grains was observed

–

1400

Dense δ-WC1±x – 6 % Co – 0.9 % Cr3C2–x hard alloys were fabricated by liquid-phase sintering (exposure – 5 h) procedure

–

1400

During the liquid-phase sintering process (holding time – 1 h) of δ-WC1±x – 20 % Co hard alloys with the addition of Cr3C2–x, the solubilities of δ-WC1±x and Cr3C2–x in the liquid binder were estimated to be 33 % and ~30 %, respectively

Vacuum, 1400 5 Pa

Powdered δ-WC1±x (99.9 %, 0.1-0.2 μm) – 6 % Co (99.9 %, 0.1-0.2 μm) – 1-3 % Cr3C2–x (99.9 %, 6 μm) mixtures (purities and initial mean particle sizes are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to fabricate dense hard alloys (with the presence of small amounts of γ-W2±xC, η1-W6Co6Cy and η2-W3Co3Cy, porosity – ~ 2-3 %)

–

1400

The solubility of Cr3C2–x in Co-based binder of δ-WC1±x – Co alloys is ~12 mol.%

H2/Ar

1410

Powdered δ-WC1±x (mean particle size – from 0.8 μm to 4 μm) – 19.5 % Co (mean particle size – 0.8 μm) – 0.8 % Cr3C2–x mixtures (preliminarily ball-milled, with high and low total C contents) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate highly dense hard alloys

(continued)

2.6 Chemical Properties and Materials Design

331

Table 2.21 (continued) (ε-Co/α-Co binder phase indexing ratio – from 0.07-0.19 to 0.20-0.62, mean δ-WC1±x grain size – from ~ 0.6-0.7 μm to ~ 2.4-3.2 μm) 1410

In the as-sintered δ-WC1±x – Cr3C2–x – Co hard alloys (contents: total C – 5.58 %, Co – 8.37 %, Cr – 0.84 %, mean δ-WC1±x grain size – ~0.4 μm, Co-based binder phase, containing, in average: 7.75±0.01 at.% Cr, 0.94±0.02 at.% W and 0.34±0.03 at.% C, fraction – 16 vol.%), (Cr,W)Cy phase was presented as a thin δ-WC1±x grain surface layer, while the Co-based binder phase contained a segregation of Cr in front of this surface layer; the equilibrium segregation of Cr in the binder phase was estimated to be of 0.8 monolayer

1420

Powdered δ-WC0.99 (mean particle size – 3.2 μm, content non-combined C – 0.10 %) – 1-6 % (2-12 vol.%) Cr3C2–x (99.5 % purity, mean particle size - ~7 μm) – 10-11 % (16.5 vol.%) Co (mean particle size – 0.8 μm, specific surface area – 2-3 m2 g–1, contents: Ag – 0.3 %, Ni – 0.2 %, C – 0.18 %, Fe – 0.005 %) mixtures (preliminarily ballmilled) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate dense hard alloys (porosity 0-1 %, mean linear intercept grain size – 0.9-1.0 μm); in the alloys with the contents of Cr3C2–x ≥ 2 % (4 vol.%) the formation of (Cr,Co,W)7C3±x phase was observed

Vacuum, 1450 5 Pa

Powdered δ-WC1±x (99.9 % purity, mean particle size – ~ 40-80 nm) – 6 % Co – 0.21.0 % Cr3C2–x (99.9 % purity, mean particle size – ~6 μm) mixtures (preliminarily milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare two-phase hard alloys

Vacuum, 1450 < 1 Pa

Powdered δ-WC1±x – Cr3C2–x – Co mixtures (preliminarily ball-milled and coldpressed, initial mean δ-WC1±x particle size – 6.75 μm; total contents: Co – 15 %, Cr – 5 %, C – various: at low and high levels) were subjected to liquid-phase sintering (exposure – 1 h) procedures; depending on total C contents, the prepared hard alloys were composed of: δ-WC1±x and η1-(W0.40Co0.49Cr0.11)12Cy carbide and α-(Co0.85Cr0.12W0.03) fcc metallic solid solution phases – at low total C contents and

–

H2

(continued)

332

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x and (Cr0.53Co0.45W0.02)7C3.31 carbide, α-(Co0.91Cr0.08W0.01) fcc metallic solid solution and α-C (graphite) phases – at high total C contents Powdered δ-WC1±x (99.95 % purity, mean particle size – ~0.2 μm) – 5 % Co (mean particle size – ~4 μm) – 2 % Cr3C2–x (99.9 % purity, mean particle size – ~6 μm) mixtures (preliminarily milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) followed by rapid cooling (up to room temperature) to fabricate nanocrystalline two-phase hard alloys (porosity – 2.8 %, mean δ-WC1±x grain size – 26 nm)

Vacuum, 1500 5 Pa

–

–

δ-WC1±x – Cr3C2–x – Co hard alloys were prepared by the infiltration of Co – Cr3C2–x alloy into δ-WC1±x sintered materials

δ-WC1±x – Cr3C2–x – Co – Cr

–

–

Powdered δ-WC1±x – Cr3C2–x – Co – Cr [10, 3321, mixtures were employed as high-velocity 3456] oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (contents: W – 79.1 %, C – 6.4 %, Co – 9.3 %, Cr – 3.4 %) composed mainly of δ-WC1±x, γ-W2±xC and Cr7C3±x phases

δ-WC1±x – Cr3C2–x – Co – Cr – Fe – Ni

–

–

Powdered δ-WC1±x – 45 % Cr3C2–x – 11.2 [3456] % Ni – 3.6 % Co – 3 % Cr – 0.2 % Fe mixtures (spray dried and sintered) were employed as feedstock powders for the deposition of hard coatings (thickness – 0.4 mm) on steel substrates via high-velocity oxy-fuel (HVOF) spraying followed by a furnace heat treatment or high-power laser irradiation; δ-WC1±x, γ-(W1–yCry)2±xC (y ≈ 0.7), Cr3C2–x and Ni-based metallic solid solution (matrix) were the major phases in the structure of prepared coatings

δ-WC1±x – Cr3C2–x – Co – Cr – Mo – Ni

–

–

Powdered δ-WC1±x – 46 % Cr3C2–x – 2 % [3322-3323] Co – 5 % Cr – 3 % Mo – 9 % Ni mixtures (total C content – 8.1 %) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (major phases – δ-WC1±x, Cr3C2–x, Cr7C3±x and Ni-based solid solution in the presence of amorphous phase, porosity – (1.1÷1.2)±(0.1÷0.2) %) on steel and Ni-based alloy substrates

(continued)

2.6 Chemical Properties and Materials Design

333

Table 2.21 (continued) δ-WC1±x – Cr3C2–x – Co – Cr – Ni

–

–

Powdered δ-WC1±x – Cr3C2–x – Co – Cr – [3324-3328] Ni mixtures (distribution sizes – 16-35 μm and 22-50 μm, total contents: C – 8.1-8.2 %, Cr – 40.2-40.7 %, Ni – 11.3-11.6 %, Co – 3.6 %) were employed as high-velocity air-fuel (HVAF) and high-velocity oxyfuel (HVOF) spraying feed-stock materials for the deposition of hard coatings (thickness – 160-270 μm, porosity – 0.9-1.6 %); additionally to δ-WC1±x, Cr3C2–x and Ni-based solid solution phases, contained in both HVAF- and HVOF-sprayed coatings, γ-W2±xC phase was identified in the prepared HVOF-sprayed coatings

–

–

Powdered δ-WC1±x – 56 % Cr3C2–x – 3 % Co – 19 % Cr – 19 % Ni mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (major phases such as Cr7C3±x, η2-W3Co3Cy and Cr-based solid solution jointly with γ-W2±xC and Cr intermetallide phases were identified in the top surface layers) on steel substrates

–

–

Powdered δ-WC1±x – 45 % Cr3C2–x – 18 % (Co + Cr + Ni) metals (in total) mixtures (agglomerated and sintered, size distribution – from 10-30 μm to 15-45 μm) were employed as high-velocity oxy-fuel (HVOF) and high-velocity air-fuel (HVAF) spraying feedstock materials for the deposition of hard coatings (main constituent phases: 32-46 vol.% Cr3C2–x (mean grain size – 1.5-1.6 μm, in the presence of small amounts of Cr7C3±x), 16-20 vol.% δ-WC1±x (mean grain size – 0.7 μm) and 38-47 vol.% metallic Ni-based solid solutions, porosity – (0.5÷0.6)±0.2 %) on steel substrates

–

–

Nanosized powdered δ-WC1±x – 12 % Co and Cr3C2–x – 25 % (Cr + Ni) metals (in total) mixtures were employed as main constituents of high-velocity liquid-fuel (HVLF) thermal spraying feedstock materials for the deposition of five-layered functionally graded hard coatings on Al alloy substrate

(continued)

334

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cr3C2–x – Co – Fe – Ni

Ar or N2, 950-1150 70 kPa

The diffusion parameters (activation ener- [3298] gy and pre-exponential factor) of Cr in the couple of δ-WC1±x – 85 vol.% binder and δ-WC1±x – 50 vol.% binder – 40 vol.% Cr3C2–x hard alloys (with Co – 40 % Fe – 40 % Ni alloyed binder) were determined experimentally to be E = 271±5 kJ mol–1 and D0 = 13.1±1.8 cm2 s–1, respectively; N2 atmosphere reduced the solubility of Cr and slightly decreased its diffusivity

δ-WC1±x – Cr3C2–x – Co – Ni

Vacuum, 1200-1400 1 Pa, or Ar, 10 kPa

Powdered δ-WC1±x – 1 mol.% Cr3C2–x – [10, 2115, 26 mol.% Co – 26 mol.% Ni mixtures 3043, 3080, were liquid-phase sintered (exposure – 1 h) 3091-3092, to prepare two-phase δ-WC1±x based hard- 3261, 3329] metals (with 38 vol.% content of metallic binder)

H2

Powdered δ-WC0.99 (mean particle size – 3.2 μm, content non-combined C – 0.10 %) – 1-6 % (2-12 vol.%) Cr3C2–x (99.5 % purity, mean particle size – ~7 μm) – 5.0-5.4 % (8.25 vol.%) Co (mean particle size – 0.8 μm, specific surface area – 2-3 m2 g–1, contents: Ag – 0.3 %, Ni – 0.2 %, C – 0.18 %, Fe – 0.005 %) – 5.0-5.4 % (8.25 vol.%) Ni (mean particle size – ~4 μm, contents: C – 0.06 %, O – 0.05 %, N – 0.003 %, Fe – 0.005 %) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate dense hard alloys (porosity 1-3 %, mean linear intercept grain size – 1.0-1.3 μm)

1470

–

δ-WC1±x – Cr3C2–x – Co – W

–

δ-WC1±x – 45 % Cr3C2–x – 9 % Co – 9 % Ni feedstock powder composition was used for the preparation of hard coatings by high-velocity oxy-fuel (HVOF) thermal spraying techniques; due to the reaction between both carbides some large Cr3C2–x grains show a core-rim structure with the appearance of W in the rims

Ar, 1410 5.5 MPa

Powdered δ-WC1±x – 0.7 % Cr3C2–x – 6.2 [3330] % Co – 0.75 % W mixture was subjected to gas pressure sintering (exposure – 1 h) to fabricate highly dense hard alloys (mean δ-WC1±x grain size – 0.90±0.02 μm)

δ-WC1±x – Vacuum 1410 Cr3C2–x – Cr7C3±x – α/ε-Co

In the sintered (exposure – 24 h) materials, [3029] (Cr0.59÷0.60W0.03Co0.37÷0.38)7C3±x carbide phase was identified

δ-WC1±x – Cr3C2–x – Cr2+xN – VC1–x – α/ε-Co

See section VC1–x – Cr3C2–x – Cr2+xN – δ-WC1±x – Co in Table III-3.16

(continued)

2.6 Chemical Properties and Materials Design

335

Table 2.21 (continued) δ-WC1±x – Ar, 1380 Cr3C2–x – 5.6 MPa La2O3–x – α/ε-Co Ar, 1430 5.6 MPa

δ-WC1±x – Cr3C2–x – La2O3 – VC1–x – α/ε-Co δ-WC1±x – Cr3C2−x – β-Mo2±xC – α/ε-Co

δ-WC1±x – Cr3C2−x – β-Mo2±xC – Co – Fe – Ni

δ-WC1±x – 10 % Co – 0.6 % Cr3C2–x – 0.06 [3032, 3287, % La2O3–x highly dense hard alloys were 3331-3332] prepared by gas pressure sintering (exposure – 40 min) procedure Powdered δ-WC1.00 (mean particle size – 0.9 μm, content O – 0.12 %) – 11 % Co (mean particle size – 0.9 μm, content O – 0.45 %) – 0.7 % Cr3C1.99 (mean particle size – ~1.5 μm, content O – 0.50 %) – 0.06 % La2O3–x (specific surface area – 12.5 m2 g–1) mixtures (preliminarily ballmilled) were subjected to gas pressure sintering (exposure – 1 h) procedure to fabricate dense hard alloys; during the sintering process of the alloy with δ-WC1±x – α-Co – η-phases structure, La can migrate directionally from the alloy to the sinter skin (surface), forming in situ La containing compounds (e.g. LaCoO3)

See section VC1–x – Cr3C2–x – La2O3 – δ-WC1±x – Co in Table III-3.16 Vacuum 1410

δ-WC1±x – Cr3C2−x – β-Mo2±xC – Co dense [10, 2919, hard alloys (metallic binder content – 11.3 3333, 3351, vol.%) were manufactured by liquid-phase 4505] sintering (exposure – 50 min) procedure

Ar, 5 MPa

Powdered δ-(W0.76Mo0.24)C1.01 (mean particle size – 2.25 μm, content non-combined C – 0.24 %) – 0.3-0.6 % Cr3C2−x – 6.7-13.2 % Co mixtures (preliminarily attritor-milled) were subjected to liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 0.5 h) to prepare highly dense hard alloys

–

1440

1350-1450 δ-WC1±x – 1.0-1.75 % Cr3C2−x – 1.0-1.75 [10, 3333, % β-Mo2±xC – 8-16 % Co – 4 % Fe – 8-16 3583] % Ni dense hard alloys (metallic binder content – 37 vol.%) were fabricated by liquid-phase sintering followed by hot isostatic pressing (HIP) procedure

Vacuum 1450

Highly dense δ-WC1±x – 4.7 % Fe – 4.7 % Ni – 2.4 % Co – 0.6 % Cr3C2–x – 0.3 % β-Mo2±xC two-phase (carbide and metallic binder) and three-phase (additionally containing α-C (graphite), or η2-(W,Fe,Ni,Co)6Cy phases) hard alloys were fabricated (using δ-WC1±x powder with mean particle size – 1.4 μm and varying total C contents) by liquid-phase sintering (exposure – 1 h) with formed γ-Fe

(continued)

336

2 Tungsten Carbides

Table 2.21 (continued) (austenitic) structured binder (content W – 5 %) δ-WC1±x – Cr3C2−x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Co – Ni δ-WC1±x – Cr3C2–x – α/β-TiAl3 – Co – Ni

See section TaC1–x – Cr3C2−x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Ni in Table II-2.21

Vacuum, 1200-1400 The powdered δ-WC1±x – 1 mol.% Cr3C2–x [2115] 1 Pa, – 1-5 mol.% TiAl3 – 25 mol.% Co – 25 or Ar, mol.% Ni mixtures were liquid-phase sin10 kPa tered (exposure – 1 h) to prepare δ-WC1±x based hardmetals with 38-45 vol.% metallic binder (contents: Co – 34-49 at.%, Ni – 35-43 at.%, Cr – 3-6 at.%, Al – 3-20 at. %, W – 1-2 at.%); the presence of minor (Ti,W)C1–x and γ′-Ni3±xAl phases was also detected in the materials

δ-WC1±x – Vacuum, 1400-1440 Powdered δ-WC1±x (~4 μm) – 21 % TiB2±x [3334] Cr3C2–x – TiB2±x 0.13 Pa (~2 μm) – 0.3 % Cr3C2–x (~2 μm) – 20 % – Co Co (~2 μm) mixtures (> 99.9 % purity, preliminarily ball-milled, initial mean particle sizes are given in brackets) were subjected to hot-pressing (exposure – 0.5 h) procedure to prepare dense ceramic materials (mean grain size – 0.6-1.5 μm), composed mainly of WCoBy, W2CoB2±y, TiB2±x, TiC1–x and Co2B phases, due to the intensive interphase interactions in the mixtures δ-WC1±x – Cr3C2–x – TiB2±x – TiC1–x – δ-TiN1±x – Co

See section TiC1–x – δ-TiN1±x – Cr3C2–x – TiB2±x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – Cr3C2–x – TiB2±x – VC1–x – Co

See section VC1–x – Cr3C2–x – TiB2±x – δ-WC1±x – Co in Table III-3.16

δ-WC1±x – Cr3C2–x – TiC1–x – Co

See section TiC1–x – Cr3C2–x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – Cr3C2–x – TiC1–x – VC1–x – Co

See section TiC1–x – Cr3C2–x – VC1–x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – Cr3C2–x – δ-TiN1±x – Co

Vacuum, 1420 Ar, N2

The characteristics of formation of cubic [3335] (W,Ti,Cr)(C,N)1±x phase in the sintered δ-WC1±x – 5.6 vol.% δ-TiN1±x – 4.4 vol.% Cr3C2–x – 13.5 vol.% Co hard alloys were studied

(continued)

2.6 Chemical Properties and Materials Design

337

Table 2.21 (continued) δ-WC1±x – Cr3C2–x – VC1–x – Co

See section VC1–x – Cr3C2–x – δ-WC1±x – Co in Table III-3.16

δ-WC1±x – Cr3C2–x – α/β-Y2O3–x – Co

–

–

The inhibitory effect of nanoparticles of [3336] Y2O3–x additive on the growth of δ-WC1±x grains in δ-WC1±x – Cr3C2–x – Co hard alloys was revealed

δ-WC1±x – Cr2+xN – Co

–

–

δ-WC1±x – Co hard alloy, modified by Cr2+xN were designed and fabricated

δ-WC1±x – CrSi2 – Co

–

δ-WC1±x – FeNi1±x – Co – (Fe – C – Mn – Si)

1500

Ar

0.5-3.0 % CrSi2 (mean particle size – 10- [3340] 40 μm) were introduced into δ-WC1±x – 6 % Co hard alloy powdered mixtures to fabricate dense composites by hot-pressing (exposure – 8 min) procedure; the CrSi2 phase does not interact with δ-WC1±x, it dissolves in Co-based metallic binder to form (Co,W,C,Cr,Si) solid solutions, decreasing the energy of the stacking fault, which contributes to α-Co (cubic) → ε-Co (hexagonal) polymorphic transformation, the Cr atoms from the binder participate as well in the formation of η2-W3Co3Cy phase –

δ-WC1±x – HfC1–x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Co δ-WC1±x – La2O3–x – Co

[3255]

δ-WC1±x – 30 % Co hard alloy – steel (C – [3006] 0.5 %, Mn – 0.6-0.9 %, Si – 0.15-0.35 %) joint was formed with FeNi~1.4 (contents: C – 0.01 %, Si – 0.40 %, Ni – 57 %, Mn – 2.8 %, Al + Ti – 1-3 %) as a filler using W – inert gas (TIG) welding techniques; the complex carbide η-(W,Fe,Co)6Cy particles were formed in the hard alloy side of the interface, the thickness of region that the η-phases were formed in 1 and 4 overlays welding joints were ~50 μm and ~150 μm in maximum value, respectively

See section TaC1–x – HfC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Co in Table II-2.21

Powdered δ-WC1±x – 10 % Co – 0.4-2.0 % [3247, 3287, La2O3–x mixtures (preliminarily ball-mil- 3341-3342, led) were subjected to microwave sintering 3360] (exposure – 20 min) procedure to fabricate dense hard alloys (porosity < 1 %, mean grain size – 0.28-0.29 μm)

N2/H2 1350 mixture flow

–

–

Ultra-fine grained La-doped δ-WC1±x – Co hard alloys were prepared via high-energy ball-milling (mean particle size – ~10 nm after 30 h milling) followed by the consolidation procedure

(continued)

338

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – La2O3–x – Co – Cu

δ-WC1±x – La2O3–x – Co – Cu – (Fe – C – Cr – Mn – Ni – Si)

–

–

Vacuum, 1060-1100 Powdered Cu – 0.25-1.0 % La2O3–x mixtu- [3344] res were used as filler (interlayer) materials 50 mPa in the brazed joints of δ-WC1±x – 10 % Co hard alloys and stainless steel (C – 0.125 %, Cr – 13.2 %, Si – 0.4 %, Mn – 0.2 %, Ni – 0.15 %) parts; the presence of δ-WC1±x, η2-W3Co3Cy, Cu- and γ-Fe-based metallic and (Fe,Cr,La)Cy carbide solid solutions was revealed in the joint interlayers

δ-WC1±x – La2O3–x – VC1–x – Co δ-WC1±x – LnOy (oxides of rare earth elements: La2O3–x, CeO2–x, Y2O3–x) – Co

Dense Cu-based metal matrix composites [3343] (porosity < 4 %), particulate reinforced by δ-WC1±x – 10 % Co hard alloy, with addition of 1 % La2O3–x were fabricated by direct laser sintering method

See section VC1–x – La2O3 – δ-WC1±x – Co in Table III-3.16 –

–

The addition of small amounts of rare earth [3245-3254, elements oxides to δ-WC1±x – Co hard al- 3287, 3341loys leads to the distribution of rare earth 3342, 3360, elements in the metallic binder – carbide 3380-3386] grain boundaries, increasing the wettability of δ-WC1±x grains by Co based binder See also section δ-WC1±x – Co – Ln (rare earth elements: misch metal, La, Ce, Nd, Dy, Pr, Y)

δ-WC1±x – γ-MoC – TiC1–x – Co δ-WC1±x – β-Mo2±xC – Co

See section TiC1–x – γ-MoC – δ-WC1±x – Co in Table III-2.22 Ar, 1350 100 MPa

Powdered δ-WC1±x (0.9 μm) – 1 % β-Mo2±xC (1-3 μm) – 8 % Co (1.3 μm) mixtures (preliminarily ball-milled, intial mean particle sizes are given in brackets) were subjected to vacuum sintering followed by hot isostatic pressing (HIP) procedure to prepare highly dense hard alloys (mean δ-WC1±x grain size – ~0.7 μm, total C content – 5.59-5.68 %)

–

1390

δ-WC1±x – 0.2-1.2 % β-Mo2±xC – 10 % Co highly dense hard alloys were fabricated by hot isostatic pressing (HIP) procedure (exposure – 75 min)

–

1400

During the liquid-phase sintering process (holding time – 1 h) of δ-WC1±x – 20 % Co hard alloys with the addition of β-Mo2±xC, the solubilities of δ-WC1±x and β-Mo2±xC in the liquid binder were estimated to be 15 % and ~40 %, respectively

[10, 64, 1997, 2564, 2786, 2919, 3256-3257, 3259, 3281, 3315, 33453351, 3741, 4291-4295, 4505]

(continued)

2.6 Chemical Properties and Materials Design

339

Table 2.21 (continued) –

1400

In δ-(W,Mo)C1±x – 16.4 vol.% Co hard alloys, the two-phase region (carbide + binder, free from η- or α-C (graphite) phases) became narrower with increasing the amount of Mo carbide

–

1400

δ-WC1±x – 1.3 % β-Mo2±xC – 6 % Co hard alloys were prepared by liquid-phase sintering (holding time – 5 h)

Vacuum ~1400

δ-(W0.3÷0.5Mo0.5÷0.7)C1±x – 10-15 % Co hard alloys were fabricated by liquid-phase sintering process

Ar, 5 MPa

Powdered δ-(W0.76Mo0.24)C1.01 (mean particle size – 2.25 μm, content non-combined C – 0.24 %) – 6.7-13.2 % Co mixtures (preliminarily attritor-milled) were subjected to liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 0.5 h) to prepare highly dense hard alloys

–

–

(Mo,W)C1±x crystals, grown from the metal Co melt, had a zoned structure with a core of nearly constant composition and an outer zone with a higher Mo concentration due to the higher solubility of Mo carbide in the Co melt compared with W carbide

–

–

The formation of cubic MoC thin films in the δ-WC1±x (0001) / Co and δ-WC1±x (1010) / Co interfaces was predicted on the basis of density functional theory (DFT)

δ-WC1±x – Vacuum β-Mo2±xC – Co – Ni

–

δ-WC1±x – β-Mo2±xC – NbC1–x – TiC1–x – δ-TiN1±x – Co – Ni

1440

~1400

–

δ-(W0.3÷0.5Mo0.5÷0.7)C1±x – 10 % Co – 10 % [10, 3352, Ni hard alloys (mean particle size – ~4 3741, 4292μm) were fabricated by liquid-phase sin- 4293] tering procedure; depending on total C content and W/Mo ratio in the alloys, the precipitation of small amounts of β-(W,Mo)2±xC or η2-(W,Mo)3(Co,Ni)3Cy phases was observed

To improve the microstructural uniformity, both carbide and binder phases were modified in δ-WC1±x – 10 % Co hard alloys by incorporating β-Mo2±xC and Ni See section NbC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Ni in Table II4.18

(continued)

340

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – β-Mo2±xC – Si3N4 – TiC1–x – δ-TiN1±x – Co – Ni

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – Si3N4 – δ-WC1±x – Co – Ni in Table III2.22

δ-WC1±x – β-Mo2±xC – TaC1–x – TiC1–x – Co – Ni

See section TaC1–x – β-Mo2±xC – TiC1–x – δ-WC1±x – Co – Ni in Table II-2.21

δ-WC1±x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Co – Ni

See section TaC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Ni in Table II2.21

δ-WC1±x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – VC1–x – Co – Ni

See section TaC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – VC1–x – δ-WC1±x – Co – Ni in Table II-2.21

δ-WC1±x – β-Mo2±xC – TiC1–x – Co – Ni

See section TiC1–x – β-Mo2±xC – δ-WC1±x – Co – Ni in Table III-2.22

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – Co

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – Co – Ni

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – δ-WC1±x – Co – Ni in Table III-2.22

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – VC1–x – Co – Ni

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – VC1–x – δ-WC1±x – Co – Ni in Table III2.22

δ-WC1±x – β-Mo2±xC – δ-TiN1±x – Co

Vacuum, 1420 Ar, N2

The characteristics of formation of cubic [3335] (W,Ti,Mo)(C,N)1±x phase in the sintered δ-WC1±x – 5.6 vol.% δ-TiN1±x – 4.4 vol.% β-Mo2±xC – 13.5 vol.% Co hard alloys were studied

δ-WC1±x – Ar, 1450 β-Mo2±xC – 100 MPa δ-TiN1±x – Co – Ni

Powdered δ-WC1±x – 17.5 vol.% δ-TiN1±x – [3353] 2.5 vol.% β-Mo2±xC – 8.5 vol.% Co – 8.5 vol.% Ni mixtures were subjected to liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 45 min) to fabricate highly dense hard alloys

(continued)

2.6 Chemical Properties and Materials Design

341

Table 2.21 (continued) δ-WC1±x – MoS2+x – Co

δ-WC1±x – MoS2+x – Co – Cu

δ-WC1±x – NbC1–x – Co

Vacuum, 1060-1240 Powdered δ-WC1±x – 2-8 mol.% MoS2+x – [3354-3355] 10 mPa 20-22 mol.% Co mixtures were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to fabricate dense self-lubricating hard alloys (porosity – ~1 %); at higher temperatures due to the interaction of MoS2+x with metallic binder, the formation of Co4S3+x, Co9S8 and CoMo2S4 sulphide phases was observed –

–

δ-WC1±x – 2 % MoS2+x – 12 % Co coatings were deposited on steel substrates using detonation gun spraying techniques

–

–

Ball-milled, sintered and crushed δ-WC1±x [3356] (15-45 μm) – 4-12 % MoS2+x (3-4 μm) – 811 % Co (15-45 μm) – 6-18 % Cu (15-50 μm) powdered mixtures (initial mean particle sizes are given in brackets) were used to deposit coatings (thickness – ~0.3 mm) on steel substrates using atmospheric plasma spraying techniques; jointly with the major phases such as δ-WC1±x, MoS2+x and Cu, the presence of small amounts of metallic W, γ-W2±xC and η1-W6Co6Cy phases was detected in the coatings

See section NbC1–x – δ-WC1±x – Co in Table II-4.18 See also section C – Co – Nb – W in Table I-2.14

δ-WC1±x – NbC1–x – TaC1–x – Co

See section TaC1–x – NbC1–x – δ-WC1±x – Co in Table II-2.21

δ-WC1±x – NbC1–x – TaC1–x – TiC1–x – Co

See section TaC1–x – NbC1–x – TiC1–x – δ-WC1±x – Co in Table II-2.21

δ-WC1±x – NbC1–x – TaC1–x – TiC1–x – δ-TiN1±x – Co

See section TaC1–x – NbC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Co in Table II-2.21

δ-WC1±x – NbC1–x – TaC1–x – TiC1–x – δ-TiN1±x – VC1–x − Co – Mo – Ni

See section TaC1–x – NbC1–x – TiC1–x – δ-TiN1±x – VC1–x − δ-WC1±x – Co – Mo – Ni in Table II-2.21

δ-WC1±x – NbC1–x – VC1–x – Co

See section NbC1–x – VC1–x – δ-WC1±x – Co in Table II-4.18

(continued)

342

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – NiAl1±x – Co

–

–

In δ-WC1±x – 10 % Co hard alloys, the me- [3357] tallic binder was particulate-strengthened by the introduction (up to 15 %) of NiAl1±x dispersion

δ-WC1±x – NiPx (Ni3P, Ni2–xP) – Co – Ni

–

–

Hardfacing nanostructured δ-WC1±x – NiPx [10, 3142, – Co – Ni coatings (poreless, thickness – 3160] ~80 μm) were deposited on Ni-based alloy substrates by electroplating process

–

–

Ni-P-coated (thickness – ~ 0.5-1.5 μm, around individual particles) hard alloy (δ-WC1±x – 12 % Co) powders (contents: Co – 11.7 %, Ni – 5.5 %, P – 0.4 %) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (thickness – 420±15 μm, porosity – 0.3±0.1 %, total C content – 4.95±0.03 %, with the presense of up to ~2 % γ-W2±xC) on steel substrates

δ-WC1±x – α/β-PbO – Co – Mo – Ni

–

1250

δ-WC1±x – α/β-SiC – α/ε-Co

–

1100-1400 Powdered δ-WC1±x – SiC – Co mixtures were treated by hot-pressing method

δ-WC1±x – α/β-SiC – Co – Ni δ-WC1±x – α/β-SiC – Co – Ti

δ-WC1±x – 5 % PbO – 20 % Ni – 10.5 % [3359] Co – 5 % Mo composites were fabricated by hot-pressing (exposure – 15 min) procedure

–

–

δ-WC1±x – SiC – Co hard coatings were deposited on steel substrates using laser cladding techniques

–

–

Plasma sprayed δ-WC1±x – Co coatings were modified by laser melting process to reinforce the coating by SiC nanoparticles

–

–

Strong adhesion of a SiC coating (thickness – ~0.1 μm) to a δ-WC1±x – Co hard alloy substrate was achieved via an ion beam mixing technique

Ar, 2 MPa

–

1380-1420 Modified δ-WC1±x – 8 % (Co + Ni) – 1-3 % SiC hard alloys were designed and fabricated by hot isostatic pressing (HIP) procedure (holding time – 1 h) –

[1836, 3214, 3361-3365]

[3365]

δ-WC1±x – 10 % Co hard alloy was modi- [3364] fied to a depth of 15-20 μm by subjecting the surface to pulse plasma jets formed by electric explosion of a Ti foil with powder batch of SiC (mean particle size – 60-80 nm); (Ti,W)C1–x and γ-W2±xC carbide and WSi2 silicide phases were detected in the modified surface layer

(continued)

2.6 Chemical Properties and Materials Design

343

Table 2.21 (continued) δ-WC1±x – (SiO2 Ar, 750-950 – B2O3 – Na2O – 0.1 MPa K2O) – Co

Practically, no interfacial reaction between [2460] δ-WC1±x – 6-25 % Co hard alloys and the crown (borosilicate) glass (SiO2 – 69 %, B2O3 – 10 %, Na2O – 9 %, K2O – 8 %) was detected

δ-WC1±x – (SiO2 Ar, 750-950 – PbO – K2O – 0.1 MPa Na2O) – Co

The flint (optical, lead) glass (SiO2 – 60 %, [2460] PbO – 22 %, K2O – 8 %, Na2O – 4 %) reacted sharply (exposure – 5-10 min) with δ-WC1±x – 6-25 % Co hard alloys; in the earlier stage of reaction it was mostly with the binder and only later with the carbide phase, pore formation and precipitation of metallic Pb were observed inside the glass near the interface

δ-WC1±x – TaC1–x – Co

See section TaC1–x – δ-WC1±x – Co in Table II-2.21 See also section C – Co – Ta – W in Table I-2.14

δ-WC1±x – TaC1–x – TiC1–x – Co

See section TaC1–x – TiC1–x – δ-WC1±x – Co in Table II-2.21

δ-WC1±x – TaC1–x – TiC1–x – δ-TiN1±x – Co – Ni

See section TaC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Ni in Table II-2.21

δ-WC1±x – TiAl1±x – TiB2±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – Co – Fe

–

–

Powdered δ-WC1±x (≥ 99.5 %, 50-150 μm, [4381] coated with 25 % Co) – 25 % TiAl1±x (≥ 99.5 %, 50-200 μm) – 20 % TiB2±x (≥ 98.5 %, 150-250 μm) – 17.5 % Fe (≥ 99.5 %, 50-200 μm) – 2.5 % α/β-ZrO2–x (> 99.9 %, 50-100 μm, partially stabilized with 8 % Y2O3–x) mixtures (purities and sizes of distributions of the components are given in brackets) were employed for the fabrication of laser cladded coatings on Ti-Al based alloy substrates; the obtained coatings were mainly consisting of crystalline α/ε-W2+xC and η1-W6Co6Cy carbide, TiB2±x boride, Ti3±xAl, FeAl3±x (or Fe4Al13±x) and Co7Zr6Al16 aluminide, α-ZrO2–x and β-(Zr,Y)O2–x oxide and γ-(Fe,Co) metallic solid solution and some amorphous phases

δ-WC1±x – TiB2±x Vacuum, 1400-1440 Powdered δ-WC1±x (~4 μm) – 21 % TiB2±x [10, 3334, – Co 0.13 Pa (~2 μm) – 20 % Co (~2 μm) mixtures 3367] (> 99.9 % purity, preliminarily ball-milled, initial mean particle sizes are given in brackets) were subjected to hot-pressing (exposure – 0.5 h) procedure to prepare dense ceramic materials (mean grain size – 1.0-

(continued)

344

2 Tungsten Carbides

Table 2.21 (continued) 2.2 μm), composed mainly of WCoBy, W2CoB2±y, TiB2±x, TiC1–x and Co2B phases, due to the intensive interphase interactions in the mixtures; the appearance of W2CoB2±y and TiC1–x phases is mainly attributed to the following reaction: 2WC + 5Co + 2TiB2 = W2CoB2 + 2TiC + + 2Co2B Vacuum, 1650 2.4-12.0 mPa

Powdered δ-WC0.99 (99 %, 0.6 μm, ~ 1-3 m2 g–1; contents: non-combined C – 0.06 %, O – 0.08 %, Fe – 0.003 %) – 72 % TiB2±x (99.3 %, 1.5 μm, ~ 3-10 m2 g–1; contents: C – 0.51 %, O – 0.09 %, Fe – 0.08 %) – 8 % Co (99 %, ~2 μm, ~ 2-5 m2 g–1; contents: C – 0.009 %, O – 0.26 %, Fe – 0.02 %) mixtures (preliminarily ballmilled; purities, initial mean particle sizes and specific surface areas, respectively, are given in brackets) were subjected to hotpressing (exposure – 1 h) procedure to produce complex ceramic materials (porosity – 2.6±0.3 %) composes mainly of TiB2±x, TiC1–x, W2CoB2±y and Co2B phases

δ-WC1±x – TiB2±x – TiC1–x – Co

See section TiC1–x – TiB2±x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – TiC1–x – Co

See section TiC1–x – δ-WC1±x – Co in Table III-2.22

α/β/ε/γ-W2±xC – TiC1–x – Co

See section TiC1–x – β/γ-W2±xC – Co in Table III-2.22

δ-WC1±x – TiC1–x – (Co – C)

See section TiC1–x – δ-WC1±x – (Co – C) in Table III-2.22

δ-WC1±x – TiC1–x – Co – Cr – Ni

See section TiC1–x – δ-WC1±x – Co – Cr – Ni in Table III-2.22

δ-WC1±x – TiC1–x – Co – Fe – Ni – W

See section TiC1–x – δ-WC1±x – Co – Fe – Ni – W in Table III-2.22

δ-WC1±x – TiC1–x – Co – Ni

See section TiC1–x – δ-WC1±x – Co – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Co

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Co – Ni

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Co – Fe – Ni

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Fe – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Co – Mo – Ni

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Co – Mo – Ni in Table III-2.22

(continued)

2.6 Chemical Properties and Materials Design

345

Table 2.21 (continued) δ-WC1±x – TiC1–x – VC1–x – ZrC1–x – Co

See section ZrC1–x – TiC1–x – VC1–x – δ-WC1±x – Co in Table II-5.24

δ-WC1±x – TiC1–x – δ-TiN1±x – VC1–x – δ-VN1–x – Co

See section TiC1–x – δ-TiN1±x – VC1–x – δ-VN1–x – δ-WC1±x – Co in Table III-2.22

δ-WC1±x – TiC1–x – ZrC1–x – Co

See section ZrC1–x – TiC1–x – δ-WC1±x – Co in Table II-5.24

δ-WC1±x – δ-TiN1±x – Co

Ar, 1450 100 MPa

Powdered δ-WC1±x – 20 vol.% δ-TiN1±x – [10, 3353, 17 vol.% Co mixtures were subjected to 3368-3371] liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 45 min) to fabricate highly dense hard alloys

δ-WC1±x – α/β-Ti3SiC2–x – Co

Pure Ar 1250

Powdered Ti3SiC2 (99.5 %, 5 μm) – 0.9- [3366] 9.0 % δ-WC1±x (99.9 %, 5 μm) – 0.1-1.0 % Co (99 %, 18 μm) mixtures (preliminarily high-energy ball-milled, purities and initial mean particle sizes, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense composites (porosity – 1.7-12.2 %); the presence of small amounts of TiC1–x phase and almost full conversion of δ-WC1±x to WSi2 phase were observed in the composites

δ-WC1±x – VC1–x – Co

See section VC1–x – δ-WC1±x – Co in Table III-3.16

δ-WC1±x – VC1–x – Co – Fe – Ni

See section VC1–x – δ-WC1±x – Co – Fe – Ni in Table III-3.16

δ-WC1±x – VC1–x – Co – Ru

See section VC1–x – δ-WC1±x – Co – Ru in Table III-3.16

δ-WC1±x – VC1–x – δ-VN1–x – Co

See section VC1–x – δ-VN1–x – δ-WC1±x – Co in Table III-3.16

δ-WC1±x – VC1–x – δ-VN1–x – Co – Re

See section VC1–x – δ-VN1–x – δ-WC1±x – Co – Re in Table III-3.16

δ-WC1±x – VC1–x – ZrC1–x – Co

See section ZrC1–x – VC1–x – δ-WC1±x – Co in Table II-5.24

δ-WC1±x – α/β-WB1±x – Co

–

–

Powdered δ-WC1.01 – 1-20 % α-WB1.00 – [3376-3377, 16-20 % Co mixtures were subjected to 4405-4406] liquid-phase sintering to prepare modified dense hard alloys; the preferential formation of WCoBy phase in the sintered alloys was observed, in the water-quenched alloys – W3CoB3±y or W2Co21B6±y phases were detected, the formation of η-phases was revealed in the sintered materials with

(continued)

346

2 Tungsten Carbides

Table 2.21 (continued) α-WB1±x contents > 10 % –

–

Powdered δ-WC1±x (> 99.9 %, 1.0 μm) – 10-40 % α-WB1±x (> 99.9 %, 2.2 μm) – 12 % Co (> 99.9 %, 1.2 μm) mixtures (preliminarily ball-milled and agglomerated, purities and initial particle sizes, respectively, are given in brackets, agglomerate size – 15-45 μm) were employed as highvelocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (thickness – 0.31-0.36 mm, porosity – (1.0÷2.0)±(0.2÷0.8) %) on steel substrates; the deposited coatings were composed of δ-WC1±x, γ-W2±xC, WCoBy and η1-W6Co6Cy

δ-WC1±x – δ-WN1±x – Co

–

–

Chemical vapour deposited (CVD) [3378] δ-W(C,N)1±x coating on δ-WC1±x – 8 % Co hard alloy was employed as a barrier to prevent Co diffusion from the alloy

δ-WC1±x – α/β-Y2O3–x – α/ε-Co

–

1150

[3246, 3249, Powdered δ-WC1±x – 12 % Co mixtures (≥ 99.9 % purity), modified by 1.3 % 3380-3386] Y2O3–x via a solid-liquid doping method, were subjected to spark-plasma sintering (exposure – 5 min) procedure to produce two-phase hard alloys (porosity – 0.3 %, mean δ-WC1±x grain size – ~1 μm); the formation of in-between Y6WO12 phase in the δ-WC1±x – α-Y2O3–x interface was revealed in the sintered alloys

Vacuum 1250

Powdered δ-WC1±x – 6 % Co – 1 % Y2O3–x mixtures were subjected to spark-plasma sintering (exposure – 10 min) procedure to produce two-phase δ-WC1±x – α-Co hard alloys (porosity – ~0.9 %, mean δ-WC1±x grain size – ~0.9 μm) with the location of α-Y2O3–x in the δ-WC1±x/α-Co grain boundaries

Vacuum 1260

δ-WC1±x – 1 % Y2O3–x – 20 % Co hard alloys were prepared by hot-pressing (exposure – 1 h) procedure

Vacuum 1450

Powdered δ-WC1±x – 6.5 % Co mixtures, modified by 5-20 % α-Y2O3–x (99.995 % purity, mean particle size – ~80 nm) via high-energy ball-milling, were subjected to liquid-phase sintering (exposure – 3 h) procedure to produce dense hard alloys (porosity – 1-18 %)

Vacuum 1470

δ-WC1±x – 1 % Y2O3–x – 20 % Co hard alloys were prepared by liquid-phase sintering (exposure – 1.5 h) procedure

(continued)

2.6 Chemical Properties and Materials Design

347

Table 2.21 (continued)

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – α/ε-Co

–

–

δ-WC1±x – 8-10 % Co hard alloys modified by introducing Y2O3–x were designed and fabricated by powder metallurgy methods

–

–

δ-WC1±x – Y2O3–x – Co alloying layers were prepared by laser alloying method on stainless steel substrates

–

1250-1450 δ-WC1±x – 5 % α-Y2O3–x – 15-25 % [10, 3239, α/β-ZrO2–x – 9 % Co cermet composites 3387-3389, (porosity < 8 %) were prepared by spark- 3392, 3945] plasma sintering (exposure – 5 min) procedure

–

1300

Powdered δ-WC1±x (99.5 %, < 1 μm) – 5-9 % β-(Zr,Y)O2–x (> 99.9 %, 45 μm, content Y2O3–x – 7.5 %) – 1-5 % Co (99.9 %, 44 μm) mixtures (preliminarily ball-milled, purity and initial mean particle size, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5-10 min) to fabricate dense composites (porosity – ~1.5-7.0 %)

Vacuum, 1300 6 Pa

Powdered δ-WC1±x (mean particle size – 0.2 μm) – 4-5 % β-(Zr0.94Y0.06)O2–x (3 mol.% Y2O3–x stabilized tetragonal, mean particle size – 27 nm, contents: Al2O3 < 0.005 %, SiO2 < 0.007 %) – 1-2 % Co mixtures (preliminarily ball-milled) were subjected to spark-plasma sintering (SPS) procedure (heating rate – ~3 K s–1, no holding time was employed) to fabricate dense nanocomposites (porosity – 1.31.8 %, mean δ-WC1±x grain size – 0.2-0.3 μm); the β → α transformation toughening effect of the ZrO2–x nanoparticles within the δ-WC1±x matrix was observed

Vacuum

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – Co – Cr – Ni

–

–

Sintered δ-WC1±x – 20 % Co hard alloys were modified by spherical particles (in different sizes) of α/β-ZrO2–x – 3 % Y2O3–x distributed uniformly in the alloys

1250-1450 δ-WC1±x – 5 % α-Y2O3–x – 15-25 % [3389] α/β-ZrO2–x – 4.5 % Co – 2 % Cr – 5 % Ni cermets (porosity < 8 %) were prepared by spark-plasma sintering (exposure – 5 min) procedure

δ-WC1±x – Vacuum 1440 α/β/γ/δ-ZrO2–x – α/ε-Co

Powdered δ-WC1±x (≥ 99.5 % purity, mean [10, 2734, particle size – ~6 μm) – 8 % Co (≥ 99.8 % 3207, 3391purity, mean particle size – ~1 μm) – 0.5- 3392, 3945] 2.0 % α-ZrO2–x (≥ 99.9 purity, mean particle size – ~10 nm) mixtures (preliminaryly ball-milled) were subjected to liquidphase sintering (exposure – 1 h) procedure

(continued)

348

2 Tungsten Carbides

Table 2.21 (continued) to prepare highly dense hard alloys Powdered δ-WC1±x (mean particle size – ~0.9 μm) – 8 % Co (99.2 % purity, mean particle size – ~70 μm) – 6 % α-ZrO2–x (monoclinic, mean particle size – ~10 μm) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare dense materials (porosity – 1.8 %) mainly composed of δ-WC1±x, β/γ-ZrO2–x, η-(W4Co2)Cy and κ-W10Co3C3.4 phases (with total volume of W-Co complex carbides – ~56 %)

Ar, 1700 206 MPa

δ-WC1±x – Cr

– –

– 25-30

Vacuum, < 1000 0.1 mPa

No confirmed data concerning the existence of ternary phases in the system Cr – 5-50 vol.% δ-WC1±x uniform coatings (thickness – 8-10 μm) were electrodeposited with different suspending contents (up to 80 g l–1) of δ-WC1±x particles (size – from micrometres to 70 nm) in aqueous electrolytes (plating solutions containing Cr3+) with contents CrCl3 (or Cr2(SO4)3) – up to 100 g l–1, pH 2-2.5 and current density – 6-20 A dm–2 W-C thin films with Cr contents – up to 21 at.% were deposited by sputtering technique; in the films with higher C contents the presence of γ-WC1–x phase was detected

[3, 5, 47, 53, 83, 155, 193, 579, 794, 1922, 1941, 1981, 1983, 1985, 1989, 19992000, 23872390, 2393, 2725, 2943, 3007-3008, 3027, 3032, 3393-3406, 3435, 3724, 3955, 4044, 4503]

Decarburization of δ-WC1±x due to the interaction between the phases is occurred

–

> 1200

–

1300-1350 The maximum solid solubility of Cr in the δ-WC1±x phase is corresponding approximately to the δ-(W0.94÷0.98Cr0.02÷0.06)C1.00 composition

–

~1400

–

1550-1750 According to the diffusion profiles, the maximum solubility of Cr in δ-WC1±x is ~1.5 mol.% and diffusion coefficient of Cr in δ-WC1±x is D = (1.5÷2.2)×10–11 cm2 s–1 (activation energy E ≈ 60-70 kJ mol–1); in spherical δ-WC1±x particles (1-2 μm in size) the maximum solubility of Cr can be attained within 10-1000 min, respectively

–

1800

The experimentally measured solubility of Cr in the δ-WC1±x phase of cemented carbides is 0.184±0.009 at.%

The maximum solid solubility of Cr in the δ-WC1±x is corresponding approximately to the δ-(W0.97Cr0.03)C1.00 composition

(continued)

2.6 Chemical Properties and Materials Design

349

Table 2.21 (continued) Ar

1830

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Cr (exposure – 5 min)

–

–

The effect of substitutional Cr impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations, the stability of the δ-(W,Cr)C1±x phase was confirmed

–

–

Some properties of Cr-doped δ-WC1±x were DFT-calculated Some data on the system reported by the different authors differ very markedly

See also section δ-WC1±x – C – Cr See also Table 2.26 See also section C – Cr – W in Table I2.14 α/β/ε/γ-W2±xC – Cr

–

1300

The maximum solid solubility of Cr in α/ε-W2+xC is corresponding to the ~(W0.15Cr0.85)2.10C composition (or ~90 mol.%); α/ε-(W0.33Cr0.67)2.10C composition is in equilibrium with δ-WC1.00 and (Cr0.94W0.06)3C2.00 (given in approximation)

–

1750

The composition of α/ε-(W,Cr)2+xC reaches from ~(W0.50Cr0.50)2C (in equilibrium with δ-WC1±x) to ~(W0.20Cr0.80)2C (in equilibrium with Cr3C2–x)

–

1800

The maximum solid solubility of Cr in α/ε-W2+xC is corresponding to the ~(W0.17Cr0.83)2.15C composition (or ~90 mol.%); α/ε-(W0.60Cr0.40)2.10C composition is in equilibrium with δ-(W0.99Cr0.01)C1.00 and α-C (graphite) phases, while α/ε-(W0.55Cr0.45)2.10C composition is in equilibrium with γ-(W0.40Cr0.60)C0.60 and α-C (graphite) phases (the compositions are given in approximation)

[53, 134, 193, 23872393, 3724, 3396-3399]

Some data on the system reported by the different authors differ markedly

See also section α/β/ε/γ-W2±xC – C – Cr See also section C – Cr – W in Table I2.14 δ-WC1±x – Cr – Cu

–

1200

99.5 % purity Cu-based metal matrix com- [3496] posites, modified by 2 % Cr (99 % purity) and reinforced by 1% δ-WC1±x (98 % purity, micro- and nanometre sizes) powders, were fabricated using stir casting technique

(continued)

350

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cr – Cu – Fe

–

δ-WC1±x – Cr – Fe

–

– 700-1100

Vacuum, 1250 1 mPa

N2

The properties of Fe – Cr – Cu binder as [2943] functions of alloying content are evaluated

[5, 10, 1021, 1063, 1985, 2943, 3080, 3337, 3394, 3407-3416, Powdered δ-WC1±x (99.7 % purity) – 70 vol.% Cr-based alloy (contents: Fe – 28.1 3639, 3751, %, C – 0.04 %, N – 0.03 %, Si – 0.40 %) 3965] mixtures (preliminarily high-energy ballmilled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to fabricate dense materials, comprising carbide particles (mean grain size of the “carbide islands” – from 0.1 μm to 2.0 μm), randomly dispersed in a Cr-Fe solid solution metallic matrix (mean grain size – 0.2-0.9 μm), the carbide phases (totally – 30 vol.%) in the prepared materials were presented mainly by γ-(W,Cr)2±xC (5.9 vol.%), η2-W3Fe3Cy (3.6 vol.%) and metastable (W2Fe21)C6±x (18.0 vol.%) and W2Fe2Cy (2.5 vol.%) phases; the addition of small amounts of Fe and C led to the appearance of δ-WC1±x phase as a main carbide constituent in the prepared materials with minor phases such as η1-W6Fe6Cy and η2-W3Fe3Cy in the Fe-added materials and (Cr,Fe)7C3±x in the C-added materials

The increase of W/Cr atomic ratio destabilizes the (Cr,W,Fe)23C6±x carbide phase in comparison with η2-(W,Fe,Cr)6Cy phase in all the materials prepared in the system

1250

In the presence of 2-20 at.% Cr in the annealed (exposure – 750 h) δ-WC1±x – Cr – Fe compositions (initially arc-melted), formed η1-(W,Fe,Cr)12Cy and η2-(W,Fe,Cr)6Cy complex carbide phases dissolved up to 4 at.% and 8 at.% Cr, respectively

> 1350

The complex carbide phase with ~W2Fe10Cr9C (or (W0.09Fe0.48Cr0.43)5C0.24) composition was revealed to be stable and decomposed into a mixture of α-Fe based solid solution and χ-FexCryWz phases on the cooling

Vacuum ~1450

δ-WC1±x – 10 % (Fe,Cr) alloy (with content Cr – 8 %) hard metals (linear intercept grain size – 0.78±0.46 μm) were prepared by liquid-phase sintering

–

–

–

δ-WC1±x based hard alloys with a Cr – Fe binder were developed and fabricated via mechanical alloying (MA) followed by spark-plasma sintering (SPS), or field-assisted hot-pressing (FAHP) processes

(continued)

2.6 Chemical Properties and Materials Design

351

Table 2.21 (continued) –

–

The properties of Fe – Cr binder as functions of alloying content are evaluated

See also section C – Cr – Fe – W in Table I-2.14 δ-WC1±x – Cr – Fe – Mn

–

δ-WC1±x – Cr – Ar Fe – Mn – Mo – Ni

Ar

δ-WC1±x – Cr – Ar Fe – Mn – Mo – Ni – Ti

–

The properties of Fe – Cr – Mn binder as [2943] functions of alloying content are evaluated

~1800-2100 Powdered δ-WC1±x (size distribution – 30- [10, 3418, 120 μm) – 50-74 % Fe-based alloy (size 3420] distribution – 20-90 μm, contents: Ni – 19.5 %, Cr – 17.6 %, Mo – 2.25 %, Mn – 1.25 %, C – 0.03 %) mixtures were employed as feedstock materials for the coating deposition on steel substrates via laser cladding; the prepared coatings were composed of δ-WC1±x, γ-W2±xC and η2-W3Fe3Cy carbide and γ-(Ni,Fe) and α-(Cr0.19Fe0.70Ni0.11) metallic solid solution phases ~1800-2100 Powdered δ-WC1±x (size distribution – 30120 μm) – 39-40 % Fe-based alloy (size distribution – 20-90 μm, contents: Ni – 19.5 %, Cr – 17.6 %, Mo – 1.8 %, C – 0.03 %) – 1.0-3.5 % Mn (99.95 % purity, size distribution – 10-40 μm) mixtures were employed for the coating deposition on Nibased alloy substrates via laser cladding; the prepared coatings were composed of γ-W2±xC, δ-WC1±x, and η2-W3Fe3Cy carbide phases and α-(Cr0.19Fe0.70Ni0.11) and γ-(Ni,Fe) metallic solid solution phases; the addition of Mn promoted the formation of α-(Cr,Fe,Ni) fcc phase and decreased the amounts of η-phase in the coatings ~1800-2100 Powdered δ-WC1±x (size distribution – 30- [3431] 120 μm) – 38-40 % Fe-based alloy (size distribution – 20-90 μm, contents: Ni – 19.5 %, Cr – 17.6 %, Mo – 1.8 %, Mn – 1.25 %, C – 0.03 %) – 1.2-4.0 % Ti (99.95 % purity, size distribution – 10-40 μm) mixtures were employed as feedstock materials for the coating deposition on steel substrates via laser cladding; the prepared coatings were composed mainly of γ-(Fe,Ni) metallic solid solution, δ-WC1±x, γ-W2±xC and η2-W3Fe3Cy phases, but also contained small amounts of (Ti,W)C1–x, σ-FeCr1–x and λ-Fe2W (the latter one – only at higher Ti contents) phases

(continued)

352

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cr – Fe – Mo

–

δ-WC1±x – Ar α/β/ε/γ-W2±xC – Cr – Fe – Mo – Nb – Ni – Ti

–

The properties of Fe – Cr – Mo binder as [2943] functions of alloying content are evaluated

–

Powdered δ-WC1±x – γ-W2±xC (spherical, [3842-3843, size distribution – 25-45 μm) – 75 % Ni- 3858] based alloy (gas atomized, spherical; size distribution – 15-45 μm; contents: Cr – 1821 %, Fe – 18-20 %, Nb – 5 %, Mo – 3-4 %, Ti – 1 %) mixtures (preliminarily highenergy ball-milled) were subjected to selective laser melting (SLM) additive manufacturing (AM) to produce metal matrix composite (MMC) graded interface layers

δ-WC1±x – Cr – Fe – Mo – Ni

Ar

~1800-2100 Powdered δ-WC1±x (size distribution – 30- [3419] 120 μm) – 38-40 % Fe-based alloy (size distribution – 20-90 μm, contents: Ni – 19.5 %, Cr – 17.6 %, Mo – 1.8 %, C – 0.03 %) – 0-4 % Mo (99.95 % purity, size distribution – 10-40 μm) mixtures were employed as feedstock materials for the coating deposition on steel substrates via laser cladding; the prepared coatings were composed of 25-28 % δ-WC1±x, 15-17 % γ-W2±xC, 10-11 % η2-W3Fe3Cy and 0.6-2.4 % η2-Mo3Ni3Cy carbide phases and 41-44 % γ-(Ni,Fe), 2.2-3.6 % α-(Cr0.19Fe0.70Ni0.11) and 0.5-1.5 % α-Fe metallic solid solution phases; the addition of Mo stabilized the γ-(Ni,Fe) phase, inhibited the appearance of α-Fe phase and promoted the formation of η2-Mo3Ni3Cy compound in the coatings

δ-WC1±x – Cr – Fe – Nb

–

–

δ-WC1±x – Cr – Fe – Ni

Vacuum, ~800-1300 The heat treatment of powdered δ-WC1±x 10 Pa – 4 % α-Fe – 1 % Cr – 0.5 % Ni composition (stainless steel coated δ-WC1±x with the traces of γ-W2±xC phase) resulted in the formation of η2-(W2.8Cr0.6)(Fe2.3Ni0.3)Cy complex carbide phase Vacuum, 1400 20 Pa

The properties of Fe – Cr – Nb binder as [2943] functions of alloying content are evaluated [10, 1982, 2725, 2943, 3394, 34173420, 34273428, 3431, 3852]

The sintering procedure (exposure – 1 h) of δ-WC0.99 (< 10 μm) – 3-10 mol.% Cr (< 38 μm) – 9-11 mol.% Fe (< 60 μm) – 9-12 mol.% Ni (3-7 μm) powdered compositions (particle sizes are given in brackets) leads to the formation of δ-WC1±x – Cr7C3±x – γ-(Fe,Ni,Cr,W), or δ-WC1±x – η2-(Fe,Cr)3(Ni,W)3C – γ-(Fe,Ni,Cr,W) three-phase cermets, depending on higher and lower Cr contents, respectively

(continued)

2.6 Chemical Properties and Materials Design

353

Table 2.21 (continued) –

δ-WC1±x – Cr – Fe – Si

Magnetron sputtering coated δ-WC1±x – 4.4-4.8 % Ni – 4.5 % Fe – 1.1-1.2 % Cr powders (mean particle size – 12-15 μm, specific surface area – ~0.1 m2 g–1) were subjected to vacuum liquid-phase sintering followed hot isostatic pressing (HIP) procedure (exposure – 1.5 h) to prepare dense hard alloys (porosity – 0-5 %, mean grain size – 3.0-3.2 μm) with the following hard phases quantifications: 92-98 % δ-WC1±x, < 9 % κ-(W,Fe,Ni,Cr)4Cy and ≤ 2 % η2-(W,Fe,Ni,Cr)6Cy

1400

–

–

δ-WC1±x powder particles (mean size – 9-10 μm, contents: Fe – 0.02 %, Cr, Ni < 0.009 %) were coated with stainless steel by d.c. magnetron sputtering method to prepare δ-WC1±x – 0.7-10.8 % α-Fe – 0.2-2.9 % Cr – 0.1-3.7 % Ni compositions (with the traces of γ-W2±xC phase) for the application in powder metallurgy

–

–

The properties of Fe – Cr – Ni binder as functions of alloying content are evaluated The surface of δ-WC1±x – 9.2 % Fe – 0.8 % [3432-3433, Cr hardmetals (composed of δ-WC1±x, 3965] α/δ-(Fe,Cr) and η2-(W,Fe,Cr)6Cy phases) were silicidated via contact reaction with Si powder to fabricate two-layered protective diffusional coating: the outer crust, presented by ε-FeSi1±x, ζβ-FeSi2 and ζα-FeSi2+x (or Fe3Si7±x) phases, and the bulk of the coating, presented by WSi2, δ-WC1±x and ε-FeSi1±x phases

Ar/H2 1000 (95/5) mixture flow

–

–

δ-WC1±x – 30-35 % Fe – 6.6-7.1 % Cr – 1.2-2.3 % Si granulated powders were employed for plasma transferred arc (PTA) welding to prepare hardfacing layers on steel substrates; the fabricated layers composed of δ-WC1±x grains, elongated grains of (Cr,Fe,W)23C6±x and dendritic grains of η2-(W,Fe,Cr,Si)6Cy (with γ-(W,Cr)2±xC inclusions) embedded in α-Fe + γ-Fe metallic binder (matrix) containing dissolved Cr, W, Si and C

δ-WC1±x – Cr – Fe – Ta

–

–

The properties of Fe – Cr – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cr – Fe – Ti

–

–

The properties of Fe – Cr – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cr – Fe – V

–

–

The properties of Fe – Cr – V binder as [2943] functions of alloying content are evaluated

(continued)

354

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cr – Fe – Zr

–

–

The properties of Fe – Cr – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cr – Mn – Ni

–

–

δ-WC1±x – Ni – Cr – Mn surface layers (composite coatings) were fabricated on steel substrates by laser cladding method

δ-WC1±x – Cr – Mo – Ni

δ-WC1±x – Cr – Mo – V

δ-WC1±x – Cr – Ni

δ-WC1±x based two-phase hard alloys with [2122, 2570, (Ni0.88÷0.91Cr0.07÷0.10Mo0.02÷0.03) metallic 3158, 3436binder were prepared from powdered mix- 3437, 3864] tures by liquid-phase sintering

Vacuum 1425

Ar, 3 MPa

1400-1500 δ-WC1±x – 1.1 % Cr – 0.6 % Mo – 8.3 % Ni two-phase hard alloys (volume fraction of Ni-based metallic binder – 18 %, mean δ-WC1±x grain size – ~0.5 μm) were prepared through 12-hour-sintering cycle of an industrial sinter-HIPing process with 1.5hour-exposure at the maximum temperature

CO2

–

–

Cr – δ-WC1±x hardfacing alloy with flux- [3405] cored wire, modified by the additions of Mo and V, was developed using gas shielded welding techniques

1250-1450 Powdered δ-WC1±x – 7 % Ni – 3 % Cr mixtures were subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare dense hard alloys (porosity – 5 %)

Vacuum 1450

Ar, 5 MPa

[3434]

1450

[1, 10, 1815, 2414, 2615, 3080, 3158, 3321, 3439Molten Ni – 10 at.% Cr alloy spreads over 3451, 3458the surface of poreless δ-WC1±x materials 3459, 3771, without penetrating into the bulk, its good 3831, 3864, adhesion to carbide is due to the high solu- 3936-3939] bility limit of δ-WC1±x in the melt Powdered δ-WC0.98 (mean particle size – 1.6 μm, contents: non-combined C – 0.03 %, O – 0.09 %, Fe – 0.02 %) – 2 % Cr (99.5 % purity, mean particle size – 43 μm, contents: C – 0.009 %, O – 0.13 %, Fe – 0.08 %) – 9 % Ni (99.7 % purity, mean particle size – 2.4 μm, contents: C – 0.055 %, O – 0.12 %, Fe – 0.005 %) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1.5 h) procedure to prepare dense hard alloys predominantly composed of δ-WC1±x and metallic Ni based binder with the small amounts of metastable (W,Cr)Cx phase (the substitution of Ni and Cr powders in the mixtures with equivalent amounts of nichrome (Ni – 18 % Cr) powder did not affect the phase composition of the sintered materials)

(continued)

2.6 Chemical Properties and Materials Design

355

Table 2.21 (continued) Ar, 38 kPa

Powdered δ-WC1±x – 0.1-5.0 % Cr – 5-10 % Ni compositions were subjected to liquid-phase sintering process (apparent activation energy E = 100÷145 kJ mol–1 was increasing with the decrease of Ni contents in the binder, the presence of Cr increased porosity and restricted the solution-reprecipitation stage of the sintering process) to fabricate dense hard alloys

1500

–

–

Powdered δ-WC1±x – Cr – Ni mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (contents: W – 67.0 %, Cr – 18.0 %, C – 6.6 %, Ni – 6.3 %) composed mainly of δ-WC1±x and γ-W2±xC phases

–

–

Powdered δ-WC1±x – 20 % Cr – 7 % Ni mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings on steel substrates; the formation of Cr carbides in the coatings was observed

–

–

Powdered δ-WC1±x – Cr – Ni mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of hard coatings (contents: W – 67.0 %, C – 6.6 %, Cr – 18.0 %, Ni – 6.3 %) composed mainly of δ-WC1±x and γ-W2±xC phases

See also section δ-WC1±x – Cr3C2–x – Ni See also section δ-WC1±x – α/β/ε/γ-W2±xC – Cr3C2–x – Cr7C3±x – Ni δ-WC1±x – Cr – Ni – W

–

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Cr – Cu

–

–

1200

δ-WC1±x compacts (porosity – ~48 %) [3452] were infiltrated under high-gravity conditions by Ni – 9 at.% W – 9 at.% Cr metallic melt (in situ synthesized from thermite reactions) to prepare dense δ-WC1±x – Nibased metallic binder cermets with the small amounts of γ-W2±xC and elemental W phases Cu (99.5 % purity) based metal matrix [3542] composites (MMC), reinforced by the addition of 1 % δ-WC1±x (98.0 %, ~1.5 μm) + 1-2 % α-Al2O3 (~99.0 %, ~1.5 μm) + 2 % Cr (99.0 %, ~60 μm) powders (purities and mean particle sizes are given in brackets), were fabricated by stir casting (holding time – 0.5 h) procedure

(continued)

356

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Vacuum, 1100 α/γ/δ/κ/θ/χ-Al2O3 10 mPa – Cr – Ni

Powdered δ-WC1±x (75 μm) – α-Al2O3 (30 [3453] nm) – Cr (45 μm) – Ni (60 μm) mixtures (initial mean particle sizes are given in brackets, preliminarily high-energy ballmilled) were subjected to hot-pressing (exposure – 0.5 h) procedure to fabricate the dense materials composed of Ni-based metallic solid solution, δ-WC1±x, α-Al2O3, Cr2O3 and Cr carbides phases

δ-WC1±x – B4±xC – α/β-BN – Cr – Cu

1200

Cu-based metal matrix composites (poro- [3454] sity – 9-16 %, crystallite size – 35-56 nm) containing 1.5 % δ-WC1±x (98 % purity) – 1 % α-BN (hexagonal, 99 % purity) – 0.51.5 % B4±xC (98 % purity) – 2 % Cr (99 % purity) were prepared using stir-casting (exposure – 0.5 h) techniques

δ-WC1±x – α/β-BN – Cr – Cu

1200

Cu-based metal matrix composites (poro- [3454] sity – 12 %, crystallite size – 68 nm) containing 1.5 % δ-WC1±x (98 % purity) – 1 % α-BN (hexagonal, 99 % purity) – 2 % Cr (99 % purity) were prepared using stir-casting (exposure – 0.5 h) techniques

1450

Powdered δ-WC0.98 (mean particle size – [10, 2414, 1.6 μm, contents: non-combined C – 0.03 3447] %, O – 0.09 %, Fe – 0.02 %) – 9 % Ni (99.7 % purity, mean particle size – 2.4 μm, contents: C – 0.055 %, O – 0.12 %, Fe – 0.005 %) – 0.6 % Cr3C2.00 (mean particle size – 2.0 μm, contents: O – 0.01 %, Fe – 0.09 %) – 1.5 % Cr (99.5 % purity, mean particle size – 43 μm, contents: C – 0.009 %, O – 0.13 %, Fe – 0.08 %) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1.5 h) procedure to prepare dense two-phase hard alloys composed of δ-WC1±x and metallic Ni based binder phases

δ-WC1±x – Cr3C2–x – Cr – Ni

Ar, 5 MPa

δ-WC1±x – Cr3C2–x – TiC1–x – δ-TiN1±x – Cr – Ni δ-WC1±x – Fe3±xAl – Cr

See section TiC1–x – δ-TiN1±x – Cr3C2–x – δ-WC1±x – Cr – Ni in Table III-2.22

Vacuum, 1150 < 10 Pa

Powdered δ-WC1±x (≥ 99.5 purity, mean [2892] particle size – 2-4 μm) – 10 % Fe3±xAl (size distribution – 10-30 μm, with 5 % Cr added) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to prepare dense composite materials

(continued)

2.6 Chemical Properties and Materials Design

357

Table 2.21 (continued) δ-WC1±x – NbC1–x – TiC1–x – VC1–x – Cr – Ni

See section NbC1–x – TiC1–x – VC1–x – δ-WC1±x – Cr – Ni in Table II-4.18

δ-WC1±x – TiC1–x – Cr – Fe – Ni

See section TiC1–x – δ-WC1±x – Cr – Fe – Ni in Table III-2.22

δ-WC1±x – α/β-WS2–x – Cr – Ni

–

950-1300

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – Cr – Ni

–

1250-1450 Powdered δ-WC1±x – 15-20 % γ-ZrO2–x – [3459] 5 % α-Y2O3–x – 7 % Ni – 3 % Cr mixtures were subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare dense cermet composites (porosity – 4 %)

δ-WC1±x – α/β/γ/δ-ZrO2–x – Cr – Cu

–

1200

Cu (99.5 % purity) based metal matrix [3542] composites (MMC), reinforced by the addition of 1 % δ-WC1±x (98.0 % purity, mean particle size – ~1.5 μm) + 1-2 % α-ZrO2–x (monoclinic, 99.5 % purity, mean particle size – ~1.5 μm) + 2 % Cr (99.0 % purity, mean particle size – ~60 μm) powders, were fabricated by stir casting (holding time – 0.5 h) procedure

δ-WC1±x – Cs

–

–

The behaviour of Cs vapour on the carbu- [1155] rized W surface was studied

δ-WC1±x – Cu

High300-900 purity N2

–

≤ 600

Vacuum 600-700

–

900-1150

Powdered δ-WC1±x –– 11 % Ni – 1 % Cr [3458] mixtures (mean particle size – 2 μm) with the addition of 5 % WS2–x powders (mean particle size – 13 μm) were subjected to pulsed electric current sintering (PECS) procedure under higher applied pressures to prepare dense materials

Magnetron sputtering deposited WCy films (thickness – 10 nm) in the prepared diffusion pairs with Cu films (thickness – 100 nm) were studied (soaking time – 1 min)

[13, 83, 484, 543, 579, 650, 1061, 1585, 1832, 1941-1942, Atomic layer deposited nanocrystalline WCy films (thickness – ~5 nm, mean grain 1983, 1991, size – ~2 nm, with the presence of γ-W2±xC 2006, 2008, and γ-WC1–x phases) blocked the diffusion 2177, 2431, 2474, 3106, of Cu at the interconnects 3116, 3460In sputter-deposited WCy films (barrier 3504, 3521, layers with thicknesses of 60 nm), the dif- 3539, 4071] fusion of Cu through the grain boundaries or localized defects was observed Powdered δ-WC1±x (99.9 % purity, spherical in shape, mean particle size < 1 μm) – 25-75 vol.% Cu (99.99 purity, irregular in shape, mean particle size < 37 μm) mixtures were subjected to hot-pressing (exposure – 5-6 min) procedure to obtain dense two-phase cermets (porosity – 5-9 %)

(continued)

358

2 Tungsten Carbides

Table 2.21 (continued) 950

Powdered δ-WC1±x (mean particle size – ~0.2 μm, specific surface area – 1.8 m2 g–1) – 50 % Cu (mean particle size – ~0.4 μm) mixtures were subjected to spark-plasma sintering (exposure – 3 min) procedure to prepare dense composite electrode (porosity < 10 %) for the subsequent fabrication of electro-spark deposited coatings on steel substrates

N2

975

Powdered δ-WC1±x (mean particle size < 1 μm) – 70-95 vol.% Cu (mean particle size < 25 μm) mixtures (preliminarily ballmilled) were subjected to hot-pressing (exposure – 40 min) procedure to fabricate dense metal matrix composites (MMC)

N2/H2 (90/10)

1000

Powdered Cu (spherical, mean particle size – 23 μm) – 5-30 vol.% δ-WC1±x (mean particle size – 70 μm) mixtures were subjectted to solid state sintering (exposure – 1 h) on the surface of Cu substrates to prepare hard coatings; sintering kinetics was affected by both rigid substrates and δ-WC1±x particles, which retarded the radial and axial densification of the powdered mixtures

–

–

~1000-1100 Practically, no solubility of δ-WC1±x in solid and liquid Cu

Vacuum, 1100 1.3 Pa

The δ-WC1±x surface is perfectly wetted by pure molten Cu; sintered WC0.98 materials (content non-combined C – 0.10%) interact with melts noticeably (exposure – 1 h)

Vacuum, ~1100 1 mPa

0.5-30 % δ-WC1±x dispersion-strengthened Cu (99.99 % purity) metal matrix composites (MMC) were produced by compocasting (exposure – ~0.5 h) procedure at a stirrer speed of 25 s–1 using of δ-WC1±x powder (mean particle size – 0.68 μm)

1200-1500 Powdered δ-WC1±x (mean particle size – ~0.1 μm) – 16 vol.% Cu (mean particle size – 1 μm) mixtures (preliminarily highenergy ball-milled) were subjected to spark-plasma sintering procedure to prepare dense hard alloys (porosity – 4 %, mean grain size – ~0.2 μm)

Ar

–

1400

The maximum solubility of δ-WC1±x in Cu melt is < 0.002 mol.%

(continued)

2.6 Chemical Properties and Materials Design

359

Table 2.21 (continued) –

Ar

1400

High-energy ball-milled δ-WC1.00 – 12 % Cu (99.9 % purity) powdered mixtures (mean particle size – 0.26±0.025 μm, crystallite sizes – 12±1 nm) were subjected to pre-sintering followed by hot isostatic pressing (HIP) procedure (exposure – 1 h) to fabricate hard alloys (porosity – ~20 %) composed of 56±1 % δ-WC1±x – 2±1 % Cu – 42±1 % metastable ~Cu2W3 phase constituents

1500

Cu – 40 vol.% δ-WC1±x nanocomposites were preliminarily fabricated via molten salt-assisted self-incorporation of nanoparticles followed finally by the melting under pressure (after salt-dissolving) procedure

Vacuum

–

Multilayered functionally graded δ-WC1±x particulate reinforced Cu metal matrix composites (MMC) were fabricated by hot-pressing techniques

–

–

δ-WC1±x – 30-40 % Cu electrical contacts were produced using the infiltration of sintered porous δ-WC1±x skeletons by Cu melt

–

–

10-40 % δ-WC1±x particulate reinforced Cu metal matrix composite (MMC) coatings on steel substrates were prepared by laser cladding techniques

–

–

Cu-based composite layers reinforced with δ-WC1±x particles were fabricated via the friction stir processing method

–

–

δ-WC1±x – Cu textured two-phase coatings were deposited on steel substrates using high-velocity oxy-fuel (HVOF) spraying

–

–

The effect of substitutional Cu impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

Cu metal monolayer supported by both Wand C-terminated δ-WC1±x (0001) was simulated on the basis of DFT calculations

See also Table 2.26 δ-WC1±x – Ar α/β/ε/γ-W2±xC – Cu

α/β/ε/γ-W2±xC – Cu

Nanostructured Cu – δ-WC1±x – α/ε-W2+xC [3500] composites were prepared via mechanical alloying (MA) with prolonged milling time followed by sintering (exposure – 1 h) procedure

900

–

–

Nanostructured Cu thin films, containing [3501] insoluble W2±xC inclusions, were prepared by sputter deposition

(continued)

360

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cu – Fe

–

980-1050

11-47 vol.% δ-WC1±x (99.5-99.9 % purity) [10, 944, reinforced Fe-based alloy (99.85-99.9 % 2177, 2943, purity, content Cu – from 1.9 % to 4.0 %) 3502-3504, was fabricated by spark-plasma sintering 3596, 3607] (SPS) procedure (exposure – 5 min); the sintered materials (poreless, mean grain size – (6.0÷12.7)±(0.1÷0.8) μm) were composed mainly of δ-WC1±x and α-Fe metallic solid solutions with the presence of θ-Fe3C, η2-W3Fe3Cy and γ-W2+xC phases at lower volume fractions of δ-WC1±x phase (moreover, the θ-Fe3C (100) and η2-W3Fe3Cy (211) crystallographic planes of the formed inclusions were parallel to each other)

Vacuum, 1250-1350 Powdered δ-WC1±x (99.9 %, 3 μm) – 7.50.1 Pa 9.5 % Fe (99.7 %, 2 μm) – 0.5-2.5 % Cu (99.67 %, 48 μm) mixtures (preliminarily high-energy ball-milled, purities and initial mean particle sizes of components are given in brackets) were subjected to liquidphase sintering (exposure – 1 h) procedure to prepare dense δ-WC1±x – γ-(Fe,Cu) solid solution hard alloys (porosity – 0.5-1.3 %) –

–

The properties of Fe – Cu binder as functions of alloying content are evaluated

δ-WC1±x – Cu – Vacuum, 1150 (Fe – C – Co – < 10 mPa Cr – Mo – V – W)

High-speed steel (size distribution < 160 [4494] μm, contents: C – 1.23 %, Cr – 4.3 %, Co – 0.4 %, Mn – 0.2 %, V – 3.1 %, W – 6.2) – 10-30 % δ-WC1±x (size distribution < 3 μm) powdered mixtures were subjected to pre-sintering procedure (exposure – 1 h) followed by the infiltration with Cu (exposure – 0.25 h) to fabricate fully dense cermet composites

δ-WC1±x – Cu – (Fe – C – Cr – Ni)

High-energy ball-milled δ-WC1.00 – 2-6 % [3503] Cu (99.9 % purity) – 6-10 % stainless steel (C – 0.03 %, Cr – 18.8 %, Ni – 10.0 %, Fe – remainder) powdered mixtures (mean particle sizes – (0.21÷0.26)±0.025 μm, crystallite sizes – (10÷12)±1 nm) were subjected to pre-sintering followed by hot isostatic pressing (HIP) procedure (exposure – 1 h) to fabricate dense hard alloys (porosity – 1-6 %) composed of δ-WC1±x (up to 78 %), η2-(W,Fe,Cr,Ni)6Cy and γ-(Fe,Cr,Ni,Cu) solid solution phase constituents

–

1400

(continued)

2.6 Chemical Properties and Materials Design

361

Table 2.21 (continued) δ-WC1±x – Cu – Fe – Ln (rare earth elements: misch metal, La, Ce, Nd, Dy, Pr, Y) – Si

–

–

δ-WC1±x particle reinforced Cu metal mat- [3504] rix composites (MMC) were prepared using direct metal laser sintering (DMLS) process and modified by the addition of Ln – Si – Fe alloy (up to 3 %) to improve the homogenization of particle dispersion and particle/matrix interfacial compatibility

δ-WC1±x – Cu – Fe – Mn

–

–

The properties of Fe – Cu – Mn binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Mo

–

–

The properties of Fe – Cu – Mo binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Nb

–

–

The properties of Fe – Cu – Nb binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Ni

–

–

δ-WC1±x – 9.2 % Ni-based alloy (contents: [10, 2943, Cu – 28-34 %, Fe ≤ 2.5 %) cermet thin3808-3809] wall parts (porosity – ~2.5 %) were deposited by laser engineered net shaping (LENS), a powder blown additive manufacturing process; various microstructures, such as eutectic, fishbone and Fe-W-rich dendrites, were observed in the fusion zone, needle-like, triangular and blocky carbides – in the central and acicular – in the top regions

–

–

The properties of Fe – Cu – Ni binder as functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Ta

–

–

The properties of Fe – Cu – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Ti

–

–

The properties of Fe – Cu – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – V

–

–

The properties of Fe – Cu – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Fe – Zr

–

–

The properties of Fe – Cu – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Cu – Hf

–

1150-1300 The interaction (exposure – 1-24 h) of [3505] bulk polycrystalline δ-WC1±x plates (trace amounts of W2±xC, porosity – 0.6 %) materials with Cu – 35 at.% Hf alloy melt (99.5-99.9 % purity) leads to the formation of metallic W (uniform in thickness, continuous, adjacent to the δ-WC1±x plate surface) layer and layer of HfC1–x (irregular, continuous, adjacent to the W layer); the reaction δ-WC1±x (s) + Hf (l) = W (s) + HfC1–x (s) is controlled by the solid state diffusion of C through the lattice of the W layer and/or through grain boundaries of HfC1–x layer

(continued)

362

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cu – In – Mn – Ni – Zn

–

900-910

Powdered δ-WC1±x (mean particle size – [3475] ~30 μm) was infiltrated (without applied pressure) by Cu – 23-25 % Mn – 14-16 % Ni – 7-9 % Zn – 1-2 % In alloys to prepare dense metal matrix (MMC) composites

δ-WC1±x – Cu – Mn

–

980

The interaction of δ-WC1±x – 20 % Co ce- [2177] mented carbide with molten Cu – 18 % Mn alloy showed that the addition of Mn to Cu melt has the pronounced effect on the yielding an additional carbide-free layer in the cemented carbide

δ-WC1±x – Cu – Mn – Ni

–

–

~63 vol.% δ-WC1±x particulate reinforced [3506-3509] Cu – Mn – Ni alloy based hardfacing coatings (multilayered, thickness > 15 mm) were deposited on steel substrates using manual O2-C2H2 weld hardfacing method followed by special heat treatments (formed α-(Cu,Ni,Mn) solid solutions in the as-deposited coatings can be decomposed with the formation of η-NiMn1±x phase

δ-WC1±x – Cu – Mn – Ni – P

–

–

δ-WC1±x particulate reinforced Cu – Mn – [3506] Ni – P alloy metal matrix composite (MMC) coatings were prepared by brazing

δ-WC1±x – Cu – Mn – Ni – Pb – Sn – Zn

–

980

Powdered 55 % δ-WC1±x (99.9 %, 10 μm) [3732] – 35 % bronze (99.9 %, 50 μm, contents: Sn – 6 %, Zn – 6 %, Pb – 3 %, Cu – remainder) – 5 % Ni (99.9 %, 75 μm) – 5 % Mn (99.9 %, 60 μm) mixtures (purities and mean particle sizes are given in brackets, preliminarily ball-milled) with added 0-3 % nano-crystalline δ-WC1±x (mean particle size – 80 nm) were subjected to hotpressing (exposure – 5 min) procedure to fabricate dense composite materials (porosity – 1.5-3.0 %)

δ-WC1±x – Cu – Mn – Ni – Si

–

1150

Powdered δ-WC1±x (three-modal in par[3466] ticle size, mean size – 0.68 mm) was infiltrated (holding time – 1-2 h) by Cu – 19 % Mn – 21 % Ni – 0.4 % Si brazing alloy to depo-sit cermet coatings on steel substrates; the δ-WC1±x volume fraction was ~80 % with the mean separation distance between the grains to be ~90 μm

δ-WC1±x – Cu – Mn – Ni – Ti – V – Zr

–

–

Powdered (Zr0.5Ti0.5)(Mn0.25V0.15Ni0.55)2 [3510] alloy (AB2-type, particle size < 40 μm) – δ-WC1±x (size distribution – 2-20 nm) – Cu (particle size < 50 μm) mixtures were subjected to cold-pressing to prepare porous electrodes

(continued)

2.6 Chemical Properties and Materials Design

363

Table 2.21 (continued) δ-WC1±x – Cu – Mn – Ni – Zn

–

δ-WC1±x – Cu – Mo

–

900-910

–

δ-WC1±x – Cu – Mo – Zr

Powdered δ-WC1±x (mean particle size – [3475] ~30 μm) was infiltrated (without applied pressure) by Cu – 23-25 % Mn – 14-16 % Ni – 7-9 % Zn alloys to prepare dense metal matrix (MMC) composites Cu – 49-50 % Mo – 0.5-1.5 % δ-WC1±x electrical contacts were fabricated by spark-plasma sintering (SPS) procedure

[3511-3512]

See section δ-WC1±x – β-Mo2±xC – Cu – Zr

δ-WC1±x – Cu – Ar Ni

Powdered Cu (40-50 μm) – 4 % Ni (40-50 μm) – 0.5-2.0 % δ-WC1±x (50-60 nm) mixtures (99.9 % purity – all the components, size distributions are given in brackets) were subjected to sintering (holding time – 2 h) procedure to prepare Cu-Ni alloy metal matrix composites (MMC)

900

[2177, 2725, 3513-3518, 3808-3809, 3866]

–

–

Powdered δ-WC1±x – 2 % Ni – 2 % Cu mixture was employed as feedstock composition for the preparation of hard coatings by cold-gas dynamic spraying at low pressures

–

–

Cu – 5 % Ni – 10 % δ-WC1±x coatings were deposited using electron-beam facing method

–

–

~25 % δ-WC1±x (with presence of W2±xC phase) particle reinforced Ni-Cu alloy composite coating was deposited on brass substrates using high-power diode laser (HPDL) cladding technique

δ-WC1±x – Cu – Vacuum, Ni – Si – Sn – Ti Ar – Zr

–

10-20 % δ-WC1±x particulate reinforced [3519] Cu47Ti33Zr11Ni6Sn2Si1 bulk metallic glass (BMG, > 99.9% purity) was fabricated by induction melting followed by injection casting procedures; no chemical interaction between δ-WC1±x particles and matrix was detected

δ-WC1±x – α/β/ε/γ-W2±xC – Cu – Ni – Sn

–

δ-WC1±x – γ-W2±xC – Cu – Ni – Sn hard al- [1752] loys were prepared using selective laser melting (SLM) techniques

–

δ-WC1±x – Cu – Vacuum 450 Ni – Sn – Ti

Preliminarily mechanically alloyed (by [3979] high-energy ball-milling) powdered Ti – Cu – Ni – Sn – δ-WC1±x compositions were subjected to high-pressure hot-pressing procedure to prepare Ti50Cu28Ni15Sn7 – 12 vol.% δ-WC1±x nanoparticles (size distribution – 20-300 nm) poreless metal glassy (amorphous) alloy matrix composites

(continued)

364

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Cu – H2 Ni – W

1350

Sintered skeletons (porosity – 35 %), pre- [3538] pared from powdered W (99.8 %, 4-6 μm) – 0.5-3.0 % δ-WC1±x (99.9 %, 1-2 μm) – 0.9 % Ni mixtures (the purities and mean particle sizes of the main components are given in brackets), were infiltrated (exposure – 2 h) by molten Cu (99.90 % purity) to prepare electrical contact materials

δ-WC1±x – α/β/ε/γ-W2±xC – Cu – Ni – W

–

–

Powdered δ-WC1±x – γ-W2±xC (spherical; [3866] with the presence of metallic W) – 9 % Nibased alloy (content Cu – 30-32 %) mixtures (size distribution – 45-90 μm) were employed as the feedstock materials in laser engineered net shaping (LENS) technology to produce thin walls and cubes on steel substrates using additive manufacturing (AM) processes

δ-WC1±x – Cu – P – Sn

–

–

2-8 % δ-WC1±x (mean grain size – 25 μm) [3477-3478] reinforced Cu alloy (contents: Sn – 0.511.0 %, P – 0.01-0.35 %) composites were designed, fabricated and studied

δ-WC1±x – Cu – Pd – Si

–

–

2-12 vol.% δ-WC1±x (micrometre-sized) [3520] particulate reinforced Pd77.5Cu6Si16.5 amorphous metallic alloy matrix composites were prepared by induction stirring method with chill block melt spinning followed by pre-annealing treatments

≤ 550-600

δ-WC1±x – Cu – N2 Si

–

–

Sputter-deposited amorphous WCx films [486-488, (thickness – 60 nm) are effective against 3469, 3522Cu diffusion into Si substrates and pre3523] serve the integrity of the Cu/WCx/Si structures without the formation of η-Cu3+xSi phase (exposure – 0.5 h); Cu diffusion into the Si substrates through local defects of the WCx films was observed at higher temperatures, it is strongly enhanced by the formation of W5Si3+x at the WCx/Si interface After high-energy planetary ball-milling, powdered Cu – 15-45 % δ-WC1±x (initial mean particle size – 3 μm) – 0.75-2.25 % Si mixtures (> 99 % purity – all the components) were subjected to sintering procedure for densification

(continued)

2.6 Chemical Properties and Materials Design

365

Table 2.21 (continued) δ-WC1±x – Cu – Vacuum 450 Ti – Zr

δ-WC1±x (submicrometer-sized) particulate [3524-3525] reinforced Cu60Ti10Zr30 bulk metallic glass (BMG) based composites were fabricated by mechanical alloying followed by highpressure hot-pressing procedures; no chemical interaction between δ-WC1±x particles and nanocrystalline/amorphous matrix was detected

δ-WC1±x – Cu – Vacuum 950 W

W – δ-WC1±x – 20 % Cu composites were [3526-3527] prepared by hot-pressing (exposure – 2 h) procedure using W powders pre-modified with organic additives via pyrolysis-carburization and then Cu-coated by electroless plating processes

–

1300

δ-WC1±x – Cu – Vacuum 650 Zn

δ-WC1±x – Cu – Ar Zr

The addition of powdered 1-10 % W (0.58.0 μm) – 1-30 % δ-WC1±x (3-300 μm) mixtures (size distributions are given in brackets) to the Cu (99.99 % purity) melts, subjected to low-frequency vibrations (LFV), leads to the formation of α/ε-W2+xC phase and WC/W2C/WC corn-shell structured (fragmentated) carbide grains in the prepared Cu-based alloys

[2035, 2725, Powdered δ-WC1±x (spherical in shape, mean particle size – 1-3 μm) – 30-70 % 3116, 3528] brass (irregular in shape, size distribution < 100 μm, content Zn – 28 %) mixtures (preliminarily ball-milled) were subjected to spark-plasma sintering (exposure – 10 min) to fabricate dense cermet materials (porosity – 3-7 %)

1050-1150 Good wettability of molten Zr – 33.3 at. % [3529-3531] Cu alloy on dense polycrystalline δ-WC1±x substrates is favouring pressureless infiltration (exposure – 20 min) of the alloy into porous δ-WC1±x preform (porosity – 46 %); the melt-carbide interaction yields W (adjacent to carbide surface with δ-WC1±x (0001) // W (111) and δ-WC1±x (1100) // W (110) crystallographic orientation relationships) and ZrC1–x (adjacent to the melt surface) at the interface through a solutionprecipitation reaction in the first stage of growth of reaction product layers 1150-1400 The interaction of δ-WC1±x with Cu – 66.7 at.% Zr melt leads to the incongruent reduction of carbide to elemental W; continuous adherent layers of W and ZrC1–x are formed at the solid-liquid interface due to the C diffusion through the contact reaction products

(continued)

366

2 Tungsten Carbides

Table 2.21 (continued) See also section δ-WC1±x – CuZr2 in Table 2.22 δ-WC1±x – Vacuum α/γ/δ/κ/θ/χ-Al2O3 – Cu –

–

Powdered δ-WC1±x (10-20 vol.%) – α-Al2O3 – Cu mixtures were subjected to hot-pressing procedure to fabricate dense metal matrix composites (MMC)

–

δ-WC1±x – α-Al2O3 particulate reinforced Cu-based metal matrix composites (MMC) were fabricated using explosive powder compaction techniques

[3532-3536]

δ-WC1±x – α/β-BN – Cu – Sn – Ti

Vacuum, 960 0.05 Pa

Powdered δ-WC1±x (0.01-0.1 mm) – 40 % [3537] cubic β-BN (0.3-0.4 mm) – ~ 40-50 % Cubased brazing alloy (< 0.125 mm, contents: Sn – 18 %, Ti – 12 %) mixtures (initial size distributions are given in brackets) were spread uniformly on the flat steel substrates and heat treated (exposure – 25 min) to prepare superhard brazed materials; due to the mutual chemical interaction between the components, the formation of TiCu1±x, TiC1–x, δ-TiN1±x and TiB2±x phases was observed in the prepared materials

δ-WC1±x – β-Mo2±xC – Cu – Zr

High1200-1600 The interaction between solid dense (or [3531] purity Ar porous) polycrystalline δ-(W~0.9Mo~0.1)C1±x (with the presence of α/ε-(W~0.9Mo~0.1)2+xC phase) and Zr – 33-78 at.% Cu melts during contact incongruent reactions and infiltration processes (exposure – 15 min) was studied; the segregations of W and Mo elements in the Zr-Cu melts and W-rich inclusions in ZrC1–x grains formed after the reaction show that both W and C in solid δ-WC1±x dissolve into the melts at the initial contact; the precipitation of W and ZrW2 is based on the Zr activity in the melts after a quick nucleation of ZrC1–x grains, in which the stoichiometry gradually increases with the reaction time and temperature; the dissolution of δ-(W,Mo)C1±x is restrained by the formation of a continuous ZrC1–x layer at higher temperatures

See also section δ-WC1±x – (Cu51Zr14, CuZr2) – α/β-Mo2±xC in Table 2.22

(continued)

2.6 Chemical Properties and Materials Design

367

Table 2.21 (continued) δ-WC1±x – MoS2+x – Cu

N2, 5 MPa

Mixtures of Cu (26 μm) – 14 % MoS2+x [3539] (68 μm) – 11 % δ-WC1±x (30 μm) spherical powders (mean particle sizes are given in brackets) were employed as feedstocks to deposit Cu – 4.0±1.2 vol.% MoS2+x – 7.5±2.2 vol.% δ-WC1±x composite coatings on Al alloy substrates using cold-spraying technique

800

δ-WC1±x – SiO2 High ≤ 600 – Cu vacuum

α/β/ε/γ-W2±xC – SiO2 – Cu

–

Nanocrystalline and amorphous WCx films [486-488, (thickness – 3-60 nm), prepared by sputte- 1882, 3469, ring and atomic layer deposition methods, 4436] are effective against Cu diffusion into SiO2 substrates

≤ 400

Chemical vapour deposited (CVD) nano- [483, 485] crystalline W2±xC films (thickness – 7 nm) are effective against Cu diffusion into SiO2 substrates and preserve the integrity of the Cu/W2±xC/Si structures (exposure – 8 h)

δ-WC1±x – SiO2 High 200-600 – δ-WN1±x – Cu vacuum

Prepared by various plasma-enhanced, ato- [1882, 3540mic layer and chemical vapour deposition 3541, 4413, methods, γ-W(CxNy) (or mixture of 4416-4418, γ-WC1–x and γ-WN1–y phases with similar 4421-4425, lattice parameters) thin films (nanocrystal- 4430, 4433, line with extremely small grain sizes or 4436] amorphous, thickness – in the range of 325 nm) were employed as diffusion barriers against Cu migration through SiO2

δ-WC1±x – δ-WN1±x – Cu

Magnetron sputtering deposited [3474, 3540δ-W(CyNz)1±x films (thickness – 10 nm) in 3541] the prepared diffusion pairs with Cu films (thickness – 100 nm) were studied (soaking time – 1 min)

High300-900 purity N2

δ-WC1±x – α/γ/δ-Fe

–

–

Ar

–

800

800-1050

The formation of η1-W6Fe6Cy, η2-W3Fe3Cy [1, 3-5, 8(or W2÷3Fe3÷4C), κ-W3FeCy (or W9Fe3C4), 10, 13, 43, (W2Fe21)C6±x (or (W,Fe)23C6±x, metastable), 53, 63, 83, WFeCy (metastable, ?) and some other ter- 87, 151, nary metastable phases 579, 626, Fe – 5-20 % δ-WC1±x composites (porosity 639, 679, – ~ 1-11 %, mean grain sizes of matrix and 944, 976, carbide – 90 μm and 110 μm, respectively) 1070-1071, 1599, 1612, were manufactured using hot isostatic pressure (HIP) procedure (exposure – 0.5 1649, 1711, h); the reaction layer around the δ-WC1±x 1727, 1799, 1808, 1811, grains achieved ~5 μm in thickness, its growth rate largely decreased with an in- 1877, 18861895, 1899, crease in HIP pressure 1924, 1928Metallic Fe can spread on the surface of 1929, 1937, δ-WC1±x phase in solid state as a thin layer 1939, 1941with high values of spreading velocities 1943, 1966due to the favourable energies of the car-

(continued)

368

2 Tungsten Carbides

Table 2.21 (continued) bide, vapour and metal interfaces; there is a relation between the solubilities of W and C in Fe, defect concentrations in Fe and viscosity of layers formed near the contact between Fe and δ-WC1±x Vacuum, < 1000 0.1 mPa

W-C thin films with Fe contents – up to 31 at.% were deposited by sputtering; in the films with high C contents the presence of γ-WC1–x phase was detected

–

1000

The initiation of solid state chemical interaction between the components

–

1000

The presence of metastable θ-Fe3C phase in the alloys containing δ-WC1±x and γ-(Fe,W,C) solid solutions was observed experimentally

Vacuum, 1000-1400 No new phases were revealed in powdered ~13 mPa δ-WC1±x – 10-50 mol.% pure Fe mixtures after the heat treatment (exposure – 2 h) procedures –

1200

The reaction between δ-WC1±x and Fe in powdered mixtures develops noticeably

–

1200

Powdered δ-WC1±x (99.95 %, 0.5 μm) – 3 % Fe (99.5 %, 10 μm) mixtures (purities and initial mean particle sizes are given in brackets, preliminarily ball-milled to 0.10.3 μm mean size) were subjected to sparkplasma sintering (exposure – ~4 min) to fabricate dense cermets (porosity – 1.2 %, mean grain size – 0.26 μm) mainly composed of δ-WC1±x and α-Fe solid solution phases with the presence of small amounts of α/ε-W2+xC and γ-WC1–x phases

Vacuum, ~1200 ~5.3 Pa

1972, 19811983, 1985, 1987-1988, 1999-2000, 2200-2201, 2447-2448, 2502, 2550, 2657, 2688, 2697-2698, 2709, 27252727, 2809, 2903, 2943, 3005, 31193120, 3127, 3133, 3298, 3349, 3394, 3498, 35023503, 35603561, 35433614, 3625, 3674-3679, 3712, 3720, 3724, 37483752, 3986, 4281, 4400, 4503, 4667]

Highly dense two-phase δ-WC1±x – 10 % Fe hard alloys (porosity – 0.3 %, mean δ-WC1±x grain size – 0.45 μm) were fabricated using ultra-fine δ-WC1±x powders (99.5 % purity, mean particle size – 0.4 μm) by high-frequency induction-heated sintering (HFIHS) process (exposure – ~40 s) of the powder preliminarily ball-milled (mixed) with 99.9 % purity Fe powder (initial mean particle size < 10 μm); the densification temperature of δ-WC1±x powder was reduced remarkably by the addition of Fe

Vacuum, 1200-1400 The formation of θ-(Fe,W)3C and ~13 mPa η2-(W,Fe)6Cy phases was revealed in powdered δ-WC1±x – 60-90 mol.% pure Fe mixtures after the heat treatment (exposure – 2 h) procedures

(continued)

2.6 Chemical Properties and Materials Design

369

Table 2.21 (continued) –

1240-1280 Highly dense sintered δ-WC1±x – 37 % Fe hard alloys were basically composed of δ-WC1±x grains dispersed in fine α-Fe – θ-Fe3C pearlite structure (metallic binder); however, at lower total C contents – ~ 10-100 μm grains of η2-W3Fe3Cy phase and at higher total C contents – ~100 μm needle-like θ-Fe3C grains were formed in the materials

–

1250

The maximum solid solubility of δ-WC1±x in γ-Fe is ~4 mol.%

Vacuum, 1250-1350 Powdered δ-WC1±x (99.9 %, 3 μm) – 10 % 0.1 Pa Fe (99.7 %, 2 μm) mixtures (preliminarily high-energy ball-milled, purities and initial mean particle sizes are given in brackets) were subjected to sintering (exposure – 1 h) procedure to prepare dense two-phase hard alloys (porosity – 1.1-1.5 %) –

1280

The metallic binder in highly dense δ-WC1±x – 20-40 % Fe cermets was composed of fine α-Fe – θ-Fe3C pearlite structure with the inclusions of η2-W3Fe3Cy phase, which were coarser than the δ-WC1±x grains formed in the sintered materials

Vacuum, ≤ 1400 ~10 mPa

No visible interaction between pure bulk Fe (content C < 0.08%) and δ-WC1±x powder (exposure – 1 h) was detected

Vacuum, 1400 20 Pa

The sintering procedure (exposure – 1 h) of δ-WC0.99 (< 10 μm) – 28 mol.% Fe (< 60 μm) powdered compositions (particle sizes are given in brackets) leads to the formation of δ-WC1±x – α-Fe – γ-Fe three-phase cermet materials

–

~1400-1500 Eutectic (pseudobinary) δ-WC1±x – δ-Fe

–

1450

The slight dissolution of Fe in δ-WC1±x materials was observed, no new phases in the contact zone were detected

–

1500

The melt composition of metallic binder in δ-WC1±x – 10 % Fe alloy varies in ranges from (Fe0.73W0.06C0.21) to (Fe0.67W0.20C0.13), depending on total C contents in the alloy

1560

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Fe (exposure – 5 min)

Ar

–

–

Fe-rich binder systems in the δ-WC1±x – Fe cermets potentially transform to bcc α-Fe upon cooling, while fcc γ-Fe is stabilized by the remaining W and C in the binder

(continued)

370

2 Tungsten Carbides

Table 2.21 (continued) –

–

Powdered δ-WC1.01 (monocrystalline, size distribution – 40-50 μm, content non-combined C – 0.10 %) – 30 % Fe (content C – 0.03 %) mixtures were employed as feedstocks to deposit hard coatings (thickness – 1.0-1.5 μm, loss of C – ~40 %) on steel substrates using O2-C2H2 torch spraying techniques; the deposited coatings were composed of κ-W3FeCy, γ-W2±xC, η2-W3Fe3Cy, δ-WC1±x and μ-Fe7W6–x phases (given in the order of decrease in their contents)

–

–

Monocrystalline δ-WC1.01 (size distribution – 150-180 μm, content non-combined C – 0.10 %) powders were filled in the steel (content C – 0.03 %) tube-shaped welding rods (mass ratio powder/steel – 2.33), which were used for hardfacing steel substrates with O2-C2H2 torch; the prepared hard layers (thickness – 1.0-1.5 μm, loss of C – ~ 40-50 %) were composed of κ-W3FeCy, δ-WC1±x, γ-W2±xC, η2-W3Fe3Cy and μ-Fe7W6–x phases (approximately given in the order of decrease in their contents)

–

–

Fe – 25 % δ-WC1±x cermet coatings were deposited on steel substrates using laser cladding technique

–

–

W-C thin films (thickness – 0.1-3.0 μm), co-sputtered with 5.6-16.0 at.% Fe, at lower Fe content were composed mainly of small grains of γ-WC1–x with a high number of defects and became amorphous at higher Fe content

–

–

The effect of substitutional Fe impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

–

–

The DFT-calculated works of adhesion of optimal Fe/δ-WC1±x interfaces (with hcp stacking geometry) were 9.7 J m–2 and 5.1 J m–2 for C- and W-terminated interface structures, respectively; for γ-Fe/δ-WC1±x interfaces (C-terminated with hcp stacking geometry), the DFT-calculated value for work of adhesion was 3.4 J m–2 (maximum in all of the possible interface geometries)

See also section δ-WC1±x – Fe – C See also section δ-WC1±x – (Fe – C) See also Table 2.26

(continued)

2.6 Chemical Properties and Materials Design

371

Table 2.21 (continued) See also section C – Fe – W in Table I2.14 δ-WC1±x – α/β/ε/γ-W2±xC – α/γ/δ-Fe

–

–

Fused δ-WC1±x – 65 % γ-W2±xC (with the presence of γ-WC1–x phase, contents: noncombined C – 0.30-0.32 %, total C – 4.34 %) powders, prepared by thermal plasma transferred arc method, with the addition of 30 % Fe (content C – 0.03 %) were employed as feedstocks to deposit hard coatings (thickness – 1.0-1.5 μm, loss of C – 40 %) on steel substrates using O2-C2H2 torch spraying techniques; the depo-sited coatings were composed of κ-W3FeCy, η2-W3Fe3Cy, γ-W2±xC, δ-WC1±x and μ-Fe7W6–x phases (given in the order of decrease in their contents)

–

–

Fused δ-WC1±x – 65 % γ-W2±xC (with the presence of γ-WC1–x phase, contents: noncombined C – 0.30-0.32 %, total C – 4.34 %) powders, prepared by thermal plasma transferred arc method, were filled in the steel (content C – 0.03 %) tube-shaped welding rods (mass ratio powder/steel – 2.33), which were used for hardfacing steel substrates with O2-C2H2 torch; the prepared hard layers (thickness – 1.0-1.5 μm, loss of C – 40 %) were composed of κ-W3FeCy, γ-W2±xC, μ-Fe7W6–x δ-WC1±x and η2-W3Fe3Cy phases (given in the order of decrease in their contents)

–

–

Hard composite layers were deposited by tubular electrodes coating using a core of blended powders containing Fe and fused δ-WC1±x – γ-W2±xC eutectic mixture at the various parameters of O2-C2H2 flame and W – inert gas (TIG) welding techniques

–

–

Cast W carbide powders added into Fe-based alloy powders were employed to fabricate hard alloyed layers on steel substrates using laser cladding techniques; the layers were mainly composed of ledeburite eutectic mixture of γ-Fe and θ-Fe3C phases

[10, 3548, 3565-3568, 3573, 3575, 3597, 3602, 3620, 3625, 4400]

See also section C – Fe – W in Table I2.14

(continued)

372

2 Tungsten Carbides

Table 2.21 (continued) α/β/ε/γ-W2±xC – α/γ/δ-Fe

–

> 1000

During the annealing, possible occurrence of the following reaction, classified as a quasi-peritectoid transformation process, γ-Fe + γ-W2±xC → η2-W3Fe3Cy + δ-WC1±x (6Fe + 4W2C = 2W3Fe3C + 2WC) is reported in literature

–

> 1340

In the W2±xC reinforced Fe-based metal matrix composites (MMC), η2-W3Fe3Cy phase was revealed to be an interfacial reaction product due to the mutual diffusion occurred between the matrix and inclusions according to the direct reaction: 6Fe + 3W2C = 2W3Fe3C + C; the appearance of interfacial reaction zone was observed experimentally in the remelted materials, but not in those prepared by spark-plasma sintering (SPS) procedures, where holding time was only ~5 min

[53, 639, 934, 3550, 3568, 3573, 3584-3585, 3588, 3620, 3708-3709, 3724, 3986]

See also section α/β/ε/γ-W2±xC – C – α/γ/δ-Fe See also section α/β/ε/γ-W2±xC – (Fe – C) See also section C – Fe – W in Table I2.14 δ-WC1±x – (Fe – C)

Vacuum, 1100 2-10 Pa

Powdered δ-WC1±x (99.95 % purity, con- [10, 53, 639, tent O – 0.52 %, mean particle size – 0.9 1886-1894, μm) – 43 % steel (particle size < 22 μm, 2427-2428, contents: C – 0.4 %, Cr – 5 %, Mo – 1 %, 2709, 2961, V – 1 %, O – 0.13 %; mass ratio 3001-3002, α-Fe/γ-Fe ≈ 6.7) mixtures were subjected 3005, 3080, to spark-plasma sintering (exposure – 5 3543, 3550min) procedure to prepare highly dense 3563, 3573, cermets; the composition of as-prepared 3589-3591, materials was evaluated to be 49 % 3595, 3613δ-WC1±x, 42 % α-Fe, 6 % γ-Fe and 3 % 3673, 3675, η2-W3Fe3Cy, after the additional heat-treat- 3724, 4400, ment (exposure – 9 h) in Ar at the same 4494] temperature the composition changed to 4 % δ-WC1±x, 21 % α-Fe, 3 % γ-Fe and 72 % η2-W3Fe3Cy

Pure Ar, 1450-1650 Pre-sintered δ-WC1±x skeletons (initial 85-90 mean particle size – 4-9 μm) were subjected to impregnation (contact and conkPa tact-free, exposure – 3 h) procedure by steel (content C – 0.19-0.21 %) to prepare dense materials composed of δ-WC1±x grains surrounded by the mixture of W-Fe complex carbides (η-phases)

(continued)

2.6 Chemical Properties and Materials Design

373

Table 2.21 (continued) Ar, or N2

–

~2200

–

The solar treatment (exposure – ~ 3-4 min) of manually-pressed layer of powdered δ-WC1±x (mean particle size – 140 μm) on the surface of steel (content C – 0.17-0.20 %) led to the formation of dispersions of δ-WC1±x (gradually disappearing with longer exposures), γ-W2±xC and η2-W2÷4Fe2÷4Cy phases in α-Fe metallic solid solution matrix; the additional formation of η2-W2÷4Fe2÷4Ny phases in these dispersions was observed in N2 atmosphere Electro-spark alloying (with δ-WC1±x electrode) of steel (content: C – 0.42-0.50 %) led to the formation of δ-WC1±x, γ-W2±xC, FeC (metastable), λ-Fe2W and μ-Fe7W6–x phases (given in the order of decrease in their contents) in the top surface layer of steel

See also section δ-WC1±x – C – Fe See also section δ-WC1±x – Fe See also Table 2.26 See also section C – Fe – W in Table I2.14 α/β/ε/γ-W2±xC – (Fe – C)

–

> 1000

The following reaction, classified in the [3708-3709] literature as a quasi-peritectoid transformation, γ-Fe + γ-W2±xC → η2-W3Fe3Cy + δ-WC1±x (6Fe + 4W2C = 2W3Fe3C + 2WC) can be occurred in steels after the annealing procedures

See also section α/β/ε/γ-W2±xC – C – α/γ/δ-Fe See also section α/β/ε/γ-W2±xC – Fe See also section C – Fe – W in Table I2.14 δ-WC1±x – (Fe – C – Co – Cr – Mo – V)

–

–

The formation of Cr23C6±x based substitu- [639, 3554, tional solid solutions in the Co – Cr – Mo 3655] – V – W alloyed steels was supposed to occur along four crystallographic nonequivalent sublattices of the compound in the accordance to the following scheme: [(Cr1–xVx)(Cr2–y–zMoyWz)(Cr8–u–qFeuCoq) Cr12]C6±x (x ≤ 1, (y + z) ≤ 2, (u + q) ≤ 8)

(continued)

374

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – (Fe – N2 C – Co – Mo – Ni)

–

–

Powdered maraging steel (size distribution [2427-2428, – 20-66 μm; contents: C ≤ 0.03 %, Ni – 3630] 17-19 %, Co – 8.5-9.5 %, Mo – 4.5-5.2 %, Fe – remainder) – ~ 2.5-8.5 vol.% δ-WC1±x (mean particle size – 3-5 μm) mixtures were subjected to selective laser melting (SLM) process (laser power – 275 W, laser scanning speed – 1.36 m s–1, layer thickness – 50 μm); due to the addition of δ-WC1±x the main phase in the materials changed from α-(Fe,Ni) to γ-(Fe,Ni) solid solution, the large-sized carbide particles in them presented γ-WC1–x phase

–

Powdered maraging steel (atomized, size distribution – 33-40 μm; composed of major α-(Fe,Ni) and minor γ-(Fe,Ni) phases; contents: C ≤ 0.03 %, Ni – 17-19 %, Co – 8.5-9.5 %, Mo – 4.5-5.2 %, Fe – remainder) – 15 % δ-WC1±x (size distribution – 1-6 μm) mixtures were employed for the additive manufacturing (AM) of steel metal matrix composites (MMC) via cold spraying (CS) or selective laser melting (SLM) techniques; in opposite to the CS-manufactured MMC with α-(Fe,Ni) – γ-(Fe,Ni) matrix, the SLM-manufactured possessed α-(Fe,Ni) single-phase matrix Data on the system reported by various authors differ markedly

δ-WC1±x – (Fe – Vacuum, 1200-1600 δ-WC1±x – 10-40 % high-Cr cast Fe (conC – Cr) 0.5 Pa tents: C – 3.1 %, Cr – 27.0 %) hard alloys were prepared by conventional sintering procedure (exposure – 1 h); the sintered alloys were composed of δ-WC1±x and (Fe,Cr)7C3±x carbide and α-Fe-based solid solution phases

[10, 2359, 3080, 3412, 3631-3632, 3637-3639]

Vacuum, 1450-1550 δ-WC1±x particle reinforced Fe-based (α-Fe ~60 kPa + θ-Fe3C, contents: C – from 3.6 % to 5.3 %, Cr – from 5.6 % to 27.4 %) metal matrix surface composites were fabricated using vacuum evaporation pattern casting (V-EPC) technique; the presence of η1-(W,Fe,Cr)12Cy, γ-(W,Cr)2±xC, (Cr,Fe,W)23C6±x and other Cr carbide phases was detected in the materials

(continued)

2.6 Chemical Properties and Materials Design

375

Table 2.21 (continued) δ-WC1±x – (Fe – Vacuum 1200-1400 Powdered δ-WC1±x – stainless steel (C – [2961, 3429, C – Cr – Mn – 0.03 %, Cr – 16.5-18.5 %, Ni – 10-13 %, 3587, 3652, Mo – Ni – Si) Mo – 2.0-2.5 %, Mn – 2.0 %, Si – 1.0 %, 3654] Fe – remainder) mixtures were subjected to sintering procedure (exposure – 1 h) to fabricate dense hard metals Powdered δ-WC1.00 (mean particle size – ~5 μm) – 20 % stainless steel (mean particle size – ~20 μm; contents: C – 0.03 %, Cr – 18 %, Ni – 13 %, Mo – 3 %, Mn – 1.3 %, Si – 0.7 %) mixtures with various total C contents (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) procedure to fabricate dense multi-phase hard alloys with the volume fraction of γ/α′-(Fe,Ni) metallic (austeniticmartensitic) binder (mass ratio Fe/Ni = 85/15) reduced from 33 vol.% in the powders to < 15 vol.% in the alloys; η2-(W,Cr,Mo)3(Fe,Ni)3Cy, (Fe,Cr)23C6±x and (Fe,Cr)7C3±x complex carbides with the compositions depending on total C contents were detected in the alloys as minor phases

Vacuum, 1400 < 1 Pa

–

δ-WC1±x – (Fe – Vacuum 1350 C – Cr – Mn – Nb)

–

Powdered δ-WC1±x – stainless steel (C – 0.03 %, Cr – 16-18 %, Ni – 10-14 %, Mo – 2-3 %, Mn – 2 %, Si – 0.75 %, Fe – remainder) mixtures were employed for the preparation of hard metal matrix composite (MMC) coating on steel substrates using laser melting deposition (LMD) techniques; the prepared coatings were composed of δ-WC1±x, γ-W2±xC, θ-Fe3C, η2-(W,Fe,Cr)6Cy, (Fe,Cr)7C3±x and (Fe,Cr)23C6±x carbide, λ-Fe2W intermetallide and γ-Fe metallic solid solution phases and matrix was formed by dendrite γ-Fe and γ-Fe – carbide eutectics δ-WC1±x – 10 % Nb stabilized austenite [10, 2961, γ-(Fe,Cr,Ni,Mn) stainless steel (C – 0.04- 3648-3649] 0.08 %, Cr – 18 %, Ni – 10 %, Mn – 2 %, Nb – 1 %, Fe – remainder) three-phase hard alloys, containing η2-W3Fe3Cy phase, were fabricated from preliminarily milled and compacted powders by liquid-phase sintering procedure

(continued)

376

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – (Fe – C – Cr – Mn – Ni)

–

–

δ-WC1±x – (Fe – Vacuum 1450 C – Cr – Mn – Ni – Si)

δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mn – Ni – Si)

In δ-WC1±x nanoparticulate strengthened [3421] steel (C – 0.37-0.45 %, Mn – 0.5-0.8 %, Cr – 0.6-0.9 %, Ni – 1.25-1.65 %, Fe – remainder) metal matrix composites fabricated via conventional casting, the δ-WC1±x nanoparticles surrounding the θ-Fe3C phase were distributed evenly within the matrix Powdered δ-WC1±x – 11-26 vol.% austeni- [3645-3647, tic-martensitic stainless steel (C – 0.03 %, 3650-3651, Mn – 1.6 %, Cr – 18.5 %, Ni – 9.8 %, Si – 3653] 0.7 %, Fe – remainder) mixtures (preliminarily high-energy ball-milled and uniaxially cold-pressed) were subjected to liquidphase sintering to fabricate hard alloys (porosity – 2-26 %) with the contents of η2-(W,Fe,Cr)6Cy complex carbide phase increasing from 11 % up to 22 % with the increase of steel fraction in the initial mixtures

–

–

Powdered γ-Fe (austenite) stainless steel (100-150 μm; contents: C – 0.03 %, Mn – 2 %, Cr – 18-20 %, Ni – 8-12 %, Si – 1 %) – 10-40 % δ-WC1.00 (30-50 μm; contents: Ti – 0.08 %, Fe – 0.07 %, Al – 0.02 %, Mn – 0.02 %, Si – 0.01 %) mixtures (size distributions are given in the brackets first) were subjected to laser cladding procedure; depending on δ-WC1±x contents, the prepared materials composed of γ-(Fe,Ni,Cr) metallic solid solution, γ-W2±xC, δ-WC1±x and η2-(W,Fe,Cr)6Cy phases (at the various contents of δ-WC1±x) and additionally – (Fe,W,Cr)7C3±x phase (at its higher contents)

–

–

Powdered δ-WC1±x – γ-W2±xC lamellar eu- [3566-3567, tectics (25-40 μm) – 50 % alloyed steel 3613] (40-80 μm, contents: C – 0.40-0.60 %, Mn – 0.65-0.80 %, Cr – 1.0-2.5 %, Ni – 4.36.0 %, Si – 1.0-2.0 %, Fe – remainder) mixtures (size distributions are given in brackets) were employed to fabricate coatings on steel substrates by laser induction hybrid rapid cladding (LIHRC) techniques; W carbide particles were dissolved almost completely to precipitate the coarse herringbone η2-W3Fe3Cy (approximate composition) eutectic carbides and fine dendritics of similar compositions, the prepared coatings consisted of supersaturated α-Fe and retained γ-Fe solid solutions, θ-Fe3C,

(continued)

2.6 Chemical Properties and Materials Design

377

Table 2.21 (continued) γ-W2±xC, η2-W3Fe3Cy and (Cr,Fe,W)7C3±x phases as well as partially dissolved δ-WC1±x grains (with an alloyed reaction layers), which were observed occasionally in the coatings δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mn – Ni – Si – Ti)

–

δ-WC1±x – (Fe – C – Cr – Mn – W)

–

575-600

The alloying of Cr-Mn stainless steels with [639, 3552, 0.75-1.0 % W stimulates the 4202] θ-(Fe,Cr,Mn,W)3C → (Cr,Fe,Mn,W)7C3±x transformation during a tempering procedure, raising the W content in the steels to 1.25 % causes the substantial enrichment of θ-(Fe,Cr,Mn,W)3C phase with W, and at higher temperatures of the interval α/ε-(W,Cr)2+xC phase is formed by the ageing mechanism

–

600-650

In the containing 0.75-1.50 % W steels, tempered in this temperature interval, the theoretically calculated compositions of complex carbide phases were in the ranges: θ-(Fe0.76Cr0.12Mn0.11W0.01)3C (in approximation), (W0.02÷0.87Cr0.07÷0.65Fe0.03÷0.37Mnz)2.02÷2.40C (with z = 0.03÷0.13) and (Cr0.36÷0.65W0.02÷0.14Fe0.14÷0.37Mnz)7C2.89÷3.23 (with z = 0.05÷0.29)

δ-WC1±x – (Fe – C – Cr – Mo – Nb – Ti – V)

–

δ-WC1±x – (Fe – C – Cr – Mo – Ni)

–

–

–

960-1040

Starting (raw) powdered materials for the [3706] synthesis of W carbides, charged in a seamless stainless steel (C ≤ 0.12 %, Cr – 17-19 %, Ni – 8-11 %, Mn ≤ 2 %, Si ≤ 1 %, Ti ≥ 0.8 %, Fe – remainder) tube, were employed for the deposition of hard layers on steel substrates via consumable electrode d.c. metallurgy techniques; the deposited layers had strong metallurgical bonding with the substrates and were composed of δ-WC1±x, γ-(W,Cr)2±xC, η2-W3(Fe,Ni)3Cy, θ-(Fe,Ni)3C, (Cr,Fe,W)7C3±x and γ-(Fe,Ni) metallic solid solution phases

Theoretically calculated compositions of [639, 3550complex carbide η2-phases in high-speed 3551] steels were in the ranges: (W0.05÷0.12Mo0.54÷0.70Cr0.11÷0.29Fe0.10÷0.12)6Cy ~40 % δ-WC1±x reinforced Ni – Cr – Mo [3640-3641, steel matrix composites were subjected to 3643] the austenization heat treatment followed by quenching and tempering procedures

(continued)

378

2 Tungsten Carbides

Table 2.21 (continued) Stainless steel (C ≤ 0.03 %, Ni – 12-15 %, Cr – 16-18 %, Mo – 2-3 %, Fe – remainder) – 20-40 % δ-WC1±x composites were fabricated from high-energy ball-milled powdered mixtures using pulsed electric current sintering (PECS) procedure

Vacuum, 1050 10 Pa

–

δ-WC1±x – (Fe – C – Cr – Mo – Si – V)

δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Cr – Mo – V)

–

δ-WC1±x reinforced steel (C – 0.5-0.6 %, Ni – 1.5-1.8 %, Cr – 0.8-1.2 %, Mo – 0.40.6 %, Fe – remainder) matrix composites were prepared by inductive electroslag casting technology; the formation of transition layers on the interfaces of δ-WC1±x grains with matrix and adjacent to it stripe-structured η2-W3Fe3Cy phase was detected in the materials

–

1000

The following compositions of complex [639, 3001, carbide phases were revealed after the heat 3555, 3621] treatment of alloyed steels: η2-(W0.16Mo0.22Cr0.04Fe0.48V0.08Si0.02)6Cy and (V0.89W0.02Mo0.04Cr0.02Fe0.03)C1–x

–

1100

The following compositions of complex carbide phases were revealed after the heat treatment of alloyed steels: η2-(W0.17Mo0.23Cr0.06Fe0.46V0.07Si0.01)6Cy and (V0.90W0.02Mo0.02Cr0.03Fe0.03)C1–x

–

–

Powdered δ-WC1±x was cladded on steel (C – 0.35-0.42 %, Cr – 4.8 %, Mo – 1.01.5 %, Si – 0.8-1.2 %, V – 0.8-1.15 %, Fe – remainder) substrates by gas W arc welding (GTAW) techniques to form η2-W3Fe3Cy – (Fe,W,Cr)7C3±x phase structured layers (the retained δ-WC1±x particles were not found in the cladded layers)

–

–

The behaviour of carbide eutectics in the [139, 639, alloyed steel (C – 1.1-1.2 %, Cr – 10-11 %, 3001, 3422Mo – 3.0-3.5 %, V – 2.5-3.0 %, W – 0.5- 3424, 3550, 1.5 %, Fe – remainder) was studied theore- 3553, 3708tically and experimentally 3709]

–

–

The following compositions of complex carbide phases were revealed in high-speed steels (C – 0.7-0.9 %, Cr – 3.8-4.4 %, Mo – 1.0-5.3 %, V – 1.0-2.1 %, W – 5.5-18.5 %, Fe – remainder): η2-(W0.42Mo0.02Cr0.04Fe0.47V0.05)6Cy, (Cr0.29W0.05Mo0.01Fe0.62V0.03)23C6±x and (V0.70W0.11Mo0.02Cr0.14Fe0.03)C1–x

(continued)

2.6 Chemical Properties and Materials Design

379

Table 2.21 (continued) –

δ-WC1±x – (Fe – C – Cr – Ni)

–

In the α-Fe (ferritic) high-speed steels (C – 0.9 %, Cr – 3.95 %, Mo – 4.8 %, V – 2.1 %, W – 5.9 %, Fe – remainder) and (C – 1.05 %, Cr – 3.9 %, Mo – 9.45 %, V – 1.15 %, W – 1.6 %, Fe – remainder), the compositions of complex semicarbide phases was found to be (W0.19Mo0.32V0.23Cr0.11Fe0.15)2±xC (plate-like structured) and (W0.05Mo0.49V0.11Cr0.10Fe0.25)2±xC (fibrous), respectively

–

≥ 750-800

The interaction of fine powders of δ-WC1±x [2961, 3080, and stainless steel (C – 0.08-0.17 %, Cr – 3430, 3503, 15-19 %, Ni – 1.5-2.5 %, Fe – remainder) 3601, 3615, leads to the formation of η2-(W,Fe,Cr)6Cy 3632, 3642, and (Fe,Cr,W)23C6±x complex carbide 3644-3654] phases

–

850-1150

Highly dense δ-WC1±x – 38 % stainless steel (C – 0.08-0.17 %, Cr – 15-19 %, Ni – 1.5-2.5 %, Fe – remainder) hard alloys were fabricated from high-energy ball-milled powdered mixtures using by using of high-energy hot-pressing (without the presence of liquid phase)

Vacuum 1200-1500 δ-WC1±x – 6-32 % steel (C – 0.08 %, Cr – 16-20 %, Ni – 12-16 %, Fe – remainder) hard alloys (porosity – 0.4-30 %) were prepared by liquid-phase sintering (holding time – 0.5-1.0 h) procedure; the reaction of Cr from the metallic binder with δ-WC1±x grains, resulting in their decarburization, led to the formation of α/ε-W2+xC phase and then – non-uniform in composition η2-(W,Fe,Cr,Ni)6Cy phases (no Cr carbides were detected in the sintered materials); the rate of formation of the η-phases in the materials was strongly dependent on the sintering temperature and only slightly – on the holding time –

1400

High-energy ball-milled δ-WC1.00 – 12 % stainless steel (C – 0.03 %, Cr – 18.8 %, Ni – 10.0 %, Fe – remainder) powdered mixtures (mean particle size – 0.23±0.025 μm, crystallite sizes – 12±1 nm) were subjected to pre-sintering followed by hot isostatic pressing (HIP) procedure (exposure – 1 h) to fabricate poreless materials composed of 52±1 % δ-WC1±x and 48±1 % η2-(W,Fe,Cr,Ni)6Cy phase constituents

(continued)

380

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1400 20 Pa

~10 % Cr-Ni stainless steel sputtering coated δ-WC1±x powders were subjected to liquid-phase sintering (exposure – 2 h) procedure to prepare highly dense threephase cermets composed of δ-WC1±x, Ferich, Cr-Ni (mainly) containing metallic binder and η2-(W2.8Fe2.3Cr0.6Ni0.3)6Cy phase constituents; the binder phase spread on the surfaces of both carbide phases with excellent interpenetration between their junctions

Ar, 2 MPa

Powdered δ-WC1±x (99.9 % purity, mean particle size – 9.1±0.5 μm) – 10 % stainless steel (99.9 % purity, mean particle size – 10 μm; contents: C – 0.03 %, Cr – 18 %, Ni – 10 %) mixtures (preliminarily highenergy ball-milled and cold isostatic pressed) were subjected to gas pressure sintering (isothermal holding time – 1.5 h) to fabricate highly dense two- or three-phase (depending on total C contents) cermets (total C contents – 5.36-5.85 %, residual binder phase contents – 3.6-9.0 %, porosity – 0.3 %, mean grain size – (2.3÷3.3)±0.2 μm); C-deficient η-phase regions with an appearance of “islands” were frequently found in the three-phase materials with lower total C content

1440

Vacuum, 1440-1520 Powdered δ-WC1±x (mean particle size – 9 30 Pa μm) – 6-15 % stainless steel (mean particle size – 22 μm; contents: C – 0.07 %, Cr – 18 %, Ni – 10 %) mixtures (preliminarily high-energy ball-milled) were subjected to liquid-phase sintering (exposure – 2 h) procedure to fabricate dense cermets (porosity – 6-8 %, mean grain size – ~3 μm) with γ-Fe solid solution metallic binder; the percentage of η2-(W,Fe,Cr)6Cy in the mass of both carbide phases increased from 0 to 12 % with increasing of initial binder amounts from 6 to 15 %, at higher binder contents η2-(W2.6Fe2.6Cr0.6Ni0.2)6Cy composition of η-phase was detected –

–

δ-WC1±x dispersed high-Cr-Ni cast Fe-based deposits low-pressure plasma-sprayed were composed of carbide fine precipitates (coarsened after the heat treatment) in α-Fe- and γ-Fe-based metallic solid solutions matrix

(continued)

2.6 Chemical Properties and Materials Design

381

Table 2.21 (continued) –

–

Powdered δ-WC1±x (polygonal in shape, size distribution – 5-15 μm) – 75 % alloyed steel (atomized, size distribution – 5-30 μm, contents: C – 0.45 %, Ni – 4.0 %, Cr – 1.35 %, Fe – remainder) mixtures (highenergy preliminarily ball milled) were employed to prepare dense metal matrix composites (MMC) using laser additive manufacturing via selective laser melting (SLM); the gradient interface formed between δ-WC1±x particles and metallic matrix (precipitated eutectic phases with fine network structures) was identified as (Fe,W,Cr,Ni)C3

δ-WC1±x – (Fe – C – Cr – V – W)

–

1000-1350 Depending on the C/W ratio in the variety [3749] of high-speed steels (C – up to 4.3 %, W – up to 28.0 %, Cr – 3.8-4.4 %, V – 1.0-2.6 %, Fe – remainder), the eutectic constituents of hypoeutectic alloyed compositions were revealed to be classified in the following types: γ-Fe – θ-(Fe,W)3C austenite-cementite binary eutectics, γ-Fe – η2-(W,Fe,Cr)6Cy binary eutectics, γ-Fe – θ-(Fe,W)3C – (Fe,Cr,W)23C6±x ternary eutectics and γ-Fe – θ-(Fe,W)3C – η2-(W,Fe,Cr)6Cy ternary eutectics

δ-WC1±x – (Fe – C – Mn)

–

1150

δ-WC1±x – ~20 vol.% Fe-based alloy (con- [3619, 2961, tents: C – 0.8 %, Mn – 4-20 %) composites 3659-3663, (porosity ≤ 0.5 %, mean δ-WC1±x grain 3666, 3675size – (2.4÷2.6)±0.3 μm, mean interlayer 3677, 4400, size – (1.2÷1.7)±0.2 μm; depending on Mn 4668] percentage in the Fe-based alloy, binder composition – bcc α′-Fe + fcc γ-Fe at 4-8 % Mn and fcc γ-Fe + hcp ε-Fe at 8-20 % Mn with maximum fcc γ-Fe content at 8.0±0.2 % Mn) were fabricated using the vacuum impregnation of porous δ-WC1±x skeletons with Fe-based melts (containing δ-WC1±x) followed by tempering procedure; the dissolution of δ-WC1±x in the FeMn-C metallic binder leads to the shift of existence (stability) areas of bcc α′-Fe and hcp ε-Fe solid solutions formed due to the occurrence of fcc γ-Fe → hcp ε-Fe → bcc α′-Fe martensitic transformations on cooling

(continued)

382

2 Tungsten Carbides

Table 2.21 (continued)

δ-WC1±x – (Fe – C – Mn – Si)

–

–

Powdered δ-WC1±x (mean particle size – 75 μm) was cladded on steel (C – 0.480.55 %, Mn – 0.60-0.90 %, Fe – remainder) substrates by multi-pass gas W arc welding (GTAW) techniques to form the vein-shaped η2-W3Fe3Cy – α-Fe eutectic structured layers

–

–

δ-WC1±x – Hadfield steel (C – 1-2 %, Mn – 13-14 %, Fe – remainder) hard alloys were fabricated by powder metallurgy methods

–

1100

In the unquenched state, conventionally sintered δ-WC1±x – 30 % steel (C – 0.9-1.5 %, Mn – 11.5-15.0 %, Si – 0.3-1.0 %, Fe – remainder) cermets were composed of δ-WC1±x (mean grain size – ~1 μm) and η1-W6Fe6Cy (up to ~10 vol.%) carbide and α-Fe- (intermediate layers interspersed with the η-phase, up to ~ 1-2 vol.%) and γ-Fe-based metallic solid solution phases; after the additional annealing followed by quenching, practically only two structural constituents δ-WC1±x (mean grain size – ~1.5 μm) and γ-Fe-based metallic solid solution (interlayers between the carbide grains with the widths ranged within 0.5-1.5 μm) phases were observed in the materials (the content of η-phase dropped up to ~1 vol.%)

–

1200

Vacuum sintered δ-WC1±x – 30 % Hadfield steel (C – 0.9-1.5 %, Mn – 11.5-15.0 %, Si – 0.3-1.0 %, Fe – remainder) hard alloys (mean δ-WC1±x grain size – 2.6 μm, mean interlayer size – 1.6 μm) were subjected to the saltpetre hardening that increased the solubility of W and C in the γ-Fe solid solution binder followed by the precipitation of metastable complex W-Fe carbides

–

–

In the δ-WC1±x – Hadfield steel matrix composites, the δ-WC1±x/steel interface was revealed to be of shell shape, in which W, Fe and Mn elements diffuse between the two phases, and – of metallurgical bond, where η2-W3Fe3Cy phase was formed

–

–

Sintered δ-WC1±x – austenite steel (C – 0.9-1.5 %, Mn – 11.5-15.0 %, Si – 0.3-1.0 %, Fe – remainder) hard alloys with stable and metastable γ-Fe solid solution matrix states were fabricated and studied, including the behaviour after dynamic load

[3633-3636, 3657-3661, 3664-3665, 3675-3677]

(continued)

2.6 Chemical Properties and Materials Design

383

Table 2.21 (continued) δ-WC1±x – α/β/ε/γ-W2±xC – (Fe – C – Mn – Si)

–

–

Fe-based alloy (contents: C – 2 %, Si – 1.4 [3667-3669, %, Mn < 1 %) flux-cored wire (diameter – 3707] 1.6 mm), filled with 50 % fused δ-WC1±x – γ-W2±xC eutectics (size distribution – 25125 μm), was used as feed-stock materials to fabricate hard coatings (porosity – (2.0÷2.3)±(0.4÷0.8) %) on steel substrates using twin wire arc spraying (TWAS) technique

δ-WC1±x – (Fe – C – Ni)

–

–

δ-WC1±x reinforced Fe-Ni steel matrix composites were fabricated

δ-WC1±x – (Fe – C – Si)

–

[3670-3671]

1300-1400 Dense δ-WC1±x reinforced Fe-based com- [3564, 3577, posite coatings were fabricated by centrifu- 3672] gal casting of gray cast Fe (contents: C – 3.6 %, Si – 2.5 %) plus in situ synthesis techniques and deposited on the similar substrates; the prepared coatings were containing α-Fe, δ-WC1±x and metastable θ-Fe3C phases (with traces of η2-W3Fe3Cy)

–

–

δ-WC1±x reinforced Fe-based double-layered coatings, containing Fe – C – Si superhard alloy particles, were fabricated on Al alloy substrates using resistance seam welding techniques

δ-WC1±x – Fe – La

–

–

The addition of minute amounts of La to [3674] the δ-WC1±x – Fe feedstock materials for the preparation of coatings on steel substrates using Ar arc cladding techniques did not change the phase composition of the fabricated coatings (δ-WC1±x, γ-W2±xC, η2-W3Fe3Cy and α-Fe solid solution), but made the distribution of carbide particles in them more homogeneously

δ-WC1±x – Fe – Ln (rare earth elements: misch metal, La, Ce, Nd, Dy, Pr, Y) – Ni

–

–

The δ-WC1±x cemented carbides, in which [3133] (Fe,Ni) metallic binder was modified by various rare earth elements and their compounds, were designed and fabricated using various methods of powder metallurgy

δ-WC1±x – Fe – Mn

Ar, 1250 0.8 kPa

[2725, 2943, Dense δ-WC1±x – 8.4 % Fe – 1.6 % Mn hard alloys were fabricated (using high 3583, 3675purity δ-WC1±x powder with mean particle 3678] size – 0.6 μm) by liquid-phase sintering (exposure – 1 h) with formed α′-Fe – γ-Fe (martensitic-austenitic) structured binder

(continued)

384

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1350-1430 Powdered δ-WC1±x (size distribution – 1-3 ~13 Pa μm) – 15-25 % Fe-based alloy (austenitic, H2O-atomized and annealed in H2; size distribution – 1-4 μm; contents: Fe – 86.4 %, Mn – 13.5 %, C – 0.07 %, O – 0.02 %) mixtures (preliminarily ball-mil-led and cold-pressed) were subjected to liquidphase sintering (exposure – 0.75 h) procedure to fabricate dense hard alloys with either fully fcc γ-Fe (austenitic), or mixed fcc γ-Fe with hcp ε-Fe / bcc α′-Fe (austenitic-martensitic) binders; at the lower total C contents the presence of W-Fe complex carbide η-phases was detected Vacuum 1380

Due to the significant losses of Mn during the heat treatment (85 % of the originally present amounts of Mn were vapourised after 1 h exposure), the alloy with δ-WC1±x – 9 % Fe – 1 % Mn composition could be prepared only in the porous state; the formation of bcc α′-Fe martensitic solid solutions in the product was observed

Vacuum 1380

Dense δ-WC1±x – 9.4-9.8 % Fe – 0.16-0.62 % Mn two-phase (carbide and metallic binder) and three-phase (additionally containing α-C (graphite), or η2-(W,Fe,Mn)6Cy phases) hard alloys were fabricated (using high purity δ-WC1±x pow-der with mean particle size – 0.6 μm and varying total C contents) by liquid-phase sintering (exposure – 1 h) with formed α′-Fe martensitic structured binder

–

–

Dense δ-WC1±x – Fe-based alloy (content Mn – 13-15 %) cemented carbides were fabricated by various powder metallurgy methods, including pulse-plasma sintering (PPS) techniques

–

–

The properties of Fe – Mn binder as functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Mo

–

–

The properties of Fe – Mn – Mo binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Nb

–

–

The properties of Fe – Mn – Nb binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Ni

–

–

The properties of Fe – Mn – Ni binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Ta

–

–

The properties of Fe – Mn – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Ti

–

–

The properties of Fe – Mn – Ti binder as [2943] functions of alloying content are evaluated

(continued)

2.6 Chemical Properties and Materials Design

385

Table 2.21 (continued) δ-WC1±x – Fe – Mn – V

–

–

The properties of Fe – Mn – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mn – Zr

–

–

The properties of Fe – Mn – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mo

–

–

The properties of Fe – Mo binder as func- [2943] tions of alloying content are evaluated

δ-WC1±x – Fe – Mo – Nb

–

–

The properties of Fe – Mo – Nb binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mo – Ni

Vacuum, 1250-1350 Powdered δ-WC1±x (99.9 %, 3 μm) – 4.5- [10, 2943, 0.1 Pa 4.9 % Ni (99.7 %, 2 μm) – 4.5-4.9 % Fe 3679] (99.7 %, 2 μm) – 0.25-1.0 % Mo (99 %, 50 μm) mixtures (initial purities and mean particle sizes are given in brackets, preliminarily high-energy ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate dense δ-WC1±x – γ-(Ni,Fe) based solid solution binder hard alloys (porosity – 0.7-1.9 %) –

–

The properties of Fe – Mo – Ni binder as functions of alloying content are evaluated

δ-WC1±x – Fe – Mo – Ta

–

–

The properties of Fe – Mo – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mo – Ti

–

–

The properties of Fe – Mo – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mo – V

–

–

The properties of Fe – Mo – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Mo – Zr

–

–

The properties of Fe – Mo – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – N

–

–

Fe-N doped mesoporous δ-WC1±x was syn- [1612] thesized by pyrolysis of well-ordered porous carbide with Fe containing porphyrins

δ-WC1±x – Fe – Nb

–

–

The properties of Fe – Nb binder as func- [2943] tions of alloying content are evaluated

δ-WC1±x – Fe – Nb – Ni

–

–

The properties of Fe – Nb – Ni binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Nb – Ta

–

–

The properties of Fe – Nb – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Nb – Ti

–

–

The properties of Fe – Nb – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Nb – V

–

–

The properties of Fe – Nb – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Nb – Zr

–

–

The properties of Fe – Nb – Zr binder as [2943] functions of alloying content are evaluated

(continued)

386

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Fe – Ni

N2

~(–196)

δ-WC1±x – 15 % Fe – 5 % Ni hard alloys were subjected to deep cryogenic treatment (exposure – 2-24 h), an increase in the treatment time led to the martensitic transformation γ-(Fe,Ni) → α-(Fe,Ni) in the binder phase (according to the internal friction studies transformation temperature was (–23) °C); due to the transformation the α-(Fe,Ni) phase content gradually increased from 12.7 % to 86.8 % (at the maximum duration of treatment), and W particles precipitation from the metallic solid solution (binder) phase was observed

Ar

500-900

Electroless Ni plated δ-WC1±x – Fe powdered mixtures were employed for the preparation of δ-WC1±x particulate reinforced Ni-Fe alloy based metal matrix composites (MMC) using microwave sintering techniques

[10, 63, 1937, 1982, 1985, 1988, 1994, 2709, 2725, 2784, 2943, 31193123, 3131, 3133, 3298, 3394, 3583, 3594, 3600, 3603, 36113612, 36793690, 36933703, 3831]

Vacuum, 1150-1200 Powdered δ-WC1±x (mechano-chemical 1 Pa synthetic, size distribution – from 0.1 μm to 14 μm) – 8 % Ni (99.95 % purity) – 8 % Fe (99.95 % purity) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate poreless two-phase hard alloys (mean grain size – 1.4 μm) with the uniform distribution of metallic binder phase –

1200

The solubility of δ-WC1±x in γ-(Ni,Fe) metallic solid solution phase increases with increasing Ni contents in it

–

1200

The η1-(W,Fe,Ni)12Cy phase is continuous between η1-W6Fe6Cy and η1-W6Ni6Cy, while the η2-(W,Fe,Ni)6Cy phase exists between η2-W3Fe3Cy and η1-W4Ni2Cy with increasing W content in it; all these complex carbides (η1-(W,Fe,Ni)12Cy and η2-(W,Fe,Ni)6Cy), as well as κ-W3(Fe,Ni)Cy phase, crystallize from the melt; in the compositions, which yield only γ-(Ni,Fe) + δ-WC1±x, or γ-(Ni,Fe) + δ-WC1±x + α-C (graphite) under the equilibrium conditions, η2-(W,Fe,Ni)6Cy and κ-W3(Fe,Ni)Cy can crystallize from the melt as metastable phases and during the annealing, they then decompose according to the following scheme: η2-(W,Fe,Ni)6Cy (or κ-W3(Fe,Ni)Cy) + α-C (graphite) → γ-(Ni,Fe) + δ-WC1±x

(continued)

2.6 Chemical Properties and Materials Design

387

Table 2.21 (continued) Vacuum, 1250-1350 Powdered δ-WC1±x (99.9 %, 3 μm) – 5 % Ni (99.7 %, 2 μm) – 5 % Fe (99.7 %, 2 0.1 Pa μm) mixtures (initial purities and mean particle sizes are given in brackets, preliminarily high-energy ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) to fabricate dense δ-WC1±x – γ-(Ni,Fe) based solid solution binder hard alloys (porosity – 0.8-1.6 %) Vacuum, 1300-1400 Powdered δ-WC1±x – 7.5 % Fe – 7.5 % Ni ~13 Pa mixtures (mean particle size – 1.8±0.5 μm) were subjected to liquid-phase sintering (soaking time – 1 h) to fabricate dense hard alloys (porosity – 2-5 %, mean grain size – ~1 μm) Vacuum 1300-1420 δ-WC1±x – ~ 3-16 vol.% Fe – ~ 4-17 vol.% Ni hard alloys (mean δ-WC1±x grain size – ~1 μm) were fabricated by liquid-phase sintering (exposure – 1 h) procedure –

1350

The maximum solid solubilities of elemental W and C in γ-(Fe,Ni) metallic solid solution phase (with ratio Fe/Ni ≈ 1) are ~9.0 % and ~4.7 %, respectively

Vacuum 1380

Highly dense δ-WC1±x – 5-18 % Fe – 1-5 % Ni two-phase (carbide and metallic binder) and three-phase (additionally containing α-C (graphite), or η2-(W,Fe,Ni)6Cy phases) hard alloys were fabricated (using high purity δ-WC1±x powder with mean particle size – 0.6 μm and varying total C contents) by liquidphase sintering (exposure – 1 h) with formed Fe based austenitic-martensitic structured binder

Dry H2

Powdered δ-WC1.00 (mean particle size – ~0.8 μm, size distribution – from 0-1 to 45 μm, contents: non-combined C – 0.04 %, O – 0.10 %, Fe – 0.006 %, Ni – 0.0002 %) – 2.5-7.5 % Fe (mean particle size – 3-4 μm, contents: total C – 0.8 %, O – 0.3 %, N – 0.9 %) – 2.5-7.5 % Ni (mean particle size – 3.7 μm, specific surface area – 0.3 m2 g–1, contents: total C – 0.06 %, O – 0.05 %, N – 0.003 %, Fe – 0.005 %, Co – 0.0003 %) mixtures were subjected to liquid-phase sintering to fabricate dense hard alloys (porosity – 0.5-11.0 %)

1400

(continued)

388

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1400 20 Pa

The sintering procedure (exposure – 1 h) of δ-WC0.99 (< 10 μm) – 14 mol.% Fe (< 60 μm) – 13 mol.% Ni (3-7 μm) powdered compositions (particle sizes are given in brackets) leads to the formation of δ-WC1±x – γ-(Fe,Ni) two-phase cermets

N2, 40 kPa

1440

δ-WC1±x – 7.7 % Fe – 1.4 % Ni hard alloys (with various total C contents) were designed using thermodynamic calculations and then fabricated via liquid-phase sintering (exposure – 1 h) procedure; in the N2 atmosphere the stability of η-phase slightly decreased, as N can replace C in it, thereby producing additional C to promote the decomposition of the phase, but this effect is limited due to the low solubility of N2

Ar, 5 MPa

1450

δ-WC1±x – 15 % Fe – 5 % Ni hard alloys (with γ-(Fe,Ni)/α-(Fe,Ni) mass ratio = 87/13 in the binder) were fabricated by hot isostatic pressing (HIP) procedure (exposure – 80 min) from various δ-WC1±x powders (with mean particle sizes – from 0.8 μm to 15 μm)

Flow 1480 Ar/H2 (96/4) mixture

Prepared by the cold-pressing of powdered mixtures, δ-WC1±x – 12.5 % Fe preforms (porosity – 38 %) were subjected to the infiltration with Ni melt (exposure – 15 min) to fabricate dense hard alloys (porosity – 3 %) with γ-(Fe,Ni) metallic solid solution binder; the presence of η2-W3(Ni,Fe)3Cy phase was detected

–

–

δ-WC1±x – γ-(Fe,Ni) cermet coatings (with the presence of η2-(W,Fe,Ni)6Cy phases) were fabricated using plasma transferred arc metallurgic reaction (PTAMR) method; the morphology evolution of δ-WC1±x grain growth included: spherelike → icosahedron → octahedron → truncated octahedron → flat tri-prism (bound by two basal and three prismatic facets)

–

–

Powdered δ-WC1±x – 40 % Fe – 30 % Ni mixtures (size distribution – from 45 μm to 180 μm) were employed as feedstock materials for the deposition of cermet coatings on steel substrates using high-velocity oxy-fuel (HVOF) spraying techniques

–

–

The properties of Fe – Ni binder as functions of alloying content are evaluated

See also section C – Fe – Ni – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

389

Table 2.21 (continued) δ-WC1±x – (Fe – – C – Cr) – Ni

δ-WC1±x – Fe – Ni – Si

–

δ-WC1±x – (Fe – Ar C – Cr – Mn – Mo – Ni – Si) – Ni – Si

–

Pre-sintered δ-WC1±x – 8 % Ni skeleton [10, 2359, (porosity – 10-45 %) was subjected to the 3425] double direction infiltration (exposure – 0.5 h) procedure by high-Cr cast Fe (contents: Cr – 15 %, C – 3.7 %) to fabricate uniform hard alloys

–

Thermodynamic calculations in the system [4667] have been undertaken in order to provide guidelines for the selection of suitable binders for hard alloys

–

Powdered δ-WC1±x (50 μm) – 40 % Si (44 [3704] μm) – 20 % Ni (150 μm) mixtures (mean particle sizes are given in brackets) were employed for the preparation of composite layers (thickness – 0.2-0.3 mm, without any pores, cracks and discontinuities) on stainless steel (C – 0.03 %, Cr – 18 %, Ni – 10 %, Mo – 2.5 %, Mn – 2 %, Si – 0.75 %, Fe – remainder) substrates using laser cladding techniques; the layers (mean dilution percentage – 44 %) were composed of δ-WC1±x, η-Fe5Si3 silicide and γ-(Fe,Ni) metallic solid solution phases

δ-WC1±x – Fe – Ni – Ta

–

–

The properties of Fe – Ni – Ta binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ni – Ti

–

–

The properties of Fe – Ni – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ni – V

–

–

The properties of Fe – Ni – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ni – Zr

δ-WC1±x – Fe – Ru

Vacuum, 850-1475 pure Ar

[2943, 3603, Powdered δ-WC1±x (mean particle size from 0.7 μm to 4 μm) – 5-15 % Fe-based 3611-3612] alloy (~10 μm particulates with ~0.1 μm substructure, additives: ~8 at.% Ni and ~4 at.% Zr) mixtures were employed to fabricate dense cermets using several different manufacturing methods, including uniaxial hot-pressing, hot isostatic pressing, fieldassisted sintering, pressureless sintering and selective laser melting (for the purpose of additive manufacturing), and various holding times of the procedures

–

–

The properties of Fe – Ni – Zr binder as functions of alloying content are evaluated

–

–

Powdered δ-WC1±x – ~30 % Fe – 0.5-5.0 [1877] % Ru mixtures (mean particle size – ~150 μm) were employed to prepare hard overlays (with 0.7-4.1 % alloyed Ru) on steel substrates using plasma transferred arc (PTA) welding techniques; in all the fabricated overlays (metal binder fraction –

(continued)

390

2 Tungsten Carbides

Table 2.21 (continued) ~ 40-50 %, mean grain size – 36-45 μm, binder mean free path – ~ 40-50 μm), the formation of θ-Fe3C phase was detected δ-WC1±x – Fe – Si

–

–

Thermodynamic calculations in the system [4667] have been undertaken in order to provide guidelines for the selection of suitable binders for hard alloys

δ-WC1±x – Fe – Ta

–

–

The properties of Fe – Ta binder as functions of alloying content are evaluated

δ-WC1±x – Fe – Ta – Ti

–

–

The properties of Fe – Ta – Ti binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ta – V

–

–

The properties of Fe – Ta – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ta – Zr

–

–

The properties of Fe – Ta – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ti

–

–

The properties of Fe – Ti binder as functions of alloying content are evaluated

δ-WC1±x – (Fe – C) – Ti

–

–

Powdered δ-WC1±x – Ti mixture were em- [10, 3705, ployed to deposit metal matrix composite 3978] (MMC) layers on unalloyed steel substrates using laser melt injection (LMI) technique; adding 9.6 % Ti, it was possible to avoid the appearance of γ-Fe and η2-W3Fe3Cy, and only α-Fe and (Ti,W)C1–x phases were presented in the deposited layers

–

–

The interfacial interaction δ-WC1±x – Ti weld-cladded layers with ferrite (α-Fe) steels led to the formation of ternary WxFeyCz compound precipitates in the cladded layers

δ-WC1±x – Fe – Ti – V

–

–

The properties of Fe – Ti – V binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – Ti – Zr

–

–

The properties of Fe – Ti – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – Fe – V

–

–

The properties of Fe – V binder as functions of alloying content are evaluated

δ-WC1±x – Fe – V – Zr

–

–

The properties of Fe – V – Zr binder as [2943] functions of alloying content are evaluated

δ-WC1±x – (Fe – C – Cr) – W

–

[2943]

[2943]

[2943]

1700-2000 Stainless steel (50-90 μm; contents: C – [3628] 0.01 %, Cr – 12 %, Fe – remainder), W (63-80 μm) and δ-WC1±x (30-80 μm) powders (size distributions are given in the brackets) were employed for the preparation of 5-layered fully densified functionally graded materials (FGM) by hot-pressing techniques; the formation of η2-W3Fe3Cy phase in the materials was observed

(continued)

2.6 Chemical Properties and Materials Design

391

Table 2.21 (continued) δ-WC1±x – (Fe – Ar C – Mn – Si) – W

δ-WC1±x – Fe – Zr

1150

–

Metallic W (99.9 % purity, wire, diameter [3591] – 2 mm) and grey cast Fe (contents: C – 3.2 %, Si – 1.3 %, Mn – 1.1 %) were used for the preparation of δ-WC1±x reinforced Fe-based metal matrix composite (MMC) with a double-scale structure, including both the reinforcement elements of δ-WC1±x particle and W – δ-WC1±x pillar, where the δ-WC1±x – Fe-based cermet was wrapped around the metal W wire, via conventional heat treatment (exposure – 40 min) processing –

δ-WC1±x – Al4C3 Vacuum 1450 – Fe – Ni

The properties of Fe – Zr binder as functions of alloying content are evaluated

[2943]

(W0.5Al0.5)C0.5 – 10-16 vol.% (Fe – 25-75 [2132] at.%) Ni alloy two-phase highly dense cemented carbides (with carbide mean grain size – 0.8-1.0 μm) were prepared by sintering procedure (exposure – 1 h) using 99.5-99.6 purity Fe and Ni powders The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

δ-WC1±x – B4±xC Ar – (Fe – C – Mn) – Mo – Ni – Zr

δ-WC1±x – CeO2–x – Fe – Ni

δ-WC1±x – Cr3C2–x – Fe

–

Vacuum, 1420 < 1 Pa

–

Pre-alloyed δ-WC1±x – B4±xC – Mo – Ni – [3733] Zr powders were employed to prepare hard composite coatings on steel (C – 0.17-0.22 %, Mn – 1.4 %, Fe – remainder) substrates using Ar arc cladding techniques; the composite coatings were strongly bonded with the substrates and consisted of carbide (Zr,Fe,Mo,W)C1–x (x ≈ 0.7), boride (Fe,Mo,W,Ni)2±xB and borocarbide (Fe,Mo,W,Ni,Zr)(B,C)y particles, evenly distributed in α-Fe-based solid solution phase matrix

–

Powdered δ-WC1±x – Fe conventional feed- [3710] stock materials, modified by nanoparticles of δ-WC1±x, CeO2–x and Ni, were employed for the preparation of hard coatings using subsonic flame spraying techniques Powdered δ-WC1±x – Cr3C2–x – Fe mixtures [3080] (preliminarily ball-milled and cold-pressed, initial mean δ-WC1±x particle size – 6.75 μm; total contents: Fe – 15 %, Cr – 5 %, C – various: at low, medium and high levels) were subjected to liquid-phase sintering (exposure – 1 h) procedures; depending on total C contents, the prepared hard alloys were composed of: δ-WC1±x, η2-(W0.36Fe0.44Cr0.20)6Cy and

(continued)

392

2 Tungsten Carbides

Table 2.21 (continued) (Cr0.50Fe0.46W0.04)7C3.82 carbide and α-(Fe0.92Cr0.07W0.01) bcc metallic solid solution phases – at low total C contents; δ-WC1±x, θ′-(Fe0.80Cr0.18W0.02)3Cy and θ′′-(Fe0.67Cr0.30W0.03)3Cy as two types of metastable cementites, α-(Fe0.97Cr0.02W0.01) bcc metallic solid solution and α-C (graphite) phases – at medium total C contents and δ-WC1±x, θ′-(Fe0.86Cr0.12W0.02)3Cy and θ′′-(Fe0.66Cr0.32W0.02)3Cy as two types of metastable cementites and α-C (graphite) phases (no metallic binder phase) – at high total C contents δ-WC1±x – Cr3C2–x – (Fe – C – Cr – Ni)

–

–

Cr3C2–x – δ-WC1±x interpenetrating network composite coatings (thickness – ~2 mm) on (Fe,Ni,Cr) steel substrates with strong metallurgical bonding were fabricated by a combustion synthesis method; apart to the main network formed from supersaturated solid solutions by eutectic precipitation, the coating also contained FeNi3±x, σ-FeCr1–x and δ-Cr3–xNi phases

δ-WC1±x – Cr3C2–x – (Fe – C – Mn)

–

–

δ-WC1±x + Cr3C2–x reinforced Fe-based al- [3713] loy hard coatings were fabricated on the surface of steel (C – 0.42-0.50 %, Mn – 0.5-0.8 %, Fe – remainder) substrates by laser cladding techniques

δ-WC1±x – Cr3C2–x – (Fe – C – Cr – Mn – Ni – Si) – Mo

–

–

Powdered δ-WC1±x – Cr3C2–x – Mo mixture [3714] was laser cladded on γ-Fe (austenitic) stainless steel (C – 0.03 %, Cr – 17.5-19.5 %, Ni – 8.0-10.5 %, Mn – 2 %, Si – 1 %, Fe – remainder) substrate to prepare hard layers

δ-WC1±x – Cr3C2–x – Fe – Ni

δ-WC1±x – Cr3C2−x – β-Mo2±xC – Fe – Ni δ-WC1±x – FeAl2±x – Fe

Ar or N2, 950-1150 70 kPa

–

[3711]

The diffusion parameters (activation ener- [3298] gy and pre-exponential factor) of Cr in the couple of δ-WC1±x – 85 vol.% binder and δ-WC1±x – 50 vol.% binder – 40 vol.% Cr3C2–x hard alloys (with Fe – 85 % Ni alloyed binder) were determined experimentally to be E = 270±7 kJ mol–1 and D0 = 9.1±2.0 cm2 s–1, respectively

1350-1450 δ-WC1±x – 0.5 % Cr3C2−x – 0.5 % β-Mo2±xC [3333] – 0.5 % Fe – 6.5 % Ni dense hard alloys (metallic binder content – 13 vol.%) were prepared by liquid-phase sintering followed by hot isostatic pressing (HIP) process

Vacuum, 1100-1250 Powdered δ-WC1±x (various in purity) – [4237, 4244] 10 Pa 2.1-4.5 % FeAl2±x – 2.0-4.4 % Fe mixtures were subjected to pulsed electric current sintering (PECS) procedure to fabricate δ-WC1±x – 10-20 vol.% FeAl0.67 dense carbide-intermetallide composites (with vari-

(continued)

2.6 Chemical Properties and Materials Design

393

Table 2.21 (continued) ous contents of O – from 0.1 % to 2.5 %) Vacuum, 1250-1475 Powdered δ-WC1±x – FeAl2±x – Fe mixtures 1 mPa were subjected to liquid-phase sintering (exposure – 1 h) procedure to prepare δ-WC1±x – 25 vol.% FeAln (0.1 ≤ n ≤ 2.0) dense carbide-intermetallide composites (with the presence of small amounts of η2-W3Fe3Cy and Fe3AlC1–x phases) δ-WC1±x – θ-Fe3C – Fe – W

–

δ-WC1±x – Ar, α/β-Mo2±xC – Fe 10 kPa – Ni

930

δ-WC1±x reinforced surface layers were [3673] prepared by a Fe – 1.6 % W alloy solid carburization process; the layers were composed of δ-WC1±x, θ-Fe3C and γ-Febased solid solution (austenite matrix) phases, the forming δ-WC1±x nucleated on γ-Fe (100) planes and grew along c-axis direction under the mutual restriction among the crystal faces of (1120), (1210) and (2110), or in the parallel crystal faces of (1120) and (1120)

1480

Powdered δ-(W0.76÷0.91Mo0.09÷0.24)C1±x (se- [4287] veral kinds with 5-15 % Mo, mean particle sizes – in the range of 0.5-1.5 μm and specific surface areas – in the range of 0.5-2.1 m2 g–1) – 16.5 vol.% metallic binder (Ni – 15% Fe) mixtures were subjected to liquidphase sintering procedure (exposure – 1 h) to fabricate dense hard alloys

α/β/ε/γ-W2±xC – α/β-Mo2±xC – α/γ/δ-Fe

–

–

The behaviour of (Mo,W)2±xC mixed car- [3708-3709] bide phases in Fe-rich matrices was studied

δ-WC1±x – TiB2±x – Fe

–

–

Powdered δ-WC1±x – TiB2±x – Fe mixtures [3717-3718] were subjected to liquid-phase sintering to fabricate dense hard alloys

δ-WC1±x – TiC1–x – Fe

See section TiC1–x – δ-WC1±x – Fe in Table III-2.22

δ-WC1±x – VC1–x – Fe

See section VC1–x – δ-WC1±x – Fe Table III-3.16

δ-WC1±x – (W2±xB, WB1±x) – Fe – Ni – W

–

1100-1460 δ-WC1±x – (Fe,Ni,W) based hard alloys [3719] (with the presence of W borides) were fabricated by reactive liquid-phase sintering

δ-WC1±x – High 1280 α/β-Y2O3–x – Fe purity Ar

Powdered δ-WC1±x (with 0.6 % non-com- [3720] bined C, mean particle size – 1-3 μm) – 60 % Fe (reduced/carbonyl mass ratio = 7/3, size distributions – 20-40 μm / 1-3 μm, respectively) – 0.5-2.0 % Y2O3–x (size distributions – 1-5 μm (microscale) and 30-40 nm (nanoscale)) mixtures (preliminarily ball-milled) were subjected to microwave sintering (exposure – 20 min) procedure to prepare dense materials (porosity

(continued)

394

2 Tungsten Carbides

Table 2.21 (continued) – 3-6 % and 2.5-5.0 % for micro- and nano-Y2O3–x, respectively); after the annealing, quenching and tempering procedures, the sintered materials were composed of metallic solid solution (matrix) α-(Fe0.94C0.06), hard η2-W2.80Fe3.20C1.66 and α-Y2O3–x phases (elemental Y, O, Fe and some impurities were detected on the interface of the hard phase with the matrix) δ-WC1±x – Ga

Vacuum, ~60 3.5 mPa

–

Amorphous WC1.02±0.03 – 34 mol.% Ga na- [753, 755, nowires (length – 10 μm, width – 0.3 μm 4066] and thickness – 0.12 μm) and thin films (length – 200 μm, width – 200 μm and thickness – 0.12 μm) were prepared by ion beam induced deposition (with operating Ga+ ion beam energy – 30 keV) technique –

The properties of W2GaC1–x (x = 0) aluminocarbide (hypothetical) phase were simulated on the basis of first principles calculations

See also Table 2.26 δ-WC1±x – Ge

–

1000

δ-WC1±x – Hf

–

The decarburization of δ-WC1±x due to the [3, 53, 86, interphase interaction with Hf is occurred 1922, 1989, 2062, 3724, ~1500-1700 The maximum solid solubility of Hf in 3730-3731, δ-WC1±x is ~1.4 mol.% 3976] – Addition of 1-2 at.% Hf effectively stabilizes γ-WC1–x cubic phase, so it is possible to preserve the cubic structured monocarbide by quenching after annealing at subsolidus temperatures

No chemical interaction between the com- [1, 1886] ponents was observed See also Table 2.26

– –

–

> 1200

–

The DFT-calculated solubility of Hf in the δ-WC1±x phase of cemented carbides is 5.7×10–6 at.%

See also section δ-WC1±x – Hf – C See also section C – Hf – W in Table I2.14 α/β/ε/γ-W2±xC – Hf

–

1500-2600 The solid solubility of Hf in α/β/ε/γ-W2±xC [3, 53, 3976] phases is low

See also section α/β/ε/γ-W2±xC – C – Hf See also section C – Hf – W in Table I2.14 δ-WC1±x – Hg

See Table 2.26

(continued)

2.6 Chemical Properties and Materials Design

395

Table 2.21 (continued) δ-WC1±x – In

–

No interaction between the δ-WC1±x and metallic In was observed

250

[1]

See also Table 2.26 δ-WC1±x – Ir

Vacuum, 1300-1600 Powdered δ-WC1±x (99.9 % purity, size [53, 83, ~1 mPa distribution of aggregates – 5-10 μm) – 50- 1585, 3435, 75 mol.% Ir (99.96 % purity, size distribu- 3721-3726, tion of aggregates – 10-30 μm, particle size 3955, 4065] ≤ 1 μm) mixtures were subjected to heat treatment (exposure – 1-4 h); the interaction between δ-WC1±x and metallic Ir occurred in two stages: the formation of Irrich disordered δ-Ir3–xW based solid solutions with constant average composition Ir2.77W and then its interaction with a residual component (Ir or δ-WC1±x) that led to the shift of δ-Ir3±xW phase composition, depending on the type of residual component (no ordered intermetallides were formed in this temperature range); in the course of the reaction, α-C (graphite) phase released on the surface of products –

No mutual solubilities between the components

2000

–

–

Ir3WC phase was calculated theoretically

–

–

Some properties of Ir-doped δ-WC1±x were DFT-calculated

–

–

The formation of Ir metal monolayer supported by δ-WC1±x (0001) is not probable, according to the DFT calculations held

See also section δ-WC1±x – C – Ir See also section C – Ir – W in Table I-2.14 α/β/ε/γ-W2±xC – Ir

–

No mutual solubilities between the compo- [53, 3723nents 3726]

2000

See also section α/β/ε/γ-W2±xC – C – Ir See also section C – Ir – W in Table I-2.14 δ-WC1±x – K – Na

–

–

Sintered δ-WC1±x materials are rather resistant to molten K – Na eutectic alloy environment

[13]

δ-WC1±x – α/β/γ-La

–

–

La reacts chemically with δ-WC1±x and forms sesquicarbide La2C3–x phase, the β-La – La2C3–x eutectic easily wets the δ-WC1±x matrix and migrates over the surface of its grains to form thin films

[3727]

(continued)

396

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Ln (rare earth elements: misch metal, La, Ce, Nd, Dy, Pr, Y) – Ni

–

δ-WC1±x – Mg

–

–

δ-WC1±x – 8 % Ni – 0.10-0.13 % rare earth [3728] elements cemented carbides were designed, fabricated by the conventional methods of powder metallurgy; the properties of these materials were studied comprehensively

See also section δ-WC1±x – La2O3–x – Ni 5-15 % δ-WC1±x reinforced Mg metal mat- [579, 1941, rix composites (MMC) were prepared by 3729] mechanical stirring techniques

650

Vacuum, 800 1.3 Pa δ-WC1±x – α/β/γ/δ-Mn

–

Ar

–

–

Sintered WC0.98 materials (content noncombined C – 0.10%) interact noticeably with pure molten Mg (exposure – 2 h) –

The formation of κ-W3MnCy, η2-W3Mn3Cy and ~(Mn0.87÷0.93W0.07÷0.13)2+xC ternary compound phases (in the remelted materials before the prolonged annealing only one ternary phase, (Mn,W)2+xC, was detected)

1270

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Mn (exposure – 5 min)

~1400

The experimentally measured solubility of Mn in the δ-WC1±x phase of cemented carbides is (9±2)×10–4 at.%

–

[10, 53, 83, 209, 579, 1941-1942, 1983, 1989, 1999, 2177, 2502, 2943, 4503]

The effect of substitutional Mn impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

See also section δ-WC1±x – α/β-C – α/β/γ/δ-Mn See also Table 2.26 See also section C – Mn – W in Table I2.14 α/β/ε/γ-W2±xC – α/β/γ/δ-Mn

–

800-1200

In metastable conditions, the maximum [209] solid solubility of Mn in β-W2±xC phase is ~25 mol.% (~10 at.%), it increases noticeably with the temperature growth; the prolonged annealing (3000 h) leads to the decomposition of metastable β-W2±xCbased solid solution and formation of κ-W3MnCy phase

See also section C – Mn – W in Table I2.14 δ-WC1±x – Mn – Ni

–

–

δ-WC1±x – 6.4 % Ni – 1.6 % Mn hard al- [3135-3136] loys were designed, fabricated and studied

(continued)

2.6 Chemical Properties and Materials Design

397

Table 2.21 (continued) δ-WC1±x – CO, H2 α/β/ε/γ-W2±xC – Mn – Rh – W δ-WC1±x – Mn – V

–

δ-WC1±x – Mo

–

–

–

–

–

300

Ordered mesoporous Rh – Mn catalysts on [1681, 1743] WC1±x – W2±xC – W supports were designed, fabricated and studied –

δ-WC1±x – 9-33 mol.% Mn – 9-33 mol.% [2725] V hard alloys were designed and studied; the presence of β-V2±xC (dendrites) and metallic V-based solid solution phases was detected in the binder, the intensive evaporation of Mn was observed during the arcmelting and annealing of alloys

99 % purity) mixtures were employed for the deposition of laser cladded coatings on steel substrates; the coatings consisted of dendritic Wrich γ-Ni-based solid solutions, interdendritic eutectics appearing as Ni-rich areas and blocks of precipitated carbides distributed through the clad with a core-rim structure of Mo between carbide grains

δ-WC1±x – Mo – Vacuum 1280-1300 Powdered δ-WC1±x – Ni – Mo – W mix- [3769-3770] Ni – W tures were subjected to sintering (exposure – 4 h) procedure to prepare Ni-based solid solution alloys (contents: C – 0.46 %, W – 12-22 %, Mo – 5-15 %)

(continued)

400

2 Tungsten Carbides

Table 2.21 (continued) α/β/ε/γ-W2±xC – Mo – W

–

–

Hard coatings (thickness – 0.6-0.9 mm) [3743] based on W-Mo metallic matrix containing 35 % γ-W2±xC phase were fabricated by plasma-spraying techniques

See also section C – Mo – W in Table I2.14 δ-WC1±x – AlN – TiC1–x – δ-TiN1±x – Mo – Ni δ-WC1±x – (CF2CF2)n (CF2CFCF3)m – Mo – Ni

See section TiC1–x – δ-TiN1±x – AlN – δ-WC1±x – Mo – Ni in Table III-2.22 –

–

δ-WC1±x – 10 % Ni cermet powders (size [3896] distribution – 15-45 μm) with the addition of 6-15 % (~ 17-36 vol.%) fluorinated ethylene propylene (co-polymer of hexafluoropropylene and tetrafluoroethylene) (CF2CF2)n(CF2CFCF3)m (FEP Teflon) based powdered compositions (metallic Mo added, encapsulated in ceramic shells, contents: FEP – ~65 vol.%, remainder – Mo and ceramics, size distribution ≤ 53 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of special coatings (thickness – ~0.4 mm, porosity – 0.6-0.8 %) with low coefficients of friction on stainless steel substrates; in the deposited threephase coatings Ni metallic binder formed continuous networks, where δ-WC1±x grains and FEP particles were embedded

δ-WC1±x – Cr3C2–x – α/β-SiC – TiC1–x – δ-TiN1±x – Mo – Ni

See section TiC1–x – δ-TiN1±x – Cr3C2–x – α/β-SiC – δ-WC1±x – Mo – Ni in Table III2.22

δ-WC1±x – Cr3C2–x – TaC1–x – TiC1–x – Mo – Ni

See section TaC1–x – Cr3C2–x – TiC1–x – δ-WC1±x – Mo – Ni in Table II-2.21

δ-WC1±x – Cr3C2–x – TiC1–x – δ-TiN1±x – Mo – Ni

See section TiC1–x – δ-TiN1±x – Cr3C2–x – δ-WC1±x – Mo – Ni in Table III-2.22

δ-WC1±x – Cr3C2–x – TiC1–x – δ-TiN1±x – VC1–x – Mo – Ni

See section TiC1–x – δ-TiN1±x – Cr3C2–x – VC1–x – δ-WC1±x – Mo – Ni in Table III2.22

δ-WC1±x – α/β-Mo2±xC – α/β-SiC – TiC1–x – δ-TiN1±x – Mo – Ni

See section TiC1–x – δ-TiN1±x – α/β-Mo2±xC – α/β-SiC – δ-WC1±x – Mo – Ni in Table III-2.22

(continued)

2.6 Chemical Properties and Materials Design

401

Table 2.21 (continued) δ-WC1±x – γ′-Ni3±xAl – TiC1–x – Mo

See section TiC1–x – γ′-Ni3±xAl – δ-WC1±x – Mo in Table III-2.22

δ-WC1±x – γ′-Ni3±xAl – TiC1–x – δ-TiN1±x – Mo

See section TiC1–x – δ-TiN1±x – γ′-Ni3±xAl – δ-WC1±x – Mo in Table III-2.22

δ-WC1±x – TaC1–x – TiC1–x – Mo – Ni

See section TaC1–x – TiC1–x – δ-WC1±x – Mo – Ni in Table II-2.21

δ-WC1±x – TaC1–x – TiC1–x – δ-TiN1±x – ZrC1–x – Mo – Ni

See section TaC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – ZrC1–x – Mo – Ni in Table II2.21

δ-WC1±x – TiB2±x Vacuum, 1650 – Mo – Ni 2.4-12.0 mPa

Powdered δ-WC0.99 (99 %, 0.6 μm, ~ 1-3 [3367] m2 g–1; contents: non-combined C – 0.06 %, O – 0.08 %, Fe – 0.003 %) – 72 % TiB2±x (99.3 %, 1.5 μm, ~ 3-10 m2 g–1; contents: C – 0.51 %, O – 0.09 %, Fe – 0.08 %) – 4 % Ni (99 %, ~2 μm, ~ 2-5 m2 g–1; contents: C – 0.065 %, O – 0.22 %, Fe – 0.006 %) – 4 % Mo (99 %, ~2 μm, ~ 1-5 m2 g–1; contents: C – 0.01 %, O – 0.25 %, Fe – 0.03 %) mixtures (preliminarily ball-milled; purities, initial mean particle sizes and specific surface areas, respectively, are given in brackets) were subjected to hot-pressing (exposure – 1 h) procedure to produce complex cermet materials (porosity – 0.9±0.2 %) composes mainly of TiB2±x, δ-WC1±x, γ-W2±xC, TiC1–x, β-Ni4+xMo and Ni4B3±x phases

δ-WC1±x – TiB2±x – TiC1–x – Mo – Ni

See section TiC1–x – TiB2±x – δ-WC1±x – Mo – Ni in Table III-2.22

δ-WC1±x – TiB2±x – TiC1–x – δ-TiN1±x – Mo – Ni

See section TiC1–x – δ-TiN1±x – TiB2±x – δ-WC1±x – Mo – Ni in Table III-2.22

δ-WC1±x – TiC1–x – Mo – Ni

See section TiC1–x – δ-WC1±x – Mo – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Mo – Ni

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Mo – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – VC1–x – Mo – Ni

See section TiC1–x – δ-TiN1±x – VC1–x – δ-WC1±x – Mo – Ni in Table III-2.22

(continued)

402

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Nb

–

~1400

Vacuum, 1700 ~ 10-100 mPa –

The experimentally measured solubility of Nb in the δ-WC1±x phase of cemented carbides is 0.61±0.02 at.%; the DFT-calculated value is 0.14 at.% Recommended conditions of diffusion bonding (welding) with pressure – 4.9 MPa and exposure – 10 min

1700

The maximum solid solubility of Nb in δ-WC1±x is 2.2 mol.%

Vacuum 1800-2200 The presence of α/ε-W2+xC, (Nb,W)C1–x and β-Nb2+xC phases was detected in the contact zone between the components Vacuum, 1900 ~0.7 Pa –

[1, 3, 13, 47, 53, 151, 217-218, 579, 585, 626, 1922, 1925, 1943, 1984, 1989, 1995, 2062, 2391-2392, 3724, 3730, 3747, 37563758, 4038]

The initiation of contact reaction between the dense bulk materials (exposure – 5 h)

2100-2300 Powdered δ-WC1.00 (contents: non-combined C – 0.1 %, Fe – 0.38 %) – 25-75 mol.% Nb (contents: Fe – 0.11 %, Si – 0.9 %) mixtures (size distribution – 5-10 μm) were subjected to hot-pressing (exposure – 10-15 min) procedure to produce dense cermets (porosity – 3-6 %); depending on the Nb contents in the initial materials, the following phase compositions were revealed in the products: for 25 mol.% Nb: δ-WC1±x + α/β/ε-W2+xC + β-Nb2+xC, for 50 mol.% Nb: α/β/ε-W2+xC + Nb + β-Nb2+xC (traces of δ-WC1±x), for 75 mol.% Nb: α/β/ε-W2+xC + Nb (traces of β-Nb2+xC)

–

–

The effect of substitutional Nb impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

See also section δ-WC1±x – C – Nb See also Table 2.26 See also section C – Nb – W in Table I2.14 α/β/ε/γ-W2±xC – Nb

–

1700

The maximum solid solubility of Nb in α/ε-W2+xC phase is corresponding to ~(W0.74Nb0.26)2.33C composition

–

2500

The maximum solid solubility of Nb in γ-W2±xC phase is corresponding to ~(W0.67Nb0.33)2.23C composition

–

2700

The maximum solid solubility of Nb in γ-W2±xC phase is corresponding to ~(W0.62Nb0.38)2.23C composition

[47, 53, 217218, 23912392, 3724, 3730, 37563758]

See also section α/β/ε/γ-W2±xC – C – Nb See also section C – Nb – W in Table I2.14

(continued)

2.6 Chemical Properties and Materials Design

403

Table 2.21 (continued) δ-WC1±x – Ni

–

–

–

50

Vacuum 300-550

Ar

500-900

CH4

800

Ar

800-1050

Ultra900 high pure H2

The formation of η1-W6Ni6Cy (or W6Ni5Cy, [1, 3-5, 8or W6Ni3Cy, ?), η2-W4Ni2Cy 10, 13, 43, (or W3÷4Ni2÷3Cy) and κ-W3NiCy 53, 63, 83, (or W16Ni3C6, W9Ni3C4, ?) ternary com- 87, 151, pound phases 579, 626, Ni – 5-33 % δ-WC1±x electrodeposited coa- 679, 792, tings (thickness – 60-150 μm) were prepa- 860, 976, red on brass substrates by direct and pulse 1079, 11401141, 1165, current electroplating processes with 1179, 1391, δ-WC1±x particles (mean size – 0.2 μm) suspended (concentration – 20 g l–1) in a 1397, 1405, Watts’ type Ni (organic-free) electrolyte 1466, 1479, 1508, 1519δ-WC1±x – Ni thin films (thickness – 0.6- 1520, 1596, 1.5 μm) were deposited onto steel, glass 1653, 1684, and δ-WC1±x – Co hard alloy substrates by 1727, 1735, non-reactive d.c. magnetron sputtering 1752, 1755, process using sintered δ-WC1±x – 6 % Ni 1788, 1799, targets; the presence of δ-WC1±x, W2±xC 1808, 1811and γ-WC1–x phases was detected in the 1812, 1815, films 1817, 1855, δ-WC1±x reinforced Ni based metal matrix 1864, 1886, composites (MMC) were prepared by mi- 1892-1893, crowave sintering of electroless Ni plated 1896, 1904δ-WC1±x powders 1906, 1924, Ni-doped δ-WC1±x nanocubes supported on 1928-1929, Ni foam for electrocatalysis purposes were 1931, 19341939, 1941synthesized via hydrothermal treatment (exposure – 6 h) followed by carbonization 1943, 19711972, 1981(exposure – 2 h) procedure 1983, 1985, Metallic Ni can spread on the surface of 1987-1988, δ-WC1±x as a thin layer, the spreading velo1991, 1999city can reach high values and depends on 2000, 2122, the heating rate, while the driving forces 2140, 2177, for it are the favourable energies of 2211, 2359, δ-WC1±x, vapour and metal interfaces 2447-2448, δ-WC1±x – Ni films on the thin foils of Ni 2466, 2473, (99.999 % purity) were produced by che- 2502, 2512, mical vapour deposition (CVD) method 2524, 2528, (exposure – from 3 min to 60 min); the 2562, 2567, films deposited for 3 min consisted mainly 2574, 2597, of η1-W6Ni6Cy and η2-W4Ni2Cy phases to- 2649, 2657, gether with some amounts of γ-W2±xC, for 2688, 2697, 15 min – mainly of γ-W2±xC phase together 2709, 2718, with the small amounts of δ-WC1±x and 2725-2727, η-phases and for 60 min – continuous 2733, 2749, δ-WC1±x films, containing only metallic Ni 2755, 2801, grains (size distribution – 50-200 nm) in 2816, 2836, the bulk as well as on the surface of the 2885, 2903, films (without any traces of other phases), 2919-2920, were prepared on the substrates

(continued)

404

2 Tungsten Carbides

Table 2.21 (continued) H2

900-1500

Powdered δ-WC1.00 (mean particle size – 2952-2953, 2.2 μm, contents: Fe – 0.02 %, Co – 0.01 2976-2977, %) – 7 % Ni (mean particle size – 9.8 μm, 3109, 3116, 3119, 3127, contents: C – 0.10 %, O – 0.15 %, Fe – 0.01 %) mixtures (preliminarily ball-mil- 3133-3136, led and injection-moulded) were subjected 3144-3160, to sintering (exposure – 1 h) to fabricate 3349, 3425dense hard alloys; decarburization initiated 3431, 3435from the surface into the core of sintered 3448, 3459, bodies, which developed a concentration 3498, 3576, gradient of C and facilitated the predomi- 3631, 3712, nant formation of η2-W4Ni2Cy phase near 3734, 3760the surface; at the temperatures higher than 3875, 3880, the eutectic temperature, the liquid phase 3891-3892, 3896, 3910, was inhomogeneous in composition, so upon cooling part of the liquid phase preci- 3988, 4071, 4281, 4287, pitated into nanocrystalline grains of η2-W4Ni2Cy or grains composed of cohe- 4505, 4542, rent δ-WC1±x and η2-W4Ni2Cy phases (with 4563, 4669] the small amounts of γ-W2±xC phase)

Vacuum, < 1000 0.1 mPa

W-C thin films with Ni contents – up to 24 at.% were deposited by sputtering; in the films with high C contents the presence of γ-WC1–x phase was observed

–

1000

The maximum solid solubilities of δ-WC1±x in Ni and Ni in δ-WC1±x are equal to ~7 mol.%

–

1100

The initiation of solid state chemical interaction between the components was observed

Vacuum, ~1200 ~5.3 Pa

–

1200

Powdered δ-WC1±x (99.5 % purity, mean particle size – 0.4 μm) – 10 % Ni (99.8 % purity, size distribution < 2 μm) mixtures (preliminarily ball-milled) were subjected to high-frequency induction-heated sintering (HFIHS) procedure (exposure – 40 s) to fabricate dense two-phase hard alloys (porosity – 0.9 %, mean grain size – ~0.5 μm); the densification temperature of δ-WC1±x powder was reduced remarkably by the addition of Ni Powdered δ-WC1±x (99.95 % purity, mean particle size – 0.5 μm) – 3 % Ni (99.5 % purity, mean particle size – ~10 μm) mixtures were subjected to spark-plasma sintering (exposure – ~4 min) procedure to fabricate hard alloys (porosity – 0.4 %, mean grain size – 0.30 μm); the presence of γ-W2±xC and γ-WC1–x phases in the alloys was detected

(continued)

2.6 Chemical Properties and Materials Design

405

Table 2.21 (continued) –

1200-1425 The maximum solid solubility of δ-WC1±x in Ni is ~4.5 mol.%

–

1250

–

1250-1450 Powdered δ-WC1±x – 10 % Ni mixtures were subjected to spark-plasma sintering (exposure – 5 min) procedure to prepare poreless hard alloys

Ar, 6 MPa

The maximum solid solubility of δ-WC1±x in Ni is ~8 mol.%

1260-1420 Powdered δ-WC1.00 (mean particle size – 2.1 μm, content non-combined C – 0.05 %) – 0-10 % δ-WC1.00 (mean particle size – 60 nm, specific surface area – 5.6 m2 g–1, content non-combined C – 0.1 %) – 8 % Ni (99.7 % purity) mixtures (preliminarily ball-milled and cold-pressed) were subjected to liquid-phase sintering via hot isostatic pressing procedure to fabricate dense two-phase hard alloys (porosity – 0.2-1.2 %, mean grain size – 1-3 μm)

Vacuum 1280-1300 Powdered Ni – 10 % δ-WC1±x mixtures were subjected to sintering (exposure – 4 h) procedure to prepare Ni-based solid solution alloys Vacuum, 1280-1320 Powdered δ-WC1±x (99.5 % purity, gene~5.3 Pa rally round in shape with some agglomeration, mean particle size – 0.4 μm) – 8-12 % Ni (size distribution – 60-80 nm) mixtures (preliminarily ball-milled) were subjected to pulsed current activated sintering (PCAS) procedure (heating time – 50 s) to fabricate dense two-phase hard alloys (porosity – 3.5-4.0 %, mean grain size – 0.340.37 μm) Ar, ~1290 100 MPa

–

1300

Pre-sintered δ-WC0.99 (contents: non-combined C – 0.02 %) – 15.6 % Ni materials were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to produce highly dense two-phase hard alloys The maximum solid solubility of Ni in δ-WC1±x is ~4 mol.%

Vacuum 1300-1600 Highly dense δ-WC1±x – 4-20 % Ni hard alloys (mean δ-WC1±x grain size – from 1.3 μm to 2.2 μm) were prepared by powder sintering (exposure – 1 h) procedure

(continued)

406

2 Tungsten Carbides

Table 2.21 (continued) –

~1340-1440 Eutectic (pseudobinary) δ-WC1±x – Ni; the maximum solid solubility of δ-WC1±x in Ni is ~5 mol.%; the solubilities of W and C in the liquid (Ni,W,C) phase (1.5 at.% and ~9 at.%, respectively) are not proportional to the contents of them in the carbide solid phase (with the solubility of C higher than that of W more than 6 times)

Ar, 1350 150 MPa

Highly dense δ-WC1±x – 10 % Ni hard alloys were prepared by hot isostatic pressing (HIP) procedure (exposure – 40 min)

Vacuum, 1350 15 Pa

Powdered δ-WC1±x (99.5 % purity, mean particle size – 0.2 μm) – 10 % Ni mixtures were subjected to spark-plasma sintering to fabricate two-phase dense hard alloys (porosity < 0.1 %); no interaction between the phase constituents in the sintered materials was revealed

Vacuum 1375-1500 Powdered δ-WC1±x (mean particle size – ~3 μm) – 8 % Ni (spiky needle-like shaped, size distribution – 2-3 μm) mixtures (preliminarily ball-milled and cold-pressed) were subjected to liquid-phase sintering (exposure – 2 h) procedure to prepare dense hard alloys (porosity – 0-3.8 %); the formation of η2-W4Ni2Cy phase occurred at temperatures ≥ 1475 °C Vacuum, 1400 ~10 mPa

The initial melting temperature of bulk pure metallic Ni in contact with δ-WC1±x powder (exposure – 1 h)

Vacuum 1400

δ-WC1±x – 16 % Ni hard alloys were prepared by liquid-phase sintering from the preliminarily ball-milled and cold-pressed mixtures of δ-WC1±x powders (initial size distribution – 40-60 μm)

1420

Powdered δ-WC1±x (size distribution – 1.54.0 μm) – 10 % Ni (mean particle size – 1.5 μm) mixtures were subjected to liquidphase sintering (exposure – 1-2 h) procedure to prepare dense hard alloys (mean δ-WC1±x grain size – 1.2-2.0 μm)

Vacuum 1430

Powdered δ-WC0.99 (contents: non-combined C – 0.02 %, Fe < 0.01 %, Co < 0.015 %, Ni < 0.002 %) – 15.6 % Ni mixtures were subjected to heat treatment (exposure – 45 min) to prepare sintered two-phase materials

–

(continued)

2.6 Chemical Properties and Materials Design

407

Table 2.21 (continued) –

1450

No new phases in the contact zone between the bulk components were detected

Vacuum, 1450 10 Pa

Powdered δ-WC1±x (3.4 μm, 0.14 m2 g–1) – 5 vol.% Ni (0.3 μm, 76 m2 g–1) mixtures (mean particle sizes and specific surface areas are given in brackets) were subjected to hot-pressing (exposure – 7-8 min) procedure to fabricate dense two-phase cermet materials (porosity – 1.7 %, mean δ-WC1±x grain size – 2.0 μm)

Vacuum 1450

Prepared using aqueous solutions of precursors, δ-WC1±x – 6 % Ni composite powders (mean particle size – 2.4 μm, contents: total C – 5.73 %, O – 0.29 %) were subjected to liquid-phase sintering (exposure – 1 h) procedure to fabricate dense hard alloys (porosity – 0.60±0.07 %, mean grain size – ~2.9 μm) with Ni/W atomic ratio ≈ 17 in Ni-based metallic binder

Ar

1460

Sintered δ-WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Ni (exposure – 5 min)

–

1500

The composition of molten metallic binder in δ-WC1±x – 10 % Ni alloy varies in the ranges from (Ni0.85W0.05C0.10) to (Ni0.76W0.18C0.06), depending on the total C contents in the alloy

–

1500-1700 δ-WC1±x reinforced Ni-based metal matrix composites (MMC) coatings on steel substrates were designed and manufactured by the addition of δ-WC1±x to molten Ni (exposure – from 1 to 30 min); a portion of δ-WC1±x reacted resulting in the dissolution into the Ni matrix

Vacuum, 1530 10 Pa

–

1600

Powdered δ-WC1±x (3.4 μm, 0.14 m2 g–1) – 5 vol.% Ni (1.7 μm, 4.0 m2 g–1) mixtures (mean particle sizes and specific surface areas are given in brackets) were subjected to hot-pressing (exposure – 10 min) procedure to fabricate dense two-phase cermet materials (porosity – 4 %, mean δ-WC1±x grain size – 2.9 μm) Addition of W in molten metallic Ni increases the solubility of C in it up to ~2.5 at.% at 8 at.% W

(continued)

408

2 Tungsten Carbides

Table 2.21 (continued) Anvil- 1600-1800 andtoroid chamber, 5-8 GPa

Powdered δ-WC~0.95 (size distribution – 40-60 μm) – 6 % Ni (content O – 0.11 %) mixtures were subjected to high-pressure heat treatment (exposure – 1-10 min) to produce dense hard alloys (porosity ≤ 1-2 %)

Vacuum, 2100-2400 Powdered δ-WC0.99 (mean particle size – ~13 Pa 1-2 μm) – 0.25 % Ni mixtures (preliminarily cold-pressed) were subjected to heat treatment to prepare sintered materials (porosity – 4-10 %) –

Powdered δ-WC1±x (1 μm) – 35-75 % Ni (2-3 μm) mixtures (mean particle sizes are given in brackets) were employed as feedstock materials for the deposition of dense hard coatings (thickness – 0.1-3.0 mm) on steel substrates using d.c. plasmatron thermal spraying process; the decarbonization rate of δ-WC1±x phase was found to be directly proportional to its contents in the initial powdered mixtures (metallic W, γ-W2±xC and γ-WC1–x phases were detected in the coating compositions)

–

–

20 % Ni plated (by electroless deposition) δ-WC1±x powder (size distribution – 10-20 μm) was employed to prepare hard alloy coatings (thickness – 0.25-0.75 mm, porosity – ~6 %) on steel substrates using the detonation techniques

–

–

Powdered δ-WC1±x – 25 vol.% Ni mixtures were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials to deposit hard coatings on steel substrates; during the spraying process, molten Ni dissolved δ-WC1±x, forming the (Ni,W,C) liquid phase, which was solidifying with a rapid cooling rate to form the coatings with 20 vol. % δ-WC1±x in the (Ni,W,C) metallic matrix (grain size distribution – 10-100 nm), also containing the small amounts of metallic W and γ-W2±xC phase inclusions

–

–

Ni – δ-WC1±x hard coatings with good metallurgical bonding were deposited on Ti alloy substrates using flame spray-welding techniques

Ar

(continued)

2.6 Chemical Properties and Materials Design

409

Table 2.21 (continued) –

–

The surface of sintered δ-WC1±x – 13 % Ni hard alloy was irradiated by high-intensity pulsed electron beam (HIPEB) at energy density of 3-34 J cm–2; the irradiation induced surface remelting and selective ablation of Ni and resulted in phase transition from δ-WC1±x to γ-WC1–x and γ-W2±xC, formation of some defects, such as microcracks and blow holes, and microstructural changes

–

–

Sintered δ-WC1±x – 13 % Ni hard alloys (mean δ-WC1±x grain size – 2 μm) were subjected to high-intensity pulsed ion beam (HIPIB) irradiation procedure; phase transformation from δ-WC1±x to γ-WC1–x, accompanied by C loss and selective ablation of Ni, was observed on the surface of materials

–

–

Composite Ni – δ-WC1±x nanoparticles for electrocatalysis purposes were synthesized through a simple heat treatment for the mixture of Ni precursor and preliminarily prepared δ-WC1±x nanoparticles (mean particles size – 2-6 nm, specific surface area – ~170 m2 g–1) with various atomic ratios of Ni/WC in them

–

–

The effect of substitutional Ni impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations Data available on the system in literature are controversial, some data reported by the various authors differ markedly

See also section δ-WC1±x – C – Ni See also Table 2.26 See also section C – Ni – W in Table I2.14 δ-WC1±x – α/β/ε/γ-W2±xC – Ni

–

Ar

85

Dense and uniform core-shell structured δ-WC1±x – γ-W2±xC cast powders were coated by 12 % nanocrystalline Ni via electroless plating (dwell time – 1 h) process –

[10, 1466, 1752, 2473, 3576, 38683875]

8.3 % Ni-coated δ-WC1±x – γ-W2±xC fused eutectic powders (spherical in shape, laminar in microstructure, mean particle size – ~72 μm) were subjected to selective laser melting (SLM) procedure; the major microstructural features, including the γ-W2±xC dendrite band (in the as-solidified molten pools and formed large-scale layered structures), η2-W3÷4Ni2÷3Cy phase (transformed

(continued)

410

2 Tungsten Carbides

Table 2.21 (continued) from γ-W2±xC), non-melted δ-WC1±x – γ-W2±xC powder grains (with prismatic δ-WC1±x formed in the molten pools along the rim of grains and nanosized γ-W2±xC network around the grains) and γ-(Ni,W,C) metallic solid solutions (matrix), could be characterized within the prepared materials

See also section δ-WC1±x – α/β/ε/γ-W2±xC – C – Ni See also section C – Ni – W in Table I2.14 α/β/ε/γ-W2±xC – CH4/H2, 630-750 Ni C2H6/H2

Ni – β-W2±xC catalysts were prepared by carbonization process

–

1300

The maximum solid solubility of Ni in α/ε-W2+xC is ~10 mol.%

–

1500

α/ε-W2+xC is in equilibrium with metallic W, η2-W4Ni2Cy and δ-WC1±x phases

–

–

Powdered Ni (99.99 % purity) – 5-20 % γ-W2±xC mixtures (size distribution – 2040 nm) were employed for the deposition of hard coatings on steel substrates using W – inert gas (TIG) welding techniques; no decomposition of γ-W2±xC phase after the technological procedure in the molten pool was observed, with the increase of amounts of γ-W2±xC the dendritic structure of prepared nanocomposite coatings was finer, the presence of γ-W2±xC in the deposited coatings led to change the preferred orientation of the Ni metallic matrix phase from (111) to (200)

[10, 1365, 1466, 1538, 1892-1893, 1904-1906, 3000, 37923793, 3860, 3872, 38763877, 3988]

See also section α/β/ε/γ-W2±xC – C – Ni See also section C – Ni – W in Table I2.14 δ-WC1±x – Ni – P

See section δ-WC1±x – NiPx (Ni3P, Ni2–xP) – Ni

δ-WC1±x – α/β/ε/γ-W2±xC – Ni – P

See section δ-WC1±x – α/β/ε/γ-W2±xC – Ni3P – Ni

δ-WC1±x – Ni – Pb – Pt

–

Pt – Ni – Pb catalysts on δ-WC1±x support [1455] were developed and fabricated

δ-WC1±x – Ni – Pd

–

–

δ-WC1±x added Pd – Ni alloys were desig- [1509] ned and prepared for electrocatalysis aims

δ-WC1±x – Ni – Pt

Ultrahigh vacuum, ~100 nPa

–

Pt and Ni were deposited on the δ-WC1±x [1170, 1491, (0001) surface (preliminarily carburized 1717, 3435] metallic W surface) by physical vapour deposition (PVD) method to prepare Pt – Ni anchored δ-WC1±x substrates for catalysis aims (continued)

900

2.6 Chemical Properties and Materials Design

411

Table 2.21 (continued)

δ-WC1±x – Ni – Re δ-WC1±x – Ni – Si

–

–

Pt – Ni alloy shell coated δ-WC1±x nanorods as catalyst support were developed and fabricated

–

–

δ-WC1±x – 4.8 % Ni – 3.2 % Re hard alloys [3135-3136] were designed, fabricated and studied

Vacuum 1300-1500 Highly dense δ-WC1±x – 10 % Ni hard al- [2235, 3764, loys, containing of 2-8 % Si in the Ni bin- 3886] der, were prepared by powder sintering (exposure – 1 h) procedure

Similar compositions were prepared by hot isostatic pressing (HIP) procedure (exposure – 40 min) from the same powders

Ar, 1350 150 MPa δ-WC1±x – Ni – Si – Ti

–

–

Powdered δ-WC1±x – Ni0.78Si0.13Ti0.09 alloy [3887] mixtures were employed as feedstocks to deposit hard coatings on Ni-matrix superalloy substrates using laser cladding techniques; the prepared coatings were mainly composed of δ-WC1±x – (Ti,W)C1–x reinforced β-(Ni,Ti)3±xSi matrix, containing also γ-(Ni,Si) metallic solid solution phase

δ-WC1±x – Ni – Sn

Vacuum 1425

δ-WC1±x – Ni – Sn hard alloys were desig- [2122] ned and manufactured

δ-WC1±x – Ni – Ti

Vacuum 1400-1450 δ-WC1±x – 8-22 % Ni – 0.04-0.4 % Ti hard [2135, 2597] alloys were prepared by liquid phase sintering (exposure – 1 h) procedure; the dissolution of small amounts of Ti in the liquid binder phase resulted in a marked change of the shape of δ-WC1±x grains in the alloys

See also section δ-WC1±x – TiNi1±x in Table 2.22 δ-WC1±x – Ni – V

δ-WC1±x – Ni – W

Vacuum 1000

–

75

δ-WC1±x – 57-63 mol.% Ni – 3-9 mol.% V [2725, 3017] alloys, decarbonized due to Ar-arc-melting (main phase constituents – γ-W2±xC, Ni3±xV and Ni2–xV), were heat-treated, metallic (Ni,V,W) solid solution and traces of ternary phases appeared additionally to the mentioned above after the annealing (exposure – 168 h) procedure in the materials with δ-WC1±x – 48-52 mol.% (Ni,V,W) – 6-14 mol.% (V,W)C1–x equilibrium composition (according to the thermodynamic calculations) δ-WC1±x – Ni – W coatings on Cu substra- [1830, 3452, tes were prepared by Ni – W co-electrode- 3769-3770, position from an aqueous sulphate bath 3888-3889, using various suspended δ-WC1±x powders 3940] (mean particle size – from 0.5 μm to 3 μm)

(continued)

412

2 Tungsten Carbides

Table 2.21 (continued) –

Ar

900-1000

Dense nanocrystalline cermets (porosity – from 3 % to 11 %) based on γ-(Ni,W) solid solution matrix (mean crystallite size – from 55±2 nm to 112±4 nm; content W – 21-23 %) with 14-18 % dispersed δ-WC1±x phase (mean grain size – from 25±1 nm to 79±3 nm) were prepared via mechanical alloying (MA) followed by spark-plasma sintering (SPS) procedure (exposure – from 3 min to 5 min)

1300

Powdered Ni (99.9 %, 3-7 μm) – 30 % W (99.9 %, 14 μm) – 2.5-5.0 % δ-WC1±x (99.5 %, 3.3 μm) mixtures (purities and initial mean particle sizes of components are given in brackets) were subjected to mechanical alloying (MA) followed by cold-pressing and finally sintering procedure (exposure – 1 h) to fabricate dense composite materials (porosity – 4-9 %) with formed “pomegranate-like” regions between the γ-(Ni,W) solid solution phase (matrix) and δ-WC1±x particles

–

–

δ-WC1±x compacts (porosity – ~48 %) were infiltrated under high-gravity conditions by Ni – 10-19 at.% W metallic melt (in situ synthesized from thermite reactions) to prepare dense δ-WC1±x – Ni-based metallic binder cermets with the small amounts of γ-W2±xC, η2-W4Ni2Cy and metallic W phases

See also section C – Ni – W in Table I2.14 δ-WC1±x – Ni – Zn

Vacuum 1000

δ-WC1±x – 57-60 mol.% Ni – 7-10 mol.% [2725] Zn alloys, decarbonized due to Ar-arc-melting (main phase constituents – γ-W2±xC and (Ni,Zn,W) metallic solid solution), were heat-treated with no changes in the phase composition after the annealing (exposure – 168 h) procedure in the materials with δ-WC1±x – 53-54 mol.% (Ni,Zn,W) – 1 mol.% α-C (graphite) equilibrium composition (according to the thermodynamic calculations)

δ-WC1±x – Al4C3 Vacuum 1300-1400 Nanostructured (W0.6Al0.4)C0.5 – 10-16 % [2139, 3893] Ni two-phase cermets were prepared via – Ni mechanical alloying (MA) followed by hot-pressing (exposure – 10-20 min) procedure

(continued)

2.6 Chemical Properties and Materials Design

413

Table 2.21 (continued) The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

See also section δ-WC1±x – Al – Ni δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Ni

–

δ-WC1±x (99 %, 55 nm) and α-Al2O3 [3890-3892] (99.95 %, 20 nm) powders (purities and mean particle sizes are given in brackets), suspended in aqueous electrolyte solutions (standard Watt’s bath formulation), were employed for the preparation of co-electrodeposited (anode – 99.9 % purity Ni, direct current density – 2 A dm–2, time – 1 h) composite coatings (produced thickness – (40÷160)±(5÷30) μm) on stainless steel substrates; the coatings were containing up to 12.5±1.5 vol.% δ-WC1±x and 9.5±1.0 % vol.% α-Al2O3 nanoparticles

50

δ-WC1±x – Al2O3 – CaF2 – TiC1–x – Ni – P

See section TiC1–x – Al2O3 – CaF2 – δ-WC1±x – Ni – P in Table III-2.22

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – Cr3C2–x – Ni

–

–

δ-WC1±x – Ni hard alloys, modified by [3890] Cr3C2–x particles and Al2O3 whiskers, were designed and prepared using sintering procedure; Al2O3 phase underwent a noticeable mass lost during the sintering that resulted in the formation of porous structure in the alloys

δ-WC1±x – Al2O3 – TiC1–x – Ni

See section TiC1–x – Al2O3 – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – B4±xC Vacuum, 1150 – Ni – Si ~1.3 Pa

Powdered δ-WC1±x (0.8 μm) – 28.5 % Ni [3894-3895] (10 μm) – 0.6-1.5 % Si (10 μm) – 0.3-1.2 % B4±xC (1 μm) mixtures (preliminarily ball-milled; mean particle sizes are given in brackets) were subjected to liquid-phase sintering procedure to prepare dense δ-WC1±x – γ-(Ni,Si,B,W,C) metallic solid solution (binder) hard alloys

See also section δ-WC1±x – B – Ni – Si δ-WC1±x – BN – VC1–x – Ni

See section VC1–x – BN – δ-WC1±x – Ni in Table III-3.16

α/β/ε/γ-W2±xC – α-C3N4 – Ni

δ-WC1±x – CeO2–x – Ni

–

N2

–

–195

Supported 5 % Ni promoted 25 % W2±xC [1655] catalyst on polymeric mesoporous α-C3N4 (graphite-like) was fabricated by incipient wetness impregnation (IWI) method δ-WC1±x – 9 % Ni two-phase hard alloys [3899-3906] (with the addition of 0.045-0.180 % CeO2–x) were subjected to cryogenic treatment (CT) procedure (exposure – 24 h) to study its influences on the alloy properties

(continued)

414

2 Tungsten Carbides

Table 2.21 (continued) Ar, 5 MPa

δ-WC1±x – 9 % Ni two-phase hard alloys (with the addition of 0.045-0.180 % CeO2–x) were produced using hot isostatic pressing (HIP) techniques (dwell time – 1.5 h)

1450

Vacuum

–

Ni – δ-WC1±x composite coatings on steel substrates with the addition of CeO2–x (up to 0.75 %) were produced using fusion sintering techniques

–

–

Powdered Ni – 20 % δ-WC1±x – 0.3-1.5 % CeO2–x mixtures (mean particle size – 40 μm) were employed for the preparation of laser-cladded coatings on stainless steel substrates; adding CeO2–x hastened the spheroidization of the eutectic structures of coatings, accelerated the dissolution of δ-WC1±x grains and made their shapes smoother

–

–

δ-WC1±x – CeO2–x – Ni coatings on steel substrate were deposited via vacuum melting techniques; the presence of CeO2–x in the coatings promoted the diffusion processes between Ni based metallic binder and δ-WC1±x grains

δ-WC1±x – CeO2–x – Cr3C2–x – Ni

–

–

CeO2–x modified δ-WC1±x – 9 % Ni – 0.4 [3897] % Cr3C2–x hard alloys were prepared by liquid-phase sintering process; depending on total contents of C in the alloys, the behaviour of CeO2–x during the sintering was different

δ-WC1±x – CeO2–x – MgO – Ni

–

–

CeO2–x + MgO modified δ-WC1±x – Ni cer- [3898] met coatings were deposited on stainless steel substrates using vacuum melting techniques

δ-WC1±x – Cr3C2–x – Ni

Powdered δ-WC1±x – 20 % Cr3C2–x – 7 % [10, 1819, Ni mixtures (size distribution – 15-45 μm) 2414, 2528, were subjected to spark-plasma sintering 2718, 2901, (SPS) procedure (exposure – 5 min) to pro- 3033, 3043, duced dense three-phase hard alloys 3080, 3261, 3298, 3447, Vacuum 1300-1400 δ-WC1±x – 1.5-42 % Cr3C2–x – 20 % Ni hard alloys were prepared by conventional 3455-3456, routes of powder metallurgy; the addition 3712, 3764, 3771-3772, of up to 3.5 % Cr3C2–x did not make any changes to the structure and/or phase com- 3775, 3890, position of the alloys, the introduction of 3897, 39077.5 % had a marked effect on the structure 3929, 3935as the number of δ-WC1±x grains with re- 3939] Vacuum, 1200 100 Pa

gular facets decreased and there was refinement of them, new carbide (Cr,W,Ni)3C2–x phases only developed

(continued)

2.6 Chemical Properties and Materials Design

415

Table 2.21 (continued) clearly with contents of ≥ 15 %, when the crystals of regular six-sided or lamellar shapes and in sizes markedly exceeding the original sizes of the Cr3C2–x grains appeared 1440

δ-WC1±x – 1-8 % Cr3C2–x – 15 % Ni hard alloys were produced using hot isostatic pressing (HIP) procedure (exposure – 1 h); depending on Cr3C2–x contents, two-phase (< 2 % Cr3C2–x) or three-phase (> 2 % Cr3C2–x) alloys have been formed

1450

Powdered δ-WC0.98 (mean particle size – 1.6 μm, contents: non-combined C – 0.03 %, O – 0.09 %, Fe – 0.02 %) – 9 % Ni (99.7 % purity, mean particle size – 2.4 μm, contents: C – 0.055 %, O – 0.12 %, Fe – 0.005 %) – 2.3 % Cr3C2.00 (mean particle size – 2.0 μm, contents: O – 0.01 %, Fe – 0.09 %) mixtures (preliminarily ball-milled) were subjected to hot isostatic pressing (exposure – 1.5 h) procedure to prepare dense two-phase hard alloys composed of δ-WC1±x and metallic Ni based binder phases

Vacuum, 1450 < 1 Pa

Powdered δ-WC1±x – Cr3C2–x – Ni mixtures (preliminarily ball-milled and coldpressed, initial mean δ-WC1±x particle size – 6.75 μm; total contents: Ni – 15 %, Cr – 5 %, C – various: from low to high level) were subjected to liquid-phase sintering (exposure – 1 h) procedures; with gradual increasing total C contents in the prepared hard alloys, the following order of changes in phase compositions was observed: δ-WC1±x + κ′-(W0.62Ni0.27Cr0.11)4Cy + κ′′-(W0.45Ni0.27Cr0.28)4Cy (two types of κ-carbides) + γ-(Ni0.80Cr0.14W0.06) fcc metallic solid solution (binder) → δ-WC1±x + γ-(Ni0.81Cr0.16W0.03) fcc metallic solid solution (binder) → δ-WC1±x + (Cr,W,Ni)3C2–x + γ-(Ni0.90Cr0.09W0.01) fcc metallic solid solution (binder) → δ-WC1±x + (Cr0.93W0.035Ni0.035)3C2–x + α-C (graphite) + γ-(Ni0.87Cr0.115W0.015) fcc metallic solid solution (binder)

H2

Powdered δ-WC0.99 (mean particle size – 3.2 μm, content non-combined C – 0.10 %) – 1-6 % (2-12 vol.%) Cr3C2–x (99.5 % purity, mean particle size – ~7 μm) – 10-11 % (16.5 vol.%) Ni (mean particle size – ~4 μm, contents: C – 0.06 %, O – 0.05 %, N –

–

Ar, 5 MPa

1470

(continued)

416

2 Tungsten Carbides

Table 2.21 (continued) 0.003 %, Fe – 0.005 %) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering (exposure – 1 h) to produce dense hard alloys (porosity 2-3 %, mean linear intercept grain size – ~1 μm) Powdered δ-WC1±x – 0.2-2.0 % Cr3C2–x – 10 % Ni mixtures (with various total C contents) were subjected to liquid-phase sintering (exposure – 1 h) procedures to prepare two- and three-phase (η-phase or α-C (graphite) additionally to δ-WC1±x and metallic Ni (binder) phases) hard alloys

Vacuum, 1480 < 1 Pa

Vacuum 1500-1550 With the addition of Cr3C2–x to the initial powdered mixtures, highly dense δ-WC1±x – 10 % Ni hard alloys, containing of 5-10 % Cr in the Ni binder, were prepared by powder sintering (exposure – 1 h) procedure –

–

δ-WC1±x – 2 % Cr3C2–x – 15 % Ni hard alloys were fabricated by powder metallurgy conventional routes

–

–

Powdered δ-WC1±x (2 μm) – 1-16 % Cr3C2–x (1.5 μm) – 15 % Ni (1.5 μm) mixtures (preliminarily ball-milled, initial mean particle sizes of components are given in brackets; with various total C contents – from 5.6 % to 7.5 %) were subjected to common liquid-phase sintering procedure to fabricate dense hard alloys; the solid solubility of Cr3C2–x into γ-Ni-based metallic solid solution phase (binder) was evaluated to be ~2 % and ~4 % in high-C and low-C alloys, respectively, so in the range of the excess Cr3C2–x content more than the solubility limit: δ-WC1±x + γ-(Ni,Cr,W) + (Cr,W,Ni)2±xC + η-(W,Ni,Cr)6Cy → δ-WC1±x + γ-(Ni,Cr,W) + (Cr,W,Ni)2±xC → δ-WC1±x + γ-(Ni,Cr,W) + (Cr,W,Ni)2±xC + (Cr,W,Ni)3C2–x → δ-WC1±x + γ-(Ni,Cr,W) + (Cr,W,Ni)3C2–x → δ-WC1±x + γ-(Ni,Cr,W) + (Cr,W,Ni)3C2–x + α-C (graphite) – phase fields appeared with gradual increasing total C content in the sintered alloys

–

–

δ-WC1±x – 20 % Cr3C2–x – 7 % Ni feedstock powder composition was used for the preparation of hard coatings by detonation gun spraying (DGS) method or also by metallurgical processes; heat treatment of this composition leads to the conversion of Cr3C2–x to Cr7C3±x due to the interaction of

(continued)

2.6 Chemical Properties and Materials Design

417

Table 2.21 (continued) Cr3C2–x with Ni, which is followed by the formation of Cr-rich semicarbide phase: δ-WC1±x + Cr7C3±x = 4(W0.125Cr0.875)2±xC

Ar

–

–

Powdered δ-WC1±x (0.55 μm) – 70-80 % Cr3C2–x (1.95 μm) – 10-20 % Ni (0.85 μm) mixtures (agglomerated and sintered, initial mean particle sizes of components are given in brackets) were employed as feedstock materials to deposit hard coatings (thickness – 0.4 mm, porosity – 1.2-1.8 %) on steel substrates using high-velocity oxyfuel (HVOF) spraying techniques; (Cr0.94W0.06)3C2–x and Ni-based metallic solid solution (binder) were the major phases in the structure of prepared coatings (the additional heat-treatment of the coatings led to the increase of W contents in the Cr carbide phase – up to the composition of (Cr0.92÷0.93W0.07÷0.08)3C2–x)

–

–

Powdered δ-WC1±x – 20 % Cr3C2–x – 7 % Ni mixtures (size distribution – 10-53 μm, mean particle size – 22 μm; contents: total C – 7.04 %, Fe – 0.1 %) were employed as feedstock materials to deposit hard coatings (thickness – 150-300 μm, volume fraction of W and Cr carbide particles – ~40 %, mean particle of carbides – 2.8 μm, mean free path – ~4.0 μm) on steel substrates using high-velocity oxy-fuel (HVOF) flame spraying techniques; the prepared coatings were composed of δ-WC1±x (major), γ-(W,Cr)2±xC and Cr3C2–x carbide and γ-(Ni,Cr,W) metallic solid solution phases

–

Powdered δ-WC1±x – Cr3C2–x – Ni based mixtures (agglomerated and sintered, porous, spheroid in shape, size distribution – 10-60 μm; contents: total C – 5 %, W – 68 %, Cr – 21 %, Ni – 6 %) were employed as feedstock materials to deposit hard coatings (thickness – ~0.3 mm, porosity – 1-3 %) on Ni-Fe-Cr alloy substrates using high-velocity oxy-fuel (HVOF) spraying techniques; the prepared coatings were composed of δ-WC1±x (major), γ-W2±xC and Cr3C2–x carbide, Ni intermetallide and γ-(Ni,Cr,W) metallic solid solution phases, the same coatings subjected to laser heating (LH) – δ-WC1±x (major) and Cr3C2–x carbide and γ-(Ni,Cr,W) metallic solid solution phases (the relative content of metallic phase after LH procedures de-

(continued)

418

2 Tungsten Carbides

Table 2.21 (continued) creased)

See also section δ-WC1±x – Cr – Ni δ-WC1±x – α/β/ε/γ-W2±xC – Cr3C2–x – Cr7C3±x – Ni

–

–

[2414, 3033, Various types of δ-WC1±x – 20-21 % Cr3C2–x – 6-7 % Ni powders (size distribu- 3935-3939] tion – 15-45 μm; with the additional presence of small amounts of γ-(W,Cr)2±xC, Cr7C3±x and γ-WC1–x phases) were employed as feedstock materials to deposit hard coatings (thickness – ~300 μm) on steel substrates using high-velocity oxy-fuel (HVOF) spraying techniques; depending on spray parameters and characteristics, the prepared coatings were composed of δ-WC1±x (major), γ-(W,Cr)2±xC (with various Cr/W ratios) and γ-WC1–x carbide and W metal phases

–

–

δ-WC1±x – 20 % Cr3C2–x – 7 % Ni powders (agglomerated and sintered, size distribution – ~ 10-45 μm, mean carbide grain size – 0.8 μm; with the additional presence of small amounts of γ-(W,Cr)2±xC and Cr7C3±x phases) were employed as feedstock materials to deposit hard coatings (thickness – ~250 μm) on stainless steel substrates using atmospheric plasma spraying (APS) techniques with different spraying powers; depending on spray parameters, the prepared coatings were composed of γ-(W,Cr)2+xC based solid solution (major), δ-WC1±x (major) and Cr3C2–x carbide and Ni-W (amorphous) and W metallic phases

–

–

δ-WC1±x – γ-(W,Cr)2±xC – Ni powders (size distribution – 10-20 μm, mean particle size – 14 μm; contents: total C – 5.8 %, Cr – 19.5 %, Ni – 6.5 %, W – remainder; with the additional presence of small amounts of Cr carbide phases) were employed as feedstock materials to deposit hard coatings (thickness – 320±20 μm, porosity < 1 %) on steel substrates using detonation spray techniques; the coatings were composed of γ-(W,Cr)2±xC (major), δ-WC1±x and Cr3C2–x carbide and W metal phases

See also section δ-WC1±x – Cr – Ni δ-WC1±x – Cr3C2–x – β-Mo2±xC – TiC1–x – Ni

See section TiC1–x – Cr3C2–x – β-Mo2±xC – δ-WC1±x – Ni in Table III-2.22

(continued)

2.6 Chemical Properties and Materials Design

419

Table 2.21 (continued) δ-WC1±x – Cr3C2–x – TiC1–x – Ni

See section TiC1–x – Cr3C2–x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – Cr3C2–x – TiC1–x – δ-TiN1±x – Ni

See section TiC1–x – δ-TiN1±x – Cr3C2–x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – Cr3C2–x – α/β/γ/δ-ZrO2–x – Ni

–

–

δ-WC1±x – HfC1–x – Ni

δ-WC1±x – Ni hard alloys, modified by [3890, 3927] Cr3C2–x and ZrO2–x nanoparticles, were designed and prepared using sintering procedure

See section HfC1–x – δ-WC1±x – Ni in Table II-3.19 See also section C – Hf – Ni – W in Table I-2.14

δ-WC1±x – HfC1–x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Ni

See section TaC1–x – HfC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-2.21

δ-WC1±x – HfC1–x – TiC1–x – δ-TiN1±x – Ni

See section HfC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-3.19

δ-WC1±x – La2O3–x – Ni

–

–

La2O3–x modified Ni – δ-WC1±x powder flame sprayed coatings were subjected to re-melting procedure using W – inert gas (TIG) welding techniques to improve the properties of prepared coatings

–

–

The addition of 0.5-2.0 % La2O3–x (> 99 % purity) to δ-WC1±x – 40 % Ni-based alloy powdered mixtures, employed as feedstock materials for the preparation of coatings with various thicknesses on steel substrates using laser cladding assisted by an induction heating (LCAIH), led to the formation of α/β-LaC2±x, La2Ni5C3 and La2Ni22C3 carbide and La2NiO2 oxide phases in the prepared coatings

[10, 1855, 3832-3834, 3930]

See also section δ-WC1±x – Ln (rare earth elements: misch metal, La, Ce, Nd, Dy, Pr, Y) – Ni δ-WC1±x – MgO Vacuum – Ni

–

Ni – δ-WC1±x – MgO composite coatings [3931] were produced via fusion sintering process

(continued)

420

2 Tungsten Carbides

Table 2.21 (continued) Powdered δ-WC1±x (2.5 μm) – 8 % Ni (5 [10, 3764, μm) – 2 % β-Mo2±xC (99 % purity; 3 μm) 3771, 3932, mixtures (preliminarily ball-milled, cold- 4287] pressed, pre-sintered and machined; initial mean particle sizes of components are given in brackets) were subjected to liquidphase sintering (dwell time – ~40 min) to fabricate highly dense, core-rim microstructured δ-WC1±x – Ni (with the complete dissolution of β-Mo2±xC and presence of η-phase) hard alloys (mean δ-WC1±x grain size – 3.0 μm)

δ-WC1±x – Vacuum, 1450 α/β-Mo2±xC – Ni 2-6 Pa

Ar, 10 kPa

Powdered δ-(W0.76÷0.91Mo0.09÷0.24)C1±x (several kinds with 5-15 % Mo, mean particle sizes – in the range of 0.5-1.5 μm and specific surface areas – in the range of 0.5-2.1 m2 g–1) – 16.5 vol.% Ni mixtures were subjected to liquid-phase sintering procedure (exposure – 1 h) to fabricate dense hard alloys

1480

Vacuum 1500-1550 With the addition of β-Mo2±xC to the initial powdered mixtures, highly dense δ-WC1±x – 10 % Ni hard alloys, containing of 5-10 % Mo in the Ni binder, were prepared by powder liquid-phase sintering (expo-sure – 1 h) procedure δ-WC1±x – β-Mo2±xC – TaC1–x – TiC1–x – δ-TiN1±x – Ni

See section TaC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-2.21

δ-WC1±x – β-Mo2±xC – TiC1–x – Ni

See section TiC1–x – β-Mo2±xC – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – Ni

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – δ-WC1±x – Ni

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – VC1–x – Ni

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – VC1–x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – MoS2+x – Ni

–

–

δ-WC1±x – 10 % Ni cermet powders (size [3896] distribution – 15-45 μm) with the addition of 1.2-3.5 % (3.5-10.0 vol.%) powdered MoS2+x (size distribution – 45-105 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of special coatings (thickness – ~0.4 mm, porosity – 0.7-1.6 %) with low coefficients of friction on stainless

(continued)

2.6 Chemical Properties and Materials Design

421

Table 2.21 (continued) steel substrates; in the deposited threephase coatings Ni metallic binder formed continuous networks, where δ-WC1±x and MoS2+x particles were embedded δ-WC1±x – NbC1–x – TiC1–x – δ-TiN1±x – Ni

See section NbC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-4.18

δ-WC1±x – NiAl1±x – NiB – Ni

–

δ-WC1±x – NiPx (Ni3P, Ni2–xP) – Ni

–

75-90

5 % δ-WC1±x particle (mean size – 80 nm) [10, 1752, reinforced Ni-P alloy composite coatings 3142, 3804, were prepared on Cu sheet substrates via 3878-3883] electroless plating (time – 2 h) procedure in a sulphate aqueous solution bath

–

400

δ-WC1±x (mean particle size in the initial powder – 1 μm) – Ni3P – Ni electroless deposited coatings (carbide contents – up to 53-55 vol.%), prepared in a sulphate aqueous solution bath on steel substrates, were subjected to heat treatment to crystallize amorphous Ni-P matrix

400-600

Ni – NiPx – 9-32 % δ-WC1±x electrodeposited coatings (thickness – 40 μm, content P – 13.0-13.7 %), prepared on brass substrates by direct and pulse current electroplating processes with δ-WC1±x particles (mean size – 0.2 μm) suspended (concentration – 20 g l–1) in a modified Watts’ type bath (with 0.1 M NaH2PO2), were subjected to gradual heat treatment to crystallize amorphous NiPx matrix to the Ni, Ni3P and Ni2–xP phases; the presence of δ-WC1±x particles in the matrix retarded duffusion process of P and resulted in the formation of finer phosphide dispersions in the heattreated coatings

880-1450

δ-WC1±x – 16 % Ni-based alloy (with various P contents and preparation methods) cermets were fabricated by spark-plasma sintering (SPS) procedures; the sintered poreless materials consisted of δ-WC1±x, phosphide Ni3P and metallic Ni phases

Air

–

–

–

–

Powdered δ-WC1±x – NiAl1±x – NiB – Ni [4307] mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering procedure to fabricate B-doped δ-WC1±x – γ′-Ni3±xAl composite rods

Hardfacing nanostructured δ-WC1±x – NiPx – Ni coatings (poreless, thickness – ~80 μm, carbide fraction – 8-13 vol.%) were deposited on Ni-based alloy substrates by electroplating process

(continued)

422

2 Tungsten Carbides

Table 2.21 (continued) –

δ-WC1±x – α/β/ε/γ-W2±xC – Ni3P – Ni

–

δ-WC1±x – NiPx (Ni3P, Ni2–xP) – Ni – W

–

δ-WC1±x – α/β-SiC – Ni

85

–

Powdered δ-WC1±x – 80 vol.% Ni-based alloy (content P – 11 %) mixtures were employed as precursors for the deposition of composite coatings (thickness – 10 μm) on stainless steel substrates using infrared (HDI) heating procedure (power density – up to 35 MW m–2) Dense and uniform core-shell structured [1752] δ-WC1±x – γ-W2±xC cast powders were coated by Ni – Ni3P composition (thickness – 5 μm) via electroless optimized plating (dwell time – 1 h) process

–

Vacuum, 1350 ≤ 6 Pa

Ar, 2 MPa

δ-WC1±x – TaC1–x – TiC1–x – δ-TiN1±x – Ni

–

δ-WC1±x – W – Ni-P alloy hard coatings [3884] were fabricated by electrodeposition (time – 40 min) procedure Powdered δ-WC1±x (purity > 99.5 %, size [10, 3365, distribution – 0-1 μm (97.5 %) and 1-2 μm 3823-3824] (2.5 %), content O < 0.31 %) – 8 % Ni (purity > 99.9 %, mean particle size – 0.7 μm) – 0.75-3.75 % SiC nanowhisker (purity > 99.0 %; diameter ≤ 0.25 μm, aspect ratio ≥ 20; content O < 0.5 %) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 6 min) to prepare dense modified hard alloys with Nibased metallic binder (traces of newly appeared δ-Ni2Si and α-C (graphite) phases were revealed in the alloys with the highest content of SiC nanowhisker; mean δ-WC1±x grain size – 0.35-0.40 μm)

1380-1420 Modified δ-WC1±x – 8 % Ni – 1-3 % SiC hard alloys were designed and fabricated by hot isostatic pressing (HIP) procedure (holding time – 1 h) 1400

Modified by 0.2-0.9 % (0.9-3.75 vol.%) SiC nanowhisker (purity > 99.0 %; diameter ≤ 0.25 μm, aspect ratio ≥ 20; content O < 0.5 %), δ-WC1±x – 10 % Ni hard alloys (porosity – 3 %, mean grain size – 0.4 μm) were prepared by hot-pressing (exposure – 1 h) procedure of powders

See section TaC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-2.21

(continued)

2.6 Chemical Properties and Materials Design

423

Table 2.21 (continued) Powdered δ-WC1±x (> 99 %, 0.5 μm) – [10, 3367, 10-30 % TiB2±x (> 98 %, 1.5 μm) – 10 % 3933-3934, Ni (> 98 %, 2.3 μm) mixtures (prelimina- 4382] rily ball-milled, purities and initial mean particle sizes of the components are given in brackets) were subjected to hot-pressing (exposure – 1 h) procedure to prepare dense hard alloys (porosity – (96.2÷99.3)±(0.2÷0.3) % composed of δ-WC1±x (major), α/ε-W2+xC, (Ti,W)B2±x, (Ti,W)C1–x, Ni4B3±x and metallic γ-(Ni,W,Ti) solid solution phases

δ-WC1±x – TiB2±x Vacuum 1650 – Ni

Powdered δ-WC0.99 (99 %, 0.6 μm, ~ 1-3 m2 g–1; contents: non-combined C – 0.06 %, O – 0.08 %, Fe – 0.003 %) – 72 % TiB2±x (99.3 %, 1.5 μm, ~ 3-10 m2 g–1; contents: C – 0.51 %, O – 0.09 %, Fe – 0.08 %) – 8 % Ni (99 %, ~2 μm, ~ 2-5 m2 g–1; contents: C – 0.065 %, O – 0.22 %, Fe – 0.006 %) mixtures (preliminarily ballmilled; purities, initial mean particle sizes and specific surface areas, respectively, are given in brackets) were subjected to hotpressing (exposure – 1 h) procedure to produce complex cermet materials (porosity – 1.8±0.2 %), composed mainly of TiB2±x, δ-WC1±x, γ-W2±xC, TiC1–x, Ni4B3±x and metallic γ-Ni solid solution phases that indicates the following interphase reaction: 3TiB2 + 6WC + 8Ni = 3W2C + 3TiC + Ni4B3, which took place during the manufacturing process in the materials

Vacuum, 1650 2.4-12.0 mPa

–

–

Hard coatings, mainly composed of γ-Ni cellular dendrites and dispersed spherical / strip / network shaped TiB2±x and equiaxial δ-WC1±x particles, were deposited on stainless steel substrates using laser cladding techniques (laser energy – 0.225 kJ mm–2)

δ-WC1±x – TiB2±x – TiC1–x – Ni

See section TiC1–x – TiB2±x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – TiC1–x – Ni

See section TiC1–x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – Ni

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – TiC1–x – VC1–x – Ni

See section TiC1–x – VC1–x – δ-WC1±x – Ni in Table III-2.22

δ-WC1±x – TiC1–x – δ-TiN1±x – ZrC1–x – Ni

See section ZrC1–x – TiC1–x – δ-TiN1±x – δ-WC1±x – Ni in Table II-5.24

(continued)

424

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – δ-TiH2–x – Ni

Vacuum 1400-1550 With the addition of δ-TiH2–x to the initial [3764] powdered mixtures, highly dense δ-WC1±x – 10 % Ni hard alloys, containing of 1-10 % Ti in the Ni binder, were prepared by powder sintering (exposure – 1 h) procedure Ar, 1350 150 MPa

Similar materials, containing of 5-10 % Ti in the Ni binder, were prepared by hot isostatic pressing (HIP) procedure (exposure – 40 min) from the same powders

δ-WC1±x – VC1–x – Ni δ-WC1±x – α/β-WS2–x – Ni

δ-WC1±x – Ar α/β-Y2O3–x – Ni – W

See section VC1–x – δ-WC1±x – Ni in Table III-3.16 –

–

1300

δ-WC1±x – Vacuum 1275 α/β-Y2O3–x – α/β/γ/δ-ZrO2–x – Ni

δ-WC1±x – 10 % Ni cermet powders (size [3896] distribution – 15-45 μm) with the addition of 1.8-5.4 % (3.5-10.0 vol.%) powdered WS2–x (size distribution – 15-45 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of special coatings (thickness – ~0.4 mm, porosity – 0.4-1.3 %) with low coefficients of friction on stainless steel substrates; in the deposited threephase coatings Ni metallic binder formed continuous networks, where δ-WC1±x and WS2–x particles were embedded Powdered Ni (99.9 %, 3-7 μm) – 30 % W [3940] (99.9 %, 14 μm) – 2.5-5.0 % δ-WC1±x (99.5 %, 3.3 μm) – 1 % α-Y2O3–x (99.9 %, 1 μm) mixtures (purities and initial mean particle sizes of components are given in brackets) were subjected to mechanical alloying (MA) followed by cold-pressing and finally sintering procedure (exposure – 1 h) to fabricate dense composite materials (porosity – ~7 %) with γ-(Ni,W) solid solution phase (matrix) and dispersed δ-WC1±x and α-Y2O3–x particles (inclusions) Powdered δ-WC1±x (99 %, 0.9 μm) – 8 % [10, 3890, Ni (99.7 %, 7 μm) – 6 % α/β-ZrO2–x (99.9 3941-3943, %, < 100 nm, 3 mol.% α-Y2O3–x partially 3945-3947] stabilized) mixtures (preliminarily ballmilled, the purities and initial mean particle sizes for the components are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 1 min) to prepare dense hard alloys with Ni-based metal binder (porosity – ~2 %, mean δ-WC1±x grain size – ~0.9 μm), containing α/β-ZrO2–x (content monoclinic α-ZrO2–x – ~8 %) oxide phases

(continued)

2.6 Chemical Properties and Materials Design

425

Table 2.21 (continued) –

1400-1500 Powdered δ-WC1±x (99 %, 0.9 μm) – 8 % Ni (99.7 %, 7 μm) – 6 % α/β-ZrO2–x (99.9 %, ~30 nm, 3 mol.% α-Y2O3–x partially stabilized) mixtures (preliminarily ball-milled and cold-pressed, purities and initial mean particle sizes for the components are given in brackets) were subjected to vacuum sintering and hot isostatic pressing (HIP) procedures (dwell time – from 0.5 h to 1 h) to prepare highly dense hard alloys with Ni metallic binder

–

–

δ-WC1±x – ZrC1–x – Ni

Powdered δ-WC1±x – 4.25-5.75 % Ni – 46 % α/β/γ-ZrO2–x (partially stabilized) – 3.54.5 % Y2O3–x mixtures (contents: total C – 2.6-3.0 %, Fe < 0.1 %, α-ZrO2–x (monoclinic) < 10 %, SiO2 < 0.35 %, Al2O3 < 0.1 %, Fe2O3 < 0.1 %) were employed as feedstock materials to deposit coatings (mean thickness – 560±5 μm, porosity – 5.5±0.1 %) on steel substrates using atmospheric plasma spraying (APS) techniques; the deposited coatings were composed of γ-(Zr,Y)O2–x oxide (cubic, major), γ-W2±xC carbide, W2±x(C,O) oxycarbide and W metallic phases

See section ZrC1–x – δ-WC1±x – Ni in Table II-5.24 See also section C – Ni – W – Zr in Table I-2.14

δ-WC1±x – Ar, 1700 α/β/γ/δ-ZrO2–x – 206 MPa Ni

δ-WC1±x – Np

–

Powdered δ-WC1±x (mean particle size – [3391, 3890, ~0.9 μm) – 8 % Ni (99.7 % purity, mean 3944] particle size – ~20 μm) – 6 % α-ZrO2–x (monoclinic, mean particle size – ~10 μm) mixtures (preliminarily ball-milled) were subjected to liquid-phase sintering followed by hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare dense materials (with negligible porosity, no significant porosity associated with the interfaces of ZrO2–x grains) mainly composed of δ-WC1±x, β/γ-ZrO2–x, η2-(W3Ni3)Cy and (Ni0.85W0.15) metallic solid solution (binder) phases –

The calculations of electronic structure of [1962] δ-WC1±x doped with Np were performed

(continued)

426

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Os

–

2000

No mutual solubilities between the compo- [53, 3723nents 3726, 3955]

–

< 2030

The formation of ~(W3Os3)C2±x ternary compound phase with homogeneity ranges

–

–

Some properties of Os-doped δ-WC1±x were DFT-calculated

See also section δ-WC1±x – C – Os See also section C – Os – W in Table I2.14 α/β/ε/γ-W2±xC – Os

–

No mutual solubilities between the compo- [53, 3723nents 3726]

2000

See also section α/β/ε/γ-W2±xC – C – Os See also section C – Os – W in Table I2.14 δ-WC1±x – α-C3N4 – P

N2

δ-WC1±x – Pb

Vacuum, 800 1.3 Pa

P-doped hollow tubular α-C3N4 (graphite- [1763] like) – 2-10 % δ-WC1±x composite photocatalyst materials were fabricated by the calcination process of a complex prepared in the aqueous solutions containing phosphoric acid

500

Sintered WC0.98 materials (content noncombined C – 0.10%) does not interact with pure molten Pb (exposure – 10 h)

[579, 1501, 1528, 1873, 1941]

–

–

Composite Pb – 14-15 % δ-WC1±x anodes were prepared on Al substrates by electrodeposition method

δ-WC1±x – [C6H4(NH)]n – Pb

–

–

Composite Pb – conductive polyaniline [1528] [C6H4(NH)]n (PANI) – δ-WC1±x inert anodes were prepared by electrodeposition method on Ti substrates

δ-WC1±x – CeO2–x – α/β/γ/δ-ZrO2–x – Pb

–

–

Composite Pb – 5.8 % δ-WC1±x – 2.3 % [1501] ZrO2–x – 1.3 % CeO2–x inert electrodes were prepared on Al alloy substrates by electrodeposition method from a bath containing suspension of carbide and oxide particles

δ-WC1±x – α/β/γ/δ-ZrO2–x – Pb

–

–

Composite Pb – 10.0 % δ-WC1±x – 3.6 % [1501] ZrO2–x inert electrodes were prepared on Al alloy substrate by electrodeposition method from a bath containing suspension of carbide and oxide particles

See also Table 2.26

(continued)

2.6 Chemical Properties and Materials Design

427

Table 2.21 (continued) δ-WC1±x – Pd

Pd-modified δ-WC1±x surfaces for electrocatalysis purposes were prepared by depositing Pd using a deposition source of Pd (99.99 % purity) wire

Vacuum, 25-30 0.01-1.0 μPa –

[1, 13, 53, 151, 393, 626, 1465, 1490, 1533, ~5 % Pd nanoparticle (facets (111), size – 1544, 1562, ~3 nm) dispersion on mesoporous γ-WC1–x 1573, 1578, – δ-WC1±x (well-defined porous structure 1580, 15851586, 1613, with mean pore size – ~8.5 nm, specific surface area – ~47 m2 g–1) materials were 1661, 1668, prepared via reduction (exposure – 1.5 h) 1686, 1713, procedures as supported electrocatalysts 1737, 17791781, 1981, Pd1–xWxCz magnetron sputtered γ-WC1–x- 1984, 3948based thin films (with the limited control 3949] of the deposited carbide phase through variation of the sputter atmosphere) were deposited on Si substrates; complete solid solubility was observed with Pd and metastable γ-WC1–x

250

Ar/CH4 400

H2

Nanocomposite γ-WC1–x – Pd (mean particle size – 10-12 nm; the atomic ratio W/(Pd + W) = 0.12÷0.39) was synthesized finally via reducing heat treatment (exposure – 12 h) for electrocatalysis purposes

450

Vacuum, < 1000 0.1 mPa

–

W-C thin films with Pd contents – up to 33 at.% were deposited by sputtering; in the films with high C contents the presence of γ-WC1–x phase was detected

1200-1500 The fracture (disintegration) of δ-WC1±x materials and formation of (Pd,W) metallic solid solution were observed after contact interactions

–

–

The effect of substitutional Pd impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

Pd metal monolayer supported by both Wand C-terminated δ-WC1±x (0001) was simulated on the basis of DFT calculations

See also section δ-WC1±x – C – Pd See also section C – Pd – W in Table I2.14 α/β/ε/γ-W2±xC – Pd

–

–

α/ε-W2+xC supported 10% Pd electrocata- [393, 1533, lysts were prepared using alkaline reduc- 1540, 1580] tion with PdCl2 as a precursor

–

–

α/ε-W2+xC – 3-6 % Pd electrocatalysts were synthesized via impregnating the unpassivated semicarbide phase with a Pd aqueous solutions

See also section C – Pd – W in Table I2.14

(continued)

428

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – MgO – α/β/γ/δ-ZrO2–x – Pd

δ-WC1±x – Pt

–

–

δ-WC1±x – ~6 % Pd particles (size – 0.2- [1713] 0.3 μm; main contaminations – PdO and Co3O4), synthesized using high-energy ball-milling, were deposited on α/β-ZrO2–x (partially stabilized by 3 % MgO) porous matrix (4 pores per 1 cm) to prepare catalyst materials

Pt – 65-80 mol.% δ-WC1±x thin film cata- [1, 13, 53, lysts were prepared by plasma sputtering 151, 313, on Si wafer using 99.99 % purity δ-WC1±x 336, 387, and Pt targets and followed post-deposition 502, 626, annealing 1366, 1369, Ar/CH4 400 Pt1–xWxCz magnetron sputtered γ-WC1–x- 1407-1408, based thin films (with the limited control 1409, 1414, of the deposited carbide phase through va- 1425, 1428, riation of the sputter atmosphere) were de- 1431, 1434, posited on Si substrates; complete solid so- 1436, 1441, 1445-1446, lubility was observed with Pt and meta1456, 1468, stable γ-WC1–x phase 1473-1475, H2 400 9-16 % Pt nanoparticle (mean size – 13.5 1481, 1487, nm) loaded δ-WC1±x powders (specific 1490, 1498, surface area – 10.6 m2 g–1) were prepared 1507, 1510, via reduction (exposure – 2 h) processes 1515, 1522, H2/Ar 600 40 % Pt deposited δ-WC1±x powders were 1532-1534, (20/80) prepared by heat treatment (exposure – 5 1536, 1539, h) processes 1542, 1549, Vacuum, 730 Pt-modified δ-WC1±x thin films (thickness 1565, 1568, ~1 μPa – ~1 μm) were prepared using the physical 1572, 1578, vapour deposition (PVD) techniques on C 1580, 15851586, 1606, (glassy) substrates 1615, 1629, – 1200-1500 The fracture (disintegration) of δ-WC1±x 1631, 1634, materials and formation of (Pt,W) metallic 1645, 1647, solid solution occurred 1682, 1685Vacuum, 1800 The considerable reaction between bulk 1686, 1689, 1.3 mPa (dense) δ-WC1±x hot-pressed materials (po- 1700, 1726, rosity < 3 %) and liquid Pt in the form of a 1728, 1737, sessile drop (exposure – 15 min) led to the 1745, 1748, formation of metallic (Pt,W) solutions in 1766, 1792, the C-rich contact zone (with α-C (gra3435, 3723, phite) flakes) 3951-3953] – ~2000 The formation of ~(W5Pt5)C1±x ternary compound phase with wide homogeneity ranges Vacuum 130-520

–

–

δ-WC1±x dots (angstrom-sized), nanorods and nanoparticles (mean size – ~10 nm) were employed as Pt electrocatalyst supports

(continued)

2.6 Chemical Properties and Materials Design

429

Table 2.21 (continued) –

20 % Pt loaded δ-WC1±x electrocatalyst was prepared by microwave-assisted process

–

–

δ-WC1±x powders (mean particle size – 20 μm, size distribution – up to 50 μm) were coated with 0.016 % Pt by ion beam sputter deposition (sputter targets – foils or hemisperes of 99.9 % purity Pt, ions for sputtering – 60 keV Xe+, Kr+ or Ar+)

–

–

Powdered single-phase δ-WC1±x (0.5-1.0 μm irregularly sized agglomerates, specific surface area – ~140 m2 g–1) synthesized via a molten solvent route was employed as a electrocatalyst support for homogeneously deposited by a galvanic procedure Pt metal clusters (mean size < ~3 nm)

–

–

Composite δ-WC1±x (0.25 nm) – Pt (0.23 nm) nanoparticles (interplanar spacings of the components are given in brackets) with the δ-WC1±x (1000) and Pt (111) preferred orientations were fabricated

–

–

Pt metal monolayer supported by both Wand C-terminated δ-WC1±x (0001) was simulated on the basis of DFT calculations

–

–

The suitability of δ-WC1±x and γ-WC1–x phases as support (core) materials for Pt shells was studied employing DFT calculations; the thermodynamic stability of 1-2 layers of Pt atoms on the carbide surfaces was examined accounting for the balance between epitaxial mismatch strains and core-shell chemical bonding

Ar

See also section δ-WC1±x – C – Pt See also Table 2.26 See also section C – Pt – W in Table I-2.14 δ-WC1±x – Ar α/β/ε/γ-W2±xC – Pt

Ar

900-1000

Mesoporous δ-WC1±x (major phase) – γ-W2±xC materials (specific surface area – 120-180 m2 g–1, mean pore size – 3.9-4.4 nm, pore volume – 0.13-0.17 cm3 g–1) prepared via carbonization (exposure – 3 h) procedure were employed as supports for Pt nanoparticles (mean size – ~10 nm) for electrocatalysis purposes

950

Two-phase γ-W2±xC (major) – δ-WC1±x (minor) microspheres (specific surface area – 256 m2 g–1) synthesized via hydrothermal method followed by carbonization were employed as supports for uniformly dispersed 10 % Pt nanoparticles (mean size – 4.3

[1354, 1367, 1370, 1390, 1407-1408, 1431, 1436, 1441, 14741475, 15331534, 1583, 1616, 3952]

(continued)

430

2 Tungsten Carbides

Table 2.21 (continued) nm) to prepare catalyst materials Vacuum, ~0.07 mPa

–

Thin films based on the mixture of W carbide phases (γ-WC1–x, δ-WC1±x and γ-W2±xC), containing from 0.6 at.% to 50 at.% Pt, were prepared by pulsed laser coablation techniques

–

–

Pt-modified δ-WC1±x (with the presence of γ-W2±xC phase) thin films were prepared for electrocatalysis purposes

See also section δ-WC1±x – α/β/ε/γ-W2±xC – C – Pt See also section C – Pt – W in Table I-2.14 α/β/ε/γ-W2±xC – Pt

–

–

Impregnated with 0.3 % metallic Pt using treatments by aqueous solutions, α-W2+xC single-phase powdered materials (specific surface areas – 24 m2 g–1 and 18.5-20.0 m2 g–1, before and after the addition of Pt, respectively) were prepared for catalysis purposes

[53, 14071408, 1441, 1495, 1583, 1533-1534, 1616]

See also section α/β/ε/γ-W2±xC – C – Pt See also section C – Pt – W in Table I-2.14 δ-WC1±x – Pt – Ru

Vacuum 130-520

(70±5) mol.% δ-WC1±x – (25±10) mol.% [1401-1402, Pt – (5±5) mol.% Ru thin film catalysts 1547, 1728, were prepared by plasma sputtering on Si 3953] wafer, using 99.99 % purity δ-WC1±x and metal targets, and followed post-deposition annealing

N2/H2 (90/10)

30 % Pt – Ru (1:1) supported on δ-WC1±x catalysts were prepared via the reduction process with NaBH4 followed by heat treatment in special gas atmosphere

–

δ-WC1±x – Ar, N2, α/β/ε/γ-W2±xC – H2 Pt – W

300

–

900-950

δ-WC1±x – Pt – Ru nanocrystalline catalyst was prepared by means of multi-sputtering systems 1 % Pt sub-nanometer nanoclusters loaded [1548-1549] mesoporous W (major phase) – δ-WC1±x – γ-W2±xC (minor phase) materials (specific surface area – 85 m2 g–1, pore size distribution < 2 nm), having complex core-shell microstructure with a core of metallic W and a shell made of a mixture of carbides (with bimodal particle size distribution: ≥ 5 nm and ≤ 2 nm), were prepared via cryogel technology for catalysis purposes

See also section C – Pt – W in Table I-2.14 δ-WC1±x – Cr3C2–x – TiC1–x – Pt

See section TiC1–x – Cr3C2–x – δ-WC1±x – Pt in Table III-2.22

(continued)

2.6 Chemical Properties and Materials Design

431

Table 2.21 (continued) δ-WC1±x – TiC1–x – Pt

See section TiC1–x – δ-WC1±x – Pt in Table III-2.22

δ-WC1±x – TiC1–x – Pt – Ru

See section TiC1–x – δ-WC1±x – Pt – Ru in Table III-2.22

δ-WC1±x – TiO2–x (rutile, anatase, brookite) – Pt

CO flow

For the preparation of core-shell structured [1574, 1587] electrocatalysts Pt nanoparticles were loaded on the δ-WC1±x – TiO2–x (rutile) composite particles, preliminarily prepared using microwave assisted heating in conjunction with ionic liquid and subsequent reductioncarbonization process (exposure – 4 h)

900

δ-WC1±x – WO2±x – α/β/γ/δ/ε/ζ-WO3–x – Pt – Ru – W

–

–

Nanosized (4.2÷25.8)±(0.2÷0.5) % Pt – [1767] (1.9÷9.9)±(0.1÷0.4) % Ru loaded δ-WC1±x – WO2±x – WO3–x (with the presence of metallic W phase) electrocatalysts were prepared by the sequence of several operations

δ-WC1±x – α/β/γ/δ/ε/ζ-WO3–x – Pt

–

–

Nanostructured Pt – δ-WC1±x – WO3–x [1494] three-phase electrode materials were prepared by means of the co-sputtering deposition method

δ-WC1±x – α/β/γ/δ/δ′/ε-Pu

–

–

No solubility of Pu in δ-WC1±x phase is revealed experimentally and that is also confirmed by the theoretical calculations

–

1400-1700 The formation of PuWC2–x (with narrow homogeneity ranges, more probably) and η-PuWC2–x (x = 0.25, or Pu4W4C7) ternary phases

–

–

[53, 1943, 1950, 19581959, 19621963, 1965, 3724, 4388]

The calculations of electronic structure of δ-WC1±x doped with Pu were performed

See also section δ-WC1±x – C – Pu See also section C – Pu – W in Table I2.14 α/β/ε/γ-W2±xC – α/β/γ/δ/δ′/ε-Pu

– –

The solubility of Pu in α/ε-W2+xC phase is [53, 1943, very low 1950, 19581400-1700 The formation of PuWC2–x (with narrow 1959, 1963, homogeneity ranges, more probably) and 1965, 3724, η-PuWC2–x (x = 0.25, or Pu4W4C7) ternary 4388] –

phases

See also section α/β/ε/γ-W2±xC – C – Pu See also section C – Pu – W in Table I2.14 δ-WC1±x – Pu – Re – U

–

2100

The formation of (U,Pu)(W,Re)C2–x comp- [1958-1959, lex solid solution phase 3954]

(continued)

432

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – Pu – U

–

1400

The occurrence of PuWC2–x – UWC2–x ter- [53, 1950, nary phase solid solution (U,Pu)WC2–x was 1958-1959, confirmed in the entire range of composi- 3724, 4388] tions

–

1700

The formation of (U,Pu)WC2–x (with narrow homogeneity ranges, more probably) and η-(U,Pu)WC2–x (x = 0.25, or (U,Pu)4W4C7) ternary phases

See also section δ-WC1±x – C – Pu – U See also section C – Pu – U – W in Table I-2.14 δ-WC1±x – Re

– –

– 1500

The formation of π-W3÷4Re2÷4C1±x ternary [13, 53, 189, phase 919, 1943, 1946-1948, Powdered δ-WC1±x (> 99.8 %, 23 μm) – 3.7 mol.% Re (> 99.99 %, 74 μm) compo- 2194, 3724, sitions (the initial purities and mean par- 3955-3956, ticle sizes of the components are given in 4071, 4620] brackets) were preliminarily high-energy ball-milled (to reduce crystallite size up to ~7 nm and mean particle size up to ~0.12 μm) and subsequently subjected to sparkplasma sintering (SPS) procedure (exposure – 10 min) to prepare single-phase carbide materials (porosity – 1.7 %, mean grain size – ~0.55 μm, maximum grain size – ~3 μm) with the estimated composition of ~δ-(W0.96Re0.04)C1.00

–

~1800-2400 Single-phase (hexagonal) δ-(W1–yRey)C1±x carbide layers with the value of y up to 0.25 were prepared by diffusion saturation (carburization) of W – Re alloys in the contact with α-C (graphite) powders; similar single-phase compositions of Re-rich mixed carbides could not be prepared by arc-melting or sintering techniques

H2

–

Ar

1500-2500 The maximum solubility of Re in δ-WC1±x is corresponding to the ~δ-(W0.90÷0.92Re0.08÷0.10)C1±x compositions and increasing with temperature growth

> 2500

–

At fast cooling metastable γ-(W,Re)C1–x phase (containing ~ 20-30 at.% Re, ?) was formed (W0.25÷0.28Re0.25÷0.28C0.44÷0.50) materials were prepared by arc-melting of the pure elements employing a water-cooled Cu hearth; the properties of materials were preliminarily predict using the combination of quantum-mechanical calculations and advanced machine-learning techniques

(continued)

2.6 Chemical Properties and Materials Design

433

Table 2.21 (continued) –

–

The structures and properties of metastable (or imaginary) δ-(W,Re)C1±x (x = 0) and γ-(W,Re)C1–x (x = 0.2) phases were calculated by various theoretical methods See also section δ-WC1±x – C – Re See also section C – Re – W in Table I2.14

α/β/ε/γ-W2±xC – Re

–

1500-2500 The continuous series of α/β/ε/γ-W2±xC – (Re,W,C) solid solutions, α/β/ε/γ-(W,Re)2±xC phase is formed in the entire range of compositions from W0.67C0.33Re0.00 to Re1.00W0.00C0.00

[1, 13, 53, 188-189, 1943, 19461948]

See also section α/β/ε/γ-W2±xC – C – Re See also section C – Re – W in Table I2.14 δ-WC1±x – Rh

–

~2000

The formation of ~(W2Rh2)C1±x ternary [53, 83, compound phase with homogeneity ranges 1585, 1637, Rh3WC phase was predicted theoretically 1984, 37233726, 3955, by DFT calculations 4065, 4563] Practically, there is no mutual solubilities between the components

–

–

–

–

–

–

The effect of substitutional Rh impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

Some properties of Rh-doped δ-WC1±x were DFT-calculated

–

–

Rh metal monolayer supported by both Wand C-terminated δ-WC1±x (0001) was simulated on the basis of DFT calculations

See also section δ-WC1±x – C – Rh See also section C – Rh – W in Table I2.14 α/β/ε/γ-W2±xC – – Rh

–

Practically, there is no mutual solubilities [53, 3723between the components 3726]

See also section α/β/ε/γ-W2±xC – C – Rh See also section C – Rh – W in Table I2.14 δ-WC1±x – Ru

Ar/CH4 400

–

~2000

Ru1–xWxCz magnetron sputtered γ-WC1–x based thin films (with the limited control of the deposited carbide phase through variation of the sputter atmosphere) were deposited on Si substrates; high solubility of Ru in metastable γ-WC1–x was observed

[53, 1490, 1585, 1984, 3723-3726, 3955]

The formation of ~(W3Ru3)C2±x ternary compound phase with homogeneity ranges

(continued)

434

2 Tungsten Carbides

Table 2.21 (continued) –

–

Practically, there is no mutual solubilities between the components

–

–

The effect of substitutional Ru impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

Some properties of Ru-doped δ-WC1±x were DFT-calculated

–

–

The formation of Ru metal monolayer supported by δ-WC1±x (0001) is not probable according to the DFT calculations

See also section δ-WC1±x – C – Ru See also section C – Ru – W in Table I2.14 α/β/ε/γ-W2±xC – Ru

–

–

Practically, there is no mutual solubilities [53, 3723between the components 3726]

See also section α/β/ε/γ-W2±xC – C – Ru See also section C – Ru – W in Table I2.14 δ-WC1±x – S

–

–

δ-WC1±x – Sb δ-WC1±x – Sc

δ-WC1±x reacts with S to form WS2–x phase [3957] within the area of friction contact under sliding friction conditions (tribosynthesis)

See Table 2.26 –

~2000-2500 The maximum solid solubility of Sc in [83, 1983, δ-WC1±x is very low and that of Sc in 3958, 4503] γ-WC1–x is approximately corresponding to γ-(W0.7Sc0.3)C1–x composition

–

–

The effect of substitutional Sc impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

α/β/ε/γ-W2±xC – Sc

–

~2500

δ-WC1±x – Se

–

–

δ-WC1±x reacts with Se to form WSe2–x [3957] phase within the area of friction contact under sliding friction conditions (tribosynthesis)

δ-WC1±x – Si

–

–

The formation of WxSiyCz (or W5–xSi3–yCx+y) ternary compound (or silicide solid solutions on the basis of W5Si3+x)

–

–

Practically, there is no mutual solubility between the components

–

–

The probable existence of W3SiC2 nanolayered ternary compound (Mn+1AXn-

See also section δ-WC1±x – C – Sc The maximum solid solubility of Sc in γ-W2±xC is low

[3958]

See also section α/β/ε/γ-W2±xC – C – Sc

[1, 13, 47, 579, 886, 1941-1942, 2395, 2575, 3469, 39593967, 4337, 4344]

(continued)

2.6 Chemical Properties and Materials Design

435

Table 2.21 (continued) phase) was estimated on the basis of ab initio calculations Ar/H2 (95/5)

≥ 1000

The contact interaction between the components is likely to be developing via the reaction: δ-WC1.0 + 3Si = WSi2 + β-SiC (cubic)

Vacuum ~1000-1200 The initiation of reaction between the components with the formation of W silicides as products in fine-powdered mixtures Vacuum, ~1300 ~5 Pa

Powdered δ-WC1±x (99.5 % purity, initial mean particle size – 1.3 μm) – 75 mol.% Si (99 % purity, size distribution < 45 μm) mixtures (preliminarily high-energy ballmilled up to the mean grain sizes of 20 nm) were subjected to the pulsed current activated combustion synthesis (PCACS) sintering, the simultaneous synthesis and densification (total exposure – 2 min, ignition temperature – 650 °C) to prepare materials consisting of nanocrystalline WSi2 – SiC equimolar composition (with porosity – 0.2 %, mean grain sizes – 40-50 nm and presence of W5Si3+x as a minor phase)

Vacuum, 1300-1500 Powdered δ-WC1±x (mean particle size – < 4 Pa 70 nm; contents: O ≤ 0.4 %, Fe – 0.003 %, Mo – 0.0004 %, Si < 0.0005 %) – 1 % Si (99.9 % purity, size distribution – 2-50 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – from 1 to 35 min) to prepare dense materials (porosity – 4-15 %, mean grain size – 0.25-0.45 μm) containing W5Si3+x, WSi2 and SiC phases in the δ-WC1±x matrix; at ≥ 1400 °C Si melted and infiltrated the matrix, forming WSi2 (with W5Si3+x as an intermediate product) throughout the microstructure with a crystal orientation relation of the WSi2 (002) // δ-WC1±x (1210) type, that was accompanied with the large abnormal growth of δ-WC1±x platelets mostly oriented along either the or long axis and the short axis and constituting ~30 vol.% of the microstructure and small faceted grains Ar

1450

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Si (exposure – 5 min)

Ar

1500

The intensive interaction between δ-WC1±x materials and Si melts is observed

(continued)

436

2 Tungsten Carbides

Table 2.21 (continued) NH3/CO 1560

Powdered δ-WC1±x (> 99.9 % purity, mean particle size – 1-2 μm) – 2-16 % Si (> 99.9 % purity, size distribution < 74 μm) mixtures were subjected to sintering procedure (exposure – 3 h) to fabricate porous ceramics (apparent porosity – 14-37 %, mean pore size < 2 μm, usage of pore-generating agents led to the bimodal pore distribution with some pores > 5 μm); during the sintering process volatilization of Si was observed, in the mixtures with Si content > 8 % the formation of γ-WC1–x phase was detected

Vacuum, 1850 15 Pa

Powdered δ-WC1±x (99.5 % purity, mean particle size – 0.1 μm) – 10 % Si (> 99 % purity, size distribution < 150 μm) mixture (preliminarily high-energy ball-milled) was subjected to spark-plasma sintering (SPS) procedure to prepare composite materials with δ-WC1±x matrix containing WSi2 disilicide and β-SiC (cubic) nanowires (with a large number of porosity) formed due to the interaction of initial components

See also section δ-WC1±x – C – Si See also Table 2.26 See also section C – Si – W in Table I-2.14 α/β/ε/γ-W2±xC – Si

–

–

[13, 47, 886, Practically, there is no mutual solubility between the components, or it is extremely 1597, 2575, low 3959]

–

–

W2±xC thin films (thickness – 2.5-14.8 nm) were deposited on Si (111) substrates to prepare photocathode systems

See also section α/β/ε/γ-W2±xC – C – Si See also section C – Si – W in Table I-2.14 δ-WC1±x – α/β-SiC – Si

H2

1750-1900 Powdered α-SiC (mainly consisting of 6H [13, 47, polytype phase, content of β-SiC < 3 %, 2395, 3959, treated to remove SiO2, size distribution – 3968] 2.5-5.0 μm) – 25 vol.% Si (analytical purity, size distribution < 74 μm) – 10 vol.% δ-WC1±x (mean particle size – 2-4 μm) mixtures (preliminarily high-energy ball-milled up to the mean grain sizes of ~0.4 μm) were subjected to hot-pressing procedure (exposure – 15 min) to fabricate dense materials (porosity – 0.2-4.1 %)

See also section δ-WC1±x – C – Si See also section δ-WC1±x – Si See also section C – Si – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

437

Table 2.21 (continued) δ-WC1±x – Vacuum 1900 α/β-SiC – ZrB2±x – Si

ZrB2±x (20 μm), α-SiC (0.8 μm), δ-WC1±x [4355] (1 μm) and Si (45 μm) powders (preliminarily ball-milled, initial mean particle sizes of the components are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare top coating (thickness – 0.8 mm) with α-SiC diffusion bond coat (thickness – 3 mm) on α-C (graphite) substrates

δ-WC1±x – Sn

No wettability by molten Sn, no chemical [13, 579, interaction 1941]

Ar

500

Vacuum, 800 1.3 Pa

Sintered WC0.98 materials (content noncombined C – 0.10%) does not interact with pure molten Sn (exposure – 10 h)

Ar

The surface of δ-WC1±x is perfectly wetted by molten Sn

1300

See also Table 2.26 δ-WC1±x – Ta

H2

900

–

~1400

–

1450

Vacuum, 1500 ~ 10-100 mPa –

1500

Vacuum, 1700 ~0.7 Pa –

1750

Vacuum 1800

Core-shell nanoparticles (mean size – 2-3 [1, 3, 13, 47, nm) of cubic γ-(W0.70Ta0.30)C1–x phase were 53, 151, synthesized for electrocatalysis purposes 579, 585, The experimentally measured solubility of 626, 1375, Ta in the δ-WC1±x phase of cemented car- 1636, 1925, bides is 0.959±0.009 at.%; the DFT-calcu- 1933, 1943, 1948, 1989, lated value is 0.23 at.% 1995, 2062, Powder with δ-(W0.914Ta0.086)C1±x composi- 2392, 3730, tion was prepared by two-step co-carburi- 3780, 3969zation process of W and Ta metallic pow- 3973, 4038] ders with α/ε-(W,Ta)2+xC powder as an intermediate product Recommended conditions of diffusion bonding (welding) with pressure – 4.9 MPa and exposure – 10 min The maximum solid solubility of Ta in δ-WC1±x is ~1.5 mol.% The initiation of contact reaction between the dense bulk materials (exposure – 5 h) The maximum solid solubility of Ta in δ-WC1±x is corresponding to ~δ-(W0.99Ta0.01)C1±x composition The presence of α-(W,Ta)2+xC, TaC1–x and α-Ta2+xC phases was detected in the contact zone

–

1950-2450 The maximum solid solubility of Ta in δ-WC1±x is corresponding to ~δ-(W0.975Ta0.025)C1±x composition

–

2760

The maximum solid solubility of Ta in δ-WC1±x is corresponding to ~δ-(W0.96Ta0.04)C1±x composition

(continued)

438

2 Tungsten Carbides

Table 2.21 (continued) See also section δ-WC1±x – C – Ta See also section C – Ta – W in Table I2.14 α/β/ε/γ-W2±xC – Ta

[1, 3, 13, 53, 134, 151, 1921-1922, Vacuum 1800-2000 No chemical interaction between the com- 2392, 3730, 3780, 3969ponents was observed 3973] – 1950 The maximum solid solubility of Ta in α/ε-W2+xC is corresponding to ~α/ε-(W0.75Ta0.25)2.25C composition –

1750

The maximum solid solubility of Ta in α/ε-W2+xC is corresponding to ~α/ε-(W0.85Ta0.15)2.25C composition

–

2300

The maximum solid solubility of Ta in β/ε-W2+xC is corresponding to ~β/ε-(W0.60Ta0.40)2.25C composition

–

2450-2750 The solid solubility of Ta in γ-W2±xC is unlimited due to the formation of γ-W2±xC – β-Ta2±xC semicarbide continuous solid solutions (γ/β-(W,Ta)2±xC)

See also section α/β/ε/γ-W2±xC – C – Ta See also section C – Ta – W in Table I2.14 δ-WC1±x – Tc

– –

– ~2200

The maximum solid solubility of Tc in δ-WC1±x is low

[1984, 3955, 3974]

The formation of γ-WC1–x – TcC1–x cubic monocarbide continuous solid solution (γ-(W,Tc)C1–x) phase

–

–

The effect of substitutional Tc impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

–

–

Some properties of Tc-doped δ-WC1±x were DFT-calculated

See also section δ-WC1±x – C – Tc See also section C – Tc – W in Table I2.14 α/β/ε/γ-W2±xC – Tc

–

1500-2200 The continuous series of α/β/ε/γ-W2±xC – [188, 3974] (Tc,W,C) solid solutions, α/β/ε/γ-(W,Tc)2±xC phase is formed in the entire range of compositions from W0.67C0.33Tc0 to Tc1.00W0C0

See also section α/β/ε/γ-W2±xC – C – Tc See section C – Tc – W in Table I-2.14 δ-WC1±x – α/β-Th

–

1500

The maximum solid solubility of Th in δ-WC1±x is very low

[13, 22, 53, 3724, 3730]

See also section δ-WC1±x – C – α/β-Th See also section C – Th – W in Table I2.14

(continued)

2.6 Chemical Properties and Materials Design

439

Table 2.21 (continued) α/β/ε/γ-W2±xC – α/β-Th

–

1500

The maximum solid solubility of Th in α/ε-W2+xC is very low

[13, 22, 53, 3724, 3730]

See also section α/β/ε/γ-W2±xC – C – α/β-Th See also section C – Th – W in Table I2.14 δ-WC1±x – α/β-Ti Vacuum, < 1000 0.1 mPa

–

1200

–

~1400

–

~1500

Vacuum, 1500 1 Pa

W-C thin films with Ti contents – up to 50 at.% were deposited by sputtering; in the films with high C contents the presence of γ-WC1–x phase was detected

[3-4, 13, 43, 48, 53, 61, 80, 83, 86, 140, 199, The presence of α/ε-W2+xC and TiC1–x was 579, 867, detected in the contact zone between the 1922, 1941, 1981, 1983, components 1988-1989, The experimentally measured solubility of 1995, 1999, Ti in the δ-WC1±x phase of cemented carbi- 2062, 3182des is (1.9±0.3)×10–3 at.%; the DFT-calcu- 3185, 3724, lated value is 1.3×10–3 at.% 3730, 3975The maximum solid solubility of Ti in 3983, 4503, δ-WC1±x is ~ 1.0-1.4 mol.% 4516] Powdered δ-WC1±x (0.125 μm) – 10 % Ti (3.6 μm) mixtures (preliminarily highenergy ball-milled, initial mean particle sizes are given in brackets) were subjected to sintering (exposure – 1 h) to prepare dense materials (porosity – 5.6 %), containing TiC1–x, (Ti,W)C1–x cubic monocarbide and (Ti,W) metallic solid solutions formed due to the interphase solid state interaction during the sintering process

Vacuum, 1550-1800 Powdered δ-WC1±x – 17.7-41.9 mol.% Ti 5 Pa mixtures (preliminarily high-energy ballmilled to 20-30 μm loose agglomerates consisted of angular δ-WC1±x (mean size < 2 μm) and greatly deformed Ti particles) were subjected to spark-plasma (field-assisted) sintering (FAST/SPS) procedure (exposure – 3-10 min) to prepare dense materials (porosity – in the range from ~3.2 % to ~8.4 %) composed of 7-49 vol.% δ-WC1±x, 32-60 vol.% α/ε-W2+xC, 18-46 vol.% TiC1–x (or mixed (Ti0.32÷0.77W0.23÷0.68)C1–x) carbide and 22 vol.% metallic W phases (the latter one was formed only at the highest Ti contents in the mixtures, while δ-WC1±x was absent in the finally prepared materials; the appearance of metallic W was observed at the molar fraction of Ti > ⅓)

(continued)

440

2 Tungsten Carbides

Table 2.21 (continued) Ar

1730

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Ti (exposure – 5 min)

–

1800

Powdered δ-WC1±x (0.7 μm) – 5.0-33.3 % Ti (~25 μm) compositions (mean particle sizes are given in brackets) were subjected to hot-pressing procedure (exposure – 20 min) to prepare δ-WC1±x – γ-W2±xC – TiC1–x ceramic materials (with the presence of (Ti,W)C1–x cubic monocarbide solid solution phase formed additionally), the interaction between the components were developing mainly according to the following reaction: (1 – n)WC + nTi → nW2C + nTiC + (1 – 3n)WC, the porosity of hot-pressed ceramics was strongly depending on Ti contents (n) in the initial compositions

–

~1900-2600 The solid solubility of Ti in δ-WC1±x phase is very low Powdered δ-WC1±x (99.5 %, 0.1 μm) – 10 % Ti (> 98 %, < 15 μm) mixtures (preliminarily high-energy ball-milled, purities and initial particle sizes, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – ~5 min) to fabricate dense materials composed of δ-WC1±x, α/ε-W2+xC, TiC1–x and (Ti,W)C1–x cubic monocarbide solid solution phases

Vacuum, 2150 15 Pa

–

The formation of γ-(W,Ti)C1–x cubic monocarbide continuous solid solution

2700

–

–

The effect of substitutional Ti impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations, the stability of the probable δ-(W,Ti)C1±x solid solutions was confirmed

See also section δ-WC1±x – α/β-Ti – α/β-C See also Table 2.26 See also section C – Ti – W in Table I-2.14 α/β/ε/γ-W2±xC – α/β-Ti

–

1500

The maximum solid solubility of Ti in α/ε-W2+xC phase is corresponding to the ~α/ε-(W0.97Ti0.03)2.10C composition

–

~1900

The maximum solid solubility of Ti in α/ε-W2+xC phase is corresponding to the ~α/ε-(W0.95Ti0.05)2.35C composition

[4, 13, 43, 48, 53, 6163, 134, 199, 1988, 3724, 3730, 3975-3976]

(continued)

2.6 Chemical Properties and Materials Design

441

Table 2.21 (continued) –

2600

The maximum solid solubility of Ti in γ-W2±xC phase is corresponding to the ~γ-(W0.92Ti0.08)2.40C composition

See also section α/β/ε/γ-W2±xC – α/β-Ti – α/β-C See also section C – Ti – W in Table I-2.14 δ-WC1±x – TiB2±x Vacuum, 550 – Ti Ar

δ-WC1±x (99.5 %), TiB2±x (99.5 %; con[538] tents: C – 0.12 %, O – 0.32 %) and Ti (99.99 %) targets (the purities are given in brackets) were applied for the deposition of thin films (thickness – ~1.4 μm) on stainless steel and polycrystalline Si substrates using simultaneous magnetron sputtering method; the mean composition of deposited films was ~W0.31C0.30Ti0.16B0.15O0.08

δ-WC1±x – TiB2±x – δ-WN1±x –Ti

δ-WC1±x (99.5 %), TiB2±x (99.5 %; con[538] tents: C – 0.12 %, O – 0.32 %) and Ti (99.99 %) targets (the purities are given in brackets) were applied for the deposition of thin films (thickness – ~1.2 μm) on stainless steel and polycrystalline Si substrates using simultaneous magnetron sputtering method; the mean composition of deposited films was ~W0.16C0.02Ti0.07B0.20N0.45O0.10

Vacuum, 550 Ar/N2

δ-WC1±x – Tl δ-WC1±x – α/β/γ-U

See Table 2.26 –

–

–

–

No solubility of U in δ-WC1±x is observed [13, 22, 53, The formation of UWC2–x (0 ≤ x < 0.25), 1943, 19491964, 3984] η-UWC2–x (x ≈ 0.25, or U4W4C7, or UWC1.75), U2W2C3 (or UWC1.5) and UW4C4 ternary phases was reported

–

900-2500

The solid solubility of U in δ-WC1±x is negligible in all studied temperature ranges

See also section δ-WC1±x – α/β-C – α/β/γ-U See also section C – U – W in Table I-2.14 α/β/ε/γ-W2±xC – α/β/γ-U

–

900-2500

The solid solubility of U in α/β/ε/γ-W2±xC [13, 22, 53, is very low in all studied temperature ran- 1943, 1949ges 1964]

See also section α/β/ε/γ-W2±xC – α/β-C – α/β/γ-U See also section C – U – W in Table I-2.14

(continued)

442

2 Tungsten Carbides

Table 2.21 (continued) δ-WC1±x – V

–

–

– Ar

[1, 3, 13, 23, 53, 83, 579, 1922, 1941, ~1400 The experimentally measured solubility of 1983, 1989, V in the δ-WC1±x phase of cemented carbi- 1999, 2062, des is 0.160±0.007 at.%; the DFT-calcula- 2392, 3027, 3424, 3730, ted value is 0.43 at.% 3758, 3981~1500-1700 The maximum solid solubility of V in 3982, 3985, δ-WC1±x is ~2 mol.% 3989-3992, 1730 Sintered WC0.98 materials (content non4503] combined C – 0.10%) interact actively with pure molten V (exposure – 5 min)

> 1200

Decarburization of carbide phase due to the interphase interaction between the components is occurred

Powdered δ-WC1±x (99.5 %, 0.1 μm) – 10 % V (> 99 %, < 45 μm) mixtures (preliminarily high-energy ball-milled, purities and initial particle sizes, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – ~8 min) to fabricate dense materials composed of δ-WC1±x, γ-WC1–x, and VC1–x phases (in the presence of small amounts of non-reacted metallic V)

Vacuum, 2000 15 Pa

–

–

δ-WC1±x-based hardfacing layers with the addition of 1-3 % V were designed and fabricated

–

–

The effect of substitutional V impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations, the stability of the probable δ-(W,V)C1±x solid solutions was confirmed See also section δ-WC1±x – α/β-C – V See also Table 2.26 See also section C – V – W in Table I-2.14

α/β/ε/γ-W2±xC – V

α/ε-W2+xC phase exists in the range of ~(W0.74÷0.96V0.04÷0.26)1.93÷2.03C compositions (stabilized by the presence of V) as a solid solution

–

1200

–

1500-2200 The solid solubility of V in α/β/ε-W2+xC is unlimited due to the formation of α/β/ε-W2+xC – β-V2±xC semicarbide continuous solid solution (α/β-(W,V)2±xC) phase

[1, 13, 23, 53, 134, 3424, 3985, 3991]

See also section α/β/ε/γ-W2±xC – α/β-C – V See also section C – V – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

443

Table 2.21 (continued) δ-WC1±x – W

W – γ-WC1–x bilayers (layer thickness – [1-6, 8-13, 0.73-0.88 μm, grain size – ~ 90-110 nm, 53, 61, 65with preferred γ-WC1–x orientation along 69, 93, 151, the (200) direction) were produced by non- 200, 579, reactive d.c. magnetron sputtering deposi- 585, 626, tion on stainless steel substrates 858, 910, He flow, 190-450 δ-WC1±x – W thin films were fabricated by 943, 1060, 5-20 kPa metal-organic chemical vapour deposition 1693, 1925, 1933, 1943(MOCVD) method 1945, 2228, CO/CO2 400-850 Mesoscopic core-shell W@δ-WC1±x archi- 2575, 3993/H2O tecture (W core and W-terminated δ-WC1±x 3995, 3998shell) with a dodecahedral microstructure 3999, 4002was synthesized for the aim of catalysis 4014, 4018, H2 1600-1800 Powdered metallic W (size distribution – 4038] 0.6-0.9 μm, content O – 0.40 %) – 5-10 vol.% δ-WC1±x (mean particle size – 0.10.2 μm) mixtures were treated by field-assisted (pulsed d.c. electric current, 10 ms on and 10 ms off) sintering (exposure – 5 min) technology (FAST) to fabricate dense materials (porosity – 0.4-5.7 %, mean grain size – 1.4-3.1 μm); full conversion of δ-WC1±x to α/ε-W2+xC phase was observed in the sintered materials Vacuum, 20-300 Ar

–

1700

The mixtures of δ-WC1±x (2.75 μm, 0.14 m2 g–1) – 10-50 vol.% W (0.12 μm, 2.58 m2 g–1) colloidally dispersed powders (theoretically calculated diameters of the particles and specific surface areas are given in brackets, respectively) were subjected to spark-plasma sintering (SPS) procedure (exposure – 10 min) to prepare dense two-phase ceramic materials; full conversion of metallic W to α/ε-W2+xC phase was observed

Vacuum 1800-2200 The presence of α/ε-W2+xC phase was detected in the contact zone between the bulk components –

1900

Vacuum, 1900 ~ 10-100 mPa

The interaction in powdered mixtures of the components led to the formation of α/ε-W2+xC phase In the conditions of diffusion bonding (welding) with pressure – 4.9 MPa and exposure – 10 min, the formation of γ-W2±xC phase was detected in the contact zone

(continued)

444

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 1900 20-50 Pa

Powdered metallic W (99.9 % purity, size distribution ≤ 1.5 μm) – 1-10 vol.% δ-WC1±x (99 % purity, mean particle size – 0.15-0.20 μm) mixtures were heat treated (exposure – 5 min) using field-assisted sintering technology (FAST) to prepare carbide containing metal based materials; conversion of δ-WC1±x to ε-W2+xC phase was observed in the sintered materials

Ar flow 1900-2100 Powdered δ-WC1±x (size distribution – 0.50.7 μm) – 0.5 % W (99.9 % purity, mean particle size – 44 μm) mixtures (preliminarily ball milled) were subjected to pressureless sintering to prepare dense twophase materials (porosity – 2-17 %, mean grain size – 1-12 μm); the contents of α/ε-W2+xC phase, formed during the sintering process, increased from 1.1 % up to 4.4 % with the increase of sintering temperature Vacuum, 2000 ~0.7 Pa

The initiation of contact reaction between the dense bulk materials (exposure – 5 h)

Pure H2, 2000 5.3-8.0 kPa

In the conditions (pressure – 9.8 MPa, exposure – 5 min) of ion beam heated diffusion bonding (welding) of hot-pressed δ-WC1±x with bulk metallic W, the layers of γ-W2±xC (adjoined to δ-WC1±x, thickness – 15-20 μm) and γ-WC1–x (adjoined to W, thickness – 5-8 μm) were detected in the diffusion contact zone

–

–

δ-WC1±x – W functionally graded (FG) hard alloys were fabricated by using sparkplasma sintering (SPS) process

–

–

δ-WC1±x – W coatings (thickness – ~17 μm) were deposited on high-speed steel substrates using electrodischarge explosion techniques

–

–

On the basis of density functional theory (DFT) studies, the W (110) / δ-WC1±x (0001) interfaces were determined to be of metallic nature in the interfacial bonding of W-terminated hollow-site interfaces and mixed covalent-ionic nature in the interfacial bonding of C-terminated hollow-site interfaces; on the basis of molecular dynamics simulations, the diffusion of C atoms in the W (100, 110, 111) / δ-WC1±x (0001, 1010) interfaces was studied

See also Fig. 2.1 See also section δ-WC1±x – α/β-C – W

(continued)

2.6 Chemical Properties and Materials Design

445

Table 2.21 (continued) See also section C – W in Table I-2.13 δ-WC1±x – Ar, or α/β/ε/γ-W2±xC – CH4, W 300 Pa

–

Ar/CH4 400-500

δ-WC1±x – W (with the presence of [2, 93, 200, γ-W2±xC phase) polycrystalline bilayer 519, 910, (layer thicknesses – 2.70 and 1.07 μm, res- 1433, 3998, pectively) on stainless steel substrates was 4002, 4005, produced by the plasma-assisted pulsed arc 4010, 4012, discharge method 4017-4018] δ-WC1±x – γ-W2±xC – W coatings on stainless steel substrates were fabricated using hot filament chemical vapour deposition (HFCVD) techniques

–

500

Poreless nanostructured W – δ-WC1±x (with the presence of γ-W2±xC phase) coatings (thickness – 50±15 μm, free from intergranular inclusions) with carbide nanoparticles dispersed in columnar structured metallic matrix were fabricated on stainless steel substrates using chemical vapour deposition (CVD) technology

–

1600

Carbonized coatings on the bulk metallic W surface, prepared by spark-plasma sintering (exposure – 10 min) procedure using α-C (graphite, 99.95 % purity) powders (size distribution – 120-125 μm), exhibit three-layer δ-WC1±x – α/ε-W2+xC – W(C) (monocarbide – semicarbide – C solid solution) structure with the thicknesses of δ-WC1±x and α/ε-W2+xC layers being ~2 μm and ~20 μm, respectively

See also section C – W in Table I-2.13 α/β/ε/γ-W2±xC – H2/C3H8 350-650 W

H2

550-600

Nanocomposite coatings based on metallic [2-6, 8-13, W matrix with dispersed γ-W2±xC nanopar- 41, 53-54, ticles were fabricated by chemical vapour 61, 66-69, deposition (CVD) method; metastable 93-94, 191, W3C and W8C phases as well as γ-WC1–x 202, 519, monocarbide phase were also presented in 1060, 3057, the prepared coatings 3063, 3743, Nanocomposite coatings, containing me- 3993-3994, tallic W and γ-W2±xC (or metastable W3C) 4000-4003, phases, were fabricated on Cu substrates 4010-4012, using atmospheric chemical vapour depo- 4015-4018] sition (CVD) method with the application of dimethyl ether (DME) as a reaction gas

H2

1600-1800 Sintered W – 8.9-17.8 vol.% α/ε-W2+xC metal matrix composite (MMC) materials (porosity – 0.4-5.7 %, mean grain size – 1.4-3.1 μm) were fabricated using field assisted (pulsed d.c. electric current, 10 ms on and 10 ms off) sintering (exposure – 5 min) procedure

(continued)

446

2 Tungsten Carbides

Table 2.21 (continued) Vacuum 1750-1850 The stereographic analysis of α-W2+xC crystals, formed on the metallic W substrates due to the solid diffusion carburization process, has indicated the existence of α-W2+xC (0001) // W (110) and α-W2+xC // W orientation relationships; W atoms on the α-W2+xC (0001) match very closely with atoms on the W (110) with respect to spacing and angular relationships, so the latter represents the conjugate plane for the formation of α-W2+xC thin films Vacuum, 1900 20-50 Pa

Sintered metallic W based materials, containing 2-18 vol.% ε-W2+xC grains embedded in the matrix grains, were prepared using field-assisted sintering technology (FAST)

See also Fig. 2.1 See also section α/β/ε/γ-W2±xC – α/β-C – W See also section C – W in Table I-2.13 δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 –W

–

δ-WC1±x – γ-W2±xC – Al2O3 – TiC1–x – W δ-WC1±x – B4±xC –W

1200-1500 Al2O3 – δ-WC1±x – W cermets were prepa- [4019] red using aluminothermic reduction process

See section TiC1–x – Al2O3 – δ-WC1±x – γ-W2±xC – W in Table III-2.22 –

1650-1900 Powdered B~4.0C (99 % purity, mean par- [3, 12, 1926, ticle size – 1.5 μm) – W (99.9 % purity, 4020, 4286, mean particle size – 6.0 μm) – δ-WC0.99 4404] (mean particle size – 0.75 μm, contents: non-combined C – 0.01 %, Mo – 0.02 %, Fe – 0.01 %) mixtures with the molar ratio W/B~4.0C = 5 and mole fraction of δ-WC0.99 from 60 % to 96 % were subjected to energization hot-pressing procedure (exposure – 20 min) to prepare dense ceramic composite materials; the δ-WC1±x – α-WB1±x compositions were formed at δ-WC1±x contents ≤ 77 mol.% and δ-WC1±x – α-WB1±x – W2±xB compositions – at δ-WC1±x contents ≥ 85 mol.%

–

2100-2200 The formation of β-W2B5–x, α/β-WB1±x and α-C (graphite) phases in the reaction mixtures

See also section C – B – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

447

Table 2.21 (continued) α/β/ε/γ-W2±xC – α/β-SiC – W

–

–

Single crystal α-SiC (6H, n-type) covered [701] with crystalline γ-W2±xC – W layer (thickness – 50-90 nm) was prepared by ion beam assisted deposition (IBAD) method

See also section C – Si – W in Table I-2.14 α/β/ε/γ-W2±xC – TiC1–x – W

See section TiC1–x – γ-W2±xC – W in Table III-2.22 See also section C – Ti – W in Table I-2.14

α/β/ε/γ-W2±xC – W2±xB – W

–

~2355-2385 Eutectic ternary γ-W2±xC – W2±xB – W(C,B)

[2184-2186]

See also section C – B – W in Table I-2.14 δ-WC1±x – δ-WN1±x – W

Ar, or 20-200 Ar/N2 (50/50), 0.3 kPa

W – δ-W(C,N)1±x bilayered coatings [4021-4023] (thickness – 0.65-1.3 μm, mean grain size – 0.65-1.2 μm) were produced on stainless steel substrates using a repetitive pulsed vacuum arc discharge techniques; chemical composition and morphology of the coatings were determined by the competition between C and N observed there

Vacuum, 0.34 mPa

γ-WC1–x (crystalline, cubic) – W(C,N)1±x (amorphous) – W (amorphous) hierarchical multilayered coatings (total thickness – 5.3±0.2 μm) were deposited on Co-based alloy substrates by unbalanced reactive d.c. magnetron sputtering method

–

See also section C – N – W in Table I-2.14 α/β/ε/γ-W2±xC – ZrC1–x – W

See section ZrC1–x – γ-W2±xC – W in Table II-5.24 See also section C – W – Zr in Table I2.14

δ-WC1±x – Y

δ-WC1±x – Zn

–

–

CO2/SF6 450-470 (99/1), or Ar

–

700

The effect of substitutional Y impurities on [1984] the properties of δ-WC1±x was simulated on the basis of first principles calculations Zn (99.995 % purity) – 2.5-10.0 vol.% δ-WC1±x particle (mean size – 0.15-0.20 μm) metal matrix nanocomposites (MMNC) were manufactured using vortex agitation induced by ultrasonication of molten metal (or cold compaction of powdered Zn (mean particle size – 50 μm) – δ-WC1±x mixtures followed by a melting process as well)

[12, 151, 579, 584, 626, 1557, 1924, 1941, 4024-4027]

Zn (99.9 % purity) – 5-10 vol.% δ-WC1±x particle (mean size – 50-200 nm) metal matrix nanocomposites (MMNC) were manufactured using salt assisted stir casting procedure (exposure – 1 h) followed by hot-rolling process

(continued)

448

2 Tungsten Carbides

Table 2.21 (continued) Vacuum, 940 1.3 Pa δ-WC1±x – α/β-Zr

Sintered WC0.98 materials (content noncombined C – 0.10%) interact slightly with pure molten Zn (exposure – 144 h)

–

> 1200

–

~1400

–

1500

Practically, there is no solubility of Zr in δ-WC1±x phase

1970

Sintered WC0.98 materials (content noncombined C – 0.10%) interact actively with pure molten Zr (exposure – 5 min)

Ar

–

Decarburization of carbide due to the inter- [3, 83, 579, phase interaction is occurred 1922, 1941, The experimentally measured solubility of 1947-1948, Zr in the δ-WC1±x phase of cemented carbi- 1984, 1989, des is < 3×10–3 at.%; the DFT-calculated 3730, 40284033] value is 1.2×10–6 at.%

2200-2600 The maximum solid solubility of Zr in δ-WC1±x phase is ≤ ~1 at.%

–

–

The contact interaction of dense δ-WC1±x materials with Zr-based alloy melts leads to the adsorption of Zr atoms at the solidliquid interface and formation of precursor films, which provide good wettability and moderate reactivity of δ-WC1±x with those melts; the interfacial reactions between δ-WC1±x containing substrates and those melts yields monocarbide ZrC1–x, W-Zr intermetallides and metallic W phases

–

–

The effect of substitutional Zr impurities on the properties of δ-WC1±x was simulated on the basis of first principles calculations

See also section δ-WC1±x – α/β-C – Zr See also Table 2.26 See also section C – W – Zr in Table I2.14 α/β/ε/γ-W2±xC – Zr

–

1500

Practically, there is no solubility of Zr in α/ε-W2+xC phase

–

1700

The maximum solid solubility of Zr in α/ε-W2+xC phase is < 0.15 at.%

–

2200-2600 The maximum solid solubility of Zr in β/ε/γ-W2±xC phases is ≤ ~0.5 at.%

[1947-1948, 4028-4029, 4032-4033]

See also section α/β/ε/γ-W2±xC – α/β-C – Zr See also section C – W – Zr in Table I2.14 a The parameters of wettability of tungsten monocarbide δ-WC1±x phase by liquid metals at various temperatures are listed in Table 2.26

2.6 Chemical Properties and Materials Design

449

Table 2.22 Chemical interaction and/or compatibility of tungsten carbide phases (and/or their compositions) with refractory and other (binary and ternary) compounds in the wide range of temperatures (reaction/design systems are given mainly in alphabetical order) System

Atmo- Temperature sphere range, °C

δ-WC1±x – AlB2 – AlN – α/β-BN – TiC1–x δ-WC1±x – Al4C3

Interaction character, products and/or compatibility

References

See section TiC1–x – AlB2 – AlN – α/β-BN – δ-WC1±x in Table III-2.23 –

25

Aluminocarbide (W1–xAlx)C1–y (0.33 ≤ x ≤ 0.86) phase (mean grain size – 2-10 nm) was synthesized via mechanical alloying (MA) procedure (exposure – 120190 h) and annealed at high temperatures to prove its thermal stability

[33, 83, 2050-2055, 2058, 2101, 2132, 2139, 2170, 2183, 3893, 40624064, 4066, Aluminocarbide (W1–xAlx)C1–y (0.10 ≤ x ≤ 0.86) phase was synthesized by 4142-4148] a solid-state chemical reaction (exposure – 24-100 h)

Vacuum 1400

Higher 1600-1700 Aluminocarbide (or solid solution system) pressure (W1–xAlx)C1–y (0.10 ≤ x ≤ 0.86, devices 0.50 ≤ y ≤ 0.90) was synthesized using (4.5-5.0 high-pressure reactive sintering technique GPa) (exposure – 5-30 min); its formation, at least at the ambient pressures, contradicts with some other obtained experimental data and results of DFT calculations as well –

–

Quantum-chemical studies (calculations) of the electronic structure and some properties of probable aluminocarbide (W1–xAlx)C1–y phases have been undertaken

–

–

The properties of WAlC2–x (x = 0), W2AlC1–x (x = 0) and W3AlC2–x (x = 0) aluminocarbide (hypothetical) phases were simulated on the basis of first principles calculations The formation of (W1–xAlx)C1–y-type phases in the system is not confirmed by some authors

See section δ-WC1±x – Al in Table 2.21 See also section C – Al – W in Table I2.14 δ-WC1±x – Al4C3 – NbC1–x

See section δ-WC1±x – Al – Nb in Table 2.21

(continued)

450

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – AlN

Powdered δ-WC1.00 (> 99.5 % purity, mean [2236, 3977, particle size – 0.6 μm, specific surface area 4149-4152] – 1.85 m2 g–1; contents: non-combined C – 0.07%, O – 0.23%) – 3-16 % AlN (99.0 % purity, mean particle size – 40 nm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense materials (porosity – 0.4-3.0 %); no interaction between δ-WC1±x and AlN phases were observed

Vacuum, 1600 ≤ 6 Pa

Ar/N2 (80/20), ptot = 1 Pa

δ-WC1±x – AlN – α/γ/δ/κ/θ/χ-Al2O3 – α/β/γ-Si3N4 – α/β-Y2O3–x

–

δ-WC1±x – AlN – Cr3C2–x – α/β-Mo2±xC – δ-TiN1±x

–

–

Nanocrystalline quaternary coatings (thickness – 3.5-8.2 μm), deposited on Si (110) substrates by reactive r.f. magnetron sputtering using Al and δ-WC1±x targets, were composed of crystalline γ-W(C,N)1–x (with partial N substitution of C atoms) and AlN phases (at atomic ratio Al/W ≤ 1), or crystalline (Al,W)N1–x (W-doped solid solution) coexisting with γ-WC1–x and small amounts of sp2-bonded C amorphous phases (at the atomic ratio of Al/W > 1) Powdered δ-WC1±x (99 %, 2-3 μm) – [4334-4335] α/β-Si3N4 (> 98 %, 0.7 μm) – AlN (> 98 %, 0.8-2.0 μm) – α-Al2O3 (> 99 %, 0.5 μm) – α-Y2O3–x (> 99 %, 1-2 μm) mixtures were subjected to spark-plasma sintering (exposure – 25 min) procedures to fabricate α-YxSi12–yAlyOzN16–z – 20-80 % δ-WC1±x ceramic composites (porosity – 0.2-0.9 %, δ-WC1±x and α-sialon mean grain sizes – ~ 1-2 μm)

1750

–

(Al0.52Ti0.48)N1±x layer (with a (111) prefer- [4201] red orientation) was deposited on hot-pressed δ-(W,Mo)C1±x – 6 % α/β-Mo2±xC – 0.7 % Cr3C2–x materials using d.c. magnetron sputtering technique; coherent and semicoherent epitaxial growth relationships at the δ-(W,Mo)C1±x/(Al,Ti)N1±x interfaces and semi-coherent epitaxial growth relationships at the α/β-Mo2±xC/(Al,Ti)N1±x interfaces were identified, the minimum lattice misfit (1.9 %) was observed when (Al,Ti)N1±x was growing along its direction (parallel to the (Al,Ti)N1±x (111) crystal plane) on δ-(W,Mo)C1±x (0001)

(continued)

2.6 Chemical Properties and Materials Design

451

Table 2.22 (continued) δ-WC1±x – AlN – Ar, CrN1±x 0.2 Pa

δ-WC1±x – AlN – N2, α/β/γ-Si3N4 – 0.5-2.2 α/β-Y2O3–x MPa

–

1750

γ-WC1–x – (Cr1–yAly)N1–x (0.40 ≤ y ≤ 0.55) [4149-4150] superlattice (2-10 nm) nanocrystalline films (contaminated with Co, thickness – 2 μm) were prepared via cathodic arc ion plating on Si (100) substrates; the crystal orientations of the hetero-structured films were , , and at lower and and at higher Al contents with the γ-WC1–x/(Cr1–yAly)N1±x interface matched coherently 0.25-0.5 % δ-WC1±x (mean particle size – [4333] 4 μm) doped, powdered α/β-Si3N4 – AlN – α-Y2O3–x mixtures (preliminarily highenergy ball-milled and cold isostatically pressed) were subjected to gas pressure sintering (exposure – 4 h) procedures to fabricate 50 % α-YxSi12–yAlyOzN16–z – 50 % β-Si6–zAlzOzN8–z sialon ceramic materials containing W5Si3+x phase particles located at the triple junctions without any influence on the materials grain morphology

δ-WC1±x – AlN – Vacuum, 150 δ-TiN1±x 0.27 Pa

γ-WC1–x – (Ti1–yAly)N1–x (0.40 ≤ y ≤ 0.57) [3977] multilayered dense coatings (total thickness – ~2 μm) on high-speed steel substrates were deposited using cathodic arc techniques; most coatings exhibited a pronounced (111) texture

δ-WC1±x – CH4/H2 650-825 α/γ/δ/κ/θ/χ-Al2O3 (20/80)

γ-Al2O3 supported δ-WC1±x (10-30 % loa- [666, 693, ding) catalysts were prepared by the carbu- 839, 931, rization method 1466, 1699, δ-WC1±x layered catalyst (specific surface 1725, 1775, area – 6.3 m2 g–1) on α-Al2O3 microfiltra- 2734, 2978, tion membrane was prepared by the carbu- 3202, 4043, rization of preliminarily chemical vapour 4069-4072, 4075-4123, deposited oxides 4125-4141, Calculated equilibrium pressure of the 4272, 4452] interaction between the components using thermodynamical analysis

CH4/H2 870

CO2, 1000 1.0×10–9 Pa

Vacuum, 1200-1400 δ-WC1±x nanocrystalline reinforced < 6 Pa α-Al2O3 ceramic composites (porosity – 0.6-1.4 %, mean grain size – 0.3-0.5 μm) were prepared via metal-organic chemical vapour deposition (MOCVD) process in a spouted bed, followed by spark-plasma sintering (SPS) procedure (exposure – 10 min); the partial decarburization of δ-WC1±x phase was observed during the sintering process

(continued)

452

2 Tungsten Carbides

Table 2.22 (continued) Vacuum 1440-1740 Powdered δ-WC1±x – 10-50 vol.% Al2O3 (mainly amorphous, with the presence of trace amounts of χ-Al2O3) mixtures (preliminarily high-energy ball-milled) were subjected to hot-pressing procedure (exposure – 1-2 h) to fabricate highly dense δ-WC1±x – α-Al2O3 ceramic composites (porosity – 0.2-5.8 %, mean grain sizes: δ-WC1±x – 2.1-4.4 μm and α-Al2O3 – 1.33.5 μm, with the presence of trace amounts of α-W2+xC); the transformation of amorphous oxide to α-Al2O3 crystalline phase suppressed the decarburization of δ-WC1±x and formation of α-W2+xC phase in the prepared composites Vacuum, 1450 ~5 Pa

Powdered δ-WC1±x (99.8 %, < 0.5 μm) – 5-10 vol.% α-Al2O3 (99.99 %, < 2.2 μm) mixtures (initial purities and mean particle sizes are given in brackets; preliminarily high-energy ball-milled) were subjected to pulsed current activated sintering (PCAS) procedure (heating time – ~3 min, without any holding time at maximum temperature) to prepare dense ceramic composites (with the presence of small amounts of α/ε-W2+xC; porosity and δ-WC1±x mean grain size decreased with the increasing fraction of α-Al2O3 from 4 % to 2 % and 0.175 μm to 0.112 μm, respectively)

N2 flow 1450-1550 Powdered α-Al2O3 (99.95 %, 0.4 μm) – 6 vol.% δ-WC1±x (99.50 %, 5.0 μm) mixture (initial purities and mean particle sizes are given in brackets; preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 1 h) to fabricate dense two-phase ceramics (porosity – 0.4 %, oxide matrix mean grain size – 1.45 μm, δ-WC1±x mean grain size – 7.7±2.4 μm) –

1450-1650 Powdered α-Al2O3 (99.99 % purity, mean particle size – 0.2 μm) – 20-40 vol.% δ-WC1±x mixtures were subjected to pulsed electric current sintering (PECS) procedure (exposure – 4 min) to prepare dense ceramic composites (porosity – in the range from 0 to 0.8 %, traces of α/ε-W2+xC phase in the bulk materials were revealed)

(continued)

2.6 Chemical Properties and Materials Design

453

Table 2.22 (continued) Ar flow 1450-1650 Powdered α-Al2O3 (1.0-2.3 μm) – 5-30 % δ-WC1±x (1.0 μm) mixtures (initial mean particles sizes are given in brackets; preliminarily high-energy ball-milled) were subjected to hot-pressing procedure (exposure – 0.5 h) to fabricate dense ceramic composites (porosity – 1-2 %) –

1470-1610 Powdered α-Al2O3 (contents: MgO – 0.4 %, Fe2O3 – 0.04 %) – 10-30 vol.% δ-WC0.99 (content non-combined C – 0.05 %) mixtures (preliminarily ball-milled to particle size – 0.3-0.4 μm) were subjected to hot-pressing procedure (exposure – 5 min) to fabricate dense ceramic materials (porosity – in the range from 0 to 11 %)

Vacuum, 1500 ~5 Pa

–

1500

Powdered δ-WC1±x (99.8 %, < 0.5 μm) – 5-15 vol.% α-Al2O3 (99.99 %, < 2.2 μm) mixtures (initial purities and mean particle sizes are given in brackets; preliminarily high-energy ball-milled) were subjected to high-frequency induction-heated sintering (HFIHS) procedure (heating time – ~2 min, without any holding time at maximum temperature) to prepare dense twophase ceramic composites (porosity and δ-WC1±x mean grain size decreased with the increasing fraction of α-Al2O3 from 2.0 % to 0.2 % and 0.185 μm to 0.101 μm, respectively) α-Al2O3 – 10 vol.% δ-WC1±x particulate composites (porosity – 0.9±0.1 %) were fabricated by hot-pressing procedure (exposure – 1 h) using 1 μm sized carbide powders

Vacuum, 1540 ~0.13 Pa

Powdered δ-WC1±x (size distribution < 74 μm) – 30 vol.% Al2O3 (amorphous, mean particle size – 75 μm) mixtures (preliminarily high-energy ball-milled) were subjected to hot-pressed procedure (exposure – 1.5 h) to prepare highly dense composite materials

Vacuum, 1600 ~5 Pa

Chemical interaction (exposure – 0.5 h), taking place in the powdered δ-WC1±x (size distribution < 1 μm) – 16.7 mol.% γ-Al2O3 mixtures, leads to the formation of ε-W2+xC and metallic W phases in accordance to the following reactions: 6WC + Al2O3 = 3W2C + 2Al↑ + 3CO↑ 3WC + Al2O3 = 3W + 2Al↑ + 3CO↑

(continued)

454

2 Tungsten Carbides

Table 2.22 (continued) 1600

α-Al2O3 – 10 % δ-WC1±x highly dense ceramic composites were fabricated by sintering procedure (exposure – 2 h) of preliminarily injection-moulded mixtures of fine powders

Vacuum, 1600 ~0.13 Pa

2.5-15.0 % γ-Al2O3 whisker reinforced δ-WC1±x ceramic matrix composites (porosity – 1-5 %) were prepared through hotpressing procedure (exposure – 1.5 h) using hydrothermally synthesized NH4Al(OH)2CO3 (AACH) as a precursor for in situ whisker formation in the hotpressed materials

Ar flow 1650

Powdered α-Al2O3 (mean particle size – 2.3 μm, specific surface area – 1.5 m2 g–1) – 30 % δ-WC1±x (mean particle size – 1.5 μm) mixtures (preliminarily high-energy ball-milled) were subjected to hot-pressing procedure to prepare dense two-phase ceramic composites (porosity – 0.5 %)

Ar

–

1650-1750 Powdered α-Al2O3 (99.99 % purity, mean particle size – 0.2 μm) – 60-80 vol.% δ-WC1±x mixtures were subjected to pulsed electric current sintering (PECS) procedure (exposure – 4 min) to prepare dense ceramic composites (porosity – 0.5-1.9 %)

–

1700

–

Ar plasma, 0.4 Pa

Powdered δ-WC1±x – 30-70 vol.% α-Al2O3 mixtures were subjected to hot-pressing procedure (exposure – 2 h) to prepare dense ceramic composites –

δ-WC1±x – 32 mol.% α-Al2O3 powders, fabricated by mechano-chemical ball-milling procedure were consolidated using plasma activated sintering method to prepare bulk dense nanocrystalline ceramic composites

–

For spectrally selective solar absorbers three-layered (δ-WC1±x – 19 vol.% α-Al2O3 / δ-WC1±x – 27 vol.% α-Al2O3 / α-Al2O3) coatings were deposited on stainless steel substrates using r.f. and d.c. magnetron sputtering methods (with 99.99 % purity targets) for α-Al2O3 and δ-WC1±x, respectively

(continued)

2.6 Chemical Properties and Materials Design

455

Table 2.22 (continued) –

δ-WC1±x – α/β/ε/γ-W2±xC – α/γ/δ/κ/θ/χ-Al2O3

–

–

The following crystallographic orientation relationships between δ-WC1±x inclusions and α-Al2O3 matrix grains in α-Al2O3 – δ-WC1±x composites were determined: δ-WC1±x (0111) // α-Al2O3 (1011) with δ-WC1±x // α-Al2O3 and also δ-WC1±x (0111) // α-Al2O3 (1105) with δ-WC1±x // α-Al2O3

[1466, 4074, 1500-1700 α-Al2O3 – ~30 vol.% (δ-WC1±x + α/ε-W2+xC) ceramic materials (porosity – 4092, 4102, in the range from 0 to 12 %, oxide matrix 4132, 4140] mean grain size – 1-2 μm) were fabricated using reactive hot-pressing procedure (exposure – 10-30 min), combining densification with carbide synthesis (carbothermal reduction); structures rich in δ-WC1±x appeared as highly dispersed fine-grained (12 μm), whereas α/ε-W2+xC-rich structures were larger grained (4-6 μm) and clumped

–

–

α/β/ε/γ-W2±xC – CH4/H2 650-850 α/γ/δ/κ/θ/χ-Al2O3 (20/80) –

–

δ-WC1±x – Al2O3 – CaF2 – TiC1–x

α-Al2O3 – 20-40 % δ-WC1±x powdered mixtures (99.9 % purity) were applied as raw materials for the preparation of α-Al2O3 – γ-W2±xC – δ-WC1±x radar absorbing coatings (thickness – 1.1-1.5 mm) on Ni-based alloy substrates by atmospheric plasma-spraying technique (no chemical interaction between α-Al2O3 and δ-WC1±x phases was observed) W2±xC – γ-Al2O3 catalysts were prepared using reduction-carburization method

[1466, 1739, 4106]

Al2O3 – W2.35C composite powder (mean grain size < 60 nm) was prepared via mechanical alloying (MA) procedure

See section TiC1–x – Al2O3 – CaF2 – δ-WC1±x in Table III-2.23

δ-WC1±x – Ar α/γ/δ/κ/θ/χ-Al2O3 – CaO – α/β-SiC – α/β-Y2O3–x

1800

Powdered β-SiC – 0.45-0.85 % α-SiC – [4124, 4350] 10-50 % δ-WC1±x – 3.5 % α-Al2O3 – 1.0 % α-Y2O3–x – 0.9 % CaO mixtures were subjected to hot-pressing procedure (exposure – 1 h) to prepare dense ceramic composites

δ-WC1±x – Ar α/γ/δ/κ/θ/χ-Al2O3 – CaO – α/β/γ/δ-ZrO2–x

1600

α-Al2O3 – 10 % δ-WC1±x ceramic compo- [4099] sites (with the addition of up to 6 % CaOdoped β-ZrO2–x, porosity – 4 %) were fabricated by sintering procedure (exposure – 2 h) of preliminarily cold-pressed mixtures of fine powders

(continued)

456

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – CeO2–x

–

–

The additive of CeO2–x was applied as a [4126] sintering aid to prepare δ-WC1±x – α-Al2O3 highly dense composites via mechanical alloying (MA) followed by hot-pressing procedure

δ-WC1±x – Vacuum, 1540 α/γ/δ/κ/θ/χ-Al2O3 ~0.13 Pa – CeO2–x – MgO

Doped with 0.05-1.0 % CeO2–x (16 μm) [4111] and 0.05-1.0 % MgO (48 μm) powdered 60 vol.% α-Al2O3 (74 μm) – 40 vol.% δ-WC1±x (74 μm) mixtures (initial mean particle sizes of components are given in brackets; preliminarily high-energy ballmilled to the size distribution of ~ 50-570 nm) were subjected to hot-pressing procedure (exposure – 1.5 h) to prepare dense ceramic composites (with trace amounts of α/ε-W2+xC, porosity – ~ 1-5 %, δ-WC1±x mean grain size – ~ 2-4 μm); whereas the each additives of MgO and CeO2–x inhibited the grain growth and suppressed the decarburization of δ-WC1±x phase, respectively, the synergistic effect of usage of both additives simultaneously was revealed

δ-WC1±x – Vacuum, 1550 α/γ/δ/κ/θ/χ-Al2O3 ~0.13 Pa – Cr3C2–x

Powdered δ-WC1±x (> 99.9 %, ~60 μm) – [4107, 4118, 14 % α-Al2O3 (> 99.9 %, ~5 μm) – 0.1-1.0 4135] % Cr3C2–x (> 99.9 %, ~2 μm) mixtures (initial purities and mean particle sizes of the components are given in brackets; preliminarily high-energy ball-milled) were subjected to hot-pressing procedure (exposure – 0.5-2.5 h) to prepare dense ceramic composites (trace amounts of α/ε-W2+xC, porosity – 1.6-6.8 %, mean grain size – ~3 μm); the presence of Cr3C2–x suppressed the decarburization of δ-WC1±x phase during the heat treatment of powder mixtures

Vacuum, 1800-2000 Powdered δ-WC1±x (mean particle size – ≤ 6 Pa ~0.1 μm, inclined to agglomerate) – 1-10 % α-Al2O3 (99.99 % purity, mean particle size – ~1 μm) – 0.8 % Cr3C2–x mixtures (preliminarily high-energy ballmilling with α-Al2O3 balls) were subjected to spark-plasma sintering procedure (isothermal holding time – in the range from 0 to 5 min) to fabricate dense ceramic composites (contents of formed during the sintering process α/ε-W2+xC phase – 4.7-7.8 %, determined fraction of α-Al2O3 in the composites – 6.8-43.6 vol.%, porosity – 0.8-1.4 %)

(continued)

2.6 Chemical Properties and Materials Design

457

Table 2.22 (continued) Vacuum, 1700-1900 Powdered δ-WC1±x (≥ 99.9 % purity, mean [4328] δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 ≤ 6 Pa particle size – ~ 0.2-0.8 μm) – 9.3 % – Cr3C2–x – α-Si3N4 (mean particle size – ~1 μm, conα/β/γ-Si3N4 – tent β-Si3N4 + SiO2 < 5 %) – 0.8 % Cr3C2–x α/β-Y2O3–x (≥ 99.9 % purity, mean particle size – ~0.8 μm) – 0.6 % α-Y2O3–x (≥ 99.9 % purity, size distribution – 5-10 μm) – 0.1 % α-Al2O3 (≥ 99.9 % purity, mean particle size – ~1 μm) mixtures (preliminarily ballmilled) were subjected to spark-plasma sintering (SPS) procedure (without holding at maximum temperature) to fabricate finegrained highly dense ceramic composites (porosity ≤ 0.5 %); the presence of Cr3C2–x does not hinder the α-Si3N4 → β-Si3N4 transformation as well as growth of elongated β-Si3N4 grains δ-WC1±x – Al2O3 – Cr3C2–x – TiC1–x – VC1–x δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – MgO δ-WC1±x – Ar α/γ/δ/κ/θ/χ-Al2O3 – MgO – α/β/γ/δ-ZrO2–x

See section TiC1–x – Al2O3 – Cr3C2–x – VC1–x – δ-WC1±x in Table III-2.23 –

–

1600

δ-WC1±x – 9 % α-Al2O3 – 1 % MgO highly [4076] dense ceramic composites were prepared using pressureless sintering followed by hot isostatic pressing (HIP) treatment α-Al2O3 – 10 % δ-WC1±x ceramic compo- [3202] sites (with the addition of up to 4.5 % MgO-doped β-ZrO2–x, porosity < 5 %) were fabricated by sintering procedure (exposure – 2 h) of preliminarily cold-pressed mixtures of fine powders

δ-WC1±x – CH4/H2 870 α/γ/δ/κ/θ/χ-Al2O3 – α/β-Mo2±xC

Bimetallic α-Mo2+xC – 5-82 % δ-WC1±x [1699] layered catalysts (specific surface area – 3.2-14.5 m2 g–1) on α-Al2O3 microfiltration membrane were prepared by carburization method

δ-WC1±x – Al2O3 – α/β-SiC – TiC1–x

See section TiC1–x – Al2O3 – α/β-SiC – δ-WC1±x in Table III-2.23

δ-WC1±x – Vacuum 1450-1600 α/γ/δ/κ/θ/χ-Al2O3 – α/β/γ-Si3N4 – α/β-Y2O3–x

Powdered α-Si3N4 (mean particle size – [4326, 43280.4 μm, contents: α-phase ≥ 95%, O – 4331] 0.90%) – 3 % α-Al2O3 (99.9 % purity) – 3 % α-Y2O3–x (99.9 % purity) mixtures, containing δ-WC1±x introduced via WCball milling operation in the amounts from ~1.2 % up to ~3.5 %, were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate fully dense δ-WC1±x nanoparticle reinforced β-Si3N4 ceramics (self-toughened by the elongated grains); the partial dissolution of δ-WC1±x

(continued)

458

2 Tungsten Carbides

Table 2.22 (continued) in α/β-Si3N4 phases was detected in the materials during the processing Vacuum, 1450-1800 Powdered δ-WC1±x (> 99.9 %, 0.8-1 μm) – ≤ 6 Pa 0.9-14.0 % α-Si3N4 (> 95 %, ~1 μm, containing non-combined Si) – 0.06-0.9 % α-Y2O3–x (> 99.9 %, 5-10 μm) – 0.01-0.15 % α-Al2O3 (> 99.9 %, ~1 μm) mixtures (preliminarily high-energy ball-milled, initial purities and mean particle sizes of the components are given in brackets) were subjected to different methods of sparkplasma sintering (SPS) procedures, including zero-time and two-step variants, to fabricate toughened by in situ elongated β-Si3N4 grains (formed during SPS), dense ceramic composites with porosities in the range from 0 to ~10 %, δ-WC1±x mean grain sizes – from 0.8 μm to ~1.4 μm and fractions of β-Si3N4, β/(α + β) – from ~4 % to ~100 %; the presence of WSi2 phase at the higher α/β-Si3N4 contents and formation of the glass layer between β-Si3N4 and δ-WC1±x phases in the prepared materials were revealed

N2

α/β/ε/γ-W2±xC – N2, α/γ/δ/κ/θ/χ-Al2O3 5 MPa – α/β/γ-Si3N4 – α/β-Y2O3–x

δ-WC1±x – Al2O3 – TiC1–x

1850

Various compositions of powdered δ-WC1±x (size distribution – 2-9 μm) – Si3N4 (with additions of 6 % Y2O3–x and 2 % Al2O3) mixtures (preliminarily ballmilled and cold isostatically pressed) were subjected to sintering (exposure – 2 h) procedure to fabricate dense ceramic composites (porosity – 1-8 %)

1850

Powdered α/β-Si3N4 (0.3 μm) – 5 % [4327] α-Y2O3–x (~1 μm) – 3 % α-Al2O3 (1 μm) mixtures (preliminarily ball-milled and infiltrated by precursors (W containing aqueous solutions), initial mean particle sizes of the components are given in brackets) were subjected to gas pressure sintering procedure (exposure – 4 h) to fabricate highly dense β-Si3N4-matrix ceramic composites (with the presence of Si2N2O phase) reinforced in situ by ~0.8 vol.% nanoparticle α/ε-W2+xC (polyhedral in shape, mean size – ~60 nm, with small amounts of metallic W and W5Si3+x phases)

See section TiC1–x – Al2O3 – δ-WC1±x in Table III-2.23

(continued)

2.6 Chemical Properties and Materials Design

459

Table 2.22 (continued) Vacuum, 1540-1640 δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 ~0.13 Pa – TiO2–x (rutile, anatase, brookite)

Powdered δ-WC1±x (size distribution [4137] < 74 μm) – 30 vol.% Al2O3 (amorphous, mean particle size – 75 μm) mixtures with 2-6 % TiO2–x (nanosized) additives (preliminarily high-energy ball-milled) were subjected to hot-pressed procedure (exposure – 1.5 h) to prepare dense materials; during this treatment, the transformations of amorphous Al2O3 to γ-Al2O3, then to δ-Al2O3 and finally to α-Al2O3 modification were observed, at the higher contents of the TiO2–x the appearance of Al2TiO5–x phase was revealed

δ-WC1±x – Al2O3 – VC1–x

See section VC1–x – Al2O3 – δ-WC1±x in Table III-3.17

δ-WC1±x – Ar flow 1650 α/γ/δ/κ/θ/χ-Al2O3 – α/β-Y2O3–x

Powdered α-Al2O3 (mean particle size – [4079, 4126] 2.3 μm) – 5-30 % δ-WC1±x (mean particle size – 1.0 μm) – 3 % α-Y2O3–x mixtures (preliminarily high-energy ball-milled) were subjected to pressureless sintering (exposure – 0.5 h) to prepare dense ceramic composites (porosity – 1.6-3.8 %)

–

–

Vacuum, 1350-1600 δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 ≤ 6-8 Pa – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x

The additive of α-Y2O3–x was applied as a sintering aid to prepare δ-WC1±x – α-Al2O3 highly dense composites via mechanical alloying (MA) followed by hot-pressing procedure Powdered δ-WC1±x (> 99.9 %, ~0.8 μm) – [4108, 4131, 0.6-7.0 % α-Al2O3 (> 99.99 %, ~0.1 μm) – 4134, 4136, 0.4-6.8 % Y2O3-stabilized (3 mol.%) 4141, 4459, β-ZrO2–x (> 99.9 %, ~0.08 μm) mixtures 4476, 4480] (initial purities and mean particle sizes are given in brackets; preliminarily high-energy ball-milled) were subjected to sparkplasma sintering (SPS) procedure (exposure – 5 min), realized through liquidphase sintering mechanisms, to prepare dense three-phase ceramic composites (with the presence of small amounts of α/ε-W2+xC) toughened by α-Al2O3 – β-(Zr0.97Y0.03)O2–x eutectic or near-eutectic compositions (binders); with the increasing total amount of oxide contents from 9.5 to ~31.5 vol.%, the mean grain size of δ-WC1±x matrix phase decreased in the ranges from 30 to ~0.8 μm and that of oxide eutectic agglomeration increased from 1 to ~50 μm

(continued)

460

2 Tungsten Carbides

Table 2.22 (continued) Vacuum, 1450 ~0.1 Pa

Powdered 2 mol.% Y2O3-stabilized α/β-(Zr,Y)O2–x (crystallite size – 27-30 nm) – 40 vol.% δ-WC1±x (crystallite size – 20 nm, agglomerate size < 10 μm) mixtures with the addition of 0.75 % α-Al2O3 powder (mean particle size – 0.6 μm) were subjected to hot-pressing procedure (exposure – 1 h) to prepare full dense ceramic composites (mean δ-WC1±x grain size – 0.11 μm)

Vacuum 1450-1650 Powdered 2 mol.% Y2O3-stabilized α/β-ZrO2–x mean particle size – 27-30 nm) – 40 vol.% δ-WC1±x (crystallite size – 18 nm, size distribution of agglomerates < 10 μm) mixtures (with the addition of 0.8 % α-Al2O3 powder with mean particle size – 0.6 μm, preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 1 h) to fabricate highly dense ceramic nanocomposites –

δ-WC1±x – α/γ/δ/κ/θ/χ-Al2O3 – α/β/γ/δ-ZrO2–x

–

δ-WC1±x – 2Al2O3∙2MgO∙ 5SiO2

–

δ-WC1±x – 3Al2O3∙2SiO2

1475-1550 Powdered α-Al2O3 (specific surface area – 8 m2 g–1) – 17 vol.% Y2O3-doped (1.5 mol.%) β-ZrO2–x – 24 vol.% δ-WC1±x (mean particle size – ~0.4 μm) mixtures (preliminarily attrition-milled with β-(Zr,Y)O2–x balls) were subjected to hotpressing procedure to prepare dense ceramic composites (porosity – 0.6-2.7 %) –

1200

[4100, 4134, δ-WC1±x – α-Al2O3 – α-ZrO2–x (monoclinic) particulate nanocomposites with 4136, 4141, various compositions were designed and 4186] produced; significant differences in thermal properties of constituent phases created during the manufacturing process meaningful residual stresses (locally exceeded 1.5 MPa) The addition of 2 % δ-WC1±x to the raw [1189] materials affects the formation (synthesis) of 2Al2O3∙2MgO∙5SiO2 (cordierite)

Vacuum, 1300-1450 Powdered 3Al2O3∙2SiO2 (mullite) – 10 % [4073] ~10 Pa δ-WC1±x (mean particle size – 3 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering procedure (exposure – 3-4 min) to fabricate dense ceramic composites (porosity – 3-22 %, mullite matrix mean grain size – 0.8-2.9 μm); at temperatures ≥ 1450 °C decarburization of δ-WC1±x and formation of α/ε-W2+xC phase were observed

(continued)

2.6 Chemical Properties and Materials Design

461

Table 2.22 (continued) δ-WC1±x – B4±xC Ultra≤ 1000 high pure Ar

No significant chemical interactions (mass change or thermal activity) were observed in powdered B4±xC – 50 vol.% δ-WC1±x mixtures

–

1200-2100 According to the thermodynamic calculations, the interaction between the components leads to the formation of α-WB1±x, β-W2B5–x and α-C (graphite) phases

–

1850-1900 Powdered B4.33C (content B2O3 – 0.5%) – 10 % δ-WC1±x mixtures were subjected to reactive pulsed electric current sintering (R-PECS) to prepare B4±xC-based composite materials containing boride β-W2B5–x phase formed there in accordance to the following reaction of δ-WC1±x conversion: 5B4C + 8WC = 4W2B5 + 13C

–

2100

The chemical interaction in the powdered δ-WC1±x – 23 % B4±xC mixtures during hot-pressing process resulted in the formation of β-W2B5–x and α-C (graphite) phases

> 2500

Powdered δ-WC1.00±0.01 (mean particle size – 4-7 μm, content non-combined C – 0.05 %) – 1-15 % B4±xC (mean particle size – 68 μm) mixtures were subjected to arcplasma melting procedure followed by an in situ furnace cooling to produce multiphase composites; depending on the initial melted composition, these composites were consisting of W2±xB, β-WB1±x and β-W2B5–x boride and γ-W2±xC and δ-WC1±x carbide phases and different forms of C (α-C (graphite), β-C (diamond-like) and β-C (nanocrystalline diamond with C-C sp3 co-ordination) phases

Ar

[3, 13, 1927, 2182, 2402, 3895, 41534157]

See also section C – B – W in Table I-2.14 δ-WC1±x – B4±xC – α/β-SiC

–

2050

SiC – δ-WC1±x ceramics (with small amo- [4337] unts of W silicides), having high porosity (≥ 40 %) in the inner part and a dense surface was fabricated using pressureless sintering (exposure – 1 h) procedure and employing 0.6 % B4±xC addition as a sintering aid

See also section C – B – Si – W in Table I2.14

(continued)

462

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – B4±xC Ar flow, 2050 – α/β-SiC – 0.1 MPa ZrB2±x

Powdered ZrB2±x (~2 μm) – 27 mol.% [4358] α-SiC (0.45 μm) – 4 mol.% δ-WC1±x (~1 μm) – 4 mol.% B4±xC (0.8 μm) mixtures (preliminarily ball-milled and cold isostatically pressed, initial mean particle sizes of the components are given in brackets, the latter component was employed as a sintering aid) were subjected to sintering procedure (exposure – 2-4 h) to prepare highly dense ultra-high temperature ceramics (UHTC) composed of (Zr,W)B2±x matrix containing embedded α-SiC phase and small isolated B4±xC grains

δ-WC1±x – B4±xC – TiC1–x

See section TiC1–x – B4±xC – δ-WC1±x in Table III-2.23

δ-WC1±x – B4±xC Ar flow, 1850-2050 Powdered ZrB2±x (> 99 %, ~2 μm, content [4358, 4466, – ZrB2±x ~0.1 MPa O – 0.9 %) – 4-16 mol.% δ-WC1±x 4468] (> 99.5 %, < 1 μm) – 4 mol.% B4±xC (0.8 μm, content O – 1.3%) mixtures (preliminarily ball-milled, purities and initial mean particle sizes of the components are given in brackets, the latter component was employed as a sintering aid) were subjected to sintering procedure (exposure – 2-4 h) to prepare highly dense ultra-high temperature ceramics (UHTC) composed of (Zr,W)B2±x matrix with small isolated B4±xC grains embedded in it (at δ-WC1±x content < 8 mol.%), or (Zr,W)B2±x matrix with δ-WC1±x and B4±xC inclusions (at δ-WC1±x content ≥ 8 mol.%) δ-WC1±x – α/β-BN

Powdered δ-WC1±x (> 99.9 % purity, mean [3225, 4071, particle size – 0.2 μm) – 0.05-0.125 % 4158, 4160α-BN (nanofiber, diameter – 20-60 nm, 4161] length – ~ 10-100 μm, turbostratic structured, specific surface area – 515 m2 g–1, total pore volume – ~0.57 cm3 g–1) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (without soaking time at the highest temperature) to fabricate dense ceramic composites (porosity – 0.3-0.6 %)

Vacuum, 1800 ≤ 6 Pa

–

–

The components are compatible with each other as constituents of hard alloys and materials; there is a strong adhesion force once β-BN (cubic) is dispersed in the δ-WC1±x matrix, the major setbacks in its addition are the β-BN (cubic) → α-BN (hexagonal) conversion at elevated temperatures and low sinterability with cemented carbides

(continued)

2.6 Chemical Properties and Materials Design

463

Table 2.22 (continued) See also section C – B – N – W in Table I2.14 δ-WC1±x – α/β-BN – α/β/γ-Si3N4 – α/β-Y2O3–x

Powdered δ-WC1±x (> 99.9 % purity, mean [4161] particle size – 0.2 μm) – 9.3 % α/β-Si3N4 (> 95 % α-phase, mean particle size – ~1 μm, content Al2O3 – 1%) – 0.6 % α-Y2O3–x (mean particle size – 5-10 μm) – 0.01-0.15 % α-BN (nanofiber, diameter – 20-60 nm, length – ~ 10-100 μm, turbostratic structured, high porosity) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (without soaking time at the highest temperature) to fabricate dense ceramic composites (with the mass ratio of α-Si3N4/β-Si3N4 – less than that in raw mixtures, being in the ranges of 2.6-4.3)

Vacuum, 1750 ≤ 6 Pa

δ-WC1±x – α/β-B2 O3

–

1400

The interaction with molten B2O3 results in [1, 3, 151, the formation of α/ε-W2+xC, β-B and CO 4037]

α/β/ε/γ-W2±xC – α/β-B2 O3

–

800-1400

The interaction with molten B2O3 results in [1, 3, 151, the formation of metallic W, elemental B 4037] and CO

δ-WC1±x – BaCl2 – NaCl

–

1100

δ-WC1±x materials have interacted (exposure – 3-5 h) with a NaCl – BaCl2 melt slightly (mass change < 10 %)

δ-WC1±x – [C(CH3)COOH]n

–

60

Flexible ~ 33-67 vol.% δ-WC1±x (grain [4181] size distribution – ~ 1-5 μm, main impurity – O) – polylactic acid (polylactide, PLA) n-type thermoelectric polymer matrix composites (PMC) were fabricated by additive manufacturing (3D printing) procedures

δ-WC1±x – (C2F4)n

–

–

Polytetrafluoroethylene (C2F4)n (PTFE) bonded δ-WC1±x electrodes for catalysis purposes were designed and produced

–

–

Porous gas-diffusion electrodes containing various δ-WC1±x based catalysts (with particle sizes from 0.07 μm to 1.2 μm) were prepared by the sintering of powdered δ-WC1±x – polytetrafluoroethylene (C2F4)n (PTFE) mixtures

–

–

2-6 % δ-WC1±x (nanosized) – 47-49 % [4182] poly(methyl methacrylate) [CH2C(CH3)COO(CH3)]n (PMMA) – 4749 % polystyrene [(C6H5)CHCH2]m (PS) polymer matrix composites (PMC) were designed and fabricated for X-ray shielding applications

δ-WC1±x – [CH2C(CH3)COO (CH3)]n – [(C6H5)CHCH2]m

[585]

[1178, 1234, 1242, 1259, 1263]

(continued)

464

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – (C2H4)n

–

–

1-9 % δ-WC1±x submicrometer reinforced [1234, 4178] particles ultra-high molecular weight polyethylene (C2H4)n (UHMWPE) composite coatings were fabricated using electrostatic spraying techniques

–

–

Polyethylene (C2H4)n bonded δ-WC1±x electrodes for catalysis purposes were designed and produced

δ-WC1±x – [(C2H4)n– (CH2CHOCO CH3)m]

–

120

50-70 % δ-WC1±x powder (size distribution [1073] ≤ 10 μm) – poly(ethylene-vinyl acetate) [(C2H4)n–(CH2CHOCOCH3)m] (PEVA) polymer matrix composites (PMC) for gamma ray shielding were fabricated by hot-pressing procedure

δ-WC1±x – [C4H2(NH)]n

–

0

10-80 % δ-WC1±x (99.9 % purity, mean [4184] grain size – 0.4 μm) – polypyrrole [C4H2(NH)]n (PPy) core-shell structured polymer matrix composite (PMC) metamaterials with tailorable negative permittivity at the radio frequency were prepared using in situ polymerization method

δ-WC1±x – [(C6H3)(CN)2O (C6H4)C(CH3)2 (C6H4)O(C6H4) (CN)2]n

–

220-340

30 % δ-WC1±x (mean grain size – 50 nm) [2403, 4183] particulate reinforced phthalonitrile resin (2,2-bis[4-(3,4-dicyanophenoxy)phenyl] propane (BAPh) with 10 % 3-aminophenoxyphthalonitrile (3-APN) as a curing agent) based polymer matrix composites (PMC) were fabricated using hot-pressing curing procedure (total curing time – 27 h)

δ-WC1±x – (C6H4CH2C6H4O CH2CHOH CH2O)n

–

20-30

1-4 % δ-WC1±x powder (mean particle size [1022, 2169, – 55 nm) filled epoxy 4056-4057, (C6H4CH2C6H4OCH2CHOHCH2O)n com- 4167-4173] posites were prepared using common procedures (curing time – 48 h) and tested ~45 vol.% δ-WC1±x powder (size distribution – 20-32 μm) filled epoxy (C6H4CH2C6H4OCH2CHOHCH2O)n composites were fabricated and tested

Vacuum ~90

–

–

1-5 % δ-WC1±x powder (nanosized) filled epoxy (C6H4CH2C6H4OCH2CHOHCH2O)n composites were fabricated and tested

–

–

10-25 vol.% (39-75 %) δ-WC1±x powder (mean particle size – ~140 μm) filled epoxy (C6H4CH2C6H4OCH2CHOHCH2O)n adhesive butt joints for Al-based alloys were designed, fabricated and tested

(continued)

2.6 Chemical Properties and Materials Design

465

Table 2.22 (continued) δ-WC1±x – (C6H4CH2C6H4O CH2CHOH CH2O)n – SiO2

–

2-6 % δ-WC1±x (mean particle size – 50-55 [4056-4057] μm) reinforced glass fibre (60 % E-Glass woven fabric, bidirectional, 360 g m–2) epoxy (C6H4CH2C6H4OCH2CHOHCH2O)n composites were designed and produced

δ-WC1±x – (C6H4CH2C6H4O CH2CHOH CH2O)n – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt)

–

–

2-8 % δ-WC1±x – 60 % basalt fibre (twill- [4171-4172] directional woven fabric, SiO2 – 47-52 %, Al2O3 – 15-18 %, CaO – 6-9 %, MgO – 3-5 %, specific surface mass – 350 g m–2) reinforced epoxy (C6H4CH2C6H4OCH2CHOHCH2O)n composites were fabricated and tested

δ-WC1±x – [C6H4 C2(NH)]n

–

–

Conductive polyindole [C6H4C2(NH)]n [4180] (PIN) – δ-WC1±x nanocomposites were synthesized and tested as electroactive materials (biosensors)

δ-WC1±x – (C6H4COC6H4O)n

–

350-400

Polyaryletherketone (C6H4COC6H4O)n [1075, 2402] (PAEK) – 0.375-1.5 % δ-WC1±x powder (size distribution – 0.1-0.2 μm) nanocomposites were fabricated via melt-mixing process by twin screw extrusion techniques

δ-WC1±x – [C6H4(NH)]n

–

10-15

Conductive polyaniline [C6H4(NH)]n [1537, 4174(PANI) – δ-WC1±x composites were syn- 4177] thesized by in situ chemical oxidative polymerization of aniline C6H5NH2 in the (NH4)2S2O8 – H2SO4 system (exposure – 6-12 h) on the surface of aqueous suspended δ-WC1±x particles resulting in the formation of a chemical C=N bond between δ-WC1±x and PANI molecular chains and core-shell microstructure in the materials

δ-WC1±x – [C6H4(NH)]n – CeO2–x

–

5-10

Polyaniline [C6H4(NH)]n (PANI) – CeO2–x [4188] – δ-WC1±x composites were designed and prepared using in situ chemical oxidative polymerization (exposure – 4 h) procedure

δ-WC1±x – [(C6H4O)2CO (C6H4)]n

–

–

15 % poly(ether etherketone) [4179] [(C6H4O)2CO(C6H4)]n (PEEK) – δ-WC1±x composite membranes (with additives (plasticizers): poly-α-pinene α-(C10H16)n (PαP), poly-β-pinene β-(C10H16)n (PβP) and triethylcitrate (C2H5)3C6H5O7 (TEC)) were prepared by the casting procedure with the solutions of additives onto a glass plate

δ-WC1±x – [C6H7O2(OH)3]n

–

–

Porous cellulose [C6H7O2(OH)3]n – [4164-4166] δ-WC1±x composite (with various organic modifying additives) were designed and prepared for expanded bed application

100

(continued)

466

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – [(C6H10O5)7(OH) (CH2)4O2CHOH (C6H10O5)7(OH) O2]n

–

60-80

δ-WC1±x – 16.7-50.0 % β-cyclodextrin po- [4162-4163] lymer (with epichlorohydrin additive) [(C6H10O5)7(OH)(CH2)4O2CHOH (C6H10O5)7(OH)O2]n composite beads for expanded bed application (regular spherical in shape, followed logarithmic normal size distribution with the range of 80-320 μm and mean diameter of 143-168 μm) were prepared by reversed-phase suspension cross-linking technique

δ-WC1±x – C12H22O11 – Co3O4 – α/β/γ/ε-Fe2O3 – α/β-NiO1±x

Vacuum, 1140-1400 The chemical interaction in the powdered [4189] or Ar δ-WC1±x (2-5 μm) – 3-13 % Co3O4 (~40 nm, 23.3 m2 g–1) – 10-23 % α-Fe2O3 (~0.1 μm, 11.8 m2 g–1) – 7-9 % β-NiO1±x (~0.13 μm, 6.1 m2 g–1) mixtures (mean particle sizes and specific surface areas of the components are given in brackets) with the addition of 30 % sucrose (saccharose) C12H22O11 subjected to heat treatment (exposure – 1 h) led to the complete reduction of metal oxides, formation of fcc γ-(Fe,Ni,Co) metallic solid solutions and complete retaining of δ-WC1±x in the twophase products; in the case of higher contents of α-Fe2O3, the two-phase δ-WC1±x – bcc α-(Fe,Ni,Co) metallic solid solution mixtures were prepared in Ar atmosphere

δ-WC1±x – C12H22O11 – α/β/γ/ε-Fe2O3

Vacuum, 900-1400 or Ar

Depending on environment, the addition of [2405] 20-30 % sucrose (saccharose) C12H22O11 into the δ-WC1±x – Fe2O3 powdered mixtures leads to the different compositions of products: η2-(W,Fe)6Cy + α-Fe in vacuum and δ-WC1±x + α-Fe (with excess of C) in Ar atmosphere

δ-WC1±x – C12H22O11 – α/β/γ/ε-Fe2O3 – α/β-NiO1±x

Vacuum, 900-1300 or Ar

Depending on environment, the addition of [2406] 20-30 % sucrose (saccharose) C12H22O11 into the δ-WC1±x – Fe2O3 – β-NiO1±x powdered mixtures leads to the different compositions of products: η2-(W,Fe,Ni)6Cy + α-(Fe,Ni) in vacuum and δ-WC1±x + α-(Fe,Ni) + γ-(Fe,Ni) (with excess of C) in Ar atmosphere

δ-WC1±x – CnH2n+2 (n = 20÷40)

–

85

10-30 vol.% δ-WC1±x powders (specially [1014] synthesized with different particle sizes) – paraffin wax CnH2n+2 (n = 20÷40) matrix compositions for electromagnetic absorption purposes were prepared by uniformly mixing procedure

(continued)

2.6 Chemical Properties and Materials Design

467

Table 2.22 (continued) δ-WC1±x – C35H28N2O7

–

–

Gas electrodes for fuel cells made from [1787] δ-WC1±x bonded with polyimide resin ~C35H28N2O7 were designed and prepared

δ-WC1±x – α-C3N4 (graphite-like)

–

–

15 % δ-WC1±x loaded α-C3N4 (graphite[1696, 1758] like) nanosheets were prepared for photocatalysis purposes 1-7 % nanocrystalline γ-WC1–x (mean size – ~2.0±0.3 nm) – α-C3N4 (graphite-like) co-photocatalysts were prepared by heat treatment (exposure – 1 h)

N2 flow 200

α/β/ε/γ-W2±xC – α-C3N4 (graphite-like) δ-WC1±x – CaO

δ-WC1±x – 3CaO∙Al2O3 – 4CaO∙Al2O3∙ Fe2O3 – 2CaO∙SiO2 – 3CaO∙SiO2

–

–

Vacuum, 1600 ~5 Pa

–

α-C3N4 (graphite-like) – γ-W2±xC compo- [1757] site photocatalysts were designed and fabricated Chemical interaction (exposure – 0.5 h), [4272] taking place in the powdered δ-WC1±x (size distribution < 1 μm) – 16.7 mol.% CaO mixtures, leads to the formation of ε-W2+xC phase in accordance to the following reaction: 2WC + CaO = W2 C + Ca↑ + CO↑

–

Containing δ-WC1±x nanopowders, obtain- [4371] ed by recycling of hard alloy waste, were employed for the modification of Portland cement (3CaO∙SiO2, 2CaO∙SiO2, 3CaO∙Al2O3, 4CaO∙Al2O3∙Fe2O3) to prepare special kinds of concrete

δ-WC1±x – CaO Pure Ar 1350-1950 Powdered α/β/γ-ZrO2–x (partially stabilized [4185] – α/β/γ/δ-ZrO2–x flow by 7 mol.% CaO, composed of equiaxed (mean size – 10 nm) and needle-like (width – 30-64 nm, length/width ratio – 2.5÷5.6) crystallites, specific surface area – ~54±1 m2 g–1, content α-ZrO2–x (monoclinic) – 50±2 vol.%) – 10 vol.% δ-WC1±x (mean particle size – ~0.6 μm) mixtures (preliminarily cold isostatically pressed) were subjected to pressureless sintering to prepare dense ceramic composites (the porosity increased with the growth of sintering temperature from 0.3 % to 4.5 %); the observed decomposition of δ-WC1±x to in situ formed metallic W phase (up to 5.6 vol.%) was proposed to proceed in accordance to the following subsequential reactions: ZrO2–x + 2yWC = yW2C + ZrO2–x–y + yCO, ZrO2–x + yW2C = 2yW + ZrO2–x–y + yCO, which changed the γ-ZrO2–x (cubic) and β-ZrO2–x (tetragonal) phase contents in the sintered materials through the creation of additional amounts of O vacancies avai-

(continued)

468

2 Tungsten Carbides

Table 2.22 (continued) lable for the stabilization processes, the formation of ZrC1–x phase accompanied these reactions above 1750 °C was also revealed δ-WC1±x – α/β-CdS

–

δ-WC1±x – α/β-CdS – TiO2–x (anatase, rutile)

α-CdS (mean grain size – ~ 30-40 nm) – [417, 1439, 2-10 % δ-WC1±x (mean grain size – ~ 5-50 1673] nm) nanocomposite photocatalysts were synthesized via autoclave (hydrothermal) treatment (exposure – 24 h) procedure

150

–

–

By loading β-CdS nanoparticles (mean size – ~5 nm, negatively charged) on δ-WC1±x hollow spheres (diameter – ~0.5 μm, wall thickness – ~50 nm, specific surface area – ~400 m2 g–1, pore diameter distribution – 4.3-29.6 nm with a maximum at 7.4 nm, positively charged) the composite photocatalysts were fabricated

–

–

By supporting CdS quantum dots (QD) [1673] (with sizes < 5 nm) and δ-WC1±x on TiO2–x (content of rutile – ~70 %), α-CdS – δ-WC1±x – TiO2–x composite photocatalysts were fabricated from aqueous solutions

1650

Powdered α-Si3N4 (0.7 μm) – 5-15 % [4332] δ-WC1±x (0.5 μm) – 5 % MgSiN2 (0.5 μm) – 3 % α-Y2O3–x (1 μm) – 1 % CeO2–x (1 μm) mixtures (preliminarily high-energy ball-milled, initial mean particle sizes are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 6 min) to prepare dense hard materials (porosity – ~ 0.6-1.0 %); the contents of β-Si3N4, formed during the processing due to the α → β transformation, increased with the increase in δ-WC1±x contents in the mixtures

δ-WC1±x – CeO2–x Vacuum, 1450 – α/β-Y2O3–x – 4 Pa α/β/γ/δ-ZrO2–x

α/β-ZrO2–x (partially stabilized by 1 mol.% [4186] α-Y2O3–x + 6-8 mol.% CeO2–x, content α-ZrO2–x (monoclinic) – 19-24 vol.%, transformability of β-ZrO2–x (tetragonal) – 20-32 vol.%) – 40 vol.% δ-WC1±x ceramic composites were prepared using pulsed electric current sintering (PECS) procedure (exposure – 4 min)

δ-WC1±x – CoF3

Powdered δ-WC1±x materials interacted [4569] (exposure – 9 h) with the formation of W fluorides and gaseous fully saturated fluorocarbons CF4, C2F6, C3F8 and C4F10

δ-WC1±x – CeO2–x – MgSiN2 – α/β/γ-Si3N4 – α/β-Y2O3–x

Ar

–

440-450

δ-WC1±x – Co3O4 CO2, 1000 500 MPa

Calculated equilibrium pressure of the [693, 4043] interaction between the components using thermodynamical analysis

(continued)

2.6 Chemical Properties and Materials Design

469

Table 2.22 (continued) δ-WC1±x – Co3O4 Vacuum, 1140-1400 The chemical interaction in the powdered [4189] – α/β/γ/ε-Fe2O3 – or Ar δ-WC1±x (2-5 μm) – 3-13 % Co3O4 (~40 α/β-NiO1±x nm, 23.3 m2 g–1) – 10-23 % α-Fe2O3 (~0.1 μm, 11.8 m2 g–1) – 7-9 % β-NiO1±x (~0.13 μm, 6.1 m2 g–1) mixtures (mean particle sizes and specific surface areas of the components are given in brackets) subjected to heat treatment (exposure – 1 h) led to the formation of intermetallide μ-(Fe,Co,Ni)7W6±x, complex oxide (Fe,Co,Ni)WO4±x and metallic W phases δ-WC1±x – CoO CO2, 7 MPa

1000

Calculated equilibrium pressure of the [693, 792, interaction between the components using 4043] thermodynamical analysis

Vacuum, 2200-2400 The addition of ~0.3 % CoO as a fugitive ~13 Pa binder was applied for sintering of δ-WC0.99 (~97 % purity) powder δ-WC1±x – Co(OH)2

–

–

Co(OH)2 hydroxide modified δ-WC1±x na- [431] norods array on Ni foam substrates were synthesized for electrocatalysis purposes using thermal evaporation and electrodeposition

δ-WC1±x – CrB2±x

–

–

Depending on composition, the arc-melted [4059] δ-WC1±x – 12-40 mol.% CrB2±x materials contained δ-WC1±x, γ-WC1–x, γ-W2±xC, and CrB2±x phases

δ-WC1±x – Cr3C2–x

Ar, 800-1200 0.1 kPa

–

Powdered δ-WC1±x (mean particle size – [3-5, 13, 43, ~ 0.1-0.4 μm) – 1 % (~3 vol.%) Cr3C2–x 47, 53, 150, (mean particle size – ~ 0.5-1.5 μm) mixtu- 155, 193, res (preliminarily ball-milled intensively, 794, 939, total C content – in the range from 5.88 % 1285, 1845, to 6.24 %) were subjected to cold isostatic 2387-2393, pressing followed by sintering (exposure – 3395-3401, 0.5 h) procedure; added Cr3C2–x particles 3456, 3724, in the mixtures with lower C content com- 4044, 4052, pletely dissociated into metallic Cr and 4190-4201, α-C (graphite) with the dissolution of Cr 4503] into the forming α/ε-(W,Cr)2+xC solid solution phases (> 1100 °C only pores remained, and no Cr or Cr carbides could be detected), and only in the mixtures with higher C content Cr-rich phases were revealed

1300-1350 The maximum solid solubility of δ-WC1±x in Cr3C2–x corresponds to ~ 4.0-8.8 at.% W (~(Cr0.85÷0.93W0.07÷0.15)3C2–x) and that of Cr3C2–x in δ-WC1±x corresponds to ~ 1-3 at.% Cr (~δ-(W0.94÷0.98Cr0.02÷0.06)C1±x)

(continued)

470

2 Tungsten Carbides

Table 2.22 (continued) 1500-1700 Powdered Cr3C2–x – 14-25 vol.% δ-WC1±x mixtures were subjected to hot-pressing (exposure – 1 h) procedure to fabricate particulate ceramic matrix composites (CMC) with porosities and matrix mean grain sizes in the ranges of 0.2-4.0 % and 2.5-6.0 μm, respectively

Ar

–

1550-1800 The maximum solid solubility of δ-WC1±x in Cr3C2–x corresponds to ~9.5 at.% W (~(Cr0.84W0.16)3C2–x) and that of Cr3C2–x in δ-WC1±x corresponds to ~1.5 at.% Cr (~δ-(W0.97Cr0.03)C1±x)

–

1750

A wide band of α/ε-(W,Cr)2+xC phase with a constant C profile and strongly varying W and Cr concentrations from 10.8 at.% W and 55.4 at.% Cr (W/Cr ≈ 0.2) at the Cr3C2–x / α/ε-(W,Cr)2+xC interface to 31 at.% W and 35.4 at.% Cr (W/Cr ≈ 0.9) at the α/ε-(W,Cr)2+xC / δ-WC1±x interface was observed in the contact zone of Cr3C2–x – δ-WC1±x diffusional couple after 6 h exposure (a significant amount of Cr was found in δ-WC1±x at a distance up to several micrometres from the interface), in the case of long isothermal annealing and by application of a heavy static load onto the diffusion couples the interface was ragged and a porous layer (explained by the Kirkendall effect) was formed in δ-WC1±x, this layer formed another layer (still located within δ-WC1±x), which contained free α/ε-(W,Cr)2+xC particles and was poreless, more likely in this case W diffuses faster into α/ε-(W,Cr)2+xC phase than Cr into δ-WC1±x, since neither the porosity nor the precipitation of α/ε-(W,Cr)2+xC was found in the couples at lower static loads, the porosity was attributed to an influence of pressure onto the microstructure of δ-WC1±x phase

–

1800

A new phase (tetragonal, ?) was revealed in the sintered δ-WC1±x – Cr3C2–x mixtures

–

1900

Powdered δ-WC1±x (mean particle size – 0.09-0.4 μm) – 0.1-0.7 % Cr3C2–x (mean particle size – ~ 0.5-1.5 μm) mixtures (preliminarily ball milled) were subjected to gas-pressurized sintering (GPS, 8 MPa), or alternatively, spark-plasma sintering (SPS, vacuum, exposure – 10 min) procedures to prepare dense ceramics (porosity – in the range from 0 to 0.9 % for GPS- and from

(continued)

2.6 Chemical Properties and Materials Design

471

Table 2.22 (continued) 1.5 % to 9.4 % for SPS-materials, materials of both types contained α/ε-(W,Cr)2+xC phase) Ar, 1900 10 MPa

–

–

Powdered δ-WC1±x (mean particle size – ~ 0.1-0.4 μm) – 1 % (~3 vol.%) Cr3C2–x (mean particle size – ~ 0.5-1.5 μm) mixtures (preliminarily ball-milled intensively) were subjected to cold isostatic pressing followed by hot isostatic pressing (HIP) procedure to prepare poreless ceramics (mean grain size – 0.22-0.27 μm); no pure Cr3C2–x phase could be found, hinting the dissolution of it within the δ-WC1±x matrix, containing 4-12 % α/ε-(W,Cr)2+xC phase The effect of substitutional Cr impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations, the stability of the probable δ-(W,Cr)C1±x solid solutions was confirmed Data available on the system in literature are controversial, some data reported by the various authors differ markedly

See also section C – Cr – W in Table I2.14 α/β/ε/γ-W2±xC – Cr3C2–x

–

1300-1350 The limit of solubility of “imaginary” phase ‘Cr2C’in α/ε-W2+xC is ~ 87-90 mol.%; Cr2C can be considered as a metastable phase stabilized by the W addition

[3, 53, 193, 794, 23872393, 3724, 3395-3401, The composition of α/ε-(W,Cr)2+xC phase 3456, 3552] reaches from ~(W0.50Cr0.50)2C (in equilibrium with δ-WC1±x) to ~(W0.20Cr0.80)2C (in equilibrium with Cr3C2–x)

–

1750

–

1800

The maximum solid solubility of Cr in α/ε-W2+xC phase corresponds to ~(W0.15Cr0.85)2C composition and that of W in Cr3C2–x corresponds to ~(Cr0.85W0.15)3C2–x composition

See also section C – Cr – W in Table I2.14 γ-WC1–x – Cr3C2–x

–

1800

The Cr-stabilized γ-WC1–x phase exists in [47, 53, ~γ-(W0.30÷0.40Cr0.60÷0.70)C1–x (x ≈ 0.42÷0.44) 2393, 3398range of compositions 3401, 3724]

See also section C – Cr – W in Table I2.14

(continued)

472

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – Ar flow 1600 Cr3C2–x – Cr7C3±x

δ-WC1±x – Cr3C2–x – Cr7C3±x coatings [1845] (thickness – 25 μm), prepared by sparkplasma sintering (SPS) procedure (exposure – 10 min) on metallic W substrates, were composed of δ-WC1±x matrix and Cr carbides particles distributed in the surface layer of the coatings

See also section C – Cr – W in Table I2.14 δ-WC1±x – Vacuum, 1450 Cr3C2–x – FeAl1±x 10 mPa

Powdered δ-WC1±x (mean particle size – [4235] 0.75 μm) – 25 vol.% FeAl0.67 (mean particle size – 5.6 μm) mixtures (preliminarily ball-milled with 0.5 % Cr3C2–x added) were subjected to liquid-phase sintering (expo-sure – 1 h) procedure to fabricate dense two-phase carbide-intermetallide compo-sites (porosity – 3.6 %, δ-WC1±x mean grain size – ~0.5 μm)

δ-WC1±x – Cr3C2–x – HfC1–x – β-Mo2±xC – TiC1–x – δ-TiN1±x

See section HfC1–x – Cr3C2–x – β-Mo2±xC – TiC1–x – δ-TiN1±x – δ-WC1±x in Table II3.20

δ-WC1±x – Cr3C2–x – MgO

δ-WC1±x – Cr3C2–x – MgO – δ-TiN1±x

Vacuum, 1650 1,3 mPa

–

1575-1750 δ-WC1±x– 5 % MgO – 1 % δ-TiN1±x – 0.6 [4200] % Cr3C2–x ceramics was fabricated using two-step hot-pressing sintering (exposure – 1 h) procedure

δ-WC1±x – Cr3C2–x – MgO – VC1–x δ-WC1±x – Cr3C2–x – β-Mo2±xC

Powdered δ-WC1±x (99.5 %, 74 μm) – 4.3 [4194, 4265] % MgO (99.5 %, 48 μm) – 0.5 % Cr3C2–x (99.9 %, 0.2 μm) mixtures (preliminarily high-energy ball-milled, initial purities and mean particle sizes are given in brackets) were subjected to hot-pressing procedure (exposure – 1.5 h) to fabricate dense fine ceramics (porosity – 0.2 %, δ-WC1±x mean grain size – 2.7±0.1 μm)

See section VC1–x – Cr3C2–x – MgO – δ-WC1±x in Table III-3.17 Vacuum 1700

δ-WC1±x – 6 % β-Mo2±xC – ~0.7 % Cr3C2–x [4201] ceramics was fabricated by hot-pressing (exposure – 1 h) procedure using ultra-fine δ-WC1±x starting powder (doped with Cr, specific surface area – 1.75 m2 g–1)

(continued)

2.6 Chemical Properties and Materials Design

473

Table 2.22 (continued) δ-WC1±x – Cr3C2–x – β-Mo2±xC – α/β-SiC

Vacuum 1600

Powdered δ-WC1.00±0.01 (mean particle [4195] sizes – 0.71-0.75 μm; contents: non-combined C – 0.01-0.03 %, Fe – 0.05%, Mo – 0.02%) – 4.85 mol.% β-SiC (mean particle size – 0.31 μm; contents: non-combined C – 1.08%, Al – 0.015%, SiO2 – 0.39%) – 1 mol.% β-Mo2.01C (size distribution – 1.01.6 μm; contents: non-combined C – 0.05%, O – 0.34%, Fe – 0.03%) – 0.1-0.3 mol.% Cr3C1.98 (mean particle size – 7.5 μm; contents: O – 0.12%, Fe – 0.025%) mixtures were subjected to hot-pressing (exposure – 10 min) procedure to prepare dense ceramics (porosity – < ~ 1-2 %, δ-WC1±x mean grain size – ~ 0.5-0.7 μm) with the presence of small amounts of (Mo,W,Cr)5Si3Cy compound (Nowotny phase)

δ-WC1±x – Cr3C2–x – β-Mo2±xC – VC1–x

See section VC1–x – Cr3C2–x – β-Mo2±xC – δ-WC1±x in Table III-3.17

δ-WC1±x – Vacuum 1600 Cr3C2–x – α/β-SiC

[4191, 4193, δ-WC1±x – 20 mol.% β-SiC – 0.1-1.5 mol.% Cr3C2–x dense ceramic matrix com- 4199] posites (CMC) were prepared by hot-pressing techniques with the presence of small amounts of (W,Cr)5Si3Cy compound (Nowotny phase)

Vacuum 1650

–

1750

Powdered δ-WC0.99 (mean particle size – ~ 0.6-0.7 μm, doped with 0.06-0.7 mol.% Cr3C2–x, contents: non-combined C < 0.01%, Fe – 0.05%, Mo – 0.02%) – 5 vol.% β-SiC (whisker, mean diameter – 0.4 μm, length – ~30 μm, content SiO2 – 0.20%) mixtures were subjected to hotpressing (exposure – 10 min) procedure to fabricate poreless ceramic matrix composites (CMC) with δ-WC1±x mean grain size – 1.2-3.5 μm δ-WC1±x – 10 mol.% β-SiC – 0.7 mol.% Cr3C2–x poreless particulate ceramic composite materials (CMC) were fabricated by pressureless sintering

δ-WC1±x – Cr3C2–x – α/β-SiC – VC1–x

See section VC1–x – Cr3C2–x – α/β-SiC – δ-WC1±x in Table III-3.17

δ-WC1±x – Cr3C2–x – Si3N4 – VC1–x – Y2O3–x

See section VC1–x – Cr3C2–x – Si3N4 – δ-WC1±x – Y2O3–x in Table III-3.17

(continued)

474

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – Cr3C2–x – TiB2±x – TiC1–x – δ-TiN1±x

See section TiC1–x – δ-TiN1±x – Cr3C2–x – TiB2±x – δ-WC1±x in Table III-2.23

δ-WC1±x – Cr3C2–x – TiC1–x

See section TiC1–x – Cr3C2–x – δ-WC1±x in Table III-2.23

δ-WC1±x – Cr3C2–x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x

Vacuum, 1500-1700 Powdered δ-WC1±x (> 99.9 % purity, mean [4197] ≤ 6 Pa particle size – ~0.2 μm, contents: Cr3C2–x – 0.8 %) – ~18 vol.% α/β-ZrO2–x (3 mol.% Y2O3-stabilized, mean particle size – ~0.1 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense ceramic composites (porosity – 0.3-1.5 %, grain sizes of δ-WC1±x and α/β-ZrO2–x phases – in the ranges of 0.18-0.25 μm and 0.18-0.21 μm, respectively); no chemical interaction between carbide and oxide phases was detected

δ-WC1±x – Cr7C3±x

– –

575-600

The alloying of Cr-containing steels with [3, 53, 193, W stimulates the formation Cr7C3±x phase 794, 23871300-1350 The maximum solid solubility of δ-WC1±x 2393, 3007in Cr7C3±x corresponds to ~ 3.8-4.5 at.% W 3008, 3029, (~(Cr0.0.94÷0.95W0.05÷0.06)7C3±x) and that of 3395-3401, Cr7C3±x in δ-WC1±x corresponds to ~ 1-3 3552, 3724, 4052, 4202] at.% Cr (~δ-(W0.94÷0.98Cr0.02÷0.06)C1±x)

See also section C – Cr – W in Table I2.14 α/β/ε/γ-W2±xC – Cr3C – Fe3C – Mn3C

–

δ-WC1±x – Cr23C6±x

–

Ar

–

The composition of complex cementite [639, 3552] phase in Cr-containing stainless steel was revealed to be ~(Fe0.76Cr0.12Mn0.11W0.01)3C

1300-1350 The maximum solid solubility of δ-WC1±x in Cr23C6±x corresponds to 10-20 at.% W ((Cr0.750÷0.875W0.125÷0.250)23C6±x) and that of Cr23C6±x in δ-WC1±x corresponds to ~ 1-3 at.% Cr (~δ-(W0.94÷0.98Cr0.02÷0.06)C1±x) 2165

Powdered δ-WC1±x (96.7 % purity, mean particle size – 20 nm, contents: α/ε-W2+xC – 1.5 %, W – 1.9 %) – 1.5-30.0 vol.% Cr23C6±x (mean particle size – 0.1 μm, content Cr2O3 – 3 %) mixtures were subjected to liquid-phase sintering to prepare threeor two-phase dense materials, containing δ-WC1±x, α/ε-(W,Cr)2+xC and α-C (graphite) phases – in the case of starting mixtures with ≤ 20 vol.% Cr23C6±x and α/ε-(W,Cr)2+xC and α-C (graphite) phases – in the case of mixtures with > 20 vol.% Cr23C6±x

[53, 193, 794, 23872393, 30073008, 33953401, 3724, 4052, 4203]

(continued)

2.6 Chemical Properties and Materials Design

475

Table 2.22 (continued) Some data on the system reported by the various authors differ markedly

See also section C – Cr – W in Table I2.14 δ-WC1±x – CrN1±x Ar/N2 (60/40), ptot = 1 Pa

–

–

Nanocrystalline quaternary coatings [2305, 4152, (thickness – 3.5-8.2 μm), deposited on Si 4204-4205] (110) substrates by reactive r.f. magnetron sputtering using Cr and δ-WC1±x targets, were composed of crystalline γ-W(C,N)1–x (with partial N substitution of C atoms) and CrN1±x phases (at atomic ratio Cr/W ≤ 1), or crystalline (Cr,W)N1–x (W-doped solid solution) coexisting with γ-WC1–x and small amounts of sp2-bonded C amorphous phases (at atomic ratio Cr/W > 1)

–

δ-WC1±x – CrN1±x super-hard nanocomposite films were designed and deposited onto steel substrates using arc ion plating technique

δ-WC1±x – Cr2O3 CO2, 1000 0.89 Pa

[1, 151, 693, Calculated equilibrium pressure of the interaction between the components using 4034-4035, thermodynamical analysis 4043]

Vacuum, 1000-1200 The start of noticeable interaction between 0.13 Pa the components in powdered mixtures Vacuum 1300-1400 The interaction (exposure – 0.5 h) in powdered mixtures of components leads to the complete reduction of oxide phase and formation of W-Cr alloys

See also section C – Cr – O – W in Table I-2.14 δ-WC1±x – Cu3N Vacuum, – δ-TiN1±x 0.85 Pa

δ-WC1±x – CuZr2 Ar

–

Thin films (thickness – ~ 0.4-0.8 μm at 1 h [4206] exposure) composed of columnar δ-WC1±x crystals (size – 3-5 nm) and amorphous Cu3N phases with various compositions were prepared on δ-TiN1±x (with the presence of metallic Ti) interlayer by the layer-plus-island mode using the hybrid technique of arc ion plating and d.c. magnetron sputtering

1050-1150 Pressureless infiltration of molten CuZr2 [3529-3531, intermetallide into a porous δ-WC1±x pre- 4207-4208] form was accompanied with the chemical interaction leading to the formation of metallic W (adjacent to the δ-WC1±x substrate) and ZrC1–x (adjacent to the intermetallide melt) layers at the solid-melt interface in accordance with dissolution-precipitation mechanism

(continued)

476

2 Tungsten Carbides

Table 2.22 (continued) –

1150-1400 Continuous adherent layers of metallic W and ZrC1–x phases were formed at the δ-WC1±x – CuZr2 melt interfaces (exposure – 1.5-24 h) due to the incongruent reduction of δ-WC1±x controlled by C diffusion through one or both of the product layers

Vacuum 1300

Pre-sintered δ-WC1±x foam with uniform microstructure (porosity – 47-56 %) was subjected to the reactive melt infiltration, known also as displacive compensation of porosity (DCP) method, by intermetallide CuZr2 (exposure – 2 h), which finally has resulted in the formation of ~58 vol.% W – ~42 % ZrC1–x dense materials

See also section δ-WC1±x – Cu – Zr in Table 2.21 δ-WC1±x – (Cu51Zr14, CuZr2) – α/β-Mo2±xC

High1200-1600 The interaction of solid dense (or porous) [3531] purity Ar polycrystalline δ-(W~0.9Mo~0.1)C1±x (containing α/ε-(W~0.9Mo~0.1)2+xC phase) materials with molten CuZr2 and Cu51Zr14 intermetallides during contact incongruent reactions and infiltration processes (exposure – 15 min) led to the dissolution of δ-(W~0.9Mo~0.1)C1±x in the melts, which is restrained by the formation of a continuous ZrC1–x layer at higher temperatures

See also section δ-WC1±x – β-Mo2±xC – Cu – Zr in Table 2.21 δ-WC1±x – FeAl3±x

δ-WC1±x – FeAl1±x

Vacuum, ~1600 10 Pa

–

400

–

650

Powdered δ-WC1±x (99 % purity, mean [4241] particle size – ~0.2 μm) – 5-10 vol.% FeAl3±x (99.9 % purity, size distribution < 45 μm) mixtures (preliminarily highenergy ball-milled up to δ-WC1±x mean particle sizes of 15-19 nm) were subjected to pulsed current activated sintering (PCAS) procedure (heating time – 100 s, without any holding at maximum temperature) to prepare dense two-phase materials (porosity – 3-4 %, δ-WC1±x mean grain size – 60-84 nm); no chemical interaction between the components were observed

[1985, 2129, FeAl~1.0 – δ-WC1±x intermetallic matrix composite powders were produced through 2239, 4071, mechanical alloying (MA) followed by an- 4210-4220, nealing heat treatment procedures 4223-4240, 4243-4245, 40 vol.% δ-WC1±x reinforced FeAl1±x in situ matrix composite coatings were prepa- 4498] red using cold spraying of mechanically alloyed (MA) powdered compositions followed by post-spray annealing (PSA)

(continued)

2.6 Chemical Properties and Materials Design

477

Table 2.22 (continued) Vacuum 1000

δ-WC1±x – 25 vol.% FeAl0.67 dense composite materials (with the small amounts of η2-W3Fe3Cy and Al oxides) were prepared using pulsed current sintering (PCS) techniques

Vacuum 1100-1300 δ-WC1±x – 35-85 vol.% FeAl0.67 (synthesized by mechanical alloying method) dense composite materials were fabricated using pulsed current sintering (PCS) or hot isostatic pressing (HIP) procedures 1100-1300 δ-WC1±x – 40 vol.% FeAl0.67 dense composites were produced by hot-pressing techniques

Ar

Vacuum, 1140-1170 Powdered δ-WC1±x (several kinds with 10 Pa mean particle sizes from 0.12 μm to 2.3 μm) – 15-45 vol.% FeAl0.67 (mean particle size – 5.6 μm, main impurity – α-Al2O3) mixtures (preliminarily ball-milled) were subjected to pulse current sintering (PCS) procedure (exposure – 3 min) to prepare highly dense composites Vacuum, 1150 1.3 Pa

Highly dense δ-WC1±x – 25 vol.% FeAl0.67 carbide-intermetallide composites were fabricated by spark-plasma sintering (SPS) procedure (exposure – 3 min) from the powdered mixtures prepared using mechanical alloying (MA) techniques

–

1150-1200 δ-WC1±x – 10 % FeAl0.54 dense composite materials were fabricated using pulsed current sintering (PCS) procedure (exposure – 5 min)

–

1230

–

1280-1350 Using δ-WC1±x – 38-40 vol.% FeAl0.67 powdered compositions, rod shape and cylindrical shape compacts were produced by traveling zone sintering (TZS) techniques

–

1450

Powdered δ-WC1±x (75 μm) – 9 % FeAl0.67 (5.6 μm) mixtures (preliminarily highenergy ball-milled, initial mean particle sizes of the components are given in brackets) were subjected to pulsed current sintering (PCS) procedure (exposure – 5 min) to fabricate cutting tools

Molten aluminide FeAl0.67 (in equilibrium with α-C (graphite) phase) dissolves ~5 at.% C and 1 at.% W

(continued)

478

2 Tungsten Carbides

Table 2.22 (continued) Vacuum, 1450 0.1-1.0 mPa

Powdered δ-WC1±x (2-10 μm) – 10-70 vol.% FeAl0.66±0.01 (< 45 μm) mixtures (size distributions of the components are given in brackets) were subjected to pressureless melt infiltration or liquid-phase sintering (exposures – 15 min) to prepare dense composite materials with various porosities; sufficiently thin (< 2 μm) ligaments of FeAl0.66±0.01 in the prepared materials tend to fracture in a ductile manner

Vacuum, 1450 0.01-0.1 Pa

Powdered δ-WC1±x (0.75 μm) – 25 vol.% FeAl0.67 (5.6 μm) mixtures (ball-milled in various conditions, initial mean particle sizes of the components are given in brackets) were subjected to liquid-phase sintering (exposure – 1 h) procedure to prepare dense δ-WC1±x-based composites with the different O contents: higher O content led to much larger increase in the Fe/Al atomic ratio of FeAl1±x phase, whereas at lower O content its composition became only a little Fe-richer than in FeAl0.67, such impurities as α-Al2O3, η2-W3Fe3Cy, FeAl2O4 and α-Fe2O3 were identified in the composites with higher O content, while only Fe3AlC1–x (with trace of α-Al2O3) phase was revealed in the lower-O materials; the rise of O content in the composites from 0.84 % to 1.58 % was accompanied with the increase of porosity from 2.9 % to 4.2 % and decrease of δ-WC1±x mean grain size from 0.84 μm to 0.60 μm

Vacuum, 1500 10 Pa

Powdered δ-WC1±x (99 %, < 2 μm) – 5-10 vol.% FeAl1±x (99 %, < 74 μm) mixtures (preliminarily high-energy ball-milled, initial purities and size distributions are given in brackets) were subjected to high-frequency induction-heated sintering (HFIHS) procedure (heating time – ~2 min, without any holding at maximum temperature) to prepare dense two-phase composites (porosity – 1.8-2.5 %, δ-WC1±x mean grain size – 92-97 nm)

–

–

By selecting two kinds of the powder mixtures, having various volume fraction of the FeAl0.67 component, δ-WC1±x – FeAl1±x double layer composites were fabricated by pressure-assisted sintering techniques

(continued)

2.6 Chemical Properties and Materials Design

479

Table 2.22 (continued) –

–

Powdered FeAl0.67 – 10-20 % δ-WC1±x mixtures (size distribution < 60 μm) were employed as high-velocity oxy-fuel (HVOF) spraying feedstock materials for the deposition of δ-WC1±x – Fe – Al (with the presence of FeAl1±x and Fe3±xAl aluminides) lamellar-structured metal matrix composite (MMC) coatings (thickness – 0.2-0.4 mm) on low alloyed steel substrates

See also section δ-WC1±x – Al – Fe in Table 2.21 δ-WC1±x – FeAl1±x – Fe2B

–

1100-1200 δ-WC1±x-based materials with 35-85 vol.% [2238, 4214, intermetallide binder (FeAl0.67 – 3-8 mol.% 4217] Fe2B) were prepared from powders by pulse current sintering (PCS) procedure

–

1150-1200 δ-WC1±x – 10 % Fe(Al0.52B0.08) highly dense composite materials were fabricated using pulsed current sintering (PCS) procedure (exposure – 5 min)

See also section δ-WC1±x – Al – B – Fe in Table 2.21 See also section δ-WC1±x – FeAl1±x – β-B in Table 2.21 δ-WC1±x – FeAl1±x – α/β-Y2O3–x δ-WC1±x – Fe3±xAl

–

–

Dense FeAl0.67 – 10-20 % δ-WC1±x – [2176] 1 % α-Y2O3–x composite coatings were deposited on steel substrates using high-velocity oxy-fuel (HVOF) spraying techniques

Vacuum, 1150 < 10 Pa

Powdered δ-WC1±x (≥ 99.5 purity, mean [2892, 4071, particle size – 2-4 μm) – 10 % Fe3±xAl 4221-4222, (size distribution – 10-30 μm) mixtures 4237, 4242] (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 8-10 min) to prepare dense carbide-intermetallide materials

Vacuum, 1200 4 Pa

Powdered δ-WC1±x (mean particle size – 0.5 μm) – 5-20 vol.% Fe3±xAl (N2-atomized, size distribution < 44 μm, containing very small amounts of α-Al2O3) mixtures (preliminarily ball-milled) were subjected to solid-state pulsed electric current sintering (PECS) procedure (exposure – 4 min) to prepare highly dense composites

–

1200-1440 The solid solubility of δ-WC1±x in Fe3±xAl phase increases with temperature growth from 3.5 % to 8.6 %

–

1440

δ-WC1±x phase is in equilibrium with both solid and liquid Fe3±xAl compositions

(continued)

480

2 Tungsten Carbides

Table 2.22 (continued) See also section δ-WC1±x – Al – Fe in Table 2.21 δ-WC1±x – θ-Fe3C

–

–

In W-containing steels, the contents of imaginary ‘W3C’ phase in complex θ-(Fe,Me1,…Men)3C cementite phases usually achieves 1-2 mol.%

–

–

The properties of some imaginary ternary θ-(Fe,W)3C cementite phases were simulated on the basis of first principles calculations

–

–

The effect of substitutional Fe impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

[639, 3550, 3582, 3749, 4209, 4503]

See also section δ-WC1±x – α/γ/δ-Fe in Table 2.21 See also section δ-WC1±x – (Fe – C) in Table 2.21 See also section C – Fe – W in Table I2.14 δ-WC1±x – FexN

δ-WC1±x – α/β/γ/ε-Fe2O3

δ-WC1±x – Fe(OH)3

δ-WC1±x – Fe3O4+x δ-WC1±x – η-Fe5Si3

–

–

δ-WC1±x (mean particle size – 10-20 nm) – [1723] FexN nanostructured electrocatalysts were designed and synthesized

Ar flow 900

The initiation of interaction between the [693, 4041powdered δ-WC1±x and α-Fe2O3 (Fe3O4+x, 4043] α-Fe, β-WO3–x and WO2±x phases were revealed in the products)

Ar flow 1000

The main products of reaction between the components were α-Fe, η2-W3Fe3Cy, β-WO3–x and WO2±x phases; the following scheme (equation) 5WC + 3Fe2O3 = W3Fe3C + WO3 + WO2 + 3Fe + 4CO was proposed for the process

CO2, 0.391000 MPa

Calculated equilibrium pressure of the interaction between the components using thermodynamical analysis

–

CO2, 90 kPa –

–

1000

Fe(OH)3 hydroxide modified δ-WC1±x na- [431] norods array on Ni foam substrates were synthesized for electrocatalysis purposes using thermal evaporation and electrodeposition Calculated equilibrium pressure of the [693, 4043] interaction between the components using thermodynamical analysis

–

Defect free δ-WC1±x – η-Fe5Si3 laser clad- [3704] ded coatings were deposited on stainless steel substrates

(continued)

2.6 Chemical Properties and Materials Design

481

Table 2.22 (continued) δ-WC1±x – H(OCH2CH2)n OH – La2O3–x

–

δ-WC1±x – HfB2±x

–

–

The addition of 2 % polyethylene glycol [363] H(OCH2CH2)nOH (PEG) and 0.1 % La2O3–x to δ-WC1±x powders, being treated by twice ball-milling in nylon vessels, improves the efficiency of process and allows to prepare nanoparticles with mean sizes up to ~27 nm

2000-2200 The interaction of δ-WC1±x with HfB2±x in [4246-4248, powdered mixtures (with δ-WC1±x content 4250, 4252] – 3-10 vol.%) resulted in the formation of (Hf,W)B2±x and (Hf,W)C1–x, two types of solid solutions with the complete dissolution of W in them; there was no evidence of a δ-WC1±x phase remaining in the heat treated materials

See also section C – B – Hf – W in Table I-2.14 δ-WC1±x – HfB2±x – α/β/γ-HfO2–x

Vacuum, 1300-2200 In the powdered mixtures with O-contami- [4246-4250] Ar nated HfB2±x, δ-WC1±x reacts according to the following reactions: HfB2 + 2WC = HfC + 2WB + C, HfO2 + 3C = HfC + 2CO↑, or if the previous reactions are merged (a vacuum decreases the favourable temperature of the process): 3HfB2 + 6WC + HfO2 = 4HfC + 6WB + 2CO↑, or 2HfB2 + 5WC + 3HfO2 = 5HfC + 5W + 2B2O3↑, and also directly interacting with the oxide: 3WC + HfO2 = HfC + 3W + 2CO↑ (or through the decomposition of δ-WC1±x: 2WC = W2C + C 3W2C + HfO2 = HfC + 6W + 2CO↑); the presence of δ-WC1±x promotes the removal of HfO2–x impurities from the surface of HfB2±x particles in the mixtures and sinterability of these mixtures

δ-WC1±x – 99.99 % 2000 HfB2±x – α/β-SiC purity, Ar flow

Powdered HfB2±x (> 99 % purity, mean [4246-4252] particle size – 1 μm, contents: C < 0.04%, O – 0.15%, impurities – HfO2–x and B2O3) – 20 vol.% α-SiC (> 98.5 % purity, mean particle size – 0.45 μm, content O – 1.04%, impurity – SiO2) mixtures with extra 5 vol.% δ-WC1±x (> 99 % purity, mean particle size – 0.8 μm) were subjected to hot-pressing (exposure – 1 h) procedure to fabricate dense ultra-high temperature ceramic matrix composites

(continued)

482

2 Tungsten Carbides

Table 2.22 (continued) (UHTCMC), containing (Hf,W)B2±x – 78 vol.%, α-SiC – ~19 vol.%, α/β-(W,Hf)B1±x – 2 vol.% and (Hf,W)C1–x < 1 vol.% (porosity – 1 %, mean grain size of phase constituents: (Hf,W)B2±x – 1.5 μm, SiC – 1.5 μm, (W,Hf)B1±x – 0.8 μm and (Hf,W)C1–x – 0.8 μm; SiC clusters with sizes ~30 μm were revealed in the microstructure of composites) –

2100

Powdered HfB2±x (99.5 % purity, size distribution < 44 μm, contents: O – 0.58%, Zr – 0.20%, Fe – 0.02%) – 15 vol.% β-SiC (size distribution < 1 μm, contents: noncombined C – 1.39%, O – 0.50%) – 3 vol.% δ-WC1±x (99.5 % purity, size distribution < 1 μm) mixtures (preliminarily ball-milled to mean particle size of HfB2±x – 1.3 μm) were subjected to field-assisted sintering (exposure – 5-9 min) procedure to fabricate highly dense (Hf,W)B2±x – β-SiC (3C, rod-shaped, mean aspect ratio – ~3) – (Hf,W)C1–x ultra-high temperature ceramic matrix composites (UHTCMC) with matrix mean grain size – 1.8 μm; no evidence of a δ-WC1±x phase remaining in the materials was found

Vacuum, 2100-2200 Powdered HfB2±x (98.5 % purity, mean ≤ 10 Pa particle size – ~1.4 μm, contents: C – 0.10%, O – 0.79%) – 20 vol.% α-SiC (98.5 % purity, mean particle size – 0.45 μm) mixtures with 1-10 % δ-WC1±x (> 99 % purity, size distribution < 1 μm) powder addition (preliminarily high-energy ball-milled, uniaxially pressed and cold isostatically pressed) were subjected to reactive liquid-phase sintering (exposure – 2 h) procedure to prepare dense ultra-high temperature ceramic matrix composites (UHTCMC) with porosities in the wide ranges from < 1 % to ~25 % (depending on δ-WC1±x content added) and matrix grain sizes ≤ ~7 μm; the minor α/β-(W,Hf)B1±x and (Hf,W)C1–x phases, forming in accordance to the following reaction: HfB2 + 2WC = HfC + 2WB + C, partial dissolution of W in the matrix with the formation of (Hf,W)B2±x solid solutions promoted by the presence of α-SiC and appearance of WSi2 phase were revealed in the as-sintered materials, containing (with the 10 % δ-WC1±x addition):

(continued)

2.6 Chemical Properties and Materials Design

483

Table 2.22 (continued) (Hf,W)B2±x – ~60 mol.%, α-SiC (6H) – ~34 mol.%, (Hf,W)C1–x – ~6 mol.% and α/β-(W,Hf)B1±x + WSi2 < 1 mol.% δ-WC1±x – HfC1–x

See section HfC1–x – δ-WC1±x in Table II3.20 See also section C – Hf – W in Table I2.14

α/β/ε/γ-W2±xC – HfC1–x

See section HfC1–x – γ-W2±xC in Table II3.20 See also section C – Hf – W in Table I2.14

γ-WC1–x – HfC1–x

See section HfC1–x – γ-WC1–x in Table II3.20 See also section C – Hf – W in Table I2.14

δ-WC1±x – HfC1–x – NbC1–x

See section HfC1–x – NbC1–x – δ-WC1±x in Table II-3.20

δ-WC1±x – HfC1–x – TaC1–x

See section TaC1–x – HfC1–x – δ-WC1±x in Table II-2.22

δ-WC1±x – HfC1–x – TiC1–x

See section HfC1–x – TiC1–x – δ-WC1±x in Table II-3.20 See also section C – Hf – Ti – W in Table I-2.14

δ-WC1±x – HfC1–x – VC1–x

See section HfC1–x – VC1–x – δ-WC1±x in Table II-3.20 See also section C – Hf – V – W in Table I-2.14

δ-WC1±x – HfC1–x – ZrC1–x

See section HfC1–x – δ-WC1±x – ZrC1–x in Table II-3.20

δ-WC1±x – α/β/γ-HfO2–x

–

δ-WC1±x – KCl – LiCl

–

δ-WC1±x – KCl – Ar NaCl

–

First principles studies of the properties of [4253] δ-WC1±x (0001) / α-HfO2–x (001) (monoclinic) interfaces having different stoichiometries were performed

500

δ-WC1±x as a consumable (sacrificial) [1869] anode is dissolved electrochemically in the molten LiCl – KCl salts

750

[1169, 1859, δ-WC1±x as a consumable (sacrificial) anode is dissolved electrochemically in the 1871, 1879molten consolute composition of NaCl – 1880] 49.4 mol.% KCl salts (> 99.5 % purity), the redox reaction of W on a Pt working electrode is reversible and controlled by W ion diffusion in the electrolyte

(continued)

484

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – KCl – Ar NaCl – Na2WO4

δ-WC1±x – KNO3 – NaNO3

–

750

δ-WC1±x as a consumable (sacrificial) [1881] anode is dissolved electrochemically in the equimolar NaCl – KCl melts, containing 0.1-5.0 % Na2WO4 as an active ingredient, to improve the dissolution rate

230-370

The interaction of δ-WC1±x with eutectic [4058] NaNO3 – KNO3 melts results in the formation of alkali metal tungstates (Me2WO4) and nitrites (MeNO2)

See also Table 2.28 δ-WC1±x – KOH Ar – NaOH

350-450

δ-WC1±x – LaAlO3

–

δ-WC1±x – LaB6±x

–

–

δ-WC1±x as a consumable (sacrificial) [1884] anode is dissolved electrochemically in the eutectic NaOH – KOH melts in accordance to the following redox reaction: WC + 6O2– → WO42– + CO2↑ + 10e– The properties of δ-WC1±x (0001) / LaAlO3 [4256] (111) interface were studied by first principles method

1700-1900 Powdered δ-WC1.01 (size distribution [4257] < 56 μm, content non-combined C – 0.03%) – 50 mol.% LaB5.94 (size distribution < 56 μm, content C – 0.27%) mixture was subjected to hot-pressing (exposure – 7-9 min) procedure followed by 6 h annealing at lower temperature to prepared bulk materials composed of LaB6±x, α/ε-W2+xC and α-WB1±x phases

δ-WC1±x – LaB6±x Pure Ar 1500 – γ′-Ni3±xAl

Powdered δ-WC1±x – 10 % γ′-Ni3±xAl – [4258] 0.10-0.38 % LaB6±x mixtures (preliminarily high-energy ball-milled) were subjected to sintering (exposure – 1 h) to prepare ultra-fine grained dense materials; the presence of LaB6±x suppressed the formation of η2-W4Ni2Cy phase in the materials, while its higher contents led to the formation of small amounts of κ-W3NiCy phase

δ-WC1±x – La2O3–x

Powdered δ-WC1±x (> 99.5 %, 0.6 μm, [363, 926] 1.85 m2 g–1) – 1-7 % La2O3–x (> 99.9 %, 40 nm, 20-40 m2 g–1) mixtures (preliminarily high-energy ball-milled; initial purities, mean particle sizes and specific surface areas, respectively, are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense ceramics (porosity – 2.53.0 %); partial decomposition of δ-WC1±x occurred during processing with the formation of α/ε-W2+xC phase

Vacuum, 1600 ≤ 6 Pa

(continued)

2.6 Chemical Properties and Materials Design

485

Table 2.22 (continued) –

–

The addition of 0.1 % La2O3–x to δ-WC1±x powders, being treated by twice ball-milling in nylon vessels, improves the efficiency of process and allows to prepare nanoparticles with mean sizes up to 28.5 nm

δ-WC1±x – La2O3–x – MgO

Vacuum, 1650 0.13 Pa

0.1-1.0 % La2O3–x doped δ-WC1±x – 8 % [4254-4255] MgO dense fine-grained ceramics (porosity – in the range from 1.5 to 13.0 %) was prepared by hot-pressing (exposure – 1.5 h) procedure of high-energy ball-milled powdered mixtures

δ-WC1±x – Li1+yV3O8–x

–

δ-WC1±x-coated Li1+yV3O8–x cathodes were [1861] deposited using plasma-enhanced chemical vapour deposition (PECVD) method

–

δ-WC1±x – MgO Vacuum, 100-400 0.013 μPa

Vacuum, 800 0.013 μPa –

1200

Epitaxial growth of γ-WC1–x (0.3 < x ≤ 0.4) [1, 151, 497single-crystal films (thickness – 0.5 μm, 498, 585, mean grain size – 1.5-8.0 nm) on MgO 666, 2734, (100) and (111) surfaces (γ-WC1–x (001) // 4034, 4038, MgO (001) and γ-WC1–x // MgO 4040-4041, , γ-WC1–x (111) // MgO (111) and 4071-4072, γ-WC1–x // MgO ) was reali- 4194, 4255, sed using magnetron sputtering techniques 4259-4272] δ-WC1±x (as a minor phase in polycrystalline phase mixtures) was deposited using magnetron sputtering techniques on MgO substrates δ-WC1±x – 35 % MgO two-phase dense ceramics (porosity – 0.8 %) were produced by plasma-activated sintering (PAC) procedure using nanocrystalline powders (mean size – ~30 nm) prepared by highenergy reactive ball-milling (mechanochemical synthesis / mechanical alloying)

Vacuum, 1550-1850 Fine-grained and fully dense δ-WC1±x – 0.13 Pa 4.3 % MgO ceramics was fabricated via two-step hot-pressing sintering (TSS) procedure (with apparent activation energy E = 360 kJ mol–1) using nanocomposite powders (size distribution – 10-50 nm, specific surface area – 18.6 m2 g–1, irregular polygonal in shape) prepared by mechanical alloying (MA) process Vacuum, 1600 ~5 Pa

Chemical interaction (exposure – 0.5 h), taking place in the powdered δ-WC1±x (size distribution < 1 μm) – 16.7 mol.% MgO mixtures, leads to the formation of ε-W2+xC phase in accordance to the following reaction: 2WC + MgO = W2C + Mg↑ + CO↑

(continued)

486

2 Tungsten Carbides

Table 2.22 (continued) Vacuum 1600-1750 δ-WC1±x – 16-22 vol.% % MgO dense ceramics (porosity – in the range from 0 to 15 %, δ-WC1±x matrix mean grain size – in the range from 60 nm to 115 nm, with the presence of 8-15 % ε-W2+xC phase) was fabricated using field-assisted sintering technology (FAST) processing (exposure – 5 min) Powdered δ-WC1±x (99.5 % purity, mean particle size – 75 μm) – 8 % MgO (mean particle size – 48 μm) mixtures (preliminarily high-energy ball-milled) were subjected to hot-pressing procedure (exposure – 1.5 h) to fabricate dense ceramics (porosity – 5.5 %); partial decomposition of δ-WC1±x occurred during processing with the formation of ε-W2+xC phase

Vacuum, 1650 0.13 Pa

–

Fully dense bulk δ-WC1±x – 18 % MgO materials were fabricated via plasma-activated sintering (PAS) process using nanocrystalline powders prepared by reactive high-energy ball-milling (mechanical alloying / mechano-chemical synthesis)

1690

Vacuum 1800-2000 The interaction between dense bulk materials is negligible (exposure – 2 h) –

≥ 2000

The formation of MgC2 phase in the contact zone between dense bulk components was observed

See also section C – Mg – O – W in Table I-2.14 α/β/ε/γ-W2±xC – Vacuum, 400 MgO 0.013 μPa

Epitaxial γ-W2±xC films were deposited on [498] MgO (111) surface using magnetron sputtering techniques

See also section C – Mg – O – W in Table I-2.14 δ-WC1±x – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

–

–

The effect of substitutional Mn impurities [4503] on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

δ-WC1±x – α/β/γ/δ/ε-MnO2±x

–

–

δ-WC1±x modified α-MnO2±x composite [4273] coating was prepared via anodic co-deposition on Ti plate (substrate) employed as a composite electrode for electrocatalysis

δ-WC1±x – α/β/γ/δ/ε-MnO2±x – α/β-PbO2±x – α/β/γ/δ-ZrO2–x

–

–

β-PbO2±x – α-MnO2±x – δ-WC1±x – [1852-1853] α-ZrO2–x top-coating for the composite electrode based on Al plate (substrate) was designed and prepared for electrocatalysis purposes

(continued)

2.6 Chemical Properties and Materials Design

487

Table 2.22 (continued) δ-WC1±x – Mn(OH)2

–

–

Mn(OH)2 hydroxide modified δ-WC1±x na- [431] norods array on Ni foam substrates were synthesized for electrocatalysis purposes using thermal evaporation and electrodeposition

δ-WC1±x – MnS

–

–

δ-WC1±x – MnS composite coatings (thick- [4274] ness – ~1 mm) were deposited on steel substrates using plasma transferred arc techniques

–

Mixed (W0.55Mo0.45)(C0.5B0.5) carboboride [2194] materials were prepared by arc-melting of the pure elements employing a water-cooled Cu hearth; the properties of materials were preliminarily predict using the combination of quantum-mechanical calculations and advanced machine-learning techniques

δ-WC1±x – α/β-MoB1±x – γ-MoC – α/β-WB1±x

Ar

δ-WC1±x – γ-MoC

CH4/H2 835-950 (21/79)

CH4/H2 900 (10/90) flow

Nanoparticles (mean size – 1-4 nm) of δ/γ-(W1–yMoy)C1±x monocarbide (hexagonal) phase in the ranges of 0.02 ≤ y ≤ 0.54 were synthesized for electrocatalysis via the removable ceramic coating method, developed for the preparation of non-sintered, ultra-small and metal-terminated carbide particles

[4, 18, 43, 47, 53, 369, 975, 1205, 1258, 1271, 1285-1286, 1292-1293, 2410, 2821, 3348, 3351, Mixed δ/γ-(Mo0.50W0.50)C1±x monocarbide 3744-3745, 4051, 4277, (hexagonal) powdered materials were 4286-4287, prepared by the carburization reactions 4290-4295, The formation of δ-WC1±x – γ-MoC 4503] (δ/γ-(W1–yMoy)C1±x) monocarbide (hexagonal) continuous solid solutions; the composition dependence of crystal cell parameters in the system does not obey to Vegard’s law

–

≤ 1200

–

–

Powdered δ-(W0.91Mo0.09)C1±x (two kinds with 5 % Mo, mean particle sizes – 1.2-1.5 μm and specific surface area – 0.65 m2 g–1) and δ-(W0.76Mo0.24)C1±x (two kinds with 15 % Mo, mean particle sizes – in the range of 0.5-1.3 μm and specific surface areas – in the range of 0.5-2.1 m2 g–1) were employed for the fabrication of hard alloys

–

–

Mixed δ/γ-(Mo0.70÷0.80W0.20÷0.30)C1±x monocarbide (hexagonal) materials were synthesized for the catalytic purposes

(continued)

488

2 Tungsten Carbides

Table 2.22 (continued) –

–

The effect of substitutional Mo impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations, the stability of the δ-(W,Mo)C1±x solid solutions was confirmed

See also section C – Mo – W in Table I2.14 δ-WC1±x – CH4/NH3 1100-1300 Mixed monocarbonitride (hexagonal) γ-MoC – δ-MoN (33/67) δ/γ-(W0.30Mo0.70)(C0.54÷0.79N0.21÷0.46)1±x – δ-WN1±x 0.1 MPa powdered materials were synthesized (exposure – 1 h)

N2, 10-160 MPa

[4278-4279, 4414]

1250-1500 Mixed monocarbonitride (hexagonal) δ/γ-(W0.30Mo0.70)(C0.52÷0.89N0.11÷0.48)1±x powdered materials were synthesized (exposure – 1 h)

δ-WC1±x – γ-MoC – SiO2

CH4/H2 835-900 (21/79)

SiO2-nanospheres (mean size – 40-50 nm) [369] encapsulated δ/γ-(Mo0.02÷0.54W0.46÷0.98)C1±x mixed monocarbide (hexagonal) nanoparticles (mean size – 1-4 nm) were synthesized (duration time – 4 h) using removable ceramic coating method

δ-WC1±x – α/β-Mo2±xC

CH4/H2 850 (20/80)

The preparation of nanosized α-Mo2+xC integrated onto δ-WC1±x nanowires (interwoven nanostructures with a mean size of 15-20 nm) was realized via hydrothermal processes followed by a carburization route

–

1500

Vacuum, 1750 ~5.3 Pa

–

2000

[3-4, 43, 53, 439, 865, 939, 975, 1464, 1892, 2391, 24092410, 2821, The maximum solid solubility of δ-WC1±x 3351, 3724, in β-Mo2±xC is formally unlimited due to 3737-3740, the formation of α/β/ε/γ-(W,Mo)2±xC semi- 3744-3745, carbide (hexagonal) continuous solid solu- 4044-4048, tions and that of β-Mo2±xC in δ-WC1±x cor- 4282, 42864287, 4290responds to ~40 at.% Mo 4295] (~δ-(W0.20Mo0.80)C1±x) Powdered δ-WC1±x (99.5 % purity, mean particle size – 0.4 μm) – 1-6 % β-Mo2±xC (99.5 % purity, size distribution ≤ 44 μm) mixtures (preliminarily ball-milled) were subjected to high-frequency induction-heating sintering (HFIHS) procedure (exposure – ~40 s) to prepare dense two-phase ceramics (porosity – ~ 0.5-1.5 %, δ-WC1±x matrix mean grain size – 0.45 μm); partial dissolution of Mo with the formation of δ-(W,Mo)C1±x solid solutions was observed during the sintering process The maximum solid solubility of β-Mo2±xC in δ-WC1±x corresponds to ~28 at.% Mo (~δ-(W0.45Mo0.55)C1±x)

(continued)

2.6 Chemical Properties and Materials Design

489

Table 2.22 (continued) –

The maximum solid solubility of β-Mo2±xC in δ-WC1±x corresponds to ~13 at.% Mo (~δ-(W0.75Mo0.25)C1±x)

2500

See also section C – Mo – W in Table I2.14 δ-WC1±x – Ar α/β/ε/γ-W2±xC – α/β-Mo2±xC

α/β/ε/γ-W2±xC – α/β-Mo2±xC

–

–

850-900

CH4/H2 900 /Ar (20/70 /10)

Eutectic β-Mo2±xC-doped δ-WC1±x – [3736, 4290] γ-W2±xC alloys (modified relit, non-doped W2±xC/WC1±x mass ratio ≈ 4) were prepared using different techniques (Tammann furnace heat treatment, electron-beam evaporation, centrifugal sputtering); depending on cooling rate, the materials (cellular-structured with the random distribution of hexagonal grains and β/γ-(Mo,W)2±xC solid solution inclusions formed at their boundaries) contained different amounts of γ-W2±xC (main constituent, 25-60 nm), δ-WC1±x (35-50 nm), β-Mo2±xC (10-15 nm) and β/γ-(Mo,W)2±xC (~50 nm) phases (coherent scattering domain (CSD) sizes of the constituents are given in brackets) Mixed α-(W1–yMoy)2+xC semicarbide nano- [3-4, 43, 53, powders (size distribution – 20-150 nm) 545, 1464, and thin coatings (thickness – 3.2-6.6 μm, 1756, 2392, crystallite sizes – in the range of 1.5-4.9 2821, 3724, μm) were prepared by electrochemical de- 3737-3740, position (duration time – 4 h) from molten 3744-3745, tungstate-molybdate-carbonate mixtures as 4044-4047, electrolytes 4050, 4275, Mixed α-(W1–yMoy)2+xC (0 ≤ y ≤ 1) semi- 4282, 4286, carbide materials were prepared by direct 4290] carburization of freeze-dried precursors for catalysis purposes The solid solubility of W2±xC in α-Mo2+xC corresponds to ~ 58-60 at.% W (α-(Mo0.11 ÷0.13W0.87÷0.89)~2.0C)

–

1000

–

1250-2500 The formation of α/β/ε/γ-W2±xC – α/β-Mo2±xC (α/β/ε/γ-(W,Mo)2±xC) semicarbide (hexagonal) continuous solid solutions

See also section C – Mo – W in Table I2.14 δ-WC1±x – α/β-Mo2±xC – α/β-SiC

Vacuum 1600

[4195, 4280, Powdered δ-WC1.00±0.01 (mean particle sizes – 0.71-0.75 μm; contents: non4283, 4285combined C – 0.01-0.03 %, Fe – 0.05%, 4286] Mo – 0.02%) – 4.85 mol.% β-SiC (mean particle size – 0.31 μm; contents: noncombined C – 1.08%, Al – 0.015%, SiO2 – 0.39%) – 0.5-3.0 mol.% β-Mo2.01C (size distribution – 1.0-1.6 μm; contents: non-

(continued)

490

2 Tungsten Carbides

Table 2.22 (continued) combined C – 0.05%, O – 0.34%, Fe – 0.03%) mixtures were subjected to hotpressing (exposure – 10 min) procedure to prepare dense ceramics (porosity < 2 %, δ-WC1±x mean grain size – ~ 0.5-0.6 μm) with the presence of small amounts of mixed (W,Mo)Si2 and (W,Mo)5Si3±x silicide phases –

1600-1800 Powdered δ-WC1±x – 8-24 mol.% β-Mo2±xC – 3-30 mol.% β-SiC mixtures were subjected to hot-pressing procedure to fabricate dense ceramic composites; due to a separation during cooling process monocarbide solid solution (mixed carbide) δ-(W,Mo)C1±x phase was formed in the prepared materials with the grains composed of a W-rich core phase (~δ-(W0.92÷0.98Mo0.02÷0.08)C~1.0) and W-deficient peripheral phase (~δ-(W0.52÷0.56Mo0.44÷0.48)C~1.0), the addition of β-SiC promoted formation of the solid solutions: two-phase ~δ-(W≥0.8Mo≤0.2)C~1.0 – β-SiC composites were obtained from the mixtures with SiC content ≥ 5 mol.% and atomic ratio W/Mo ≥ 4 (only with the presence of very small amounts of unreacted β-Mo2±xC phase and (Mo,W)5Si3Cy compound (Nowotny phase) as a product of interaction with SiC)

δ-WC1±x – β-Mo2±xC – TiC1–x – δ-TiN1±x – VC1–x δ-WC1±x – η-MoC1–x

See section TiC1–x – δ-TiN1±x – β-Mo2±xC – VC1–x – δ-WC1±x in Table III-2.23

–

2000-2100 δ-WC1±x (in the range of ~(W0.45Mo0.55)C1.00 – ~(W0.53Mo0.47)C1.00 compositions) is in equilibrium with η-MoC1–x phase (in the range of ~(Mo0.65W0.35)C0.64 – ~(Mo0.75W0.25)C0.68 compositions)

[2392, 2821, 3737-3740, 4286]

See also section C – Mo – W in Table I2.14 α/β/ε/γ-W2±xC – η-MoC1–x – α-MoC1–x

–

2500

The composition of semicarbide (hexago- [3737-3740] nal) continuous solid solution phase ~β/γ-(W0.55Mo0.45)1.87C is in equilibrium with ~η-(Mo0.47W0.53)C0.59 (corresponds to the maximum solid solubility of W in the phase) and ~α-(Mo0.46W0.54)C0.61 compositions

See also section C – Mo – W in Table I2.14

(continued)

2.6 Chemical Properties and Materials Design

491

Table 2.22 (continued) δ-WC1±x – α-MoC1–x

–

[2392, 2821, 2000-2100 ~δ-(W0.45Mo0.55)C1.00 and ~α-(Mo0.78W0.22)C0.71 compositions, which 3737-3740] are corresponding to the maximum solid solubilities of Mo and W in the respective phases, are in equilibrium with each other

–

2500

δ-WC1±x phase (in the range of ~(W0.75Mo0.25)C1.00 – ~(W0.99Mo0.01)C1.00 compositions) is in equilibrium with α-MoC1–x phase (in the range of ~(Mo0.44W0.56)C0.69 – ~(Mo0.04W0.96)C0.61 compositions)

See also section C – Mo – W in Table I2.14 γ-WC1–x – α-MoC1–x

–

~2550-2650 The formation of γ-WC1–x – α-MoC1–x (γ/α-(W,Mo)C1–x) monocarbide (cubic) continuous solid solutions; the composition dependence of crystal cell parameters in the system does not obey to Vegard’s law

[4, 53, 2392, 3724, 37373740, 40484049]

See also section C – Mo – W in Table I2.14 γ-WC1–x – α-MoC1–x – TiC1–x – δ-TiN1±x δ-WC1±x – MoS2+x

δ-WC1±x – α/β/ε/γ-W2±xC – (Na,Ca)(Al,Mg)6 (Si4O10)3(OH)6⸱ nH2O

δ-WC1±x – NaOH

See section TiC1–x – δ-TiN1±x – α-MoC1–x – γ-WC1–x in Table III-2.23 –

Nanocomposite MoS2+x – δ-WC1±x thin [4288-4289] films (Mo/W atomic ratio ≈ 4.4, thickness – 1.8 μm, MoS2+x crystalline domain sizes – 4-12 nm, content O – 7.2 at.%) were deposited using r.f. magnetron sputtering techniques

–

–

Multilayered δ-WC1±x – MoS2+x coatings (total thickness – 85-100 μm) on cast Fe substrates were deposited via ultrasonic flame and film sprayings

–

–

Montmorillonite [1643] (Na,Ca)(Al,Mg)6(Si4O10)3(OH)6⸱nH2O – δ-WC1±x – α/ε-W2+xC nanocomposites (with WC/W2C molar ratio ≈ 4.6) were fabricated by the combination of chemical immersion with in situ reduction and carbonization processes for electrocatalysis purposes; δ-WC1±x phase formed a uniform loaded layers on the surfaces of exfoliated montmorillonite as the supports

Ar, 0.5-0.7 Pa

Ar 450 (+ H2O vapour)

The anodic dissolution/oxidation of [1870] δ-WC1±x parts in a molten NaOH bath was realized

(continued)

492

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – Na2S2O8 – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x δ-WC1±x – Na2SO4

δ-WC1±x – NbC1–x

–

Pure 630 dried O2

–

S2O82– / α/β-ZrO2–x (partially stabilized) [1373, 1380] solid super-acid catalysts promoted by δ-WC1±x were designed and produced using calcination and activation procedures Interaction in the powdered δ-WC1±x [4296] (99.9 % purity) – 33-67 mol.% Na2SO4 mixtures (exposure – up to 20 h) results in a mass gain at 33 mol.% Na2SO4 and mass losses at 50-67 mol.% Na2SO4; δ-WO3–x and Na2WO4 phases, identified in the reaction products at 50 mol.% Na2SO4, very likely were being formed in accordance to the following reaction: 8WC + 2Na2SO4 + 19O2 = = 6WO3 + 2Na2WO4 + 2SO2↑ + 8CO2↑

See section NbC1–x – δ-WC1±x in Table II4.19 See also section C – Nb – W in Table I2.14

α/β/ε/γ-W2±xC – NbC1–x

See sections NbC1–x – α-W2+xC and NbC1–x – γ-W2±xC in Table II-4.19 See also section C – Nb – W in Table I2.14

γ-WC1–x – NbC1–x

See section NbC1–x – γ-WC1–x in Table II4.19 See also section C – Nb – W in Table I2.14

α/β/ε/γ-W2±xC – β/γ-Nb2±xC

See sections β-Nb2+xC – α/β-W2±xC and γ-Nb2±xC – γ-W2±xC in Table II-4.19 See also section C – Nb – W in Table I2.14

δ-WC1±x – NbC1–x – δ-NbN1–x

See section NbC1–x – δ-NbN1–x – δ-WC1±x in Table II-4.19 See also section C – N – Nb – W in Table I-2.14

δ-WC1±x – NbC1–x – TaC1–x

See section TaC1–x – NbC1–x – δ-WC1±x in Table II-2.22 See also section C – Nb – Ta – W in Table I-2.14

δ-WC1±x – NbC1–x – TiC1–x

See section NbC1–x – TiC1–x – δ-WC1±x in Table II-4.19 See also section C – Nb – Ti – W in Table I-2.14

δ-WC1±x – NbC1–x – UC1±x

See section NbC1–x – UC1±x – δ-WC1±x in Table II-4.19

(continued)

2.6 Chemical Properties and Materials Design

493

Table 2.22 (continued) δ-WC1±x – NbC1–x – VC1–x

See section NbC1–x – VC1–x – δ-WC1±x in Table II-4.19

δ-WC1±x – NbC1–x – ZrC1–x

See section NbC1–x – δ-WC1±x – ZrC1–x in Table II-4.19

α/β/ε/γ-W2±xC – α/β/γ-Nb2±xC – α/β-Ta2±xC

See section α-Ta2+xC – β-Nb2+xC – γ-W2±xC in Table II-2.22 See also section C – Nb – Ta – W in Table I-2.14

δ-WC1±x – β-Nb2O5–x

Vacuum, 1000-1200 The start of noticeable interaction between [1, 151, 0.13 Pa the components in powdered mixtures 4034-4037] Vacuum 1400

The main product of reaction (exposure – 0.5 h) between the powdered components was metallic W-Nb solid solution (alloy); depending on molar carbide/oxide ratios, the various small amounts (or traces) of NbC1–x, γ-NbO2±x and α/ε-W2+xC phases were also revealed in the products

See also section C – Nb – O – W in Table I-2.14 δ-WC1±x – Nd2Fe14B

δ-WC1±x is not compatible with Nd2Fe14B [4297] phase (among the expected products of interaction between the components, there is complex compound WFeB); maximum solid solubility of δ-WC1±x in Nd2Fe14B is ~0.9 %

Ultra1000 high pure Ar

δ-WC1±x – NiAl3 Vacuum, 1300 5.3 Pa

δ-WC1±x-based nanocomposites containing [2140, 4315] 5-10 vol.% NiAl3 were fabricated using high-frequency induction-heated sintering (HFIHS) procedure (exposure – 3 min)

δ-WC1±x – NiAl3 – TiC1–x

See section TiC1–x – NiAl3 – δ-WC1±x in Table III-2.23

δ-WC1±x – NiAl1±x

Air

Ar

Dense NiAl1±x – 5-30 % δ-WC1±x two[275, 2140, phase composites (porosity – ~ 7-10 %) 4305, 4320, were fabricated using self-propagating 4322, 4324] high-temperature synthesis (SHS) in the thermal explosion mode; δ-WC1±x grains in the composites are not only distributed at the NiAl1±x boundaries, but also embedded in the matrix within the NiAl1±x grains

700

–

Cast NiAl1±x – ~6 mol.% δ-WC1±x materials were prepared by self-propagating high-temperature synthesis (SHS) reactions having an aluminothermic reduction step

(continued)

494

2 Tungsten Carbides

Table 2.22 (continued)

δ-WC1±x – NiAl1±x – γ′-Ni3±xAl

δ-WC1±x – γ′-Ni3±xAl

–

–

δ-WC1±x – NiAl1±x nanocomposite layers (grain size distribution – 6-35 nm) were prepared using pulsed laser deposition techniques; no solubility of NiAl1±x in δ-WC1±x was revealed

–

–

The importance of control of C contents in δ-WC1±x – NiAl1±x materials was proved

–

–

δ-WC1±x – NiAl1±x two-phase nanocomposite powders (mean particle size – 36-42 nm) were synthesized during mechanical alloying (MA) procedures followed by subsequent annealing treatment

–

–

The ultra-fine grained δ-WC1±x layers, con- [2140, 2142] taining γ′-Ni3±xAl and NiAl1±x (NiAl0.82) intermetallides, were fabricated by the combination of laser cladding and friction stir processings

Ar, 1150-1450 Powdered δ-WC1±x (mean particle size – [2118, 21350.1 MPa 2.5 μm) – 17-68 vol.% γ′-Ni3±xAl (several 2136, 2140, kinds of inert gas atomized powders, size 2239, 4212distribution ≤ 44 μm) mixtures (prelimina- 4213, 4217, rily ball-milled) were subjected to hot4258, 4298pressing procedure (exposure – 0.25-2.0 h) 4314, 4316to prepare dense ceramic composites 4319, 4321, 4323] Ar, 1300-1500 Pre-sintered (in different conditions) 150 MPa

δ-WC1±x – 8 vol.% γ′-Ni3±xAl materials were subjected to barothermal processing (BTP) to prepare highly dense composites with special properties

–

~1355-1360 Eutectic quasi-binary δ-WC1±x – γ′-Ni3±xAl; the mutual solubilities of the components in each other are low

–

~1370-1375 The appearance of liquid phase in the contact zone between δ-WC1±x and γ′-Ni3±xAl solid phases

Vacuum, 1400-1700 The chemical nature of the interaction (ex~13 mPa posure – 0.5-24 h) at the boundary of hotpressed δ-WC1±x (porosity ≤ 2-3 %) – molten γ′-Ni3.03Al phase (contents: O – 0.11%, Ca – 0.23%) is indicated by the temperature dependence of the surface tension of molten aluminide amounted to 3.01-3.19 J m–2 in this temperature interval; the strong interphase interaction is caused by the diffusion of Ni and Al into δ-WC1±x and dissolution of W and C in the melt leading to the recrystallization of δ-WC1±x, which is accompanied by surface smoothing of the δ-WC1±x materials due to the preferential dissolution of protuberances

(continued)

2.6 Chemical Properties and Materials Design

495

Table 2.22 (continued) and/or irregularities (the concentration of W in the Ni3±xAl reaches a value of 3-5 %) and realized through the solution-precipitation mechanisms on the surface of δ-WC1±x – Ar, 6 MPa

–

1450

The equilibrium at the δ-WC1±x – Ni3±xAl melt interface is reached in 3-6 min

1450

δ-WC1±x – 40 vol.% Ni3±xAl dense bulk composites (mean grain size – 2.4 μm) were prepared by gas pressure sintering (exposure – 1 h) procedure; besides many random orientation relationships, the preferential relationship between the phase substituents, existing with low lattice mismatches, δ-WC1±x (0001) // Ni3±xAl (001) and δ-WC1±x // Ni3±xAl was found in the composites, the interface δ-WC1±x / Ni3±xAl (with composition, at.%: Ni – 66.9±3.6, Al – 22.8±1.7, C – 8.2±5.3, W – 2.0±0.1) had a sharper compositional gradient and a smaller width of transition region than common industrial hard alloys

1500

The maximum solubility of δ-WC1±x in molten γ′-Ni3±xAl was evaluated to be 3-4 %, and it is considerably lowered with decrease of temperature Powdered δ-WC1±x – 10 % γ′-Ni3±xAl mixtures (preliminarily high-energy ball-milled) were subjected to sintering (exposure – 1 h) to prepare dense ultra-fine grained materials (with the presence of η2-W4Ni2Cy phase)

Pure Ar 1500

H2 flow 1520-1540 Powdered δ-WC1±x – 8 vol.% γ′-Ni3±xAl were subjected to liquid-phase sintering to prepare dense composites Vacuum, 1540-1560 Powdered δ-WC1±x – 8 vol.% γ′-Ni3±xAl 0.1 Pa were subjected to liquid-phase sintering to prepare dense composites Ar

–

γ′-Ni3±xAl – 5-30 % δ-WC1±x composite welded overlays on Cr-Ni-steel substrates were fabricated by arc welding; with the increase of δ-WC1±x content, the oxidation of Al in the welding melt decreased due to the growth of protection ability resulting from the increase of C content, so no Al was oxidized in the materials containing ≥ 30 % δ-WC1±x

(continued)

496

2 Tungsten Carbides

Table 2.22 (continued) –

Cast γ′-Ni3±xAl (matrix) – δ-WC1±x (inclusions) composite coatings (thickness – 2.02.5 mm) on the surface of γ′-Ni3±xAl materials, fabricated by self-propagating hightemperature synthesis (SHS), were obtained via electron-beam cladding with the usage of relativistic electrons

–

–

δ-WC1±x particulate reinforced γ′-Ni3±xAl intermetallic matrix composite coatings were prepared by laser powder deposition on steel substrate

–

–

W carbides – 50 % γ′-Ni3.08Al coatings [2136, 2140] were prepared via laser cladding and aging heat treatment processes; the dissolution of δ-WC1±x and subsequent reprecipitation of δ-WC1±x and γ-W2±xC during the cladding and precipitation of ordered γ′-Ni3±xAl phase from metastable supersaturated Nibased solid solution during the heat treatment were occurred in the coatings

Air

δ-WC1±x – α/β/ε/γ-W2±xC – γ′-Ni3±xAl

δ-WC1±x – γ′-Ni3±xAl – TiC1–x δ-WC1±x – α/β-NiO1±x

See section TiC1–x – γ′-Ni3±xAl – δ-WC1±x in Table III-2.23 Vacuum, 2200-2400 The addition of ~0.3 % β-NiO1±x as a [585, 792, fugitive binder was applied for sintering of 3811-3812] ~13 Pa δ-WC0.99 (~97 % purity) powder –

–

Powdered δ-WC1±x (0.9-1.1 μm) – 48 % β-NiO1±x (5-20 μm) mixtures (preliminarily ground and mixed, initial size distributions are given in brackets) with the addition of different C sources were employed for the fabrication of δ-WC1±x – 35 % Ni cermets

δ-WC1±x – Ni(OH)2

–

–

Ni(OH)2 hydroxide modified δ-WC1±x na- [431] norods array on Ni foam substrates were synthesized for electrocatalysis purposes using thermal evaporation and electrodeposition

δ-WC1±x – NiPx (Ni3P, Ni2–xP)

–

60-100

Ni3P – 5-55 vol.% δ-WC1±x composite coa- [2412, 3804, tings were produced on steel substrates 3879] using electroless deposition technique from citrate-sulphate-hypophosphite aqueous solution (content Ni sulphate – 35 g l–1) baths, containing δ-WC1±x powders (mean particle size – 1 μm, content – 20 g l–1), with constant stirring (operation time – 0.5 h, rate – 150 rpm) to provide uniform powder suspensions

(continued)

2.6 Chemical Properties and Materials Design

497

Table 2.22 (continued) –

–

NiPx (Ni3P, Ni2–xP) – δ-WC1±x electrodeposited coatings (thickness – 40 μm) were prepared on brass substrates via direct and pulse current electroplating processes with δ-WC1±x particles (mean size – 0.2 μm) suspended in a modified Watts’ type bath (with 0.1 M NaH2PO2, particle content – 20 g l–1)

–

–

δ-WC1±x – NiPx composite materials were designed and manufactured

δ-WC1±x – α/β-PbO2±x

–

–

δ-WC1±x and β-PbO2±x are compatible to [1701, 1852each other as phase constituents of electro- 1853, 4273] catalyst materials

δ-WC1±x – Pd3±xAu

–

–

δ-WC1±x-supported Pd3±xAu overlayers [3948] were studied using periodic density functional theory (DFT) calculations

δ-WC1±x – α/β-PuC2

–

The expected interaction between δ-WC1±x [1958, 4388] and β-PuC2 can be expressed by the reaction: WC + PuC2 = PuWC2 + C with the formation of PuWC2–x (ternary compound) phase

1700

See also section C – Pu – W in Table I2.14 δ-WC1±x – PuC1–x

–

1400-1700 No mutual solubilities or chemical interac- [53, 1950, tion was revealed experimentally between 1958-1959, the components 1963, 1965]

See also section δ-WC1±x – C – Pu in Table 2.21 See also section δ-WC1±x – α/β/γ/δ/δ′/ε-Pu in Table 2.21 See also section C – Pu – W in Table I2.14 δ-WC1±x – PuC1–x – UC1±x

–

No mutual solubilities or chemical interac- [1950, 1958tion was revealed between (U,Pu)C1±x 1959, 1963, (UC1±x – PuC1–x monocarbide continuous 1965, 4388] solid solution) and δ-WC1±x phases

1700

See also section δ-WC1±x – C – Pu – U in Table 2.21 See also section δ-WC1±x – Pu – U in Table 2.21 See also section C – Pu – U – W in Table I-2.14 δ-WC1±x – ScC1–x

–

–

The solid solubility of Sc in δ-WC1±x is [3958, 4503] negligible, while the maximum solubility of W in ScC1–x phase corresponds to the (Sc~0.6W~0.4)C1–x composition (~25 at.% W)

(continued)

498

2 Tungsten Carbides

Table 2.22 (continued)

γ-WC1–x – ScC1–x

δ-WC1±x – α/β-SiC

–

–

The effect of substitutional Sc impurities on the structure and properties of δ-WC1±x phase was simulated on the basis of first principles calculations

–

–

Being isomorphic in their atomic struc[3958] tures, the components form the system of limited extended solid solutions with the γ-(W~0.65Sc~0.35)C1–x and (Sc~0.6W~0.4)C1–x compositions (in the equilibrium to each other) corresponding to the maximum mutual solid solubilities of the phases

Ar, 350 ~1.3 Pa

Within the compositional range, the microstructure of WC – 10-38 % SiC thin films, deposited by dual r.f. magnetron sputtering on Si (100) substrates, was transforming from crystalline to amorphous, the crystalline thin films were consisting primarily of γ-WC1–x along with a small amount of γ-W2±xC; the presence of SiC had a disordering effect on the microstructure of thin films: the films containing 10-25 mol.% SiC possessed mainly nanocrystalline structures, while with the contents of SiC > 25 mol.% – mostly amorphous, at the highest SiC content a clear two-phase morphology was evolved, consisting of two nearly amorphous but distinct phases, which suggested a finescale partial-phase separation between WC and SiC

Vacuum, > 700 0.1 μPa

Substantial changes in interface roughness and/or interface width of WC – SiC magnetron sputtered multilayers start taking place due to probable redistribution of C and changing densities of the layers

–

1550-1800 Powdered δ-WC0.99 (mean particle size – 0.7 μm, contents: non-combined C – 0.01%, Fe – 0.05%, Mo – 0.02%) – 3-30 vol.% β-SiC (whisker, mean diameter – 0.4 μm, mean length – 30 μm, content SiO2 – 0.20%) mixtures were subjected to hot-pressing procedure (exposure – 20 min) to prepare fully dense ceramic composites (with the presence of WSi2, W5Si3+x and α/ε-W2+xC minor phases)

–

1600-1800 Powdered δ-WC1.00 (mean particle size – 0.75 μm, contents: non-combined C – 0.03%, Fe – 0.05%, Mo – 0.02%) – 2-10 mol.% α/β-SiC (mean particle size – ~0.3 μm, contents: non-combined C – 1.08%, SiO2 – 0.39%, H2O – 0.20%, Fe – 0.02%,

[155, 482, 515, 866, 895, 938, 955, 2236, 3362, 3364, 3959-3960, 3966, 3968, 4124, 4191, 4193, 4283, 4286, 43374346, 4348, 4350, 4352, 4362-4365]

(continued)

2.6 Chemical Properties and Materials Design

499

Table 2.22 (continued) Al – 0.015%) mixtures were subjected to hot-pressing procedure to fabricate dense ceramic composites (porosity – in the range from 0 to 2 %); in the composites with SiC content < ~5 mol.%, where δ-WC1±x grains grew abnormally and had an irregular plate-like morphology (thickness – ~3 μm, length –50-100 μm), the reaction products (WSi2 and W5Si3+x) were formed in small amounts, while in the composites with SiC content > 7.5 mol.%, both these features were not observed 1800

α/β-SiC coexist with monocarbide δ-WC1±x (practically, without mutual solid solubilities) and WSi2 and W5Si3+x, but not with semicarbide α/ε-W2+xC (on the phase diagram it is cut off by a tie line between δ-WC1±x and W5Si3+x phases)

Vacuum, 1820 10-100 Pa

Powdered δ-WC1±x (99.5 % purity, mean particle size – 0.5 μm, content O – 0.21%) – 5 vol.% β-SiC (> 99 % purity, mean particle size – 0.6 μm, content O – 1.00%) mixtures (preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 10 min) to fabricate dense ceramics (porosity – ~1.3 %); the prepared materials with δ-WC1±x as a major phase (present both as squared submicrometric grains and elongated rod-like grains with an aspect ratio – up to 37) were containing traces of W5Si3+x (or W5Si3+xCy), WSi2, α/ε-W2+xC and SiC phases

Vacuum, 1850 15 Pa

β-SiC nanowires dispersed δ-WC1±x matrix composites (with the presence of WSi2 phase) were prepared by spark-plasma sintering (SPS) procedure

–

–

2050

α/β-SiC – δ-WC1±x ceramics (with small amounts of W silicides), having high porosity (≥ 40 %) in the inner part and a dense surface was fabricated by pressureless sintering (exposure – 1 h) procedure

> 2200

The mixtures of coarse and fine powders of α-SiC with the addition of δ-WC1±x powders were subjected to liquid-phase sintering procedure to fabricate α-SiC (6H) – δ-WC1±x recrystallized composite ceramics (with the small amounts of γ-W2±xC phase formed in the sintering process)

(continued)

500

2 Tungsten Carbides

Table 2.22 (continued) Ar, 0.27 Pa

–

WC – SiC multilayered coatings with ultra-short periods between 1 and 2 nm were deposited on Si (100) substrates using d.c. magnetron sputtering techniques; neither WC- nor SiC-layers showed any indication of strong crystalline texture, although the presence of nanocrystalline phases could not be discarded

–

–

SiC-inner and δ-WC1±x-outer layers of double-layered coatings with strong interface bonding were prepared on the surface of carbon-carbon composites (CCC) using pack cementation (PC) and supersonic atmosphere plasma spraying (SAPS) methods, respectively

Ultrahigh pure Kr, 0.2 Pa

–

WC – SiC multilayers with different periods ranging from 3.8 nm to 29 nm were deposited on super-polished Si wafers (substrates) using special magnetron sputtering techniques

–

–

The evaluation of probable existence and properties of hypothetical W3SiC2 nanolayered ternary compound (Mn+1AXnphase) was undertaken on the basis of ab initio calculations

See also section δ-WC1±x – C – Si in Table 2.21 See also section δ-WC1±x – α/β-SiC – Si in Table 2.21 See also section C – Si – W in Table I-2.14 δ-WC1±x – C3H8/H2 800-900 α/β/ε/γ-W2±xC – α/β-SiC

Ar

1550

Mixed layers (thin films) of W carbides [515, 4338(with dominant γ-W2±xC phase) on thin 4339, 4342α-SiC (1000) layers or Si nitride substrates 4343, 4345, were prepared using d.c. magnetron sput- 4351] tering followed by subsequent annealing in different gas environments δ-WC1±x – α/ε-W2+xC – β-SiC nanostructured composite materials (mean grain sizes: SiC – 21-22 nm, WC – 26-29 nm, W2C – 14 nm; specific surface area – ~ 25-50 m2 g–1, total pore volume – ~ 0.10-0.26 cm3 g–1, mean pore radius – ~ 7-10 nm) were prepared using W-promoted carbothermal reduction procedure (exposure – 1.5-3.0 h)

See also section C – Si – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

501

Table 2.22 (continued) α/β/ε/γ-W2±xC – α/β-SiC

Vacuum 600-1200

Epitaxial γ-W2±xC (0001) // 4H α-SiC (0001) Schottky contacts with smoother interface morphology were fabricated via magnetron sputtering deposition of ultrathin W layers (< 10 nm) followed by its carburization during rapid thermal annealing (RTA) processes

1200

α-W2+xC nanoparticles (mean size – 3-5 nm) dispersed SiC composite fibres were fabricated by electrospinning and pyrolysis processes of polycarbosilane precursors

CH4/H2 1400

β-SiC – α/ε-W2+xC nanocomposite powders were prepared by chemical vapour deposition (CVD); the powders were mixtures of β-SiC (shell, with various thickness – from 1 nm up to 6 nm) – α/ε-W2+xC (core, with unchanged size – ~18 nm) composite particles with hollow β-SiC particles (mean size – 40-70 nm)

–

–

–

[701, 4336, 4338-4339, 4342-4343, 4349, 4353]

Single crystal α-SiC (6H, n-type) covered with crystalline γ-W2±xC layer (thickness – 50-90 nm, with the presence of metallic W) was prepared by ion beam assisted deposition (IBAD) techniques

See also section C – Si – W in Table I-2.14 δ-WC1±x – α/β-SiC – TiC1–x

See section TiC1–x – α/β-SiC – δ-WC1±x in Table III-2.23

δ-WC1±x – α/β-SiC – VC1–x

See section VC1–x – α/β-SiC – δ-WC1±x in Table III-3.17

δ-WC1±x – α/β-SiC – WSi2

Vacuum, 1850 15 Pa

δ-WC1±x – Ar α/β-SiC – ZrB2±x

1900

Ceramic composites on the basis of [3966] δ-WC1±x matrix, containing β-SiC nanowires and WSi2 disilicide phase, were prepared by reactive spark-plasma sintering (SPS) procedure (with the powdered Si addition) in accordance to the reaction: WC + 3Si = SiC + WSi2 Powdered ZrB2±x (> 99 % purity, mean particle size – 2 μm) – 10-30 vol.% α-SiC (98.5 % purity, mean particle size – 0.7 μm) mixtures, containing 1.4-2.3 vol.% δ-WC1±x introduced through the attrition milling with δ-WC1±x media and spindle, were subjected to hot-pressing procedure (exposure – 45 min) to fabricate dense ultra-high temperature ceramics (UHTC) with porosities in the range from 0.3 % to ~7 % and matrix mean grain size – 3 μm (the appearance of unknown phase (content – ~9 vol.%), more probably ZrxWyBz, as a product of δ-WC1±x – ZrB2±x

[4248-4249, 4251, 4272, 4340, 43464347, 43544361, 4467, 4469-4470]

(continued)

502

2 Tungsten Carbides

Table 2.22 (continued) interphase interaction, was detected) Ar

1900

Powdered ZrB2±x (mean particle size – ~1 μm, contents: O – 0.46%, C – 0.10%, Hf – 0.08%) – 20 vol.% α-SiC (mean particle size – ~0.5 μm, contents: O – 1.00%, B – 0.33%, Ca – 0.24%) – 5 vol.% δ-WC1.00 (size distribution 99 %, < 1 μm) mixtures (preliminarily ball-milled, initial purities and mean particle sizes of the components are given in brackets) were subjected to hot-pressing procedure (exposure – 1 h) to prepare dense ultra-high temperature ceramics (UHTC) composed of ~(Zr0.81W0.09)B2±x matrix (mean grain size – 1.0±0.4 μm), containing embedded in it grains of α-SiC, β-(W,Zr)B1±x and (Zr,W)C1–x phases (two latter formed in the prepared materials in situ)

(continued)

2.6 Chemical Properties and Materials Design

503

Table 2.22 (continued) Vacuum 1950

Ar

Powdered ZrB2±x (2.1 μm) – 20 vol.% α-SiC (0.5 μm) – 5 vol.% δ-WC1±x (< 1 μm) mixtures (preliminary ball-milled, initial mean particle sizes of the components are given in brackets) were subjected to spark-plasma sintering (SPS) procedure (exposure – 7 min) to prepare dense ultra-high temperature ceramics (UHTC) (porosity – 0.9 %)

2000-2200 Powdered ZrB2±x (mean particle size – 1.4 μm, contents: O – 1.70%, Hf – 1.50%, Ti – 1.90%, Fe – 0.20%, Ca – 0.06%, Al – 0.01%) – 19 vol.% α-SiC (mean particle size – 0.45 μm, contents: O – 1.00%, B – 0.33%, Ca – 0.24%, Fe – 0.16%) – 5-9 vol.% δ-WC1.00 (size distribution < 1 μm, contents: O – 0.20%, Cr – 0.03%, Co – 0.01%, Mo – 0.01%) mixtures were subjected to pressureless sintering procedure (exposure – 2 h) to prepare dense ultrahigh temperature ceramics (UHTC) with porosities in the range from 0 to 3 %, the liquid-phase sintering in the mixtures was accompanied by the dissolution-diffusionprecipitation processes, as its result three new formed solid solution (mixed) phases (Zr,W)C1–x, β-(W,Zr)B1±x and (W,Zr)Si2 were identified in the prepared materials; the presence of δ-WC1±x promoted elongation of ZrB2±x matrix grains, as their length raised from 5-15 μm (aspect ratio – 2.9) to 10-30 μm (aspect ratio – 3.8) with the increase of δ-WC1±x fraction in the materials

δ-WC1±x – α/β-SiC – ZrC1–x

See section ZrC1–x – α/β-SiC – δ-WC1±x in Table II-5.25

δ-WC1±x – α/β/γ-Si3N4

–

N2

~1800-2000 Powdered β-Si3N4 (size distribution – [994, 41600.6-1.0 μm, contents: non-combined Si – 4161, 43250.30%, C – 1.20%, O – 4.50%, Ca – 4335] 1.50%, Fe – 0.65%, Al – 0.50%) – 10 vol.% δ-WC1±x (≥ 99 % purity) mixtures were subjected to hot-pressing procedure to prepare dense composite materials (with the presence of small amounts of silicide phases formed during processing) 1850

During sintering procedures (holding time – 2 h), no chemical interaction between Si3N4 and δ-WC1±x phases was revealed in the powdered mixtures with various compositions

(continued)

504

2 Tungsten Carbides

Table 2.22 (continued) Ar, 2050 180 MPa

α/β/ε/γ-W2±xC – N2, α/β/γ-Si3N4 5 MPa

Powdered Si3N4 (high purity) – 25 vol.% δ-WC1±x (platelet-shaped, mean particle size – 25 μm) mixtures (preliminarily ballmilled) were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to produce dense ceramics (porosity < 0.5 %) ~0.8 vol.% nanoparticle α/ε-W2+xC (poly- [4327] hedral in shape, mean size – ~60 nm, with small amounts of metallic W and W5Si3+x phases) reinforced β-Si3N4 (with the presence of Si2N2O phase) ceramic composites with almost full density were produced via gas pressure sintering procedure (exposure – 4 h)

1850

δ-WC1±x – SiO2 CH4/H2 900 (22/78)

SiO2-encapsulated core-shell δ-WC1±x nanoparticles (mean size – 2.2±1.1 nm) were designed and synthesized using reverse microemulsion (RME) procedure (exposure – 1 h)

[346, 483, 485, 1636, 4351, 43664369]

1250-1350 δ-WC1±x nanoparticles (mean size – 23 nm) were synthesized in the SiO2 gel matrix by in situ generation of H2 and extremely fine C

N2

–

–

The mesoporous SiO2 nanobamboo structures with bimodal size – distributed δ-WC1±x nanoparticles, in which 2 nm particles were distributed in mesoporous walls and 10-20 nm particles were on the inner surfaces and internodes, was designed and synthesized

δ-WC1±x – CH4/H2 700 α/β/ε/γ-W2±xC – 20/80 SiO2

Ordered mesoporous SiO2, containing [4368] δ-WC1±x and α/ε-W2+xC particles (with the formation of both Si–O–W and W–O–W bonds) dispersed in the intrachannel surfaces, were prepared by temperature-programmed carburization (TPC) procedure (exposure – 2 h) at the atomic ratio Si/W = 7.5 in the precursors

α/β/ε/γ-W2±xC – CH4/H2 700 SiO2 20/80

Ordered mesoporous SiO2, containing [4368] thin layers of single phase α/ε-W2+xC mainly inside its channels (with the remainder of W2C being incorporated into the framework with the formation of Si–O–W bonds), were prepared by temperature-programmed carburization (TPC) procedure (exposure – 2 h) at the atomic ratio Si/W = 15÷30 in the precursors

(continued)

2.6 Chemical Properties and Materials Design

505

Table 2.22 (continued) δ-WC1±x – 2SiO2∙Al2O3∙ ∙Na2O∙xH2O

CO flow 550-700

The compositions of δ-WC1±x nanophases [287] (mean particle sizes – from 25 nm to 100 nm) with zeolite-X were prepared for the catalysis purposes using reduction-carburization technique improved by mechanical mixing

δ-WC1±x – CH4/H2 900 α/β/ε/γ-W2±xC – 2SiO2∙Al2O3∙ ∙Na2O∙xH2O

The compositions of δ-WC1±x and W2±xC [1502, 1563] nanophases (mean particle sizes – 29-31 nm and 18-21 nm, respectively; WC/W2C mass ratio from 1/4.9 to 1/5.7) with zeolite were prepared for the catalysis purposes by combining a mechano-chemical approach with reduction-carburization techniques

δ-WC1±x – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt)

Hot-pressed δ-WC1±x materials (porosity – [585, 4038, 1.8-6.8 %) were intensively corroded (ex- 4171, 4370] posure – 2-3 h) in molten basalt (SiO2 – 47 %, Al2O3 – 15 %, CaO – 13 %, Fe2O3 – 13 %) with mass losses from 27 % to 50 % (strong volume decreasing at lower or disintegration at higher porosities)

–

1400

–

δ-WC1±x – (SiO2 N2 – MeI2O – B2O3 – MeIIO)

–

–

δ-WC1±x and basalt fibre (twill-directional woven fabric, SiO2 – 47-52 %, Al2O3 – 1518 %, CaO – 6-9 %, MgO – 3-5 %, specific surface mass – 350 g m–2) employed jointly in various polymer matrix composites (PMC)

680-820

The interaction of δ-WC1±x molds with op- [4054-4055] tical glasses (SiO2 – 40-60 %, alkali oxides MeI2O – 16-36 %, B2O3 – 0-18 %, alkaline-earth oxides MeIIO – 7-17 %, other oxides (Al2O3, ZnO, TiO2 etc.) – 5-15 %; viscosity – around 103.7 dPa s) depends on glass composition and varies with the ratio of the molar number of O atoms in a glass to the field strength of the cations (Q); when Q is high, glasses fuse strongly to the mold accompanied with the migration of W and Na atoms near the glass/mold interface, the increase of Q accelerates the oxidation of W and reduction of Na and leads to the interfusion of the oxidized layer due to the high affinity between δ-WC1±x and molten glasses

> 800

Due to the interaction with optical glass (SiO2 – 60-70 %, K2O – 10-20 %, B2O3 – 10-20 %, fluorides – 1-10 %, Sb2O3 < 1 %) δ-WC1±x molds were suffering degradation, including physical damage and chemical adherence and reaction

(continued)

506

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – Ar/H2 α/β/ε/γ-W2±xC – (10/1) SnO2

δ-WC1±x – TaC1–x

700

Core-shell 5-50 % (WC + W2C) doped [1842] SnO2 nanoparticles were synthesized using a wet chemical method followed by reduction-carbonization heat treatment (exposure – 3 h)

See section TaC1–x – δ-WC1±x in Table II2.22 See also section C – Ta – W in Table I2.14

α/β/ε/γ-W2±xC – TaC1–x

See sections TaC1–x – α-W2+xC in Table II2.22 See also section C – Ta – W in Table I2.14

γ-WC1–x – TaC1–x

See section TaC1–x – γ-WC1–x in Table II2.22 See also section C – Ta – W in Table I2.14

δ-WC1±x – α/β-Ta2±xC

See section α-Ta2+xC – δ-WC1±x in Table II-2.22 See also section C – Ta – W in Table I2.14

α/β/ε/γ-W2±xC – α/β-Ta2±xC

See sections α-Ta2+xC – α-W2+xC, β-Ta2±xC – β-W2+xC and β-Ta2±xC – γ-W2±xC in Table II-2.22 See also section C – Ta – W in Table I2.14

δ-WC1±x – TaC1–x – TiC1–x

See section TaC1–x – TiC1–x – δ-WC1±x in Table II-2.22 See also section C – Ta – Ti – W in Table I-2.14

δ-WC1±x – TaC1–x – VC1–x

See section TaC1–x – VC1–x – δ-WC1±x in Table II-2.22 See also section C – Ta – V – W in Table I-2.14

δ-WC1±x – TaC1–x – ZrC1–x

See section TaC1–x – δ-WC1±x – ZrC1–x in Table II-2.22

α/β/ε/γ-W2±xC – α/β-Ta2±xC – α/β-V2±xC

See section α-Ta2+xC – β-V2±xC – α-W2+xC in Table II-2.22 See also section C – Ta – V – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

507

Table 2.22 (continued) δ-WC1±x – α/β-Ta2O5

Vacuum, 1000-1200 The start of noticeable interaction between [1, 151, 0.13 Pa the components in powdered mixtures 4034-4037] Vacuum 1400

The main product of reaction (exposure – 0.5 h) between the powdered components was metallic W-Ta solid solution (alloy); depending on molar carbide/oxide ratios, the various small amounts (or traces) of TaC1–x, TaO2 and α/ε-W2+xC phases were also revealed in the products

See also section C – O – Ta – W in Table I-2.14 δ-WC1±x – α/β/γ-ThC2–x

–

1500

The maximum mutual solid solubilities of [13, 22, 53, δ-WC1±x and γ-ThC2–x are ≤ 0.5-1.0 mol.% 3724]

See also section δ-WC1±x – C – α/β-Th in Table 2.21 See also section δ-WC1±x – α/β-Th in Table 2.21 See also section C – Th – W in Table I2.14 δ-WC1±x – ThC1±x

–

1500

The maximum solid solubility of δ-WC1±x [13, 22, 53, in ThC1±x is ≤ 2 mol.% and that of ThC1±x 3724] in δ-WC1±x ≤ 1 mol.%

See also section δ-WC1±x – C – α/β-Th in Table 2.21 See also section δ-WC1±x – α/β-Th in Table 2.21 See also section C – Th – W in Table I2.14 α/β/ε/γ-W2±xC – ThC1±x

–

1500

The maximum solid solubility of [13, 22, 53, α/ε-W2+xC in ThC1±x is ≤ 2 mol.% and that 3724] of ThC1±x in α/ε-W2+xC ≤ 0.5-1.0 mol.%

See also section α/β/ε/γ-W2±xC – C – α/β-Th in Table 2.21 See also section α/β/ε/γ-W2±xC – α/β-Th in Table 2.21 See also section C – Th – W in Table I2.14 α/β/ε/γ-W2±xC – Vacuum ≥ 1700 ThO2–x

In γ-W2±xC – 0.7 % ThO2–x coatings (thick- [4372-4375] ness – ~1 μm), the course of two possible reactions ThO2 + W2C = Th + 2W + CO2↑ and ThO2 + 2W2C = Th + 4W + 2CO↑ was proposed on the basis of obtained experimental data

(continued)

508

2 Tungsten Carbides

Table 2.22 (continued) Powdered δ-WC1±x (99.8 %, ~0.5 μm) – 5- [928, 932] 10 vol.% TiAl3 (99 %, < 45 μm) mixtures (preliminarily high-energy ball-milled, initial purities and mean particle sizes of the components are given in brackets) were subjected to pulsed current activated sintering (PCAS) procedure (exposure – 2 min) to fabricate dense materials (porosity – 1.5 %, δ-WC1±x mean grain size – ~ 50-70 nm); no interaction between the phase constituents was revealed

δ-WC1±x – TiAl3 Vacuum, 1600 ~5.3 Pa

–

δ-WC1±x – TiAl1±x

–

Powdered δ-WC1±x – TiAl3 mixtures were subjected to high-frequency induction-heated sintering (HFIHS) procedure to prepare fine-grained dense materials Powdered δ-WC1±x (99.8 %, ~0.5 μm) – [929, 4381] 10 vol.% TiAl1±x (99 %, < 45 μm) mixtures (preliminarily high-energy ball-milled, initial purities and mean particle sizes of the components are given in brackets) were subjected to high-frequency induction-heated sintering (HFIHS) procedure (exposure – 1 min) to fabricate dense materials (porosity – 1.5 %, δ-WC1±x mean grain size – ~70 nm); no interaction between the phase constituents was revealed

Vacuum, 1600 ~5.3 Pa

δ-WC1±x – TiAl1±x – TiB2±x

See section δ-WC1±x – TiAl1±x – TiB2±x – α/β-Y2O3–x – α/β/γ-ZrO2–x – Co – Fe in Table 2.21

δ-WC1±x – TiB2±x Vacuum, 1900 13 mPa

[3367, 4059, Powdered δ-WC1.00 (mean particle size 0.8 μm, contents: non-combined C – 4376-4383] 0.01%, Fe – 0.02%, Mo – 0.01%) – 10-90 vol.% TiB2.00 (mean particle size 9.0 μm, con-tents: O – 1.48%, C – 0.18%, N – 0.12%, H – 0.12%, Fe – 0.13%) mixtures were subjected to hot-pressing procedure (expo-sure – 0.5 h) to fabricate dense ceramics (porosity ≤ ~3 %) consisted of δ-WC1±x, (Ti,W)B2±x, α-(W,B)1±x and β-(W,B)1±x phases (in the various ratios depending on initial mixture compositions)

–

δ-WC1±x – TiB2±x – TiC1–x – δ-TiN1±x

–

Depending on composition, the arc-melted δ-WC1±x – 13-41 mol.% TiB2±x materials contained δ-WC1±x, γ-WC1–x, γ-W2±xC, β-WB1±x and TiB2±x phases (with the traces of W2±xB phase)

See section TiC1–x – δ-TiN1±x – TiB2±x – δ-WC1±x in Table III-2.23

(continued)

2.6 Chemical Properties and Materials Design

509

Table 2.22 (continued) δ-WC1±x – TiC1–x

See section TiC1–x – δ-WC1±x in Table III2.23 See also section C – Ti – W in Table I2.14

δ-WC1±x – α/β/ε/γ-W2±xC – TiC1–x

See section TiC1–x – δ-WC1±x – W2±xC in Table III-2.23 See also section C – Ti – W in Table I2.14

α/β/ε/γ-W2±xC – TiC1–x

See section TiC1–x – α/β/γ-W2±xC in Table III-2.23 See also section C – Ti – W in Table I2.14

γ-WC1–x – TiC1–x

See section TiC1–x – γ-WC1–x in Table III2.23 See also section C – Ti – W in Table I2.14

δ-WC1±x – TiC1–x – δ-TiN1±x

See section TiC1–x – δ-TiN1±x – δ-WC1±x in Table III-2.23 See also section C – N – Ti – W in Table I2.14

δ-WC1±x – TiC1–x – TiNi1±x – Ti2±xNi

See section TiC1–x – TiNi1±x – Ti2±xNi – δ-WC1±x in Table III-2.23

δ-WC1±x – TiC1–x – VC1–x

See section TiC1–x – VC1–x – δ-WC1±x in Table III-2.23

δ-WC1±x – TiC1–x – Y2O3–x – α/β-ZrO2–x

See section TiC1–x – δ-WC1±x – Y2O3–x – α/β-ZrO2–x in Table III-2.23

δ-WC1±x – TiC1–x – δ-TiN1±x – Y2O3–x – α/β-ZrO2–x

See section TiC1–x – δ-TiN1±x – δ-WC1±x – Y2O3–x – α/β-ZrO2–x in Table III-2.23

δ-WC1±x – TiC1–x – ZrC1–x

See section ZrC1–x – TiC1–x – δ-WC1±x in Table II-5.25

δ-WC1±x – δ-TiN1±x

Ar/N2 320 (20/50), ptot = 0.85 Pa

Nanostructured δ-WC1±x – 37-60 mol.% [4201, 4384] δ-TiN1±x thin films (thickness – 50-90 nm; mean crystallite sizes: δ-WC1±x – 18-26 nm, δ-TiN1±x – 22-24 nm) on steel substrates were prepared using arc ion plating (AIP) for the deposition of δ-TiN1±x interlayer and d.c. and r.f. magnetron sputtering (MS) for the deposition of thin films themselves (exposure for each operation – 1 h); the thin films were grown by 15-25 nm nanodots along the primarily growth direction of δ-TiN1±x in the interlayer

(continued)

510

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – TiNi1±x

–

750-950

The solid-state interaction between the [2135] powdered components during a sintering procedure led to the formation of Ti2±xNi and η2-W3Ni3Cy phases (TiNi1±x phase does not exist at temperatures ≥ 950 °C in the presence of δ-WC1±x)

–

1500-1800 The contact interaction of solid δ-WC1±x phase with molten TiNi1±x led to the formation of η2-W3Ni3Cy (ternary compound) and (Ti,W)C1–x (TiC1–x-based solid solution) phases, when the time of contact is limited the annular structures similar to those formed during the sintering process at lower temperatures has been appeared

See also section δ-WC1±x – Ni – Ti in Table 2.21 δ-WC1±x – TiO2–x Vacuum 1300 (rutile, anatase, brookite)

The interaction (exposure – ~0.5 h) in powdered mixtures of components leads to the 60 % reduction of TiO2–x and formation of W-Ti alloys

Vacuum 1400

The interaction (exposure – 0.5 h) in powdered mixtures of components leads to the 85 % reduction of TiO2–x and formation of W-Ti alloys

[1, 151, 427, 430, 1497, 4034-4035, 1574]

See also section C – O – Ti – W in Table I2.14 N2 δ-WC1±x – α/β/ε/γ-W2±xC – TiO2–x (rutile, anatase, brookite)

450

δ-WC1±x – α/ε-W2+xC nanorods (diameter – [427, 430] 90-95 nm, length – 0.35-0.40 μm) – 20 % TiO2–x (rutile) electrode films were prepared using sintering procedure (exposure – 0.5 h)

See also section C – O – Ti – W in Table I2.14 δ-WC1±x – H2/CH4 850-900 α/β/ε/γ-W2±xC – (80/20) TiO2–x (rutile, anatase, brookite) – TinO2n–1 (n = 4÷6)

Nanocomposite TiO2–x (support phase, [1497, 1504, rutile with the presence of anatase or broo- 1511-1512, kite and/or TinO2n–1 (n = 4÷6) Magnéli 1514] phases, crystallite size distribution – 19-96 nm) – δ-WC1±x (mean particle size – 15-16 nm) – α/ε-W2+xC (with the presence of γ-WC1–x phase, size distribution – 17-24 nm) electrocatalysts with Ti-O-core – WC-shell structures were fabricated using mechano-chemical (or spray drying) approaches followed by reduction-carbonization heat treatment See also section C – O – Ti – W in Table I2.14

(continued)

2.6 Chemical Properties and Materials Design

511

Table 2.22 (continued) N2 δ-WC1±x – α/β/ε/γ-W2±xC – TiO2–x (rutile, anatase, brookite) – α/β/γ/δ-ZrO2–x δ-WC1±x – β-Ti2O3

450

CO2, 1000 3.2×10–8 Pa

δ-WC1±x – α/ε-W2+xC nanorods (diameter – [427] 90-95 nm, length – 0.35-0.40 μm) – TiO2–x (rutile) – γ-ZrO2–x (cubic) electrode films were prepared using sintering procedure (exposure – 0.5 h) Calculated equilibrium pressure of the in- [693, 4043] teraction between the components using thermodynamical analysis

See also section C – O – Ti – W in Table I2.14 δ-WC1±x – α/β-UC2–x

–

1500

The interaction between δ-WC1±x and α-UC2–x phases can be expressed by the reaction: WC + UC2 = UWC2 + C with the formation of UWC2–x (ternary compound) phase

[13, 22, 53, 3724]

See also section C – U – W in Table I-2.14 α/β/ε/γ-W2±xC – α/β-UC2–x

–

1500

The interaction between α/ε-W2+xC and α-UC2–x phases can be expressed by the reaction: W2C + 2UC2 = 2UWC2 + C with the formation of UWC2–x (ternary compound) phase

δ-WC1±x – UC1±x

–

1400-1700 The maximum solid solubility of δ-WC1±x [13, 22, 53, in (U,W)C1±x phase grows with tempera- 1949-1964, ture increase from 0.8 mol.% to 2.1 mol.% 3724, 43874390] 1500 Mutual solid solubilities of the compo-

[13, 22, 53, 3724]

See also section C – U – W in Table I-2.14

–

nents are rather low, with the solubility of δ-WC1±x in UC1±x being a bit higher than that of UC1±x in δ-WC1±x Ar

1800-2000 Powdered UC1±x – 5-95 mol.% δ-WC1±x mixtures, subjected to hot-pressing treatment followed by annealing procedure (exposure – 4 h), had a single-phase composition and contained mixed (U,W)C1±x carbide phase at the contents of δ-WC1±x < 10 mol.%, at all other δ-WC1±x contents – besides pure δ-WC1±x phase (with the traces of α-W2+xC), the prepared materials also contained UWC2–x (x ≈ 0) ternary compound

See also section δ-WC1±x – α/β-C – α/β/γ-U in Table 2.21 See also section δ-WC1±x – α/β/γ-U in Table 2.21 See also section C – U – W in Table I-2.14

(continued)

512

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – UC1±x – ZrC1–x

See section ZrC1–x – UC1±x – δ-WC1±x in Table II-5.25

δ-WC1±x – VC1–x

See section VC1–x – δ-WC1±x in Table III3.17 See also section C – V – W in Table I-2.14

δ-WC1±x – α/β/ε/γ-W2±xC – VC1–x

See section VC1–x – δ-WC1±x – α-W2+xC in Table III-3.17 See also section C – V – W in Table I-2.14

α/β/ε/γ-W2±xC – VC1–x

See section VC1–x – α/β/γ-W2±xC in Table III-3.17 See also section C – V – W in Table I-2.14

γ-WC1–x – VC1–x

See section VC1–x – γ-WC1–x in Table III3.17 See also section C – V – W in Table I-2.14

α/β/ε/γ-W2±xC – α/β-V2±xC

–

1500-2000 The formation of α/ε-W2+xC – β-V2±xC [13, 23, 53, semicarbide (hexagonal) continuous solid 2392, 3730, solutions 4391]

See also section C – V – W in Table I-2.14 δ-WC1±x – α/β/ε/γ-W2±xC – VC1–x – (W2±xB, WB1±x)

See section VC1–x – (W2±xB, WB1±x) – δ-WC1±x – W2±xC in Table III-3.17

δ-WC1±x – VC1–x – Y2O3–x – α/β-ZrO2–x

See section VC1–x – δ-WC1±x – Y2O3–x – α/β-ZrO2–x in Table III-3.17

δ-WC1±x – VC1–x – ZrC1–x

See section ZrC1–x – VC1–x – δ-WC1±x in Table II-5.25

δ-WC1±x – V2O5

–

900-1400

The interaction in powdered mixtures of [1, 151, components leads to the formation of V-W 4036] metallic solid solutions

See also section C – O – V – W in Table I2.14 δ-WC1±x – β-V2O3+x

CO2, 15 kPa

1000

[1, 151, 639, Calculated equilibrium pressure of the interaction between the components using 4034-4035, thermodynamical analysis 4043]

Vacuum, 1000-1200 The start of noticeable interaction between 0.13 Pa the components in powdered mixtures Vacuum 1300

The interaction (exposure – 10 min) in powdered mixtures of components leads to the 60 % reduction of oxide phase

Vacuum 1400

The interaction (exposure – 0.5 h) in powdered mixtures of components leads to the complete reduction of oxide phase and formation of W-V alloys

(continued)

2.6 Chemical Properties and Materials Design

513

Table 2.22 (continued) See also section C – O – V – W in Table I2.14 δ-WC1±x – δ-VO1±x

CO2, 1000 0.78 mPa

Calculated equilibrium pressure of the in- [693, 4043] teraction between the components using thermodynamical analysis

See also section C – O – V – W in Table I2.14 δ-WC1±x – β-W2B5–x

–

δ-WC1±x – α/β-WB1±x

–

2350-2400 No chemical interaction between the com- [3, 1926] ponents

See also section C – B – W in Table I-2.14 1650-1900 Dense δ-WC1±x – α-WB1±x ceramics (with δ-WC1±x contents – 66-77 mol.%) were fabricated using reactive energization hotpressing (exposure – 20 min) process

–

–

δ-WC1±x – β-WB1±x two-phase materials were prepared by the arc-melting procedures of W – 20-33 at.% B – 19-34 at.% C compositions

–

–

Quantum-chemical studies (calculations) of the electronic structure and some properties of probable borocarbide W(C1–xBx) phases have been undertaken

[53, 83, 919, 2187, 4020, 4059, 4061, 4286, 4404]

See also section C – B – W in Table I-2.14 δ-WC1±x – α/β-WB1±x – W2±xB

–

–

1650-1900 δ-WC1±x – α-WB1±x – W2±xB ceramics [4020, 4059] (with δ-WC1±x contents – 85-96 mol.%) were fabricated using reactive energization hot-pressing (exposure – 20 min) process –

δ-WC1±x – β-WB1±x materials (with the presence of traces of W2±xB phase) were prepared by the arc-melting procedures of W – 6.5-12.5 at.% B – 37.5-40.0 at.% C compositions

See also section C – B – W in Table I-2.14 δ-WC1±x – W2±xB

–

~2270-2310 Eutectic pseudobinary δ-WC1±x – W2±xB (?); no mutual solubilities between the components were observed

δ-WC1±x – α/β/ε/γ-W2±xC – β-WB1±x

–

~2300-2325 Eutectic ternary δ-WC1±x – γ-W2±xC – [2184-2186] β-WB1±x; practically, no solubility between W carbides and boride

α/β/ε/γ-W2±xC – β-WB1±x

–

~2325-2330 Eutectic γ-W2±xC – β-WB1±x; the maximum [2184-2186] solid solubility of γ-W2±xC in β-WB1±x is ~5.5 mol.% and that of β-WB1±x in γ-W2±xC is ~5 mol.%

[2184-2186, 4053]

See also section C – B – W in Table I-2.14

See also section C – B – W in Table I-2.14

See also section C – B – W in Table I-2.14

(continued)

514

2 Tungsten Carbides

Table 2.22 (continued) α/β/ε/γ-W2±xC – β-WB1±x – W2±xB

–

~2305-2325 Eutectic ternary γ-W2±xC – β-WB1±x – W2±xB; practically, no solubility between the components

α/β/ε/γ-W2±xC – W2±xB

–

~2370-2390 Eutectic γ-W2±xC – W2±xB; the maximum [2184-2186] solid solubility of γ-W2±xC in W2±xB is ~3 mol.% and that of W2±xB in γ-W2±xC is ~7 mol.%

[2184-2186]

See also section C – B – W in Table I-2.14

See also section C – B – W in Table I-2.14 δ-WC1±x – α/β/ε/γ-W2±xC

C3H8/H2 700-850

–

Ar

~730

750

H2/C3H8 1200

Ar

1300

The mixture of crystalline δ-WC1±x and [2-4, 9-10, γ-W2±xC phases were obtained in the thin 13, 47, 53, films prepared on Ta foils by low-pressure 61, 65-66, chemical vapour deposition (CVD) process 68, 93, 111, During non-equilibrium solidification un- 125, 137, 148, 156, der ultra-high cooling rates (e.g. ~108 158, 317, K s–1), the crystallization of metastable γ-W2±xC (or γ-WC1–x) completes at nearly 404, 407, the same undercooling as that of δ-WC1±x 666, 843, 858, 868, Eutectoid-structured α/ε-W2+xC – 20-37 880, 1433, mol.% δ-WC1±x crystal heterostructures 1541, 1728, were synthesized during heat treatment 1768, 1988, (exposure – 3-5 h) for catalysis purposes 2986, 3706In the δ-WC1±x – γ-W2±xC layers, prepared 3707, 3780, using d.c. magnetron sputtering deposition 4008, 4284, followed by the short thermal processing 4392-4403, (RTP) procedure (exposure – 1 min), the 4410-4412] WC/W2C ratio could be controlled by the composition of gas media

Nanocrystalline δ-WC1±x – α/ε-W2+xC particles (size distribution – 50-200 nm, with the presence of metallic W phase) were prepared by solid-state thermal reaction (exposure – 7 h) for electrocatalysis aim

Vacuum, 1500-1750 Powdered δ-WC1±x (size distribution – 4010 Pa 70 nm) was subjected to spark-plasma sintering (SPS) procedure (under various heating rates, without holding at the highest temperature) to prepare dense δ-WC1±x (with α/ε-W2+xC minor phase) materials (porosity – in the range from 0 to 5 %, mean grain size – 0.25-0.31 μm); the amount of α/ε-W2+xC phase increased with increasing sintering temperature

(continued)

2.6 Chemical Properties and Materials Design

515

Table 2.22 (continued) Vacuum, 1500-2000 During the carburization procedure (exH2 posure – 1.5-3.5 h), in the transition area α/ε-W2+xC → δ-WC1±x, the crystals of δ-WC1±x grow in the form of platelets into the α/ε-W2+xC matrix, some fast-growing δ-WC1±x platelets can be found forming big δ-WC1±x grains inside the polycrystalline particles, it occurs independently on the carburization temperature, but particle size and size of platelets increase with increasing temperature Vacuum 1625

–

N2

δ-WC1±x – 5 % α/ε-W2+xC ceramics (porosity – ~1 %, mean grain size – 1 μm) prepared using spark-plasma sintering (SPS) procedure were characterized by the preferred orientation of crystallites near the surface layers (< 50 μm)

1700

δ-WC1±x – α/ε-W2+xC highly dense ceramic materials were prepared by spark-plasma sintering (SPS) of colloidally processed δ-WC1±x (with the various addition of nanosized pure metallic W) powders

1800

Plasma-produced powders (size distribution – 10-20 nm, composed of γ-WC1–x and γ-W2±xC phases) were subjected to hotpressing (exposure – 1 h) procedure to prepare dense single-phase δ-WC1±x materials (porosity – 4 %, crystallite size – 70 nm)

Ar flow 1900-2100 Dense δ-WC1±x – 0.6-4.4 % γ-W2±xC materials (porosity – in the range from 2 % to 18 %, mean grain size – in the range from 1 μm to 12 μm) were fabricated from δ-WC1±x powder with the small additions of powdered elemental W and C using pressureless sintering procedure –

Ar

~2735-2755 Eutectic γ-WC1–x – γ-W2±xC; the eutectic materials transform to δ-WC1±x – γ-W2±xC compositions at lower temperatures ~3000-3100 γ-W2±xC – 20 % δ-WC1±x fused materials (with the small amounts of γ-WC1–x phase) were fabricated by melt solidification techniques, including electron beam melting and centrifugal atomization in a Tammann furnace; the significant refinement of microstructure was achieved using higher cooling rates (up to 105 K s-1) in the materials processing

(continued)

516

2 Tungsten Carbides

Table 2.22 (continued) Ar/N2

–

3100

Eutectic alloy γ-W2±xC – 18-20 % δ-WC1±x (relit), containing (depending on the working gaseous medium) up to 4-11 % γ-WC1–x phase, was prepared using centrifugal sputtering of castings (the most fine-grained microstructure was obtained in the Ar protective medium with N2 plasma-forming gas)

~3400

δ-WC1±x – γ-W2±xC composites were synthesized from W – C equiatomic powdered mixture by electrothermal explosion

Ar

–

Directionally solidified δ-WC1±x – γ-W2±xC ceramics with composition corresponding to the eutectoid transformation were produced by laser surface melt processing; the obtained materials had a lamellar-type eutectic-eutectoid microstructure (smallest interlamellar spacing – 331±36 nm) with the δ-WC1±x minor phase embedded in the γ-W2±xC matrix phase; the lamellar-type microstructures had preferred nominal growth directions (crystallographic orientation relationship) of δ-WC1±x // γ-W2±xC along the solidification direction (with an average mistilt between the phases of ~2°), the majority of interface habit planes were found to be δ-WC1±x (0001) // γ-W2±xC (0001), the interfaces – semicoherent, with a misfit Burger’s vector of ⅓

Ar

–

δ-WC1±x – γ-W2±xC fused materials (with the presence of γ-WC1–x phase, varying WC/W2C ratios and lamellar/acicular morphology, which was developed in C-rich areas when martensite structures grew by diffusionless transformation) were fabricated using arc plasma melting procedure

–

–

α/ε-W2+xC – 40 % δ-WC1±x nanopowders (mean particle size – 40 nm) were prepared using plasma-mechanochemical method for catalysis purposes

–

–

δ-WC1±x – α/ε-W2+xC fine-grained dense ceramics was manufactured using rapid omni-directional compaction technology (ROCT)

–

–

δ-WC1±x – α/ε-W2+xC nanocomposites, having a core (WC) – shell (W2C) structure, were prepared for electrocatalysis purposes via a combination of surface coating and in situ reduction-carbonization processes

(continued)

2.6 Chemical Properties and Materials Design

517

Table 2.22 (continued) –

–

γ-WC1–x – γ-W2±xC particles were prepared using spark-discharge (electroerosion) synthesis

–

–

γ-WC1–x – α/ε-W2+xC and γ-WC1–x – δ-WC1±x thin films (thickness – 2-3 μm) were deposited on high-speed steel substrates using non-reactive r.f. and d.c. sputtering techniques

–

–

During processing in ball mills, the powdered mixture of δ-WC1±x – γ-W2±xC was being enriched with the latter due to the decarbonization, which was intensified with grinding

–

–

γ-WC1–x – γ-W2±xC materials and coatings (with the presence of δ-WC1±x and metallic W) were prepared under the cumulative explosion conditions; γ-WC1–x and γ-W2±xC had the lattice parameters significantly exceeding the common ones for these phases)

See also sections δ-WC1±x – α/β-C – W, α/β/ε/γ-W2±xC – α/β-C – W and δ-WC1±x – W in Table 2.21 See also section C – W in Table I-2.13 δ-WC1±x – WCoBy

–

–

δ-WC1±x – WCoBy hard coatings (with [3376-3377, small amounts of minor phases, thickness 4405-4406] – ~0.3 mm) on steel substrates were fabricated using high-velocity oxy-fuel (HVOF) spraying techniques

See also section δ-WC1±x – α/β-WB1±x – Co in Table 2.21 See also section C – B – W in Table I-2.14 See also section W – B – Co in Table I-3.6 δ-WC1±x – δ-WN1±x

–

–

The lattice constants of monocarbonitride (hexagonal) δ-W(CxN1–x) (δ-WC1±x – δ-WN1±x) solid solution phase a and c can be generally expressed as a linear relation of the composition: from aWC ≈ 0.2906 nm to aWN ≈ 0.2893 nm (c/a ≈ 0.977) and cWC ≈ 0.2838 nm to cWN ≈ 0.2826 nm (c/a ≈ 0.977)

Ar/N2 20-500 (50/50), Ptot = 0.3 kPa

δ-W(CxNy) thin polycrystalline films (thickness – 0.45 μm, with the presence of crystalline metallic W, carbide α/ε-W2+xC, oxycarbide W2±x(C,O) and amorphous α-C and CNx phases) were deposited on stainless steel substrates using repetitive pulsed vacuum arc techniques

[53, 81, 83, 148, 530, 919, 979, 1000, 1164, 1175, 1600, 1656, 1678, 1708, 1882, 1981, 3378, 3540-3541, 4022-4023, 4061, 42784279, 44074436]

(continued)

518

2 Tungsten Carbides

Table 2.22 (continued) Ar, NH3 200-400

Thin nanocrystalline films (mixture of γ-WC1–x and γ-WN1–y or γ-W(CxNy) solid solutions, thickness – 5 nm, with the presence of O in the form of W oxides) were prepared on Si (100) substrates (with 6-10 nm SiO2 layers) using remote plasma atomic layer deposition (RPALD) employing metallorganic sources

250-400

Thin films of γ-W(C0.55N0.27) (thickness – ~25 nm, content O < 1 at.%) were prepared on various substrates (Cu, SiO2, SiC, Si3N4 and others) by atomic layer chemical vapour deposition (ALCVD) techniques

NH3

300

Thin films of γ-W(C0.55÷0.65N0.45) (thickness – in the range of 2.4-40.5 nm, the thinner films contained less W and more C than the thicker films; density – in the range of 4.6-13.1 g cm–3) were prepared on various substrates (SiO2, SiC, Si3N4 and others) by atomic layer deposition (ALD) process; the film properties change as a function of thickness

NH3

~310

Thin (nanocrystalline with extremely small grain sizes, or amorphous) films of ~γ-W(C0.67N0.42) (or more likely mixture of γ-WC0.67 and γ-WN0.42 phases with similar lattice parameters) with thicknesses – ~ 20-24 nm) were prepared on Si (or SiO2) substrates using atomic layer deposition (ALD) techniques

–

N2, 350 ≤ 200 Pa

Thin continuous films of ~W(C0.70N0.30) were prepared on polymer substrates by atomic layer deposition (ALD) techniques (with minimum thickness – ~10 nm on untreated polymer and 1.4-2.3 nm on N2-rich reactive ion etch plasma-treated polymer)

Ar/NH3 400-1050 or CH4/NH3

Ceramic δ-W(C,N)1±x coatings (thickness – ~1.2 μm) on various substrates, including cemented carbides for cutting tools, were prepared by chemical vapour deposition (CVD) techniques using W carbonyl precursors, or carbonitridation of metallic W CVD films (exposure – 20 min)

NH3

Thin films of γ-W(CxNy) (amorphous at < 500 °C and polycrystalline at ≥ 500 °C, thickness – 50-250 nm, mean grain size – in the range of ~ 35-60 nm) were prepared by chemical vapour deposition (CVD) techniques on Si (100) substrates using metallorganic precursors; microstructural

450-750

(continued)

2.6 Chemical Properties and Materials Design

519

Table 2.22 (continued) analysis of the films suggested the absence of any hexagonal phases and the presence of monocarbonitride (cubic) γ-W(CxNy) solid solution phase or the existence of separate cubic phases of γ-WC1–x (x ≈ 0.4) carbide and γ-WN1–y (y ≈ 0.5) nitride CH4/N2/ 500 /Ar gas mixture flow, Ptot = 1 Pa –

W(C0.75N0.25) N-doped W carbide thin films were deposited using d.c. reactive magnetron sputtering (exposure – 2 h) in gaseous mixture discharge; the γ-W(C,N)1–x → δ-W(C,N)1±x phase transition occurred when N-doping was in the range of 2.9-4.7 at.%

500-650

Thin films of monocarbonitride (cubic) γ-W(C0.21÷0.38N0.62÷0.76) solid solutions (with the N/W and C/W atomic ratios decreasing from 0.76 to 0.62 and 0.38 to 0.21, respectively, with increasing the temperature of deposition) were fabricated on Si substrates by metallorganic chemical vapour deposition (MOCVD) techniques

500-800

Thin films of monocarbonitride (cubic) ~γ-W(C0.67N0.42) (granular-like structured, thickness – ~ 12-24 nm, mean grain size – in the range of 3-7 nm) were prepared on Si or SiO2 substrates via atomic layer deposition (ALD) followed by annealing (exposure – 0.5 h); during the annealing at higher temperatures, due to the losses of N, the microstructure and phase composition of the films were drastically changed: the formation of larger grains of metallic W and smaller grains of α/ε-W2+xC and δ-WC1±x was observed

NH3, CO 700-800

Porous monocarbonitride (hexagonal) δ-W(N,C)1±x (C-doped W nitride) catalytic materials (specific surface area – ~45 m2 g–1, pore volume – ~0.2 cm3 g–1, mean pore size ~15 nm) were synthesized by alcoholysis method followed by a temperature-controlled ammonification and carbonization reactions (total holding time of heat treatments – 3.5-6.0 h)

N2, 700-1500 0.1-190 MPa

The powders (mean grain size – 0.3 μm) of monocarbonitride (hexagonal) δ-W(C,N)1±x phase were fabricated by the nitridation of W – C mixtures (synthesis duration – 1 h); the composition of δ-W(C0.80N0.20)1±x, having the highest content of combined N, was obtained at 1250 °C and pN2 = 160 MPa

NH3

(continued)

520

2 Tungsten Carbides

Table 2.22 (continued) –

≥ 900

The phase transformation of monocarbonitride (hexagonal) δ-W(C,N)1±x → monocarbonitride (cubic) γ-W(C,N)1–x was detected in atomic layer deposited thin films

NH3 / < 1200 CnH2n+2 (gas)

N2, 10-150 MPa

During the carbonitridation of metallic W phase, the predominant diffusion of C and N through the formed reaction products and retarding effect of N on the diffusion of C into W were revealed

1250-1500 ~δ-W(C0.90N0.10)1±x monocarbonitride (hexagonal) powdered materials were synthesized under higher gaseous pressure

N2, 1250-1500 The contents of combined N in the synthe160 MPa sized (by the nitridation of W – C mixtures, exposure – 1 h) δ-W(CxN1–x) phase decreased with increasing temperature from the composition of δ-W(C0.80N0.20) (at 1250 °C) up to the composition of δ-W(C0.86N0.14) (at 1500 °C) NH3/H2 1300 or CH4/NH3 (ptot = 0.1 MPa)

The powders of monocarbonitride (hexagonal) δ-W(C0.95÷0.98N0.03÷0.05)1±x phase were fabricated by the nitridation of W – C and W oxide – C mixtures (synthesis duration – 1 h)

N2, 1400 0.1-100 MPa

The contents of combined N in the synthesized (by the nitridation of W – C mixtures, exposure – 1 h) monocarbonitride (hexagonal) powdered materials increased with increasing N2 pressure from the composition of δ-W(C0.96N0.04)1±x (pN2 = 0.1 MPa) up to the composition of δ-W(C0.83N0.17)1±x (pN2 = 100 MPa)

Ar/N2 (50/50) mixture flow, ptot = 0.3 Pa

–

Monocarbonitride (cubic) γ-W(CxNy) solid solution (γ-WC1–x – γ-WN1–y) coatings (thickness – ~2 μm, with slight (111) preferential orientation) were deposited on Al alloy substrates via reactive magnetron sputtering process

Ar/N2 (50/50) mixture flow, ptot = 0.3 Pa

–

Monocarbonitride (cubic) γ-W(CxNy) solid solution coatings (thickness – 1.5±0.1 μm, mean grain size – decreasing from 15 nm to 6 nm while C content increases in the range of 3.1-19.2 at.%, with slight (111) preferential orientation and presence of amorphous α-C (~ 1-3 %) and CNx (~ 3-7 %) phases) were deposited on Si (100) and stainless steel substrates via r.f. reactive magnetron sputtering process

(continued)

2.6 Chemical Properties and Materials Design

521

Table 2.22 (continued) –

–

Quantum-chemical studies (calculations) of the electronic structure and some properties of monocarbonitride (hexagonal) δ-W(C1–yNy) (0 ≤ y ≤ 0.5) phases have been undertaken

See also section C – N – W in Table I-2.14 δ-WC1±x – δ-WN1±x – α/β/γ/δ/ε/ζ-WO3–x

–

700

NH3, ~700-900 CH4/H2 (80/20)

The W(C,N) coatings prepared by reactive [1356, 4435] magnetron sputtering could improve their stability by increasing the bonding energy, decreasing the pores among the columnar grain boundaries, squeezing the amorphous phase to withstand the expansion and consuming some O by amorphous phase oxidation Monooxycarbonitride (hexagonal) W(CxOyNz) phase with the atomic ration C/N/O = 50/46/4 was synthesized

δ-WC1±x – H2 δ-WN1±x – α/β/γ/δ/ε/ζ-WO3–x – WO2±x

300-700

γ-W(CxNy) (solid solution or a mixture of [1356, 4425] γ-WC1–x and γ-WN1–y phases) – α/β-WO3–x (0 ≤ x ≤ 0.28) – WO2±x thin films (amorphous at < 550 °C and polycrystalline at ≥ 550 °C, thickness – ~ 50-60 nm, mean grain size < 7 nm, contents (depending on deposition temperature): W – 34-63 at.%, C – 9-62 at.% (9 at.% – at 300-400 °C), N – 5-24 at.% (24 at.% – at 350 °C, 5 at.% – at 650 °C), O – 2-20 at.%) were prepared on Si (100) substrates by metallorganic chemical vapour deposition (MOCVD) techniques

γ-WC1–x – NH3 γ-WN1–x – α/β/γ/δ/ε/ζ-WO3–x

450-750

Thin films based on monooxycarbonitride [1356, 4416] (cubic) W(CxNyOz) (or coexisting monooxynitride (cubic) γ-W(NyOz)0.5 and monooxycarbide (cubic) γ-W(CxOz)0.6 phases) with varying contents of W – 36-61 at.%, C – 18-54 at.%, N – 8-23 at.% and O – 2-5 at.% were deposited on Si (100) substrates using metallorganic routes (the films deposited at < 500 °C were not crystalline)

NH3, ~700-900 CH4/H2 (80/20)

Monooxycarbonitride (cubic) W(OxCyNz) phase with the atomic ratio C/N/O = 28/13/59 was synthesized

(continued)

522

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – O2, α/β/γ/δ/ε/ζ-WO3–x 1-10 mPa –

(–190)(+630) 200

The formation of δ-W(CxOy) oxycarbide [83, 161, phase was detected on the surface of single 171, 530, crystal δ-WC1±x (0001) 709, 1164, 1288, 1297, 2D δ-WC1±x – β/γ-WO3–x heterogeneous hybrid (ultra-thin sheets with ~ 3.0-3.3 nm 1331, 1339, thicknesses, layer-by-layer stacked carbide 1356, 1443, and oxide hexagonal phases) was in situ 1489, 1742, fabricated via autoclave solvothermal reac- 4060, 4437tion (exposure – 24 h) for catalysis aims 4439, 4529]

H2/CH4 550-600 (80/20) mixture

The formation of W(OxCy) and/or W3(OxCy) oxycarbide phases was observed on the intermediate stages of gaseous reduction of W oxides

Vacuum, 1300 ~6.7 Pa

The presume formation of oxycarbide (cubic) γ-W(CxOy) (or γ-W(C,O)1–x) phase (subsequently decomposed to α/ε-W2±xC phase)

Vacuum, 1500-1800 Powdered δ-WC0.99 (mean particle size – 13 mPa 12 μm, contents: non-combined C – 0.09%, Fe – 0.14%) – 0.25-0.75 % α-WO3–x mixtures (preliminarily ball-milled) were subjected to sintering (exposure – 0.5 h) procedure to prepare dense materials (porosity – in the wide range from 2 % to 39 %); increasing the amount of α-WO3–x led to the increase of porosity of sintered bodies –

–

Crystalline hollow nanowires γ-W(C1–xOy) (0.64 ≤ x ≤ 0.87, 0.11 ≤ y ≤ 0.13, diameter – 32 nm, length/diameter aspect ratio – 200) were synthesized

–

–

Ab initio total energy calculations of oxycarbide WO3–xCx phases, formed by partial substitution of C atoms for O atoms and appeared in the carburization processes, was performed to predict their properties

δ-WC1±x – Ar, α/β/ε/γ-W2±xC – 1.3 Pa α/β/γ/δ/ε/ζ-WO3–x

20-275

See also section C – O – W in Table I-2.14 Thin films (thickness – 0.75 μm, content O [4439] – in the range from 1.4 at.% to 13.5 at.%), deposited on Si (111) substrates using r.f. planar magnetron sputtering process, were composed of γ-WC1–x and W2(CxOy) (or γ-W(C,O)1–x) cubic and γ-W2±xC hexagonal phases; the presence of O stabilizes the cubic phase in the form of W2(CxOy) (or γ-W(C,O)1–x), while in the absence of O, hexagonal γ-W2±xC phase becomes more stable

(continued)

2.6 Chemical Properties and Materials Design

523

Table 2.22 (continued) H2/CH4 550-600 (80/20) mixture

The formation of W(OxCy) and/or W3(OxCy) oxycarbide phases was observed on the intermediate stages of gaseous reduction of W oxides

See also section C – O – W in Table I-2.14 α/β/ε/γ-W2±xC – Ar/N2 20-500 α/β/γ/δ/ε/ζ-WO3–x (50/50), Ptot = 0.3 kPa

Oxycarbide W2±x(C,O) phase was identi- [161, 530, fied in the δ-W(CxNy) thin polycrystalline 1331, 1772, films (thickness – 0.45 μm) deposited on 4438, 4440] stainless steel substrates using repetitive pulsed vacuum arc techniques

H2/CH4 550-600 (80/20) mixture

The formation of W2(OxCy) and/or W3(OxCy) oxycarbide phases was observed on the intermediate stages of gaseous reduction of W oxides

H2 flow

–

α/ε-W2+xC – ζ-WO3 thin composite films were synthesized on Cu substrates using hot filament chemical vapour deposition (HFCVD) techniques to fabricate electrodes for electrochemical capacitors

He/O2

–

Bulk oxycarbide α/ε-W2+x(C,O) materials were synthesized for catalysis purposes

–

–

The dispersions of W2(CxOy) nanoparticles were prepared by thermolysis of Si-containing polymers in micro- and meso-porous matrices

See also section C – O – W in Table I-2.14 δ-WC1±x – Ar, α/β/γ/δ/ε/ζ-WO3–x 0.45 Pa – α/β-WS2–x

–

δ-WC1±x – ~ 24-29 mol.% WS2–x – ~ 9-14 [4441] mol.% WO3–x thin films (thickness – 1.01.1 μm, with the presence of small amounts of W metallic phase; contents: W – 35-43 at.%, S – 24-34 at.%, C – 22-28 at.%, O – 5-10 at.%) were deposited on Si substrates using d.c. magnetron sputtering techniques

δ-WC1±x – WO2±x

–

–

Superconductive amorphous thin films [83, 161, (thickness – 0.5 μm, contents: W – 47.4 530, 709, at.%, C – 42.0 at.%, O – 10.6 at.%) were 1489, 4060] prepared using plasma-enhanced chemical vapour deposition (PECVD) techniques on polycrystalline SiO2 substrates

–

–

DFT-calculations of the electronic structure and some properties of probable oxycarbide (hexagonal) δ-W(C1–xOx) phases have been undertaken

See also section C – O – W in Table I-2.14

(continued)

524

2 Tungsten Carbides

Table 2.22 (continued) δ-WC1±x – α/β-WS2–x

α/β/ε/γ-W2±xC – α/β-WS2–x

δ-WC1±x – WSe2–x

Ar, 0.45 Pa

–

–

–

δ-WC1±x – WSi2 Vacuum 1600 – W5Si3+x

δ-WC1±x – α/β-Y2O3–x

δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x

–

Powdered γ-W2±xC@β-WS2–x heterostruc- [563, 769] tured nanomaterials (“nanoflowers”) with abundant flower-shaped active sites ranging from 0.1 μm to 1 μm in size were prepared using autoclave hydrothermal process (exposure – 8-20 h); the obtained materials remained strained due to the lattice mismatch of the phase constituents

250

Ar, 0.5 Pa

Thin films (thickness – 1.0-1.1 μm, with [4441] the molar ratio WC/WS2 = 0.93÷2.21) were deposited on Si substrates using d.c. magnetron sputtering techniques

Nanocomposite WSe2–x – δ-WC1±x thin [4289] films (Se/C atomic ratio ≈ 2.8, thickness – 1.8 μm, WSe2–x crystalline domain sizes – 4-12 nm, content O – 8.7 at.%, with the presence of small amount of W2±xC phase) were deposited using r.f. magnetron sputtering techniques The powdered compositions of δ-WC1±x [4442] with added 5-10 % WSi2 + W5Si3+x silicide mixtures (preliminarily homogenized) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate δ-WC1±x – WSi2 two-phase porous ceramics (porosity – (37÷44)±(4÷13) %)

1600-1700 Powdered δ-WC1±x (mean particle size – [4465] 0.2 μm), preliminarily treated by chemical liquid mixing method with Y nitrate aqueous solution, was subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to prepare δ-WC1±x – 1-4 % Y2O3–x dense ceramic materials (porosity – in the range from 0 to 0.3 %); at higher temperatures in the sintered materials with Y2O3–x content > 2 % the formation of α/ε-W2+xC phase was detected

Vacuum, 1300-1400 Powdered δ-WC1±x (99.5 % purity, mean 6,7 Pa particle size – 0.2 μm) – 6-10 % α/β-(Zr,Y)O2–x (3 mol.% Y2O3-stabilized, mean particle size – 27 nm, contents: SiO2 < 0.007%, Al2O3 < 0.005%) mixtures (preliminarily ball-milled) were subjected to spark-plasma sintering (SPS) procedure (holding time – in the range from 0 to 20 min) to fabricate dense ceramic nanocomposites (porosity – ~ 1-2 %, grain size distributions of δ-WC1±x matrix and α/β-(Zr,Y)O2–x inclusions – ~ 0.3-0.5 μm and ~ 30-100 nm, respectively); the presence of newly formed ε-W2+xC (its frac-

[585, 1373, 1380, 2672, 2718, 3392, 4091, 4095, 4141, 4186, 4197, 44434464, 44734487]

(continued)

2.6 Chemical Properties and Materials Design

525

Table 2.22 (continued) tion increased from 5.1 vol.% to 7.6 vol.% with the holding time increasing from 5 to 20 min, due to the reaction: 2yWC + ZrO2–x = yW2C + ZrO2–x–y +yCO, where y is the additional vacancy concentration created in oxide phase) and δ-ZrO2–x (orthorhombic, metastable; appeared due to the β → δ polymorphic transformation caused by large residual stress induced by thermal expansion anisotropy in the treated materials) phases was observed, the formation of ε-W2+xC grains, detected in the materials mainly at the interface between the δ-ZrO2–x and δ-WC1±x grains, leads to a depletion of C content in the latter ones Ar flow 1400-1500 Powdered α/β-(Zr0.95Y0.05)O2–x (stabilized by 2.8 mol.% α-Y2O3–x, tetragonal phase with 9 % monoclinic, mean particle size – ~ 18-19 nm, specific surface area – ~52 m2 g–1) – 10-50 vol.% δ-WC1±x (with the traces of α/ε-W2+xC and metallic W, mean particle size – 1.6±0.6 μm, specific surface area – 0.23 m2 g–1) mixtures (preliminarily ball-milled for homogenization) were subjected to hot-pressing (exposure – 40 min) or pressureless sintering (exposure – 2 h) procedures to prepare dense ceramic particulate composites (porosity – 0.1-2.0 %); in the materials sintered at higher temperatures the small amounts of ZrC1–x and α/ε-W2+xC phases were revealed, the mixtures with δ-WC1±x powder having smaller mean particle size (0.13 μm) were being densified a bit worse CO

1400-1500 According to the thermodynamic calculations, the equilibrium pressure of CO in the reaction ZrO2 + 6WC = ZrC + 3W2C + 2CO↑ is in the range from 95 kPa to 520 kPa; so, this reaction can proceed towards the formation of ZrC1–x and α/ε-W2+xC phases under the potentially necessary conditions for the sintering process of δ-WC1±x and α/β/γ-ZrO2–x powdered mixtures, while the probability of formation of any W oxides in such conditions is rather negligible

(continued)

526

2 Tungsten Carbides

Table 2.22 (continued) –

1400-1700 In the β-(Zr0.95Y0.05)O2–x (tetragonal) – 10-30 vol.% δ-WC1±x sintered and hotpressed composite materials (mean matrix grain size – 0.5-1.8 μm) in the adjacent oxide and carbide grains some crystal directions, mainly and in β-(Zr0.95Y0.05)O2–x and and in δ-WC1±x are nearly parallel, and the following crystal relationships between the phases were identified: δ-WC1±x (0001) // β-(Zr0.95Y0.05)O2–x (001) and δ-WC1±x (1010) // β-(Zr0.95Y0.05)O2–x (010); in the materials prepared at higher temperatures, where α/ε-W2+xC and α/β-(Zr0.95Y0.05)O2–x grains coexisted, the crystallographic correlations α/ε-W2+xC (1000) // β-(Zr0.95Y0.05)O2–x (001) and α/ε-W2+xC (0100) // β-(Zr0.95Y0.05)O2–x (010) were observed

Vacuum 1400-1700 Powdered compositions of β-ZrO2–x (stabilized by 2.6 mol.% α-Y2O3–x, mean particle size – ~0.1 μm, specific surface area – 10.4 m2 g–1) with 10-20 vol.% δ-WC1±x (mean particle size – ~0.7 μm, specific surface area – 2.5 m2 g–1), ball-milled and compacted (porosity – 40-44 %) via slipcasting techniques, were subjected to sintering procedure (exposure – 3 h) to prepare dense ceramic particulate composites (porosity – in the range from 0 to 16 %) Vacuum, 1450 4 Pa

α/β-ZrO2–x (partially stabilized by 1.75-2.0 mol.% α-Y2O3–x, content α-ZrO2–x (monoclinic) – ~ 4-25 vol.%, transformability – ~ 22-44 %) – 40 vol.% δ-WC1±x ceramics were prepared using pulsed electric current sintering (PECS) procedure (exposure – 4 min)

Vacuum 1450

Powdered 2 mol.% Y2O3-stabilized α/β-ZrO2–x (mean particle size – 27-30 nm) – 5-40 vol.% δ-WC1±x (crystallite size – 18 nm, size distribution of agglomerates < 10 μm) mixtures (preliminarily ball-milled) were subjected to hot-pressing procedure (exposure – 1 h) to fabricate highly dense ceramic nanocomposites

(continued)

2.6 Chemical Properties and Materials Design

527

Table 2.22 (continued) Vacuum, 1450 ~10 Pa

3 mol.% Y2O3-stabilized α/β-(Zr,Y)O2–x powders (mean particle size – 30 nm) mixed, respectively, with 30, 40 and 50 vol.% δ-WC1±x (mean particle size – 40 nm), were employed for the fabrication of functionally (continuously) graded composites with up to 55 % δ-WC1±x (porosity – in the range of 0 to 7 %), processed by electrophoretic deposition (EPD) and cold isostatic pressing (CID) followed by sintering or hot-pressing procedures (exposure – 1 h)

Vacuum, 1450 ~0.1 Pa

Powdered 2.0-3.0 mol.% Y2O3-stabilized α/β-(Zr,Y)O2–x (crystallite size – 27-30 nm) – 20-50 vol.% δ-WC1±x (crystallite size – 20-40 nm, agglomerate size – 49 μm) mixtures were subjected to hot-pressing procedure (exposure – 1 h) to prepare full dense ceramic composites with the composite transformability decreasing from 51±1 % to 21±1 % and transformability of α/β-ZrO2–x phase – from 61±1 % to 41±1 % with increasing fraction of δ-WC1±x phase in the materials; the maximum δ-WC1±x mean grain size, observed in the materials with 20 vol.% δ-WC1±x, was determined to be < 1 μm

–

1450-1550 Powdered 2.0-3.5 mol.% Y2O3-stabilized β-(Zr,Y)O2–x (submicrometer-sized) – 5-40 vol.% δ-WC1±x (bi-modal, including 75 % nanosized particles) mixtures were subjected to hot-pressing procedure to prepare highly dense ceramic composites

–

1500

3 mol.% Y2O3-stabilized β-ZrO2–x – 10 vol.% δ-WC1±x particulate ceramic composites (porosity – 0.1 %) were fabricated by hot-pressing procedure (exposure – 1 h) using micrometer-sized carbide powders

Vacuum, 1500-1700 Powdered δ-WC1±x (> 99.9 % purity, mean ≤ 6 Pa particle size – ~0.8 μm) – 2.6-22.4 vol.% α/β-ZrO2–x (3 mol.% Y2O3 partially stabilized, mean particle size – ~0.1 μm) mixtures (preliminarily high-energy ball-milled) were subjected to spark-plasma sintering (SPS) procedure (exposure – 5 min) to fabricate dense ceramic composites (porosity – < 0.5 %, grain sizes of δ-WC1±x and α/β-ZrO2–x phases – in the ranges of 0.610.92 μm and 0.22-0.55 μm, respectively); no chemical interaction between carbide and oxide phases was revealed

(continued)

528

2 Tungsten Carbides

Table 2.22 (continued) Powdered α/β-ZrO2–x (2-3 mol.% Y2O3 stabilized, mean particle size – ~0.6 μm) – 10-20 vol.% δ-WC1±x (mean particle size varying from ~0.2 μm to ~1.5 μm and specific surface area – from ~0.9 m2 g–1 to ~1.6 m2 g–1 for different sorts) mixtures were subjected to the injection molding followed by sintering procedure (exposure – 4-6 h) to prepare dense ceramic composites (porosity – in the range from 0 to ~13 %); the presence of α/ε-W2±xC, ZrC1–x and ZrW2 phases as side products in the prepared composites was detected

Ar flow 1550

Vacuum, 1600-1700 Powdered δ-WC1±x (99.5 % purity, mean 8 Pa particle size – 0.2 μm) – 6 % α/β-(Zr,Y)O2–x (2-3 mol.% Y2O3-stabilized, mean particle size – 27 nm, contents: SiO2 < 0.007%, Al2O3 < 0.005%) mixtures (preliminarily ball-milled) were subjected to pressureless solid-state sintering (exposure 1-3 h) to fabricate dense ceramic composites (porosity – 0.5-7.5 % with the presence of closed pores, mean grain sizes of δ-WC1±x matrix and β-(Zr,Y)O2–x inclusions – ~ 1-2 μm and < 1 μm, respectively); thermodynamic compatibility of δ-WC1±x and β-(Zr,Y)O2–x phases was proved experimentally Vacuum, 1700-1800 Powdered δ-WC1±x – 5-10 vol.% ~4 Pa α/β-(Zr,Y)O2–x (2 mol.% Y2O3 stabilized, introduced by different ways, including an alkoxide (metallorganic) route) mixtures (preliminarily ball-milled) were subjected to pulsed electric current sintering (PECS) procedure (exposure – 2-4 min) to fabricate highly dense ceramic composites; the presence of small amounts of α/ε-W2±xC and ZrC1–x phases as side products in the prepared composites was detected that implied the formation of CO trapped in the form of pores during the processing, the β-(Zr,Y)O2–x (tetragonal) phase disappeared in the fractured composites indicating its transformation to α-(Zr,Y)O2–x (monoclinic) modification

N2

–

Powdered α/β-(Zr,Y)O2–x – 40 vol.% δ-WC1±x mixtures were subjected to pressureless sintering to produce ceramic composite grinding balls (beads) for high-energy ball-milling

(continued)

2.6 Chemical Properties and Materials Design

529

Table 2.22 (continued) –

–

α/β-(Zr,Y)O2–x (3 mol.% Y2O3 partially stabilized matrix) – 20 vol.% δ-WC1±x (micrometer-sized dispersion) composites were produced by ceramic injection molding (CIM) and subsequent pressureless sintering

See also section δ-WC1±x – α/β/γ/δ-ZrO2–x δ-WC1±x – Vacuum, 1500-1700 ε-W2+xC – δ-WC1±x – α/β-(Zr,Y)O2–x bulk [4464] α/β/ε/γ-W2±xC – Ar nanocomposites were produced from the α/β-Y2O3–x – δ-WC1±x and β-(Zr,Y)O2–x powders, preliα/β/γ/δ-ZrO2–x minarily subjected to high-energy ball-milling treatment, using pressureless sintering and spark-plasma sintering (SPS) techniques δ-WC1±x – ZrB2±x

–

–

No interaction in the near-equimolar pow- [4059, 4248dered mixtures of the components was de- 4249, 4251, tected 4272, 4340, 1650-1800 The chemical interaction in the near-equi- 4346-4347, molar δ-WC1±x – ZrB2±x powdered mixtu- 4354-4361, res leads to the appearance of (Zr,W)C1–x 4466-4470] 1450

and α-(W,Zr)B1±x solid solution (mixed) phases, formed in accordance to the following reaction: 2WC + ZrB2 = ZrC + 2WB + C Ar

– –

1900

An unknown phase as a product of δ-WC1±x – ZrB2±x interphase interaction (ZrxWyBz, ?) was detected in the obtained hot-pressed materials

~2000

The maximum solid solubility of δ-WC1±x in ZrB2±x was determined to be ~8 mol.%

–

Depending on composition, the arc-melted δ-WC1±x – 15-63 mol.% TiB2±x materials contained δ-WC1±x, γ-W2±xC and ZrB2±x phases

See also section δ-WC1±x – α/β-SiC – ZrB2±x See also section δ-WC1±x – ZrB2±x – α/β/γ/δ-ZrO2–x δ-WC1±x – ZrB2±x – α/β/γ/δ-ZrO2–x

–

1450-1800 The chemical interaction in the powdered δ-WC1±x – 30 mol.% ZrB2±x – 10 mol.% α-ZrO2–x mixtures leads to the appearance of (Zr,W)C1–x and α-(W,Zr)B1±x solid solution (mixed) phases, formed in accordance to the following reactions: 2WC + ZrB2 = ZrC + 2WB + C and ZrO2 + 3C = ZrC + 2CO↑, or in the summarized version:

[4248-4249, 4272, 43464347, 4356, 4469]

(continued)

530

2 Tungsten Carbides

Table 2.22 (continued) 6WC + 3ZrB2 + ZrO2 = 6WB + 4ZrC + 2CO↑ (an unknown phase (ZrxWyBz, ?) was also detected in the products at the intermediate temperatures) δ-WC1±x – ZrC1–x

See section ZrC1–x – δ-WC1±x in Table II5.25 See also section C – W – Zr in Table I2.14

α/β/ε/γ-W2±xC – ZrC1–x

See section ZrC1–x – α/β/γ-W2±xC in Table II-5.25 See also section C – W – Zr in Table I2.14

γ-WC1–x – ZrC1–x

See section ZrC1–x – γ-WC1–x in Table II5.25 See also section C – W – Zr in Table I2.14

δ-WC1±x – ZrN1±x N2/Ar (67/33), ptot = 1.2 Pa δ-WC1±x – α/β/γ/δ-ZrO2–x

–

ZrN1±x – δ-WC1±x nanocomposite hard [4471-4472] layers/films (contents, at.%: W – 11.9, Zr – 40.5, N – 32.8, C – 14.8) were deposited on stainless steel substrates using arc ion plating techniques

[1, 151, 585, 666, 1373, 1380, 2672, 2718, 2734, 3391-3392, 4034-4035, 4038-4041, 4072, 4095, 4141, 4185Vacuum, 1300-1400 Practically, no chemical interaction in the 4186, 4197, 0.13 Pa δ-WC0.99 (> 99.9 % purity, mean particle 4249, 4340, 4346-4347, size < 10 μm) – α-ZrO2–x (monoclinic, > 99 % purity) powdered mixtures (expo- 4443-4464, 4469, 4473sure – 0.5-1 h) 4487, 4662] Vacuum 1300 In the reaction mixtures with molar ratio δ-WC1±x/α-ZrO2–x = 3, according to the thermodynamic calculations, the amounts of residual α-ZrO2–x phase achieve up to 31 % Vacuum 800-1600

In the reaction mixtures with molar ratio δ-WC1±x/α-ZrO2–x = 3, according to the thermodynamic calculations, the existence of the intermediate phase α/ε-W2±xC is limited by this temperature range and controlled by the following reactions: 2WC = W2C + C 2C + ZrO2 = ZrC + 2CO↑ 3W2C + ZrO2 = 6W + ZrC + 2CO↑

Vacuum, ≤ 1400 0.67 Pa

No noticeable chemical interaction in the reaction powdered mixtures with molar ratio δ-WC1±x/α-ZrO2–x = 2

Vacuum 1400

The interaction (exposure – 0.5 h) in δ-WC1±x – α-ZrO2–x powdered mixtures of components leads to the ~40 % reduction of oxide phase and formation of W-Zr alloy

(continued)

2.6 Chemical Properties and Materials Design

531

Table 2.22 (continued) –

1450-1650 In the powdered δ-WC1±x – 50 vol.% α-ZrO2–x mixtures, the propagation of the following reaction: 6WC + ZrO2 = 3W2C + ZrC + 2CO↑ was confirmed experimentally (with the formation of (Zr,W)(C,O)1–x solid solution (mixed) monooxycarbide phase)

Vacuum, 1500 0.67 Pa

In the products of reaction powdered mixtures with molar ratio δ-WC1±x/α-ZrO2–x = 2, the major phases of metallic W and residual α-ZrO2–x with traces of (Zr,W)(C,O)1–x and α/ε-W2±xC phases were detected

Vacuum, 1500-1700 Powdered δ-WC1±x (mean particle size – 8 Pa 0.2 μm) – 6 % α-ZrO2–x (mean particle size – 27 nm, contents: SiO2 < 0.007%, Al2O3 < 0.005%) mixtures (preliminarily ballmilled) were subjected to solid-state pressureless sintering (exposure 1-3 h) to fabricate ceramic composites (porosity – in the range from 6.1 % to 33.3 %, during cooling the concomitant cracking retarded the densification) Vacuum 1600

The formation of ZrC1–x and traces of α/ε-W2+xC were revealed in the heat treated powdered mixtures of the components (exposure – 1 h)

Vacuum, 1600-2000 In the products of reaction powdered mix0.67 Pa tures with molar ratio δ-WC1±x/α-ZrO2–x = 2, the phases of metallic W, mixed monooxycarbide (Zr,W)(C,O)1–x and residual α-ZrO2–x were detected –

1650-1850 In the powdered δ-WC1±x – 50 vol.% α-ZrO2–x mixtures, the propagation of the following reaction: 3WC + ZrO2 = ZrC + 3W + 2CO↑ was confirmed experimentally (with the formation of (Zr,W)(C,O)1–x solid solution (mixed monooxycarbide phase)

Vacuum 1700

In the reaction mixtures with molar ratio WC/ZrO2 = 3, according to the thermodynamic calculations, the residual α-ZrO2–x phase amounts to 1 %

Ar, 1700 206 MPa

Powdered δ-WC1±x (mean particle size – ~0.9 μm) – 14 % α-ZrO2–x (monoclinic, mean particle size – 10 μm) mixtures (preliminarily ball-milled) were subjected to hot isostatic pressing (HIP) procedure (exposure – 1 h) to prepare bulk ceramic composites; the formation of γ-ZrO2–x (cubic)

(continued)

532

2 Tungsten Carbides

Table 2.22 (continued) phase in the treated materials was detected Vacuum 1700-1800 ZrC1–x, α/ε-W2+xC and metallic W phases are the products of chemical interaction in powdered mixtures of the components (exposure – 1 h) Vacuum 1900-2000 ZrC1–x and metallic W phases are the products of interaction in powdered mixtures of the components (exposure – 1 h) –

>2200-2300 Slight interaction in the contact zone between the dense bulk components (exposure – 1 h) with the formation of new phase, probably oxycarbide Zr(C,O)1–x, with columnar structured crystals

See also section δ-WC1±x – α/β-Y2O3–x – α/β/γ/δ-ZrO2–x See also section C – O – W – Zr in Table I-2.14 δ-WC1±x – α/β/ε/γ-W2±xC – α/β/γ/δ-ZrO2–x

N2

δ-WC1±x – α/ε-W2+xC nanorods (diameter – [427] 90-95 nm, length – 0.35-0.40 μm) – γ-ZrO2–x (cubic) electrode films were prepared using sintering procedure (exposure – 0.5 h)

450

See also section C – O – W – Zr in Table I-2.14

Table 2.23 Chemical interaction of tungsten carbide phases with gaseous media at ambient, elevated, high and ultra-high temperatures (reaction systems are given in alphabetical order) System

Atmosphere

Temperature range, °C

–

–

δ-WC1±x – Br2

δ-WC1±x – CH4 CH4 Ar/CH4

≥ 2500 > 5000

Interaction character, products and/or compatibility

References

δ-WC1±x-based hard alloys were implanted [1119] with Br+ to dose levels from 2×1016 cm–2 to 5×1017 cm–2 Decarburization of δ-WC1±x phase was ob- [11, 153, served 670, 1328, 4509] Powdered δ-WC1±x (size distribution < 44 μm) with a carrier gas flow (feed rate – ~13 mg s–1) was injected into thermal plasma jet to produce γ-WC1–x (maximum conversion of δ-WC1±x into γ-WC1–x – 62 %) in prepared powdered products (particle size – from 0.5 μm to > 10 μm)

α/β/ε/γ-W2±xC – CH4

CH4

≥ 2500

Partial decarburization of semicarbide W2±xC materials

[11, 670, 4509]

(continued)

2.6 Chemical Properties and Materials Design

533

Table 2.23 (continued) δ-WC1±x – CH4 H2, CH4 – H2

δ-WC1±x – C2H4

–

800-1300

–

CH4 added to H2 in the amounts exceed- [4551] ing its equilibrium concentration with respect to δ-WC1±x, but not exceeding its equilibrium concentration with respect to α-C (graphite) not only slows down the process of δ-WC1±x decarburization, but recarburizes W and W2±xC impurities present in the initial powders of δ-WC1±x with no risk of non-combined C liberation Density functional theory (DFT) calcula- [4568] tions gave the following trend in ability to bind C2H4 (as a model compound of unsaturated hydrocarbons): δ-WC1±x (C-terminated) > δ-WC1±x (W-terminated) > γ-WC1–x, with the binding energy varying in the range from –0.72 eV to –2.91 eV

C2H6

≥ 2500

Partial decarburization of δ-WC1±x materi- [11, 670, als 4509]

α/β/ε/γ-W2±xC – C2H6 C2H6

≥ 2500

Partial decarburization of semicarbide W2±xC materials

δ-WC1±x – C6H6

C6H6

(–100)-1330 The interaction/adsorption of benzene [4561-4562] C6H6 vapour with δ-WC1±x (0001) surface was studied in detail in the wide range of temperatures; it depended strongly on the precoverage of O atoms on the surface

δ-WC1±x – CH3OH/ CH3OD

CH3OH/ CH3OD

δ-WC1±x – C2H6

δ-WC1±x – CO CO

–

(–170)-0

[11, 670, 4509]

Decomposition of CH3OH/CH3OD on the [502, 1428, carburized and/or carburized/oxidized 1498, 1553, surfaces of W was studied 4544, 4563] The reactivity of δ-WC1±x (0001) surface was characterized by its strong interaction with CO molecules, which were stable and coordinated to the surface via their C ends, standing upright on the surface; strong surface – CO bonding made up by a 2π interaction with occupied substrate levels and an interaction of the 5σ state with unoccupied substrate states resulting in a shift of the 5σ state near to the 1π level was observed

CO

(–70)-(–20) A part of adsorbed at lower temperatures CO molecules were desorbing from the δ-WC1±x (0001) surface in this temperature range

CO

(–70)-20

[110, 174, 1076, 1291, 1318, 1389, 1445, 1553, 1738, 4544, 4556, 45594561, 4563]

CO is adsorbed molecularly (non-dissociatively) on the surface of clean singlephase δ-WC1±x materials, including thin films; surface – CO bonding appears to be rather weak

(continued)

534

2 Tungsten Carbides

Table 2.23 (continued) ≥0

Upon warming up, the complete dissociation of adsorbed CO molecules on the δ-WC1±x (0001) surface took place, the dissociation products of CO could modify the surface composition

–

20

Surface number densities for irreversibly chemisorbed species CO (nCO) on fresh samples of highly dispersed δ-WC1±x (~6 nm, ~30 m2 g–1) and γ-WC1–x (~4 nm, ~100 m2 g–1) powders (mean crystallite sizes and specific surface areas are given in brackets) are 0.39×1015 cm–2 and 0.24×1015 cm–2, respectively (1 monolayer corresponds to ~1.0×1015 cm–2)

–

400

Powdered δ-WC1.00 (mean crystallite size – ~ 20-60 nm, specific surface area – 6.7 m2 g–1) materials pretreated in a isothermal manner were characterized by the CO up-take value of 4.5 μmol g–1 (number density of sites – 0.40×1014 cm–2)

430-830

Reactive/recombinative desorption from the δ-WC1±x (0001) surface took place

830-1080

The heat treatment of δ-WC1±x (0001) surface led to the removal of C and O in the form of CO release

CO

CO –

–

–

The adsorption properties of CO on δ-WC1±x (0001) surface were studied using spin-polarized density functional theory (DFT) calculations

–

–

Systematic studies on the adsorption of CO on δ-WC1±x (0001) and γ-WC1–x (001) surfaces were undertaken using periodical density functional theory (DFT); it was showed that adsorbed CO is more stable on a C- than on a W-terminated surface

δ-WC1±x – CO2 CO2

–

CO2

–

The adsorption behaviour of δ-WC1±x sur- [174, 456, faces was studied 1310, 1553, The resistance of δ-WC1±x detonation gun 1738, 4564]

See also section C – O – W in Table I-2.14

coatings in the CO2 environments was evaluated –

–

The adsorption properties of CO2 on δ-WC1±x (0001) surface were studied using spin-polarized density functional theory (DFT) calculations

(continued)

2.6 Chemical Properties and Materials Design

535

Table 2.23 (continued) –

–

Systematic studies on the adsorption of CO2 on δ-WC1±x (0001) and γ-WC1–x (001) surfaces were undertaken using periodical density functional theory (DFT); it was showed that adsorbed CO2 is more stable on a C- than on a W-terminated surface, and only this latter termination is able to cleave spontaneously a C-O bond of the CO2 molecules

–

–

Density functional theory (DFT) simulation of the adsorption of CO2 molecules on a (4, 0) W carbide single-wall nanotube (WCNT) indicated that a CO2 prefers to be adsorbed at the WCNT surface site and adsorption results in strong W-O bondings and charge transfers from W and C atoms in the WCNT toward the CO2 molecule

See also section C – O – W in Table I-2.14 δ-WC1±x – Cl2

Cl2 flow

Cl2

< ~600-700 Dense δ-WC1±x materials were resistant to [6, 12-13, corrosion and chemically stable in Cl2 151, 601, environment 646, 1119, 600-750 While performing chlorination of δ-WC1±x 2557, 4511, 4570-4574] WC + 3Cl2 = C + WCl6↑, in this range of temperatures, the formal activation energy E ≈ 150 kJ mol–1 was determined that allows to qualify the process as predominantly diffusion controlled (corresponding to parabolic kinetics) Powdered δ-WC1±x materials interacted (exposure – 1 h) with Cl2 in accordance with the following reaction: WC + 3Cl2 = C + WCl6↑; α-C (carbide-derived) with 94 % sp2-bonding prepared by the chlorination was characterized by very high specific surface area (1250 m2 g–1) and pore volume (0.65 cm3 g–1)

Cl2 flow

700-900

Cl2

~750-1000 The chlorination process of δ-WC1±x in this range of temperatures was revealed to proceed with the formal activation energy E ≈ 40 kJ mol–1 that allows to qualify it as predominantly reaction controlled (corresponding to linear kinetics)

Cl2

800-1100

Powdered δ-WC1±x (99 % purity, size distribution < 10 μm) materials were subjected to chlorination (exposure – 1.5-2.5 h) procedure to prepare α-C (carbide-derived) microporous materials with specific surface area – 1270-1580 m2 g–1 and pore volume – 0.59-0.89 cm3 g–1; at lower tem-

(continued)

536

2 Tungsten Carbides

Table 2.23 (continued) peratures the δ-WC1±x → α-C conversion was only ~50 % even after the exposure for 15 h –

–

δ-WC1±x-based hard alloys were implantted with Cl+ to dose levels from 2×1016 cm–2 to 5×1017 cm–2

α/β/ε/γ-W2±xC – Cl2 Cl2

300-400

Weak corrosion resistance of powders, intensive chemical interaction with the formation of WCl6 and α-C (graphite)

[6, 12-13, 118, 151]

δ-WC1±x – F2

F2

20

Intensive chemical interaction (initiation of powder combustion)

F2 (N2 – dilutant)

20-30

Powdered δ-WC1±x materials interacted (exposure – 1.5 h) with the formation of W fluorides and gaseous products of reaction, mol.%: CF4 – 67, C2F6 – 26, C3F8 – 7, n-C4F10 – 0.6, i-C4F10 – traces (greater percentages of CF4 were observed at higher temperatures)

[4, 11, 13, 43, 646, 1119, 4569, 4571]

–

–

δ-WC1±x-based hard alloys were implanted with F+ to dose levels from 2×1016 cm–2 to 5×1017 cm–2

α/β/ε/γ-W2±xC – F2 F2

20

Intensive chemical interaction (combustion of powders)

δ-WC1±x – H2/D2

H2

20

Surface number densities for irreversibly chemisorbed species H (nH) on fresh samples of highly dispersed δ-WC1±x (~6 nm, ~30 m2 g–1) and γ-WC1–x (~4 nm, ~100 m2 g–1) powders (mean crystallite sizes and specific surface areas are given in brackets) are 0.37×1015 cm–2 and 0.21×1015 cm–2, respectively (1 monolayer corresponds to ~1.0×1015 cm–2); only a fraction of O chemisorbed on W carbides reacted with H2 to release H2O: 0.1 – for δ-WC1±x and much lower – 0.01 for γ-WC1–x

H2

20

[11, 13]

[6, 11, 91, 110, 174, 200, 455, 581, 586, 670, 842, 846, 998, 1081, 10941095, 1132, 1153, 1250, 1253, 1328, 1459, 1625, 1810, 23632375, 4014, 4375, 4509, Non-oxidized δ-WC1±x synthesized from 4513-4515, W oxides adsorbed H2 from the gas phase 4543-4558] more strongly than those prepared from W acids; the chemisorption of molecular H2 was suppressed at the surface of δ-WC1±x by polymeric C but enhanced by surface O as some of the latter react in the presence of H2O with H2 spilling over from the δ-WC1±x parts of the surface

(continued)

2.6 Chemical Properties and Materials Design

537

Table 2.23 (continued) D2

25

The interaction of surface of δ-WC1±x materials with 0.02-1.5 keV D+ 3×1015 cm–2 fluxes at normal incidence of the ion beam led to the preferential erosion of C due threshold effects caused by the large W/C mass ratio

H2, CH4

25-1225

The equilibrium content of CH4 in gaseous phase for the reaction 2WC + 2H2 ↔ W2C + CH4 declines gradually within this temperature interval from 99.69 vol.% to 0.12 vol.% with increasing temperature (similarly to the reaction C + 2H2 ↔ CH4, where it declines from 99.996 vol.% to 0.3 vol.%)

H2, CH4

25-1225

The equilibrium content of CH4 in gaseous phase for the reaction WC + 2H2 ↔ W + CH4 declines gradually within the indicated temperature interval from 95.95 vol.% to 0.0063 vol.% with increasing temperature

–

< 150

Thin W – C – H films magnetron sputtered on steel (with C contents > 48 at.%) were composed of γ-WC1–x nanocrystalline grains dispersed in amorphous CHx matrix

–

≤ 150

Thin magnetron sputtered on steel layers (thickness – 4.2-5.7 μm) with formal ~W0.05÷0.75C0.25÷0.65H0.05÷0.35 composition (with the presence of small amounts of O) consisted of very small WC particles embedded in an amorphous CHx matrix; an increasing amorphous or glassy structure with increasing C contents was observed

–

150-425

Thin W – C – H magnetron sputtered films (thickness – 2.3-2.7 μm) contained β-C (diamond-like) phase

–

< 200

Thin W – C – H films (contents: W – ~ 5-70 at.%, C – ~ 25-85 at.%) magnetron sputtered on steel were composed of γ-WC1–x microcrystalline clusters embedded in amorphous CHx matrix

–

250

Thin W – C – H films (contents: W – 6-29 at.%, thickness – 1-2 μm) deposited by cathodic arc ion plating on Si (100) substrates were containing γ-WC1–x (mean grain size – 2.5 nm)

(continued)

538

2 Tungsten Carbides

Table 2.23 (continued) Dry H2

600-900

Water-milled δ-WC1.00 (specific surface area – ~0.5 m2 g–1; contents: non-combined C – 0.04%, H2O – 0.19%, O – 0.64%, Co – 0.57%, Fe – 0.34%, Ni – 0.05%) powders interacted (exposure – 1-4 h) according to the reaction WC + 2H2 = W + CH4 ↑ with the loss of ~ 1.5-11 at.% C in δ-WC1±x

H2

700

Being accompanied with the formation of CH4, the removal of C due to the hydrogenation from the surface of δ-WC1±x powders (specific surface area was changing from ~8 m2 g–1 to 36 m2 g–1 with constant mean crystallite size of ~6 nm), reached ~8 monolayers for 2 h (with the growth of number density for CO chemisorption up to nCO = 0.39 ×1015 cm–2 after 1 h and appearance of W phase after 2 h treatment)

H2, 0.1 MPa

890-1280

Mass losses of bulk δ-WC1±x materials (porosity – 14 %) in the ranges from ~0.05% to ~0.5 % were observed during the gas heat treatment (exposure – 1-16 h)

Dry H2

≤ 900

No reaction (exposure – up to 6 h) with ascarburized δ-WC1.00 (specific surface area – ~0.1 m2 g–1; contents: non-combined C – 0.05%, H2O – 0.04%, O – not detected, Co < 0.01%, Fe < 0.01%, Ni < 0.01%) powders (no changes in C content was detected), in contrast with water-milled δ-WC1±x powders interacting with the loss of C

H2 flow, ~60 cm3 s–1

940

Nanosized δ-WC1±x (total content of C – 9.74 %) powders were subjected to the purification procedure (exposure – 100 min) to decline total content of C – up to 6.20 %

H2 flow, ~60 cm3 s–1

970

Gas heat treatment (exposure – 100 min) of nanosized δ-WC1±x (total content of C – 9.74 %) powders resulted in massive loss of C, decarburization, formation of W2±xC phase and noticeable growth of δ-WC1±x grain size

H2, 0.1 MPa

1100

Powdered δ-WC1±x (contents: non-combined C – 2.0%, O – 6.7%) materials were subjected to the purification procedure (exposure – 1 h) to eliminate all the amount of non-combined C and decline the contents of O – up to 0.13 % (no changes in the W content was detected)

(continued)

2.6 Chemical Properties and Materials Design

539

Table 2.23 (continued)

α/β/ε/γ-W2±xC – H2/D2

H2

~1730

δ-WC1±x coatings prepared by the carburization of metal interacted on the surface with the formation of CH4

H2

~2200

Powdered δ-WC1±x materials are stable in the static conditions

H2

≥ 2600

Partial decarburization and decomposition of δ-WC1±x were observed

–

–

Systematic studies on the adsorption of atomic H and molecular H2 on δ-WC1±x (0001) and γ-WC1–x (001) surfaces were undertaken using periodical density functional theory (DFT); it was showed that atomic H adsorbs quite strongly while H2 does, in general, dissociatively on the studied surfaces, with very small energy barriers (< 0.35 eV) for the cleavage of the HH bonds

–

–

According to density functional theory (DFT) simulations, the interstitial H atoms prefer to diffuse in δ-WC1±x along the c axis

–

–

Adsorption of atomic H at several coverages on δ-WC1±x (0001), (0010) and (1120) surfaces were studied using density functional theory (DFT) formalism

–

–

According to classical molecular dynamics (MD) simulations, after the D bombardment of δ-WC1±x, D atoms are mainly trapped forming small molecules and the initial lattice structure is completely lost, the composition of δ-WC1±x in the topmost layers is mostly W, due to the preferential sputtering of C

–

–

Density functional theory (DFT) simulation of the adsorption of molecular H2 on W carbide single-wall nanotubes (WCNTs, metallic type) indicated that H atoms and molecules prefer to be adsorbed at the W atop site The equilibrium content of CH4 in gaseous [11, 586, phase for the reaction 670, 1081, W2C + 2H2 ↔ 2W + CH4 1153, 2372declines gradually within the indicated 2373, 4551] temperature interval from 52.4 vol.% to 0.00023 vol.% with increasing temperature

H2, CH4

25-1225

H2

≥2000-2500 Partial decarburization of semicarbide W2±xC materials

(continued)

540

2 Tungsten Carbides

Table 2.23 (continued) –

–

The phase transformation α-W2+xC → γ-WC1–x was observed in nanocrystalline thin films containing β-C (diamond-like), which ranged from nanocomposite to amorphous microstructures

–

–

According to classical molecular dynamics (MD) simulations, after the D bombardment of W2±xC, D atoms are mainly trapped forming small molecules and the initial lattice structure is completely lost, the composition of W2±xC in the topmost layers is mostly W, due to the preferential sputtering of C

δ-WC1±x – H2 – H2, H2O H2O

700-900

Water-milled δ-WC1.00 (specific surface [3, 200, area – ~0.5 m2 g–1; contents: non-com1081, 4543, bined C – 0.04%, H2O – 0.19%, O – 4551] 0.64%, Co – 0.57%, Fe – 0.34%, Ni – 0.05%) powders interacted (exposure – 14 h) with wet H2 according to the reactions WC + 2H2 = W + CH4 ↑ WC + H2O = W + H2↑ + CO↑ with the loss of ~ 1.5-40 at.% C in δ-WC1±x

H2, H2O

800-900

As-carburized δ-WC1.00 (specific surface area – ~0.1 m2 g–1; contents: non-combined C – 0.05%, H2O – 0.04%, O – not detected, Co < 0.01%, Fe < 0.01%, Ni < 0.01%) powders interacted (exposure – 1-4 h) with wet H2 according to the reactions WC + 2H2 = W + CH4 ↑ WC + H2O = W + H2↑ + CO↑ with the loss of 0.5-14 at.% C in δ-WC1±x

H2, H2O

800-1000

The presence of H2O vapour (ppart = 4÷10 kPa) in H2 atmosphere led to the significant decarburization of δ-WC1±x phase

H2, H2O

830-1230

The equilibrium content of CH4 in gaseous phase for the reaction 4WC + H2 + H2O ↔ 2W2C + CO + CH4 declines gradually within the indicated temperature interval from 0.78-9.85 vol.% to 0.12-0.40 vol.% with the contents of H2O varying around 0.01 vol.% and temperature growth

δ-WC1±x – HCN

HCN

–

HCN on the carburized surface of W de- [4559] sorbed molecularly and dissociated into H2 and N2, leaving C at the surface, a protonation occurred at the N of the HCN (the decomposition occurred more readily on the pristine surface)

(continued)

2.6 Chemical Properties and Materials Design

541

Table 2.23 (continued) δ-WC1±x – H2CO

H2CO

δ-WC1±x – H2O H2O

– (–70)

H2O

Decomposition of H2CO on the carburized [4544] surface of W was studied H2O adsorbed molecularly on the surface [3, 1081, of clean single-phase δ-WC1±x thin films 1250, 1253, Non-oxidized δ-WC1±x synthesized from 1389, 1553, W oxides adsorbed H2O vapour from the 1738, 4375, gas phase weakly than those prepared from 4527, 45654567] W acids; after a partial oxidation of the

20

δ-WC1±x surface the adsorption of H2O vapour was diminished ~1730

δ-WC1±x coatings prepared by the carburization of metal have interacted on the surface with the formation of CO and CO2

–

The adsorption and dissociation of H2O on the W- and C-terminated δ-WC1±x (0001) surfaces were studied using spin-polarized and periodic density functional theory (DFT) calculations

δ-WC1±x – H2O Humid – O2 (60-90 %) air

20

The oxidation (exposure – 168 h) of [3, 1081, δ-WC1±x hot-pressed materials (porosity – 4527] 0.5 %, content Co – 0.75 %) resulted in the formation of thin surface films of WO3–x with the thicknesses increasing from 2.4 nm to 3.4 nm with the growth of humidity

δ-WC1±x – H2S H2S

–

Adsorption of H2S on the carburized sur- [4544] face of W was studied

H2O

–

δ-WC1±x – I2

–

–

δ-WC1±x-based hard alloys were implanted [1119] with I+ to dose levels from 2×1016 cm–2 to 5×1017 cm–2

δ-WC1±x – N2

–

–

Various types of monocarbonitride [3, 6, 11, 13, W(CxNy) thin films and coatings deposited 110, 530, on several substrates were synthesized 670, 919, using different methods and approaches 979, 1175, mainly not connected with direct interac- 1600, 1656, tion between δ-WC1±x with N2 1678, 1708, 1719, 1882, Surface number densities for irreversibly 1981, 2898, chemisorbed species N (nN) on fresh sam3378-3379, ples of highly dispersed δ-WC1±x 3474, 35402 –1 (~6 nm, ~30 m g ) and γ-WC1–x (~4 nm, 3541, 4022~100 m2 g–1) powders (mean crystallite si4023, 4278zes and specific surface areas are given in 4279, 440715 –2 brackets) are 0.34×10 cm and 4436, 4509, 15 –2 0.22×10 cm , respectively (1 monolayer 4540-4542] corresponds to ~1.0×1015 cm–2)

–

20

–

20

70-120 keV N+ and N2+ ions were implanted into high-purity δ-WC1±x-based hard alloys with a dose of 1×1017-1×1018 cm–2

(continued)

542

2 Tungsten Carbides

Table 2.23 (continued) –

The γ-W(C0.75N0.25) → δ-W(C0.75N0.25) phase transition was observed in the magnetron sputtered thin films deposited on Si (100) when N-doping was in the range of 2.9-4.7 at.%

500

N2, 700-1500 0.1-190 MPa, or CH4/NH3 N2, 0.1-27 MPa

Monocarbonitride (hexagonal) δ-W(CxNy) powders (content N – up 5-10 at.%) were prepared by simultaneous direct carburization and nitridation of metal (exposure – up to 4 h)

1100-1700 Cold-pressed δ-WC0.99 (contents: noncombined C – 0.08%, O – 0.20%) powders had no evidence of any types of chemical interaction and/or gas dissolution

N2, higher ≤ 1400 pressures

Prepared upon carbide synthesis, N-containing δ-WC1±x (δ-W(C,N)1±x) powders had relatively high N contents (depending on the N2 pressure) and its uniform distribution throughout the particles (with the lattice parameters a and c decreasing noticeably); upon the sintering of hard alloys based on these powders, N2 was evolving from them due to the low N diffusivity in δ-W(C,N)1±x that led to the substantial final porosity of sintered products

N2

~1400

Prepared from common δ-WC1±x powders, the nitridated δ-W(C,N)1±x powders had only slightly lower lattice parameters because of a thin N-enriched rim with unchanged interior, this rim dissolved upon the sintering procedure evolving all the contained N; poreless hard alloys could thus be obtained from these powders, the N-rich rim prevented the δ-WC1±x phase from grain growth upon the sintering due to the stabilising effect of N, leading to the finer microstructure of sintered hard alloys

N2

≤ 2700

Practically, δ-WC1±x materials are chemically stable up to its melting point

–

–

The adsorption of N atoms on the δ-WC1±x (100) surface with 4 possible high symmetry sites on top of the W-terminated surface was studied using first principles density functional theory (DFT); the overlapping and hybridization between 2p and 2s orbits of N and 5d of surface W atoms play a major role in the bonding

See also section δ-WC1±x – δ-WN1±x in Table 2.22 See also section C – N – W in Table I-2.14

(continued)

2.6 Chemical Properties and Materials Design

543

Table 2.23 (continued) α/β/ε/γ-W2±xC – N2

≤ 2700

N2

Practically, α/β/ε/γ-W2±xC materials are chemically stable up to its melting point

[11, 13, 670, 1719, 4509]

See also section C – N – W in Table I-2.14 δ-WC1±x – NH3

530-930

NH3 was desorbed from the surface of highly dispersed powders (specific surface area – ~30 m2 g–1) as N2 molecules

δ-WC1±x – NO NO

< (–165)

The reactivity of δ-WC1±x (0001) surface [1358, 1379, was characterized by its strong interaction 4560-4561] with the molecules of NO, the adsorbed (mainly in an upright geometry) NO molecules were stable on the surface

NO

≥ (–165)

The start of partial dissociation of adsorbed molecules of NO on the δ-WC1±x (0001) surface

NO

≥ (–110)

Upon warming up, the complete dissociation of adsorbed molecules of NO on the δ-WC1±x (0001) surface took place, the dissociation products of NO could modify the surface composition

NO

430-830

Reactive/recombinative desorption from the δ-WC1±x (0001) surface took place

–

–

δ-WC1±x – O2a, b O2, 10 μPa

–

Decomposition of NO occurred readily over all the carburized W surfaces with only reaction products – N2 and N2O

~(–190)

Temperature-programmed desorption (TPD) spectrum of δ-WC1±x (0001) surface after dosing O2 showed two CO peaks, which were assigned to O atoms reacting with the surface and subsurface C atoms, respectively

O2, (–190)1-10 mPa (+630)

The adsorption/interaction of O2 with single crystal δ-WC1±x (0001) led to the formation of a mixture of WO oxide, δ-W(CxOy) oxycarbide and metallic W phases on the surface

Air, O2

20

Highly dispersed powders (specific surface area – ~30 m2 g–1) were subjected to a special passivation treatment in order to prevent their spontaneous ignition

20

Surface number densities for irreversibly chemisorbed species O (nO) on fresh samples of highly dispersed δ-WC1±x (6 nm, 30 m2 g–1) and γ-WC1–x (4 nm, 100 m2 g–1) powders (mean crystallite sizes and specific surface areas are given in brackets) are 1.39×1015 cm–2 and 1.03×1015 cm–2, respectively (1 monolayer corresponds to ~1.0×1015 cm–2)

–

[110]

[1, 3-4, 6, 11-13, 110, 118, 151, 200, 270, 323, 581, 584, 601, 626, 670, 709, 726, 1016, 1156, 1164, 11801184, 1275, 1288, 1297, 1302, 1308, 1312-1314, 1319, 13231324, 1328, 1330, 1339, 1348, 1356, 1431, 1474, 1553, 2031, 2204, 2286, 2489, 2500, 2526, 2532, 2539, 2563,

(continued)

544

2 Tungsten Carbides

Table 2.23 (continued) O2

20

O2, 20 kPa 20-200

O2/N2 (20/80) mixture flow

40-1000

Air

50-900

2567, 2596, 2654, 2665, 2714, 2756, 2780, 2810, 2852, 3135, The oxidation (exposure – 1 h) of 3147, 3377, δ-WC1±x hot-pressed materials (porosity – 3891, 4005, 0.5 %, content Co – 0.75 %) in the indica- 4052, 4060, ted temperature interval resulted in the 4204-4205, formation of thin surface films of WO3–x 4223, 4243, with the thicknesses increasing from 0.6 4253, 4319, nm to 1.2 nm with the growth of tempera- 4352, 4375, ture 4438-4439, The non-isothermal oxidation of δ-WC1±x 4466, 4468, (99 % purity, size distribution < 10 μm) 4471-4472, 4483, 4506powders at the heating rates h = 5-20 K min –1 and reaction gas flows f = 10-150 4511, 4517cm3 min –1 was dependent on both these 4539, 4565oxidation parameters significantly with the 4566] increasing value of formal activation energy E from 120 to 220 kJ mol–1 during the growth of oxidation degree in the ranges from 0.1 to 0.8, indicating a complex mechanism of the oxidation of δ-WC1±x; at the low values of oxidation parameters h < 15 K min –1, or f ≤ 10 cm3 min –1 the reaction tended to be in apparent one step, at h ≈ 5÷10 K min –1 it was governed by nucleation and growth of nuclei (Kolmogorov – Johnson – Mehl – Avrami model) and at h ≈ 10÷15 K min –1 the process was deviated to the autocatalytic (Šesták and Berggren) model Single crystal δ-WC1±x (1010) adsorbs O2 molecularly at first (at least 2 adsorption sites exist, the O–O bond is considerably weakened)

The non-isothermal oxidation of various types of δ-WC1±x powders (mean particle sizes – in the wide ranges from 20 nm to 6 μm) at the heating rate – 10 K min –1 showed the increase of oxidation rates and decrease of the temperatures of the exoeffect peak of δ-WC1±x with the decrease in its particle sizes, according to the model based on experimental data from several sources: with the increase of particle size from 10-102 to 106-107 nm, exo-effect temperature and formal activation energy of oxidation process of δ-WC1±x increased from 490 °C to 1095 °C and from 85 kJ mol–1 to 160 kJ mol–1, respectively; irrespectively to their dispersity, all the δ-WC1±x powders were oxidizing stoichiometrically to the only one product – ε-WO3–x (monoclinic) modification of

(continued)

2.6 Chemical Properties and Materials Design

545

Table 2.23 (continued) higher W oxide (no traces of elemental C and/or W and/or semicarbide phases was detected in the oxidation products) –

160-880

From the surface of the highly dispersed δ-WC1±x (~6 nm, ~30 m2 g–1) and γ-WC1–x (~4 nm, ~100 m2 g–1) powdered materials (mean crystallite sizes and specific surface areas are given in brackets), O was removed in the forms of H2O, CO2 and CO

O2, 10 kPa

330

The oxidation of single crystal δ-WC1±x (0001) led to the formation of WO3–x phase

Air

~380

The start of oxidation of high surface area δ-WC1±x (~ 50-200 m2 g–1) powdered materials

O2

~390

The start of oxidation of fine δ-WC1±x (mean particle size – ~0.5 μm) powders

Ar/N2/H2 > 400 (83/11/6) (impurity – O2)

Powdered δ-WC1±x (spherical in shape, size distribution – 20-50 μm) was slightly oxidized during supersonic atmosphere plasma spraying (SAPS) procedure; WO3–x, W20O58, W18O49 and WO2±x phases were identified as oxidation products

O2

440-550

Assuming a linear oxidation rate, the results of oxidation of δ-WC~1.0 powders (content non-combined C – 0.04-0.07 %) with various particle sizes ranging from 0.3 μm to 7.1 μm indicated that the same mechanism was operating in the oxidation process for all the powders and demonstrated linear correlation between inverse particle diameters and oxidation rate constants of the oxidized powders with the average value for the formal activation energy E ≈ 130 kJ mol–1

Air

< 500

The intrusion of O atoms into the δ-WC0.98 phase lattice was not accompanied by the precipitation of elemental C and W phases, due to the adsorption of O2 by structural defects of the lattice

Air

500

Practically, there was no solubility of O in the δ-WC1±x phase constituent of Co-containing hard alloy during the oxidation (exposure – up to 2.5 h) of these alloys

Air

500

Due to the noticeable oxidation of δ-WC0.98 hot-pressed materials (content non-combined C – 0.05 %, porosity ≤ 1 %), the formation of polychromic oxide thin films consisting of α/β/γ-WO3–x

(continued)

546

2 Tungsten Carbides

Table 2.23 (continued) and β-WO2±x phases was observed on the surface O2/N2 (2/98) mixture

500

The oxidation (exposure – 1 h) of highly dispersed δ-WC1±x powders led to the direct conversion to WO3–x (only a small portion of carbide retained, no intermediate phases were detected)

O2, 20 kPa 500

The oxidation (exposure – 1 h) of δ-WC1±x hot-pressed materials (porosity – 0.5 %, content Co – 0.75 %) resulted in the formation of thin surface films of WO3–x (thickness > 10 nm)

Air

~ 500-520

The start of oxidation for δ-WC1±x fine powders

O2

500-650

The oxidation of δ-WC1±x powders was ruled by a linear law with formal activation energy E ≈ 190 kJ mol–1; microcracks were detected in the WO3–x scales and deviation from the linear law at higher temperatures and partial pressures of O2

Air

500-900

The oxidation (exposure – up to 5 h) process of δ-WC1±x hot-pressed materials (practically, poreless) was governed by a linear law with the formal activation energy E ≈ 110 kJ mol–1

Air

> 500

The massive oxide formation causing the degradation on the tribological properties was observed on pure δ-WC1±x surface during friction loading

Air

~530-630

The anomalous behaviour, due to significant changes in the gas permeability of forming oxide scales (with a ridge temperature at around 530 °C), during the oxidation of δ-WC1±x-based complex hard alloys was observed in this post-ridge interval, which was characterized by a decrease of the oxidation rates with the growth of temperature; below 530 °C, a formal activation energy of E ≈ 119±8 kJ mol–1 has been found, whereas above 630 °C, the value of E ≈ 208±8 kJ mol–1 was obtained

Air

545-1000

The degree of oxidation in the non-isothermal conditions (conversion to WO3–x at heating rate – 5 K min –1) of powdered δ-WC1±x varied in these temperature ranges from 4.7 % to 60.5 %

Air

~ 570-600

The start of oxidation for δ-WC1±x coarse powders

(continued)

2.6 Chemical Properties and Materials Design

547

Table 2.23 (continued) Air

≤ 600

Practically, δ-WC1±x bulk dense materials are stable and resistant to oxidation

Vacuum

~600

According to temperature-programmed decomposition and reaction (TPD/TPR) procedure measurements, highly dispersed powdered δ-WC1±x catalysts contain up to 25 at.% O on/in its surface/lattice

Air

600

The formation of ε-WO3–x (monoclinic) oxide scales (containing 0.5 % C) on the surface of δ-WC0.98 hot-pressed materials (content non-combined C – 0.05 %, porosity ≤ 1 %), in accordance to the following reactions: WC + 2O2 = WO3 + CO↑, 2WC + 5O2 = 2WO3 + 2CO2↑ was occurring (exposure – 5-6 h)

Air

≥ 600

Due to the high exothermicity of the oxidation reaction of powdered δ-WC1±x, it is very difficult to provide isothermal conditions for the similar samples; therefore, the kinetic curves for higher temperatures are very close to each other, which complicates their analysis

O2/Ar (10÷50/ /50÷90) mixture flow

600-800

During the isothermal oxidation of δ-WC1±x grains (mean size – ~8 μm) in 6-12 % Co hard alloys, WO3–x phase formed in scales at the initial stages of oxidation has changed from a strong (001) texture at lower temperatures to a weak (200) texture at higher temperatures

O2/N2 (20/80) mixture flow

600-1000

The isothermal oxidation (exposure – 0.005-15 h) of dense bulk δ-WC1±x materials (porosity < 1 %) with the formation of outer oxide scales mainly consisting of δ-WO3–x (orthorhombic) phase at 600 °C, δ-WO3–x and ζ-WO3–x (triclinic) phases at 700 °C, δ-WO3–x, ζ-WO3–x and α/β/γ-WO3–x (tetragonal) phases at 800 °C, ζ-WO3–x and α/β/γ-WO3–x phases at 9001000 °C and increasingly cracking at lower temperatures (thickness – ~200 μm, porosity – up to 45 %) is obeyed by a linear law; the formation of dense interlayer (thickness – ~10 μm) with the protective to oxidation properties, adjacent to the substrate/oxide interface and consisting of W oxides with the lower O/W atomic ratios, was detected during the oxidation at 9001000 °C

(continued)

548

2 Tungsten Carbides

Table 2.23 (continued) Air

600-1000

The isothermal oxidation (exposure – up to 3 h) of powdered δ-WC1±x materials (filled to ⅓ of the height into SiO2 crucibles) was following a parabolic law

Air

~670

The oxidation of nanocrystalline powdered γ-WC1–x (mean particle size – 12 nm) proceeded via the transformation into cubic W3+xC phase and then to WO3–x oxide

O2 (dry), 0.1 MPa

700

The oxidation of δ-WC~1.0 hot-pressed materials (porosity – ~10 %) was following a linear rate law with the constant determined to be 4×10–6 g cm–2 s–1, the stoichiometric (without preferential oxidation C or W) character of oxidation was observed corresponding to the over-all reaction 2WC + 5O2 = 2WO3 + 2CO2↑; the rupture of the oxide film due to the formation of gaseous C oxides was suggested

Air

700

For the dense sintered δ-WC1±x materials the oxidation mass gain was 16.5-18.2 mg cm–2 (exposure – 1-2 h)

Air

700

The mass gain of hot-pressed δ-WC1±x materials due to the oxidation process was increasing from 0.06 % (exposure – 1 h) up to 3.0 % (exposure – 48 h)

Air

700-1000

The formation of oxide scales, consisting of ε-WO3–x (monoclinic) and α/β/γ-WO3–x (tetragonal) phases (containing ~0.3 % C), on the surface of δ-WC0.98 hot-pressed materials (content non-combined C – 0.05 %, porosity ≤ 1 %) was occurring (exposure – 5-6 h); due to the porous structure of scales, intensive gas (CO, CO2) release and volatility of W oxides, the rate of oxidation of δ-WC1±x did not depend on the diffusion of O through the scales, but it depended on the interaction of carbide with O2 at the oxide-carbide interface, raising the temperature has markedly accelerated the process of oxidation

Air

750-850

The oxidation of δ-WC1±x grains (in the range of 3.8-14.0 μm) in Co hard alloys was controlled by the oxide-alloy interfacial reaction and ruled by a linear law

880

Only 50 % of O adsorbed on the surface of δ-WC1±x materials (specific surface area – ~30 m2 g–1) could be desorbed (mainly as CO); it is very difficult to rid a δ-WC1±x surface of O once it was exposed to O2

–

(continued)

2.6 Chemical Properties and Materials Design

549

Table 2.23 (continued) Air

900

For the bulk dense (sintered) δ-WC1±x materials the oxidation mass gain is ~1.1 mg cm–2 (exposure – 1-2 h)

Air

900

The mass gain of hot-pressed δ-WC1±x materials due to the oxidation process was increasing from 4.6 % (exposure – 1 h) up to 17.6 % (exposure – 5 h)

O2 (dry), 0.1 MPa

1000

The exceedingly high rate of oxidation of δ-WC~1.0 hot-pressed materials (porosity – ~10 %) was observed

Air

1000

For the bulk dense (sintered) δ-WC1±x materials the oxidation mass gain was 27.437.6 mg cm–2 (exposure – 1-2 h)

Air

1000

The mass gain of δ-WC0.99 materials due to the oxidation process was increasing from 0.14 % (exposure – 2 h) up to 2.76 % (exposure – 44 h)

O2, 1030 1-10 mPa

–

Air

> 1030

The oxidation of single crystal δ-WC1±x (0001) led to a loss of all C in the surface region, O2 reacted with C and desorbed as CO leading to a layer of WOy (1 < y < 2, thickness – 0.6-2.8 molecular layers) directly at the surface and metallic W layer below From the highly dispersed δ-WC1±x (~6 nm, ~30 m2 g–1) and γ-WC1–x (~4 nm, ~100 m2 g–1) powdered materials (mean crystallite sizes and specific surface areas are given in brackets) O could be removed completely only at elevated temperatures (mainly in the form of CO)

1100-1200 The formation of oxide scales, consisting of α/β/γ-WO3–x (tetragonal) phases (with some inclusions of C at the lower temperatures; no nitrides were observed in the scales), on the surface of δ-WC0.98 hot-pressed materials (content non-combined C – 0.05 %, porosity ≤ 1 %), in accordance to the following reactions: 2WC + 3O2 = 2WO3 + 2C, WC + 2O2 = WO3 + CO↑, 2WC + 5O2 = 2WO3 + 2CO2↑, was observed (exposure – 5-6 h); the process of oxidation was slowed down by the sintering of the scales forming on the carbide surfaces, but when the scales were subjected to cracking, and O2 could reach unoxidized parts of the materials, the rate of oxidation raised significantly

(continued)

550

2 Tungsten Carbides

Table 2.23 (continued) O2, 1120-1780 The oxidation of δ-WC1±x hot-pressed ma~ 10–2-103 terials (porosity – in the range from 4 % to Pa 30 %) led to the formation of metallic W surface layers produced due to the fast CO/CO2 reactions: 2WC + O2 = 2W + 2CO↑, WC + O2 = W + CO2↑, in addition to these reactions volatile oxides evaporated according to the reaction equation: 2W + 3O2 = 2WO3↑, the interrelation between all the reactions mentioned finally ended up in a steady state reaction with a constant metallic layer thickness and a constant mass loss according to an overall reaction: WC + 2O2 = WO3↑ + CO↑; the value of mass loss rate of the δ-WC1±x materials increased significantly with increasing porosity Air

≥ 1200

The cracking and volatility of WO3–x resulted in the absence of protective scales and led to the catastrophic oxidation of δ-WC0.98 hot-pressed materials (content non-combined C – 0.05 %, porosity ≤ 1 %)

O2 flow

1400

Powdered δ-WC1±x materials can be burned rapidly and completely

–

1500-1600 The vapour pressures of (WO3–x)n species in equilibrium with solid WO3–x (scales on δ-WC1±x) in Pa: WO3–x – (1.08÷8.25)×10–3, (WO3–x)2 – 12.2÷75.2, (WO3–x)3 – 112÷565, (WO3–x)4 – 35.3÷20.4

O2, lower ~1730 pressures

Partial decarburization and decomposition of δ-WC1±x coatings prepared by the carburization of metal were observed on its surface

Air

During the ablation process, the molten WO3–x and δ-WC1±x flew on the surface, filled in the interfaces, cracks and pores of the heated composites and effectively obstructed the diffusing channels for oxidation gases; part of the molten WO3–x and δ-WC1±x splashed about, and holes was for-med at those original locations of δ-WC1±x components, which greatly increased a roughness of the surface, therefore, the molten WO3–x and δ-WC1±x could not flow over the bulges and cover all the ablation surface

~3000

(continued)

2.6 Chemical Properties and Materials Design

551

Table 2.23 (continued) References on oxidation of δ-WC1±x based composites and alloys are given in this section, although the behaviour of similar materials are not described in the table

See also section δ-WC1±x – H2O – O2 See also section δ-WC1±x – α/β/γ/δ/ε/ζ-WO3–x in Table 2.22 See also section C – O – W in Table I-2.14 α/β/ε/γ-W2±xC – O2a, c

Air, O2

20

Highly dispersed powders (specific surface area – 30 m2 g–1) were subjected to a special passivation treatment in order to prevent their spontaneous ignition

[3, 11, 13, 670, 1275, 1308, 1427, 1772, 1774, Semioxycarbide α/ε-W2+x(C,O) materials 1878, 2500, (specific surface area – 15 m2 g–1) for the 4509, 4520catalysis purposes were synthesized via 4522, 4538] temperature-programmed reaction (TPR) followed by the passivation procedure

O2/He (1/99) mixture

20

Air

500

The start of oxidation with the formation of WO3–x scales: 2W2C + 7O2 = 4WO3 + 2CO↑, W2C + 4O2 = 2WO3 + CO2↑

Air

700

The mass gain of cast γ-W2±xC materials due to the oxidation process was increasing from 0.065 % (exposure – 1 h) up to 2.075 % (exposure – 48 h)

Air

≥ 800

Severe oxidation of W2±xC materials was observed

Air

900

The mass gain of cast γ-W2±xC materials due to the oxidation process was increasing from 3.4 % (exposure – 1 h) up to 12.3 % (exposure – 5 h)

O2, 1030-1830 The oxidation (exposure – up to 5 h) of ~ 10–2-103 α-W2+xC semicarbide layers (thickness – Pa 0.3 mm) prepared by gaseous carburization of metal led to the formation of metallic W surface layers produced due to the fast CO/CO2 reactions: 2W2C + O2 = 4W + 2CO↑, W2C + O2 = 2W + CO2↑, in addition to these reactions volatile oxides evaporated according to the reaction equation: 2W + 3O2 = 2WO3↑, the interrelation between all the reactions mentioned finally ended up in a steady state reaction with a constant metallic layer thickness (~2 μm) and a constant mass loss according to an overall reaction: 2W2C + 7O2 = 4WO3↑ + 2CO↑;

(continued)

552

2 Tungsten Carbides

Table 2.23 (continued) the temperature dependence of mass loss rate α was corresponding to the formal activation energies E = 85÷125 kJ mol–1, while the pressure dependence was given by a relation α ~ pO2n with 0.4 < n < 1.2 O2, 1.3-13.3 mPa

1230-1530 The oxidation of single crystal α-W2+xC led to an oriented transformation to single crystal metallic W; an orientation relationship represented by α-W2+xC (0001) // W (110) with α-W2+xC // W is eventually effected between the starting and transformed crystals

See also section α/β/ε/γ-W2±xC – α/β/γ/δ/ε/ζ-WO3–x in Table 2.22 See also section C – O – W in Table I-2.14 δ-WC1±x – SiO 830-1230 SiO

The chemical reactions between SiO mo- [4575] lecular beams and δ-WC1±x led to the formation of CO + SiO surface complexes, at the higher temperatures only elemental Si thin films were detected on the δ-WC1±x surface a Fine tungsten monocarbide and semicarbide powders, similar to other carbides of groups 4-6 transition metals, are pyrophoric and susceptible to oxidation at room temperature [6, 12-13, 581, 1275, 1356, 1427, 1772] b For the stoichiometric δ-WC1±x phase, the value of the Pilling-Bedworth ratio α = MOdC/MCdO = 2.55÷2.60 >> 1, where MO is molecular mass of the oxide phase formed on the surface due to the oxidation of 1 mol of carbide phase, MC is molecular mass of the carbide phase, dC and dO are the densities of carbide and oxide phases, respectively; in the case when the value of this criterion significantly exceeds 1, stresses usually arise inside a scale, leading to its cracking, which causes the oxidation process to proceed according to a linear law [4508, 4528] c For near-stoichiometric W2±xC phases, the value of the Pilling-Bedworth ratio α = MOdC/MCdO = 2.94 >> 1.

conversion of lignin, including formation of arenes [1628, 1660, 1695, 1725, 1739, 1747]; cracking of heavy hydrocarbons [405, 1707, 1736]; decomposition (dissociation) and conversion of carbon monoxide [1368, 1390, 1553, 1644, 1738] decomposition (dissociation) of methanol [288, 1235, 1272, 1276, 1304, 1319, 1353, 1366-1368, 1370, 1389-1390, 1393, 1401-1402, 1411, 1498, 1512-1513, 1553, 1582, 1781]; decomposition and anodic oxidation of hydrazine [1190, 1198, 1255, 1344, 1356, 1364, 1452-1453, 1462, 1500, 1678]; decomposition and conversion of nitrogen oxides [1286, 1328, 1358, 1379, 1423, 1553]; decomposition and conversion of oxygenates (ethanol, ethylene glycol, propanol and others) [1457, 1513, 1520, 1553, 1606, 1617, 1637, 1777];

2.6 Chemical Properties and Materials Design

553

Fig. 2.25 Isothermal oxidation kinetics curves for 8 mm diameter disk-like samples of hotpressed and subsequently annealed tungsten monocarbide δ-WC1±x materials (porosity 1-2 %) in air [1180-1184, 4506-4507]

decomposition and dehydration of propanol, isopropanol and butanol [1359, 1443, 1513, 1516, 1527, 1553, 1676]; decomposition and oxidation of ammonia [1255, 1395-1396, 1421, 1435, 1447, 1449, 1508, 1911]; decomposition and oxidation of formic, lactic, oxalic and related acids and their derivatives [454, 1147, 1158, 1202, 1212, 1221, 1255, 1157, 1278, 1446, 1460, 1553, 1562, 1595, 1621, 1633, 1661, 1779-1780]; degradation of antibiotics [1763]; dehydrogenation of decalin [3830]; dehydrogenation of ethylbenzene to styrene [1190, 1192, 1255, 1909]; dehydrohalogenation of chloropentafluoroethane [1359]; detection of organophosphate compounds (e.g. fenitrothion) [415]; dissociation of hydrogen [1338, 1370, 1625]; electrochemical evolution (generation) of oxygen and splitting (dissociation) of molecular water [274, 356, 1175, 1179, 1219, 1366-1368, 1370, 1390, 1428, 1501, 1528, 1553, 1664, 1694, 1700-1701, 1738, 1757, 1764, 2379, 3510];

554

2 Tungsten Carbides

electrochemical reduction of H+ ions and evolution (generation) of hydrogen [298, 352, 369, 389, 391, 397, 401, 404, 416-418, 431, 439-440, 462, 506, 1147, 1157-1158, 1167, 1241-1242, 1249, 1251-1253, 1260, 1267, 1274, 12771278, 1281-1284, 1289-1290, 1295-1296, 1298, 1377, 1400, 1405, 1411, 1414, 1425, 1430, 1439, 1458, 1461, 1469, 1487, 1507, 1533, 1536, 1539, 1542, 1546, 1556, 1558, 1560, 1566, 1573, 1575, 1585-1586, 1589, 1597, 1600, 1622, 1625, 1630, 1634, 1636, 1638, 1641-1642, 1647, 1656-1657, 1663, 1669-1670, 1672-1673, 1687, 1689, 1693, 1696-1698, 1702, 1705, 1714-1716, 1718-1719, 1726-1727, 1729-1730, 1732, 1735, 1751, 1753, 1758, 1760, 1762, 1768-1769, 1771, 1790, 1792, 1794, 1814, 1851, 2396, 2415, 2420-2421, 3143, 3865, 3948, 3952]; electrochemical reduction of oxygen and formation of water [288, 327, 353, 387, 390, 1170, 1172, 1217, 1219, 1261-1262, 1278, 1375, 1392-1394, 1419, 1424, 1434, 1444, 1468, 1474, 1477, 1480, 1496, 1515, 1521, 1532, 1537, 1545, 1553, 1570-1571, 1575, 1581, 1583, 1590-1591, 1594, 1602, 1605, 1607, 1609, 1612, 1614, 1616, 1635, 1639-1640, 1652, 1656, 1666, 1671, 1680, 1686, 1690, 1694, 1710-1712, 1717, 1723, 1728, 1746, 1748, 1761, 1770, 1773, 2316, 2358, 2377-2378, 2397, 2407]; fragmentation and interconversion of lithium polysulphides [410, 1721]; graphitization of amorphous carbon [1347]; high-temperature ortho/para conversion of hydrogen [1190, 1193, 1255, 1625]; hydrodehalogenation of some halogenated organic compounds [1378]; hydrodenitrogenation and isomerization of organonitrogen compounds (e.g. carbazole) [1325, 1381, 1427, 1495, 1772]; hydrodeoxygenation of benzofuran [428]; hydrodesulphurization and isomerization of organosulphur compounds (e.g. dibenzothiophene) [1381, 1397, 1415, 1420, 1426, 1495, 1608]; hydrogenation (hydrodeoxygenation, decarbonylation and decarboxylation) of triglycerides, oleic and other fatty acids and related compounds [451, 1540, 1596, 1646, 1740]; hydrogenation and conversion (decomposition) of toluene [1448-1449, 1706, 1756]; hydrogenation and isomerization of paraffinic hydrocarbons [1291, 1679]; hydrogenation and isomerization of propene, 1-butene, cis-2-butene and related compounds [259, 1338, 1352]; hydrogenation of carbon dioxide [770, 1310, 1553, 1649]; hydrogenation of carbon monoxide [1255, 1270, 1318, 1328, 1372, 1529, 1553, 1681]; hydrogenation of cardanol [1691]; hydrogenation of ethylene [1280, 1317, 1355, 1505];

2.6 Chemical Properties and Materials Design

555

hydrogenation of nitroarenes [1655]; hydrogenation of organic compounds (n-nitrophenol, n-nitrobenzylamine, nitrobenzene and others) in aqueous solutions [1220, 1222, 1229, 1245, 1255, 1514]; hydrogenation of tetralin (1,2,3,4-tetrahydronaphthalene) [1351-1352]; hydrogenolysis and isomerization of 2-methyl 2-pentene, 4-methyl 1-pentene and related compounds [1339]; hydrogenolysis of guaiacol [1747]; hydrogenolysis, dehydrogenation and decomposition of methyl cyclopentane, 2-methyl cyclopentane, ethyl cyclopentane, cyclohexane and some related compounds [502, 725, 1280, 1291-1293, 1297, 1303, 1317, 1320-1321, 1327, 1336-1338, 1354, 1363, 1482, 1491, 1907]; hydrogenolysis, dehydrogenation and isomerization of butane [1292-1293, 1317, 1322, 1334, 1346]; isomerization, hydrogenolysis and conversion of 2,2-dimethyl propane, 2methyl pentane, 3-methyl pentane, 3,3-dimethyl pentane and related compounds [1219, 1255, 1307, 1323, 1327, 1330, 1337, 1342, 1348]; isomerization, hydrogenolysis and dehydrocyclization (dehydroaromatization) of n-pentane, neopentane, n-hexane, n-heptane and related compounds [110, 725, 1291, 1297, 1302, 1307-1308, 1311-1317, 1320, 1324, 1327-1328, 1339, 1342, 1373, 1380, 1552, 1557]; oxidation of carbon [1268, 1294]; oxidation of carbon monoxide [1202, 1212, 1255, 1286, 1445, 1553, 1615, 1685, 1700, 1765, 1767, 1912-1915]; oxidation of dibenzothiophene [1626]; oxidation of ethanol [327, 450, 1166, 1410, 1418, 1437-1438, 1481, 1520, 1553, 1564, 1565, 1588, 1606, 1675, 1709, 1777, 3949]; oxidation of formic acid, formaldehyde and acetaldehyde [393, 1157, 1202, 1212, 1221, 1246, 1258, 1278, 1553, 1562, 1595, 1621, 1633, 1661, 1779]; oxidation of glycerol [1592]; oxidation of hydrogen [313, 352, 1158, 1167, 1190, 1194-1197, 1201, 1205, 1208, 1214, 1218-1219, 1236-1240, 1244, 1247-1248, 1253, 1255-1258, 1263, 1266, 1269, 1271, 1278, 1287, 1301, 1317, 1328-1329, 1332-1333, 1345, 1361-1362, 1376, 1388, 1408-1409, 1424, 1433, 1436, 1460-1461, 1464-1465, 1469, 1471, 1489, 1506, 1509, 1518, 1535, 1542, 1549, 1580, 1586, 1625, 1631-1632, 1724, 2303]; oxidation of methanol [288, 345, 369, 392, 444, 461, 468, 507-508, 1147, 1246, 1258, 1265, 1271, 1273, 1278, 1285, 1288, 1328, 1332, 1382, 1393, 1401-1402, 1412, 1428-1429, 1432, 1441, 1446, 1455-1456, 1467, 1471-1473, 1478, 1483-1485, 1488, 1493-1494, 1498, 1506, 1510, 1512-1513, 1517, 1522-

556

2 Tungsten Carbides

1523, 1534, 1541, 1543-1544, 1547-1548, 1550, 1553-1555, 1560-1561, 1568, 1572, 1574, 1576-1579, 1582, 1584, 1587, 1593, 1599, 1603-1604, 1610, 1613, 1618-1620, 1623, 1629, 1643, 1645, 1650, 1654, 1658-1659, 1665, 1667, 1674-1675, 1683, 1692, 1704, 1708, 1717, 1734, 1745, 1750, 1761, 1766, 1773, 1776, 1801, 2312]; oxidation of propane [1286]; oxidation of urea [1624, 1651, 1741]; reduction of cobalt bipyridine complexes [1698]; reduction of hydrogen peroxide [1261-1262]; reduction of hydroxylamine [1254]; reduction of iron, cobalt, nickel oxides and related compounds by hydrogen [1190, 1192, 1216, 1916-1917]; reduction of nitric and nitrous acids [1254, 1423]; reduction of nitrobenzene and some other nitroarenes [1454, 1486, 1693, 1755]; reduction of nitromethane [422, 1161, 1404]; reduction of perchlorate ions by hydrogen [1225-1226, 1230]; reduction of p-nitrophenol (4-nitrophenol) [505, 1383-1385, 1403, 1413, 1497, 1499, 1502, 1504, 1526]; reduction of sulphuric acid by hydrogen [1, 1190-1191, 1255, 1259]; reduction of triiodide ions [1759]; reduction of tungsten dioxide and trioxide by hydrogen [1219, 1255, 1291]; reduction of α-nitronaphthalene [1399]; reversible formation and decomposition of lithium oxides [1731]; synthesis of alcohols based on carbon monoxide and hydrogen [1255, 1529, 1553, 1681, 1743] synthesis of ammonia [1, 1188, 1190, 1328]; synthesis of carbon nanotube [1451]; synthesis of cordierite from magnesia, alumina and silica [1, 1189-1190]; synthesis of methyl formate [1272, 1276, 1304, 1553]; synthesis of p-xylene [1722]; water – carbon monoxide shift reaction [1417, 1551, 1553, 1775]. Including the electrocatalytic properties and some electrical characteristics of corrosion in liquid media and performance in fuel cell engineering systems, as the most important factors for technical applications, the electrochemical behaviour of tungsten carbide phases and various materials based on them is described in numerous sources [427, 439, 449, 545, 941, 1146, 1157, 1169, 1218, 1259-1261, 1277, 1281, 1283-1284, 1289, 1301, 1332, 1345, 1376, 1428, 1436, 1446, 1460,

2.6 Chemical Properties and Materials Design

557

Table 2.24 Static potential of tungsten monocarbide δ-WC1±x materials with reference to the saturated calomel electrode a [200, 4512] Electrolyte composition

Static potential, φ, V

0.001M HCl (pH = 3)

+ 0.617

0.001M HCl + 1 % NaCl

+ 0.278

0.001M HCl + 6.6 % NaCl

+ 0.507

0.001M HCl + 1 % NaCl + 10 % H3C6H5O7 (citric acid)

+ 0.647

5 % NaOH

– 0.293

5 % NaOH + 1 % NaCl

– 0.270

5 % NaOH + 10 % NaCl

– 0.348

5 % NaOH + 1 % H3C6H5O7 (citric acid)

– 0.213

5 % NaOH + 10 % H3C6H5O7 (citric acid) a Determined by a compensation method

– 0.058

Table 2.25 Wettability of single crystal tungsten monocarbide δ-WC1±x surfaces by some liquids at room temperature and common atmospheric conditions a Contact angle θ, degree  (1010) surface (1010) surface

Liquid Water Phosphate ester

b

Mineral oil (purified) a

References

22

42

[245]

28

18

[245]

7

6

[245]

Determined by sessile drop method

b

Phosphate ester of alkylphenol ethoxylate (polar liquid – in opposite to the mineral oil, but similar viscosity to it)

1463, 1518, 1525, 1556, 1601, 1609, 1636, 1639, 1648, 1664, 1701, 1782-1884, 2356, 2512, 2524, 2570, 2615, 2656, 2659, 2726-2727, 2729, 2784, 2819, 2880, 2931, 2950, 2959, 2989, 3013, 3022, 3026, 3028, 3030, 3037, 3045, 3048, 3071, 3091, 3098, 3125, 3130, 3143, 3146, 3149, 3151, 3156, 3158-3159, 3205-3206, 3250-3252, 3261, 3272, 3276, 3278, 3282, 3321, 3327, 3358, 3386, 3393, 3425, 3445-3450, 3496, 3510, 3540-3541, 3586, 3608, 3627, 3631, 3637-3638, 3642, 3652-3653, 3693, 3810, 3827-3828, 3860, 3881, 3883-3884, 3888, 3909-3910, 3923, 3939, 3953, 4175, 4180, 4273, 4282, 4512, 4672]. The dependence of the static potential of tungsten monocarbide δ-WC1±x materials on the pH of the reagents and composition of the electrolyte with respect to saturated calomel reference electrode carried out [4512] by a compensation method is given in Table 2.24. The parameters of wettability of tungsten monocarbide δ-WC1±x phase by some liquids at room temperature and molten metals and alloys (melts) in the wide ranges of temperatures are listed in Tables 2.25 and 2.26, respectively; the diffusion rates for the systems, containing tungsten carbide phases in species pairs,

558

2 Tungsten Carbides

Table 2.26 The parameters of wettability of tungsten monocarbide δ-WC1±x phase by some molten metals and alloys (melts) in the wide range of temperatures a Melt (purity)

Atmo- Temperasphere ture, °C

Time, s

γl-g, mJ m–2

Wa, Wmb, θ, References –2 mJ m kJ mol–1 degree

δ-WC~1.0 Ag (pure)c

Pure Ar 960 flow

~60

–

–

–

94

[2019]

Ag (pure)c

Pure Ar 1000 flow

~60

–

–

–

58

[2019]

Ag (pure)c

Pure Ar 1060 flow

~60

–

–

–

39

[2019]

Ag (pure)c

Pure Ar 1100 flow

~60

–

–

–

31

[2019]

Ag (Cu-0.2 %)c

Pure Ar 960 flow

~60

–

–

–

95

[2019]

Ag (Cu-0.2 %)c

Pure Ar 1000 flow

~60

–

–

–

90

[2019]

Ag (Cu-0.2 %)c

Pure Ar 1060 flow

~60

–

–

–

39

[2019]

Ag (Cu-0.2 %)c

Pure Ar 1100 flow

~60

–

–

–

31

[2019]

Ag (Cu-0.2, Ni-0.15 %)c

Pure Ar 960 flow

~60

–

–

–

61

[2019]

Ag (Cu-0.2, Ni-0.15 %)c

Pure Ar 1000 flow

~60

–

–

–

36

[2019]

Ag (Cu-0.2, Ni-0.15 %)c

Pure Ar 1060 flow

~60

–

–

–

18

[2019]

Ag (Cu-0.2, Ni-0.15 %)c

Pure Ar 1100 flow

~60

–

–

–

10

[2019]

Ag (Cu-1.0 %)c

Pure Ar 940 flow

~60

–

–

–

80

[2019]

Ag (Cu-1.0 %)c

Pure Ar 960 flow

~60

–

–

–

75

[2019]

Ag (Cu-1.0 %)c

Pure Ar 1000 flow

~60

–

–

–

52

[2019]

Ag (Cu-1.0 %)c

Pure Ar 1060 flow

~60

–

–

–

28

[2019]

Ag (Cu-1.0 %)c

Pure Ar 1100 flow

~60

–

–

–

20

[2019]

Ag Pure Ar 960 (Ni-0.15 %)c flow

~60

–

–

–

72

[2019]

Ag Pure Ar 1000 (Ni-0.15 %)c flow

~60

–

–

–

31

[2019]

Ag Pure Ar 1060 (Ni-0.15 %)c flow

~60

–

–

–

21

[2019]

(continued)

2.6 Chemical Properties and Materials Design

559

Table 2.26 (continued) Ag Pure Ar 1100 (Ni-0.15 %)c flow

~60

Al

Vacuum 900

900

914

275

Al

Vacuum 1000

900

914

290

Al (99.97 %) Ar

1000

Bi Vacuum 320 (99.9999 %) Bi

– Ar

700

Bi

Ar

900

Bi

Ar

10001100

Bi

–

–

900

914

1240

390

75

– 900

– 390

– 900

1200

–

–

–

– 630

11

[2019]

135±1.3 [1, 151, 1885, 4576, 4584]

–

133±0.3 [1, 151, 1885, 4576, 4584]

–

69

3.3

90

390

– 12.6

900

500

Bi

–

[1, 1942]

144±3 [1, 3, 151, 1885, 4576, 4584] –

~150

[3, 13, 4583]

–

140

[1, 9, 12, 584, 626, 4577, 4584]

–

95

[9, 4589]

–

52

[1, 9, 12, 584, 626, 4577, 4584]

–

–

–

20

[3, 13, 4583]

Cod

Vacuum ~13001400

35

–

–

–

~7

[2890]

Coe

Vacuum ~13001400

35

–

–

–

~15

[2890]

Co

Vacuum 1420

–

–

–

–

~0

[9, 151, 4584, 4586, 4589]

Cof, g

Vacuum, 1420Ar, H2 1500

–

–

–

–

~0

[3]

Co (99.98 %) Vacuum, 1500 Ar

900

1805

> 3610

–

~0

[1, 3, 151, 626, 1885, 4576, 4584]

Coh

Vacuum 1500

1200

1805

> 3700

–

~0

[1, 12-13, 671, 4579]

Co

H2

–

~0

[12, 584, 626, 4585]

Cri

1500 –

–

≥ 1860

–

–

–

–

–

–

~0

[2943]

Cu (99.9 %)j Vacuum, 1080 20 Pa

< 10

–

–

–

> 90

[3106]

Cu (99.9 %)j Vacuum, 1080 20 Pa

100

–

–

–

31

[3106]

Cu (99.9 %)j Vacuum, 1080 20 Pa

400

–

–

–

25

[3106]

Cu (99.9 %)k Vacuum, 1080 20 Pa

< 10

–

–

–

> 90

[3106]

(continued)

560

2 Tungsten Carbides

Table 2.26 (continued) Cu (99.9 %)k Vacuum, 1080 20 Pa

100

–

–

–

26

[3106]

Cu (99.9 %)k Vacuum, 1080 20 Pa

400

–

–

–

13

[3106]

Cu (99.9 %)l Vacuum, 1080 20 Pa

< 10

–

–

–

> 90

[3106]

Cu (99.9 %)l Vacuum, 1080 20 Pa

100

–

–

–

19

[3106]

Cu (99.9 %)l Vacuum, 1080 20 Pa

400

–

–

–

6

[3106]

Cum

Vacuum 1100

60

1270

2400

–

27

[1, 4578, 4586]

Cum

Vacuum 1100

600

1270

2465

–

20

[1, 9, 12, 151, 4578, 4584, 4586]

Cum

Vacuum 1100

900

1270

2465

–

20

[1, 9, 12, 151, 4578, 4584, 4586]

Cum

Vacuum 1100

1200

1270

2465

–

20

[1, 9, 12, 151, 4578, 4584, 4586]

Cun

Vacuum 1100

1200

1350

2700

–

20

[1, 12, 151, 584, 626, 4579, 4584]

Cu

Ar

1100

–

–

–

–

~30

[3, 12-13, 584, 626, 671, 4583]

Cu

N2

11001110

–

–

–

–

135

[3104]

Cu

N2

1120

Cu (99.99 %) Vacuum 1130 Cu

N2

Cuk

Vacuum 1150

Cum

– 900

11301150

– 1351

–

– 675

– 31

134

[3104]

120

[1, 1885, 4576]

–

–

–

129-130 [3104]

60

1255

2450

–

18

[1, 4578, 4586]

Vacuum 1150

600

1255

2470

–

15

[1, 4578, 4586]

Cum

Vacuum 1150

900-1200 1255

2470

–

14

[1, 9, 4578, 4586, 4589]

Cum

Vacuum 1200

60

1240

2450

–

13

[1, 4578, 4586]

Cum

Vacuum 1200

600

1240

2460

–

10

[1, 4578, 4586]

(continued)

2.6 Chemical Properties and Materials Design

561

Table 2.26 (continued) Cum

Vacuum 1200

900-1200 1240

2470

–

7

[1, 9, 151, 4578, 4584, 4586, 4589]

Cu

N2

1240

–

–

–

–

99

[3104]

CuZr2

Ar

1050

150-1200

–

–

–

41

[3530]

CuZr2

Ar

1100

150-1200

–

–

–

31

[3530]

CuZr2

Ar

1150

60-750

–

–

–

29-30

[3530]

CuZr2

Ar

1150

750-1200

–

28

[3530]

Feo

Ar

14001450

1200

1805

> 3610

–

~0

[1, 2471]

Fe

Vacuum 1420

300

1910

> 3820

–

~0

[1, 4578]

Fe

Vacuum 1490

< 60

1900

> 3800

–

~0

[1, 9, 151, 4578, 4584, 4586, 4589]

Fef

Vacuum, 1490Ar 1550

–

–

–

~0

[3, 3580, 4587-4588]

Fe

Vacuum 1500

–

–

–

–

~0

[3, 2447]

Fe (pure)

Vacuum 1550

–

1830

3540

–

20

[1]

1780

> 3560

–

~0

[1, 151, 1885, 4576, 4584]

Fe (99.999 %) Vacuum, 1550 Ar

900

–

–

–

Fe (C-1.0 %)p Vacuum 1550

–

–

–

–

33

[1]

Fe (C-2.0 %)p Vacuum 1550

–

–

–

–

39

[1]

Fe (C-3.0 %)p Vacuum 1550

–

–

–

–

49

[1]

Fe (C-4.0 %)p Vacuum 1550

–

–

–

–

65

[1]

Fe (C-0.35, Vacuum 1550 Mn-0.5, Si0.35, Ni ≤ 0.3, Cr ≤ 0.3 %)

–

1200

–

24

[1]

Fe (C-0.5, Mn-0.2, Si0.2 %)q

300

Pure Ar 15001550

900

–

–

–

~0

[1, 4582]

Fe (C-1.0, Cr- Pure Ar 15001.4, Mn-0.4, 1550 Si-0.3 %)q

900

–

–

–

~0

[1, 4582]

Fe (C-1.0, Cr- Pure Ar 15001.35, Mn-1.1, 1550 Si-0.6 %)q

900

–

–

–

~0

[1, 4582]

Fe (C-0.15, Pure Ar 1500Cr-14.5, Ni1550 2.7, Mn-0.5, Si-0.5 %)q

900

–

–

–

~0

[1, 4582]

Fe (C-2.6, Mn-1.0, Si1.0, Cr-0.3 %)q

900

–

–

–

~0

[1, 4582]

Pure Ar 14001450

(continued)

562

2 Tungsten Carbides

Table 2.26 (continued) Fe (C-3.1, Si- Pure Ar 14001.6, Mn-0.4 1450 %)q

900

–

–

–

~0

[1, 4582]

Fe (C-2.65, Si-1.2, Mn0.4, Cr-0.05 %)q

Pure Ar 14001450

900

–

–

–

~0

[1, 4582]

Fe (C-4.0, Si- Pure Ar 14002.5, Mn-1.4, 1450 S-0.1 %)q

900

–

–

–

~0

[1, 4582]

Fe (C 90

[3651]

Fe (C 3620

–

~0

[1, 9, 151, 4578, 4584, 4586, 4589]

Nif

Vacuum, 1380Ar 1450

–

~0

[3]

–

–

3.8

–

148±1 [1, 3, 151, 1885, 4576, 4584]

(continued)

2.6 Chemical Properties and Materials Design

563

Table 2.26 (continued) Ni (99.99 %) Vacuum, 1450 Ar Nit

Vacuum, 1450 ~7 mPa

900

1700

–

> 3400

–

–

–

~0

[1, 151, 1885, 4576, 4584]

–

~0

[675] [1, 3, 4581]

Ni

Vacuum 1500

300

–

~0

γ′-Ni3±xAlu

Vacuum 1400

15

–

–

–

30

[4298]

γ′-Ni3±xAlu

Vacuum 1400

30

–

–

–

8

[4298]

γ′-Ni3±xAlu

Vacuum 1400

60-120

γ′-Ni3±xAlv

Vacuum 1450

< 60

γ′-Ni3±xAlv

Vacuum 1450

60

3160

6303

–

6

[4310-4311]

γ′-Ni3±xAlv

Vacuum 1450

120

3160

6318

–

2

[4310-4311]

γ′-Ni3±xAlv

Vacuum 1450

~0

[4310-4311]

1700

> 3400

–

–

–

~0

[4298]

3160

5716

–

36

[4310-4311]

180-360 3160

~6320

Pb (99.98 %) Vacuum 400

900

85

Pt Vacuum, 1800 (high purity)u ~1.3 mPa

900

Sb (99.999 %)

Vacuum 700

900

Si

Ar

1410

900

860

1605

–

30

[1, 1942]

Si Ar (99.9999 %)

1500

900

860

> 1720

–

~0

[1, 3, 151, 4576]

480

– 384

– 330

Sn (99.999 %)

Vacuum 300

900

554

125

Sn

Ar

500

900

554

275

Sn

Ar

700

–

–

Sn

Ar

900

–

–

Sn

Ar

1100

Sn

Ar

1300

Tii

–

≥ 1660

– 900

– 554

– 3.8

145±2 [1, 3, 151, 1885, 4576, 4584] –

15.0

5.4

20

[3951]

98±2

[1, 3, 151, 1885, 4576, 4584]

141±0.6 [1, 3, 151, 1885, 4576, 4584] –

120

[1, 9, 12-13, 584, 626, 4577]

–

–

98

[9, 4589]

–

–

75

[9, 4589]

–

–

53

[9, 4589]

1030

–

30

[1, 12-13, 584, 626, 4577]

~0

[2943]

–

–

–

Tl (99.99 %) Vacuum 400

900

490

145

Vi

–

≥ 1890

–

–

–

–

~0

[2943]

Zri

–

≥ 1850

–

–

–

–

~0

[2943]

50

[4030]

Zr (Cu-30, Al Vacuum, 860 -10, Ni-5%)w 0.5 mPa

– 6.6

135±0.3 [1, 3, 1885, 4576]

(continued)

564

2 Tungsten Carbides

Table 2.26 (continued) Zr (Cu-30, Al Vacuum, 860 -10, Ni-5%)w 0.5 mPa

15

–

–

–

25

[4030]

Zr (Cu-30, Al Vacuum, 860 -10, Ni-5%)w 0.5 mPa

600

–

–

–

14

[4030]

Zr (Cu-30, Al Vacuum, 860 -10, Ni-5%)w 0.5 mPa

1200

–

–

–

12

[4030]

Zr (Cu-30, Al Vacuum, 900 -10, Ni-5%)w 0.5 mPa

35

[4030]

Zr (Cu-30, Al Vacuum, 900 -10, Ni-5%)w 0.5 mPa

10

–

–

–

22

[4030]

Zr (Cu-30, Al Vacuum, 900 -10, Ni-5%)w 0.5 mPa

600

–

–

–

18

[4030]

Zr (Cu-30, Al Vacuum, 900 -10, Ni-5%)w 0.5 mPa

1200

–

–

–

13

[4030]

Zr (Cu-30, Al Vacuum, 940 -10, Ni-5%)w 0.5 mPa

27

[4030]

Zr (Cu-30, Al Vacuum, 940 -10, Ni-5%)w 0.5 mPa

5

–

–

–

23

[4030]

Zr (Cu-30, Al Vacuum, 940 -10, Ni-5%)w 0.5 mPa

600

–

–

–

21

[4030]

Zr (Cu-30, Al Vacuum, 940 -10, Ni-5%)w 0.5 mPa

1200

–

–

–

20

[4030]

Zr (Cu-30, Al Vacuum, 980 -10, Ni-5%)w 0.5 mPa

27

[4030]

Zr (Cu-30, Al Vacuum, 980 -10, Ni-5%)w 0.5 mPa

2.5

–

–

–

26

[4030]

Zr (Cu-30, Al Vacuum, 980 -10, Ni-5%)w 0.5 mPa

600

–

–

–

17

[4030]

Zr (Cu-30, Al Vacuum, 980 1200 – – – 16 [4030] -10, Ni-5%)w 0.5 mPa a The parameters of wettability are given in accordance with Young-Dupré equation Wa = γl-g × (1 + cosθ) and Young’s equation γs-l = γs-g – γl-gcosθ, where Wa is the work of adhesion, γl-g is the liquid-vapour interfacial energy (surface tension), γs-l is solid-liquid interfacial energy, γs-g is the solid-vapour interfacial energy and θ is the wetting contact angle [1]; compositions of melts are given in mass (weight) percentage b Wm = Wa(M/d)2/3NA1/3, where Wm is the molar work of adhesion, M is the molecular mass and d is the density of chemical compound, NA is the Avogadro constant [4580] c Measured on spark-plasma sintered δ-WC1±x materials (porosity – 0.1 %) during the heating with a gradual increase in temperature (5 K min–1) d Measured on hot isostatic pressed δ-WC1±x materials (porosity (closed) – ~2 %) using liquid metallic Co with the slight addition of C e Measured on hot isostatic pressed δ-WC1±x materials (porosity (closed) – ~2 %) using liquid metallic Co saturated with C f Based on several sources g In δ-WC1±x – Co hard alloys, only the minority of δ-WC1±x/δ-WC1±x grain boundaries are completely wetted by Co melt during the liquid-phase sintering, while most of them are pseudopartially wetted, as they have the higher contact angle (up to 40-80 degrees) with Co

2.6 Chemical Properties and Materials Design

565

binder, but nevertheless, contain the 2-3 nm thin uniform Co-rich layer [2839, 2872] h γs-l > 610 mJ m–2 i Calculated and evaluated theoretically j Measured on hot-pressed single-phase δ-WC1±x materials (99 % purity, mean particle size – 2.5 μm) k Measured on δ-WC1±x (with the presence of small amounts of γ-WC1–x phase) thin films (thickness – ~1 μm), sputter-deposited on the surface of sintered δ-WC1±x-based hard alloys (content Co – 3.5 %); the formation of η2-W3Co3Cy phase in the solid-liquid interface was detected l Measured on sintered δ-WC1±x-based hard alloys (content Co – 3.5 %); an increased concentration of Co in the solid-liquid interface was detected, more likely due to the diffusion of Co into Cu m Metal impurities: Fe – 0.1 %, Si – 0.1 %, Mg – 0.1 %, Pb – 0.1 %, Ag – 0.2 % n γs-l = 1520 mJ m–2 o γs-g > 2475±200 mJ m–2, γs-l > 575±220 mJ m–2 p Alloys prepared by refusion of carbonyl Fe and α-C (graphite) with spectral purity q Measured on sintered δ-WC1±x materials (porosity – 3-8 %) r Measured on single crystal δ-WC1±x (1010) by sessile drop method s Measured on single crystal δ-WC1±x (1010) by sessile drop method t Measured on hot-pressed and annealed (in H2 atmosphere) δ-WC1±x materials (porosity ≤ 5 %) u Measured on hot-pressed δ-WC1±x materials (porosity ≤ 3 %) v Measured on hot-pressed δ-WC1±x materials (porosity < 1 %) w Measured on highly dense δ-WC1±x materials (purity > 99 %) in a high vacuum with O partial pressure – ~10–14 Pa; slightly anomalous dependence of contact angle θ on temperature was caused by the interaction between Zr in the melt and the substrate and formation of ZrC1–x, metallic W and W-Zr intermetallide phases on the δ-WC1±x surface

C → W b, c

Species pair

300-1000 (25-730)

370-670 (100-400) 570-670 (300-400) 850-1100 (580-830) 1000-1100 (730-830)

1070-1270 (800-1000)

3.15×10−3exp[(−20,700±1,800)/T]

~ exp(−22,700/T)

~ exp[(−27,700±3,500)/T]

~10−18 < D < ~10−14

3.17×10−3exp(−25,900/T)

Temperature range, K (°C)

2.56×10−3exp(−16,900/T)

Temperature dependence of the diffusion coefficient (diffusivity) D = D0exp[(−EA/R)/T], cm2 s−1

[4634]

References

[4624-4625]

[4644, 4648]

(continued)

Polycrystalline thin films of metallic W (thickness ≥ 60 nm, [4642-4643] crystallite size – from ~10 nm to ~20 nm, before and after annealing, respectively) deposited using magnetron sputtering on paracrystalline C (glassy) substrate (crystallite size – 2.6 nm), measurements of carbide (α/ε-W2+xC + δ-WC1±x) layer growth by the Rutherford backscattering spectroscopy (RBS) using a special software for the simulation of RBS spectra

Polycrystalline metallic W layers (thickness – ~0.1 μm) cre- [4630] ated using magnetron sputtering on pyrolytic α-C (graphite) substrate, measurements by the Rutherford backscattering spectroscopy (RBS) using 2 MeV 4He and 1.5 MeV 7Li ions (the diffusion of C in W was found to depend strongly on the C concentration)

Polycrystalline metallic W, measured by means of field emission microscopy (surface diffusion)

Polycrystalline metallic W, summarized evaluation based on various methods

Polycrystalline metallic W wire, indirect method by internal [4617, 4621, friction 4639, 4644]

Calculated on the basis of density functional theory (DFT) using the generalized gradient approximation (GGA) of Perdew and Wang and projector augmented wave (PAW) potentials

Remarks on materials characteristics and measurement method

Table 2.27 Diffusion rates and related parameters in the systems containing tungsten, carbon and tungsten carbide phases at various temperatures a

566 2 Tungsten Carbides

1170-1720 (900-1450) 1200-1400 (930-1130) 1300-2100 (1030-1830) 1350-1420 (1080-1150) 1370-1720 (1100-1450)

1370-1720 (1100-1450)

1470-1870 (1200-1600)

~1500-2500 Determined by the measurements of decarburization (gene- [1979, 4596, (~1230-2770) ration of CO) rate on C-containing polycrystalline pure me- 4644] tallic W ribbons in atmosphere of O2 (estimated values) (continued)

~ exp[(−30,100±1,800)/T

1.2×10−2exp(−22,500/T)

3.0exp[(−29,700±4,000)/T]

4.0×10−2exp(−27,000/T)

3.0×10−1exp(−25,000/T)

8.91×10−2exp(−26,900/T)

1.60×10−6exp(−25,500/T)

[4521]

[4597, 4644, 4651-4652]

Preliminarily annealed polycrystalline (arc-melted) metallic [1, 1979, W (99.51 % purity, rectangular specimens), mechanical 4601, 4622, sectioning with 14C radiometric method 4639, 4644]

Polycrystalline metallic W wire (diameter – 0.8 mm, depth [1, 1979, > ~2.0 μm) in H2 atmosphere (formation of α/ε-W2+xC), 4607, 4639, chemical and mechanical sectioning with 14C radiometric 4644] method

Polycrystalline metallic W wire (diameter – 0.8 mm, depth [1, 1979, – 1.5-2.0 μm) in H2 atmosphere (formation of α/ε-W2+xC), 4607, 4644] chemical and mechanical sectioning with 14C radiometric method

Parameters of the kinetics of C segregation in the system of [1, 4597, single crystal W (100) plus two monolayers of total C con- 4644, 4651tent e 4652]

Parameters of temperature variation of W carbides layer growth rate constant, summarized on several sources

Parameters of the kinetics of C segregation in the system with metallic W (110) ribbon e

Polycrystalline (sintered) metallic W (porosity > 3 %), che- [4644, 4648] mical and mechanical sectioning with 14C radiometric method (grain boundary diffusion) d

[4644, 4648]

~ exp(−17,200/T)

Polycrystalline metallic W, summarized evaluation based on various methods (bulk diffusion) d

1170-1720 (900-1450)

2.24×10−2exp[(−24,200±2,300)/T]

[4644, 4649]

~1170 (~900) Polycrystalline metallic W wire, chemical and mechanical sectioning with 14C radiometric method (D0 was assumed on the basis of other works)

~3.0×10−1exp[(−31,000±800)/T] (D = 2.15×10−12)

Table 2.27 (continued)

2.6 Chemical Properties and Materials Design 567

1770-2810 (1500-2535) 1810-2080 (1535-1805)

~1970 (~1700)

~2070-2370 Parameters of temperature variation of decarburization rate [4644, 4646(~1800-2100) of preliminarily carburized polycrystalline metallic W wire 4647, 4650] in low-pressure O2 atmosphere 2070-3070 (1800-2800)

2090-2490 (1820-2220) 3720-4070 (3450-3800)

(3.40+1.40−0.90)×102exp[(−50,100±600)/T]

3.1×10−1exp[(−29,700±2,500)/T]

~ (1.2÷25.5)×10−13exp(−62,900/T)

~ exp(−36,300/T)

9.22×10−3exp(−20,300/T)

~ exp(−27,700/T)

~ exp[(−15,100±4,500)/T] (0.39×10−3 ≤ D ≤ 0.54×10−3)

[8-9, 46184620]

[1, 151, 1979, 4595, 4599, 4610, 4621, 4626]

Determined from the dissolution rate of C in liquid metallic [4644-4645] W during the saturation of these melts with C in an arc furnace (continued)

Determined by the measurements of surface coverage de- [4644, 4653crease on pure metallic W field emission microscopy tips e 4654]

Polycrystalline metallic W wire (99.86 % purity, content C – 0.09 %), diffusion couple method with the determination of c ~ x curves by calculation from an analytical solution, mechanical sectioning with 14C radiometric method f

Polycrystalline metallic W, measured by means of thermio- [4624] nic emission with EA calculated from the Dushman-Langmuir equation (estimated values)

Contact saturation of polycrystalline (cast) spherical W par- [8-9, 1979, ticles in contact with C (black) in H2 flow (two-phase diffu- 4615, 4624] sion zone – δ-WC1±x + metallic W, with traces of α/ε-W2+xC phase), metallography method

Parameters of temperature variation of α/ε-W2+xC layer growth rate constant during the contact saturation of solid pure metallic W by C (black)

Randomly oriented single-crystal metallic W (99.994 % pu- [1, 151, rity), mechanical sectioning with 14C radiometric method 1979, 4602, 4639, 4644]

1770-2070 (1500-1800)

(3.45±0.12)×10−3exp[(−19,040±70)/T]

Parameters of C diffusion into and within δ-WC1±x (0001), [4007] (1010) / W (100), (110), (111) interfaces for the 50-80 at.% depletion of C, calculated using classical molecular dynamics (MD) simulation with the analytical bond order potential (ABOP) as a basis for the accuracy of the simulation

< 1520 (< 1250)

(1.2÷9.4)×10−7exp[−(2,900÷5,500)/T]

Table 2.27 (continued)

568 2 Tungsten Carbides

1270-2870 (1000-2600)

1270-2870 (1000-2600)

1370-1620 (1100-1350)

1470-2270 (1200-2000)

1470-2270 (1200-2000)

3.91exp[(−38,500±1,200)/T]

(5.3±2.6)×10−1exp[(−38,800±1,300)/T]

18.3exp(−46,100/T)

1.8×10−4exp(−34,680/T)

1270-2170 (1000-1900)

6.70exp[(−37,300±2,000)/T]

C → α/ε-W2+xC 1.64×103exp(−52,400/T)

Table 2.27 (continued)

[4632-4633]

[1, 85, 251, 4604]

(continued)

Polycrystalline hot-pressed α-W~2.0C materials (with small [4604] amounts of (0001) preferred orientation, porosity – lower, mean grain size – 0.3-0.4 mm, contents: O < 0.003%, N < 0.001%, Mo < 0.005%, Fe < 0.002%), mechanical sectioning with 14C radiometric method and calculation within the Suzuoka analysis scheme (grain boundary diffusion)

Polycrystalline hot-pressed α-W~2.0C materials (with small amounts of (0001) preferred orientation, porosity – lower, mean grain size – 0.3-0.4 mm, contents: O < 0.003%, N < 0.001%, Mo < 0.005%, Fe < 0.002%), mechanical sectioning with 14C radiometric method (bulk diffusion)

Determined by the isothermal measurements of carbide [4284] layer (α/ε-W2+xC + δ-WC1±x) growth rate constant in the pure metallic W film (thickness – 10 μm) deposited on C fibre composite (coated preliminarily with a Mo interlayer) and annealed in Ar atmosphere, cross sections were examined in a device combining ion beam and scanning electron microscopy

Determined by the non-isothermal measurements (heating [4631] rates – 40-500 K s−1) of single-phase α/ε-W2+xC layer growth rate constant on polycrystalline W (99.97 % purity) wires in CH4 atmosphere under static conditions, metallography method

Determined by the isothermal measurements of α/ε-W2+xC layer growth rate constant on polycrystalline W (99.97 % purity) wires in CH4 atmosphere under static conditions, metallography method

Parameters of reaction chemical diffusion, measurements of [1, 4594temperature variation of α/ε-W2+xC layer growth rate cons- 4595, 4611, tant, metallography method 4614]

2.6 Chemical Properties and Materials Design 569

1670-2270 (1400-2000) 1770-2120 (1500-1850) 1770-2810 (1500-2535)

~1770-2770 Parameters of reaction chemical diffusion of C in W during [4604] (~1500-2500) the contact saturation of solid metal (measured and reported by Wash) 1800-2120 (1525-1850)

1870-1970 (1600-1700)

1.82×106exp[(−19,900±6,700)/T]

2.0exp(−42,800/T)

6.0×102exp(−49,000/T)

102exp(−49,650/T)

2.50×104exp[(−56,400±1,500)/T]

1.56×10−3exp[(−52,400±4,600)/T]

Parameters of reaction chemical diffusion determined by the measurements of carbide layer (α/ε-W2+xC with thin δ-WC1±x sublayer formed at the outer interface) growth rate constant during the contact saturation of solid pure metallic W in the contact with α-C (graphite), metallography method

(continued)

[1, 8-9, 151, 579, 1979, 4594, 4600, 4623, 4659]

Determined by the measurements of carbide layer growth [8-9, 1979, rate on polycrystalline metallic W (> 99.95 % purity) bars 4612-4613, in the contact with calcinated C (black) in H2 flow, metallo- 4624] graphy method

Parameters of reaction chemical diffusion of C in W during [8-9, 4618the contact saturation of solid metal by C (the parameters 4620] relate to α/ε-W2+xC layer, although at outer α-C (graphite) – carbide boundary a thin layer of δ-WC1±x was formed with the ratio of WC/W2C thicknesses decreasing with the growth of temperature)

Parameters of reaction chemical diffusion of C in W during [1, 151, the contact saturation of solid metal, sectioning with 14C ra- 1933, 4598] diometric method

Parameters of reaction chemical diffusion, measurements of [624, 791, temperature variation of α/ε-W2+xC layer growth rate cons- 4624] tant, metallography method

Polycrystalline hot-pressed α-W~2.0C materials, mechanical [1, 85, 4603] sectioning with 14C radiometric method

1670-2270 (1400-2000)

33.0exp(−47,200/T)

Determined by the measurements of carbide layer growth [624, 791, rate constant on polycrystalline sintered pure W parts in the 1979, 4593] contact with C (black)

1670-2270 (1400-2000)

1.6×10−4exp(−17,100/T)

Table 2.27 (continued)

570 2 Tungsten Carbides

C → δ-WC1±x 1170 (900)

8.20×10−9 (*) 1170 (900) 1220 (950) 1470 (1200)

1270-2610 (1000-2340) 1415-2865 (1140-2590)

1320-2100 (1050-1830)

2240-2640 (1965-2370)

7.02×10 (**)

7.16×10−9 (**)

3.41×10−4 (**)

2.6×10−2exp(−70,000/T) (*)

2.9×10−6exp(−78,600/T) (**)

1.02×10−4exp(−29,300/T)

1.90×10−6exp(−44,300/T)

−9

1970-2320 (1700-2050)

3.0×105exp(−63,000/T)

Polycrystalline hot-pressed δ-WC1±x (with small amounts of (0001) preferred orientation, porosity ≤ 1 %, mean grain size – 21-26 μm, content O – ~0.03 %), chemical and mechanical sectioning with 14C radiometric method (bulk diffusion)

Parameters of temperature variation of δ-WC1±x layer growth rate constant upon the carburization of metallic W spherical powders in contact with C heated in H2 atmosphere (kinetics model based on diffusion of C through δ-WC1±x growing shells)

(continued)

[1, 8-9, 85, 151, 1933, 1979, 22562257, 4608]

[4629, 4644]

Bulk diffusion coefficients, calculated using density func- [1065] tional theory (DFT) atomic simulations within the PerdewBurke-Ernzerhof (PBE) formalism of the generalised gradient approximation (GGA) for the parallel (*) and perpendicular (**) directions to the basal planes in the δ-WC1±x crystals

Obtained from the numerical simulation of neck growth [4636-4637] pro-cess of free-packed fused spherical-shaped δ-WC1±x particles (with the traces of γ-W2±xC phase, mean size – (120÷128)±(5÷7) μm, content O – 1.09 %) during the initial stage of spark-plasma (*) and microwave sintering (**) processes of these powders examined by scanning electron microscopy (SEM) method (the presence of metallic W and γ-W2±xC phases was detected in the sintered bodies)

Parameters of reaction chemical diffusion of C in W (for- [1, 151, mation of α/ε-W2+xC) during the contact saturation of solid 4598] metal, sectioning with 14C radiometric method

~1970-2070 Determined by the measurements of growth rate of carbide [1979, 4646(~1700-1800) layer (thickness of layer was measured by the variation of 4647, 4650] electrical conductivity) on polycrystalline W filament during the carburization in a hydrocarbon vapour g

~ exp(−54,400/T)

Table 2.27 (continued)

2.6 Chemical Properties and Materials Design 571

2000-2865 (1730-2590)

2240-2640 (1970-2370) 1820-2020 (1550-1750)

5.5×10−3exp(−126,000/T) (**)

7.33exp[(−69,500±9,600)/T]

(0.66÷2.90)×10−9exp[−(7,000÷10,700)/T]

~ exp(−65,000/T)

2000-2865 (1730-2590)

8.2×10−3exp(−124,000/T) (*)

[1, 85, 1933, 1979, 4606]

Obtained from the Cr concentration profiles in annealed [3395] Cr3C2–x – δ-WC1±x hot-pressed diffusion couples (exposure – 6-18 h), wavelength-dispersive electron-probe microanalysis method (with chemically characterized standards)

Polycrystalline δ-WC1±x (content O ≤ 0.03 %), mechanical sectioning with 185W radiometric method

Bulk diffusion coefficients, calculated using density func- [1065] tional theory (DFT) atomic simulations within the PerdewBurke-Ernzerhof (PBE) formalism of the generalised gradient approximation (GGA) for the parallel (*) and perpendicular (**) directions to the basal planes in the δ-WC1±x crystals

Polycrystalline hot-pressed δ-WC1±x (with small amounts of [1, 8-9, 85, (0001) preferred orientation, porosity ≤ 1 %, mean grain 1979, 2256size – 21-26 μm, content O – ~0.03 %), sectioning and spe- 2257] ctro-photometric analysis with 14C radiometric method (grain boundary diffusion via autoradiography, dominated at depths > 1 μm and calculated within the Suzuoka analysis scheme)

2570-2770 Single-crystal δ-WC1±x embedded in TiC0.95 powder and [4608-4609] (2300-2500) hot-pressed (no powder porosity effect) a The rates of penetration of C into metallic W, having a very small solid solubility of C, are much higher than the growth rates of W carbide phases layers (e.g. a W rod (diameter – 5 mm) at 2320 °C (exposure – 0.75 h) was saturated by C completely, while the thickness of carbide layer was less than 0.1 mm [50]); the approximate values of apparent activation energy for some diffusion controlled processes in δ-WC1±x: (a) degree of conversion for the carburization reaction in powdered mixtures of metallic W with C (black) – 210 kJ mol−1 [4644]; (b) recrystallization (grain growth) of sintered bodies – ~165 kJ mol−1 (up to 2030 °C) [818, 4605, 4627-4628, 4663]; (c) powder sintering densification (isothermal) – 45 kJ mol−1 (spark-plasma sintering, nanocrystalline powders, mean particle size – 70-100 nm, > 1300 °C) [4638], ~110 kJ mol−1 (spark-plasma sintering, nanocrystalline powders, mean particle size – 70-100 nm, 9001050 °C) [4638]; (d) powder sintering densification (non-isothermal) – ~40 kJ mol−1 (spark-plasma sintering, nanocrystalline powders, mean particle size – 70-100 nm, 1350-1500 °C) [4638], ~60 kJ mol−1 (spark-plasma sintering, nanocrystalline powders, mean particle size – 70-100 nm, 900-1000 °C) [4638], ~100 kJ mol−1 (spark-plasma sintering, nanocrystalline powders, mean particle size – 70-100 nm, 1050-1200 °C) [4638], ~ 160-180 kJ mol−1 (spark-plasma sintering, powders with mean particle sizes – from 0.1 μm to 3 μm, in the highest temperature range) [2986], 230 kJ mol−1 (spark-plasma sintering, powders

Ti → δ-WC1±x

Cr → δ-WC1±x

W → δ-WC1±x

2240-2640 (1965-2370)

4.57×102exp(−35,750/T)

Table 2.27 (continued)

572 2 Tungsten Carbides

with mean particle sizes – from 0.1 μm to 0.8 μm, in the intermediate temperature (intense shrinkage) range/stage) [2986], 305 kJ mol−1 (spark-plasma sintering, powders with mean particle sizes – 3 μm, in the intermediate temperature (intense shrinkage) range/stage) [2986], ~ 360-380 kJ mol−1 (spark-plasma sintering, powders with mean particle sizes – from 0.1 μm to 3 μm, in the higher temperature (decreased shrinkage) range/stage) [2986]; (e) powder hotpressing (conventional) densification – 590 kJ mol−1 (δ-WC1.01, power-law creep, mean particle size – 5 μm, 2100-2500 °C) [4641]; (f) initial stage of consolidation of free-packed fused spherical-shaped powders, mean particle size – ~125 μm) – ~50 kJ mol−1 (spark-plasma sintering, 900-1400 °C) [4637], 50 kJ mol−1 (microwave sintering, 1200-1400 °C) [4637], 60-70 kJ mol−1 (microwave sintering, 900-1200 °C) [4636-4637], ~75 kJ mol−1 (conventional sintering, 950-1250 °C) [268], ~270 kJ mol−1 (conventional sintering, 1200-1400 °C) [4637]; data on creep [990] – see section 2.4 (Table 2.15), see also section 2.5 (Table 2.19) b The diffusion mobility of C in metallic W is strongly increased by the lattice defects, which, in turn, facilitate C segregation around the defects, different diffusion mechanisms were established in the ranges of temperatures 20-800 °C, 800-1850 °C, 1850-2400 °C and ≥ 2400 °C [4644]; intense carbide formation, especially on the structure defects, occurred in all the indicated temperature intervals [4644], at ≤ 800 °C local carbide formation occurred by C segregation on dislocations [4648], local segregations of C in W by diffusion processes were studied in several works [4655-4658] c Carbonitriding experiments at 1000-1200 °C showed that N has a retarding effect on the diffusion of C in W (it was suggested that the diffusion of C and N took place mainly through the reaction products [4412] d For comparison: the coefficients of bulk (grain) (*) and grain boundary (**) diffusion, cm2 s−1, at 900 °C were determined to be 5.2×10−12 (*) and 4.0×10−10 (**), when a packing of spherical grains was assumed, and 10.4×10−12 (*) and 8.5×10−10 (**), when a cylindrical-grain model was used taking account of the actual columnar structure of wire test specimens [4644] e The values are probably too high due to a potential barrier just below the surface [4644] f The deviation from the Arrhenius law (from a linear variation of lnD0 as a function of 1/T) was found at the temperature interval > 2600 °C, where a distinct temperature dependence of the activation energy of diffusion was observed due to the presuming diffusion of interstitial C atoms via a vacancy mechanism [89, 1979, 4599, 4610, 4644] g Without a sufficient reason, it was assumed that only the α/ε-W2+xC carbide layer grows on the metallic W surface [1979, 4646-4647]

2.6 Chemical Properties and Materials Design 573

574

2 Tungsten Carbides

Table 2.28 The interaction of tungsten monocarbide δ-WC1±x materials and δ-WC1±x phase constituent in various alloys and composites with some common chemical reagents in aqueous (or organic) solutions and/or molten (fused) conditions [1, 3, 6, 11-12, 41, 45, 48, 68, 86, 151, 153, 200, 245, 584-585, 601, 626, 661, 787, 792, 800, 813, 847, 850, 858, 860, 872, 886, 896, 899, 926, 931, 940-941, 1119, 1247-1248, 1264, 1281, 1345, 1460, 1783, 1789, 1806, 1809, 1812, 1818-1821, 1824, 1831, 1835, 1843-1847, 1851, 1856, 1859-1860, 1864, 1867, 18691871, 1875-1877, 1879-1881, 1884, 1930, 1950, 2082, 2110, 2147, 2212, 2226, 2304, 2320, 2409, 2411, 2416, 2505, 2508, 2512, 2516, 2531, 2546, 2597, 2697, 2729, 2733, 2854, 2869, 2885, 2938, 2942, 3004, 3104, 3127, 3134, 3213, 3253, 3294, 3381, 3423-3424, 3437, 3447, 3650, 3654, 3692-3693, 3706, 3751, 3841, 3846, 3875, 3902, 3957, 3961, 3967, 4005, 4008, 4058, 4111, 4118, 4194, 4203, 4239, 4264, 4271, 4296, 4386, 4493, 4511, 4527, 4565-4566, 4607, 4660-4662, 4665-4666, 4670-4675] (see also Table 2.22) Reagent, formula (density or concentration of aqueous solution) a HCl (1:1) c

Treatment conditions Tempera- Exposure time, h ture, °C

Character of interaction b

20

24

Decomposes up to 4 %

20

120

Corrosion rate of mass loss d – 1.18×10–5 mg cm–2 s–1

130

2

Decomposes up to 8 %

20

24

Decomposes up to 3 %

130

2

Decomposes up to 52 %

HF (1:1)

20

24

Decomposes completely

H2SO4 (5 %)

20

120

Corrosion rate of mass loss d – 3.1×10–7 mg cm–2 s–1 (surface films – WO3–x, 3WO3∙H2O)

H2SO4 (1:4)

20

24

Decomposes up to 4 %

110

2

Decomposes up to 5 %

20

24

Decomposes up to 9 %

280

2

Decomposes completely

HNO3 (5 %)

20

120

Corrosion rate of mass loss d – 1.7×10–7 mg cm–2 s–1

HNO3 (1:1)

20

24

Decomposes up to 28 %

110

2

Decomposes up to 90 % e

20

24

Decomposes up to 37 %

110

2

Decomposes completely e

20

24

Decomposes up to 4 %

200

2

Decomposes up to 10 %

20

24

Decomposes up to 9 %

200

2

Decomposes up to 7 %

20

24

Decomposes up to 2 %

110

2

Decomposes up to 7 %

20

24

Decomposes up to 2 %

200

2

Decomposes up to 60 %

HCl (d = 1.19)

H2SO4 (d = 1.84)

HNO3 (d = 1.43) H3PO4 (1:3) H3PO4 (d = 1.70) HClO4 (1:3) HClO4 (d = 1.35)

(continued)

2.6 Chemical Properties and Materials Design

575

Table 2.28 (continued) H2C2O4 f (saturated solution)

20

24

Decomposes up to 5 %

105-110

2

Decomposes up to 5 %

20

120

Corrosion rate of mass loss d – 6.22×10–6 mg cm–2 s–1

3HCl (d = 1.19) + HNO3 (d = 1.43) 20 (aqua regia) 120

24

Decomposes up to 72 %

2

Decomposes up to 97 % e

2H2SO4 (d = 1.84) + HNO3 (d = 1.43)

20

24

Decomposes up to 8 %

150

2

Decomposes up to 58 % e

H3C6H5O7 g

H2SO4 (1:3) + H2O2 (30 %)

110

1

Decomposes completely

H2SO4 (1:4) + H3PO4 (1:3)

20

24

Decomposes up to 4 %

110

2

Decomposes up to 7 %

24

Decomposes up to 4 %

H2SO4 (d = 1.84) + H3PO4 (d = 1.75) 20 250

2

Decomposes completely

H2SO4 (1:4) + H2C2O4 f (saturated solution)

20

24

Decomposes up to 6 %

180

20

Decomposes up to 5 %

H2SO4 (d = 1.84) + H2C2O4 f (saturated solution)

20

24

Decomposes up to 5 %

250

2

HNO3 (1:4) + HF (1:1)

100

4HNO3 (d = 1.43) + HF (d = 1.15)

20

Decomposes up to 30 % –

Decomposes completely

24

Decomposes completely

H2C2O4 f (saturated solution) + H2O2 100 (30 %)

1

Decomposes completely

H2O (deionized)

20

168

No oxide films form on the surface h

H2O (content O – 0.0009 %)

20

120

Corrosion rate of mass loss c – 1.1×10–7 mg cm–2 s–1

H2O2 (30 %)

90

1

Decomposes completely i

NaCl (5 %, content O – 0.0007 %) j 20

120

Corrosion rate of mass loss d – 8.3×10–8 mg cm–2 s–1

NaCl (10 %, content O – 0.0005 %) j

20

120

Corrosion rate of mass loss d – 8.3×10–8 mg cm–2 s–1

NaCl (20 %, content O – 0.0003 %) j

20

120

No corrosion was detected d

NaCl (25 %, content O – 0.00015 %) j

20

120

No corrosion was detected d

NaCl – KCl (molten consolute composition)

750

NaCl – BaCl2 (melt)

1100

LiCl – KCl (melt)

500

Na2SO4 (powdered)

630

KOH – KNO3 (melt)

480

NaNO3 – KNO3 (eutectic melt)

450

–

3-5

Decomposes slightly (mass change < 10 %) –

Anodic (electrochemical) dissolution Mass loss – 5 % l

20 – 4

Anodic (electrochemical) dissolution with the redox reaction of W on Pt working cathode k

Partial decomposition Decomposes completely (loss of mass – ~88 g mol–1) m

(continued)

576

2 Tungsten Carbides

Table 2.28 (continued) NaNO3 – KNO3 (eutectic melt) + MeIICl2 (MeII = Ca, Ba)

450

4

Decomposes completely n

NaNO3 – KNO3 (eutectic melt) + MeIICl2 (MeII = Ni, Zn)

450

4

Decomposes completely (loss of mass – ~136 g mol–1) o

NaOH (melt)

450

NaOH (5 %) p

20

120

Corrosion rate of mass loss d – 3.1×10–7 mg cm–2 s–1

NaOH (10 %)

20

24

Decomposes up to 3 %

100

2

Decomposes up to 2 %

20

24

Decomposes up to 2 %

NaOH (20 %)

105 4NaOH (20 %) + Br2 (HBrO, HBr) 20 4NaOH (20 %) + H2O2 (30 %) 4NaOH (20 %) + K3[Fe(CN)6] (10 %) q, r

–

Anodic (electrochemical) dissolution

2

Decomposes up to 2 %

24

Decomposes up to 30 %

105

2

Decomposes up to 40 %

20

24

Decomposes up to 12 %

110

2

Decomposes up to 13 %

20

24

Decomposes up to 32 %

110 2 Decomposes up to 42 % All the ratios are given in volume fractions and percents in mass (weight) b When it is not indicated specially, the characteristics reported are related to the common powders of δ-WC1±x with mean particle size of about 40-50 μm c The general oxidation mechanism of corrosion in acidic environment is described by the equations: WC + 6H2O → WO42– + CO2↑ + 12H+ + 10e– [1789, 1824-1825] or WC + 5H2O → WO3 + CO2↑ + 10H+ + 10e– [1875] d For hot-pressed δ-WC1.00 materials (poreless, content non-combined C – 0.28 %) e Salt/oxide precipitation is observed; the treatment can be broadly expressed as follows: WC + 5HNO3 + 5HCl = H2WO4 + CO2↑ + 5NOCl + 4H2O f Oxalic acid g Citric acid h Storing preoxidized hot-pressed δ-WC1.01 materials (poreless, polished, content Co – 0.75 %) in H2O led to the removal of the oxide layer formed prior to exposure, δ-WC1±x materials exposed to H2O were resistant to further oxidation [4527] i Peroxopolytungstic acids CO2∙12WO3∙7H2O2∙nH2O (20 ≤ n ≤ 25) were synthesized by the direct reaction of δ-WC1±x with H2O2 and solidified at room temperature [4666, 4671] j It should be noted that the corrosion of δ-WC1±x – Co alloys in the aqueous solutions of NaCl is caused by local galvanic action between δ-WC1±x grains and Co matrix on the surface of the alloys. In this case, because soluble O plays as a depolarizer, the increased content of O in the NaCl solutions increases the corrosion rate due to the reactions: Co → Co+2 + 2e–, Co+2 + 2Cl– ↔ CoCl2, 2Na+ + 2e– → 2Na (on δ-WC1±x), 2Na + 2H2O → 2Na+ + 2OH– + 2H (adsorbed on δ-WC1±x) and 2H (on δ-WC1±x) + ½O2 (in NaCl solution) → 2H2O (depolarization reaction) [1783, 2512] k The reaction is reversable and controlled by W ion diffusion through the molten salt electrolyte l Phases δ-WO3–x and Na2WO4, identified as reaction products in the powdered mixtures of δ-WC1±x (99.9 % purity) with 50 mol.% Na2SO4 treated in pure dried O2 environment, are being formed in accordance to the reaction: 8WC + 2Na2SO4 + 19O2 = 6WO3 + 2Na2WO4 + 2SO2↑ + 8CO2↑ [4296] a

2.6 Chemical Properties and Materials Design m

577

The reaction of the δ-WC1±x (under flowing air) with molten alkali metal (Me = Na, K) nitrates is a single-step redox reaction leading from W (IV) to W (VI): 12WC + 36MeNO3 = 12Me2WO4 + 12MeNO2 + 8CO2↑ + 4CO↑ + 2NO2↑ + 11NO↑ + N2O↑ + 4½N2↑, where various oxidation states of N does not allow to determine the composition of the gas phase, which should also evolve with the temperature of reaction [4058] n The reaction of the δ-WC1±x (under flowing air) with molten alkali metal (MeI = Na, K) nitrates and alkaline earth metal (MeII = Ca, Ba) chlorides: WC + 5MeINO3 + MeIICl2 = MeIIWO4 + 3MeINO2 + 2MeICl + CO2↑ + NO2↑ +NO↑ [4058] o The reaction of the δ-WC1±x (under flowing air) with molten alkali metal (MeI = Na, K) nitrates and transition metal (MeII = Ni, Zn) chlorides: WC + 6MeINO3 + MeIICl2 = MeIIWO4 + 4MeINO2 + 2MeICl + CO2↑ + 2NO2 ↑ [4058] p The general oxidation mechanism of corrosion in alkaline environment is described by the equation: WC + 14OH– → WO42– + CO32– + 7H2O + 10e– [1824, 4672]; an average corrosion rate of pure δ-WC1±x spark-plasma sintered materials (porosity – 0.4 %) is less than ⅙ that of δ-WC1±x – 10 % Co hard alloy (exposure – 672 h, evenly divided by 4 stages), after a continuous immersion only slight enlargement in the originally existed pores and distinct grain boundaries could be identified in pure δ-WC1±x materials [941] q The dissolution takes place rapidly in accordance with the reaction WC + 9[Fe(CN)6]3– + 11OH– = WO42– + 9[Fe(CN)6]4– + 5½H2O + ½CO↑ + ½CO2↑, which can be used for the aim of chemical analysis as a volumetric determination of the δ-WC1±x (or combined C) contents [200, 4661] r Recommended chemical and electrochemical etching (dissolving), swab-etching and polishing agents for various δ-WC1±x and δ-WC1±x containing materials: a) mixture of 1 g K3[Fe(CN)6], 1 g KOH and 10-100 ml H2O at room temperature for ~ 0.25-2 min (Murakami’s reagent, for microstructural analysis of δ-WC1±x materials and various δ-WC1±x containing alloys, composites and coatings) [48, 847, 850, 860, 872, 896, 899, 926, 1877, 2409, 2546, 2697, 2854, 2938, 3213, 3253, 3654, 3841, 3875, 3957, 3961, 4008, 4111, 4118, 4194, 4264, 4271, 4493, 4674-4675]; b) mixture of 10-20 % KOH and 10 % K3[Fe(CN)6] (warm or hot) aqueous solutions (Murakami’s reagent, for metallographic phase analysis of arc-melted materials and sintered hard alloys) [86, 2320, 2531, 3381, 3447, 3751]; c) mixture of 10-30 % NaOH and 10-30 % K3[Fe(CN)6] aqueous solutions at room temperature for ~ 1-5 min (Murakami’s reagent, for metallographic phase analysis of hot-pressed and sintered δ-WC1±x materials and various alloys containing δ-WC1±x in different ratios) [41, 68, 931, 940, 1930, 2110, 2505, 2516, 2733, 2854, 2869, 2942, 3127, 3381, 3423-3424, 3692, 3706, 4203, 4239]; d) boiling aqueous solution of 5 % KOH and 5 % K3[Fe(CN)6] in the ratio of 1:3 (for metallographic studies of hot-pressed and sintered materials) [792, 813]; e) 25 % SnCl2 solution in concentrated HCl (for metallographic studies of reaction with Na2SO4) [4296]; f) mixtures of HF (d = 1.15) and HNO3 (d = 1.43) in the ratios from 4:1 to 1:3 (sometimes diluted with H2O) at room temperature for ~ 3-30 min using an ultra-sonic bath (for metallographic phase analysis of sintered and plasma-chemical synthesized materials and observation of grain boundaries in various δ-WC1±x containing materials) [153, 2416, 2938, 3957, 3967]; g) mixture of 1 % HF, 1.5 % HCl and 2.5 % HNO3 aqueous solutions for 5-10 s (for metallographic phase analysis of δ-WC1±x containing metal matrix composites (MMC) and welding joints of δ-WC1±x based hard alloys) [2147, 3692]; h) mixture of 15.5 ml HNO3 (d = 1.43), 0.5 ml HF (d = 1.15), 3 g chromic acid H2CrO4 and 84 ml H2O (for microstructural examinations of δ-WC1±x containing metal matrix composite (MMC) coatings and surface protective layers [2082]; i) molten mixture of 75 % KOH and 25 % KNO3 at 480 °C (for observation of grain shapes and crack pathways in hot-pressed δ-WC1±x materials and various δ-WC1±x containing composites) [661, 858, 2304]; j) mixture of HNO3, acetic acid CH3COOH and H2O in the ratio of 9:9:2 (for microstructural analysis of δ-WC1±x containing materials) [1950]; k) mixture of 2.5-3.0 g FeCl3, 7.5-10 ml HCl and 100 ml H2O for 1-5 min or saturated solution of FeCl3 in concentrated HCl for 20-30 s (for metallographic studies of δ-WC1±x based materials and hard alloys) [2226, 2546, 3381]; l) mixture of 1-20 g FeCl3, 75 ml HCl and 25 ml

578

2 Tungsten Carbides

HNO3 (for metallographic studies of δ-WC1±x based hard coatings) [3437, 3846]; m) mixture of 5 g FeCl3, 3 ml HCl, 10 ml HNO3 and 87 ml ethanol C2H5OH for 30 min (deep-etching treatment, for special microstructural analysis of δ-WC1±x containing alloys) [3423]; n) mixture of HNO3 (d = 1.43) and ethanol C2H5OH in the ratio of 3:1 at room temperature for 10 min (for microstructural analysis of δ-WC1±x containing sintered hard alloys) [4386]; o) 2-4 % nital (mixture of HNO3 and alcohol (methanol CH3OH, ethanol C2H5OH or methylated spirits)) solution for 40 min using an ultrasonic bath (for metallographic studies of δ-WC1±x based hard alloys and coatings) [2546, 3004, 3253, 3654, 3846]; p) 10-50 % HCl solution for 0.5-10 min (for metallographic studies of δ-WC1±x based hard alloys) [1119, 2597]; q) mixture of HCl (d = 1.19) and HNO3 (d = 1.43) in the ratio of 3:1 for 5 s (aqua regia, for metallographic studies of δ-WC1±x based hard alloys) [3294, 3650, 3846, 3902]; r) HNO3 (1:1) aqueous solution (for microstructural studies of δ-WC1±x based hard coatings) [2212]; s) mixture of 25 % HNO3 and 10 % H2O2 aqueous solutions (for microstructural analysis of δ-WC1±x based hard alloys) [2885]; t) 30 % H2O2 solution (for microstructural analysis of δ-WC1±x containing materials) [2409]; u) 2 % Na2CO3 – 25 % ethyl alcohol aqueous solutions (for electrochemical etching of δ-WC1±x containing hard alloys) [800]; v) 5 % monosodium tartrate NaC4H5O6 aqueous solution (DC voltage – 2.0-3.5 V, current – 0.01 A) for 4 h (for electrochemical etching of δ-WC1±x containing nanocomposites) [68, 4672]; w) mixture of 6.25 g Na-K tartrate, 6.25 g NaOH, 12.5 g Na2CO3 and 100 ml H2O (DC voltage – 2 V, current density – 0.1 A cm–2) for 12 h (for electrochemical etching of δ-WC1±x containing materials) [3654]; x) 10 % NaOH aqueous solution (current density – 0.95 A cm–2) for 5 min (for electrochemical etching of layers) [4607]; y) 20 % NaOH aqueous solution (current density – 0.2 A cm–2) for 2-5 s (for electrochemical etching of arc-melted δ-WC1±x containing materials) [3751]; z) mixture of 16.0 g NaOH, 22.4 g KOH and 100 ml distilled H2O (DC voltage – 1.5-3.5 V) at 23 °C for 10-60 min (during electrochemical etching, the oxidation reaction occurs on the anode: WC + 10OH– → WO42– + CO↑ + 5H2O + 8e– and the reduction reaction occurs on the cathode: H2O + 8e– → 8OH– + 4H2↑, the molecular reaction occurring during electrochemical etching of the δ-WC1±x containing materials is WC + 2NaOH + 3H2O = Na2WO4 + CO↑ + 4H2↑) [3104]; a1) 5 g K2CO3 + 100 ml H2O (DC voltage – 6 V) for 5 s (for electrochemical etching of single crystal surfaces) [245]; a2) mixture of HF, HNO3 and acetic acid CH3COOH in the ratio of 3:5:3 with traces (several drops) of Br2 (DC voltage – 4.5 V, current – 1 A, cathode – Ta wire; for surface electrochemical polishing of hot-pressed and sintered materials) [787]; a3) 0.5 % oxalic acid H2C2O4 aqueous solution (for electrochemical etching of δ-WC1±x containing materials) [48]; a4) HCl (1:3) aqueous solution (for electrochemical etching of δ-WC1±x based hard alloys) [2508]; a5) mixture of 14 % NaOH, 3 % tartaric acid H2C4H4O6 and 2 % NaClO4 aqueous solutions (DC voltage – 0.4 V) for 12 h (for selective electrochemical etching in order to decrease the interference from δ-WC1±x phase constituent on metallic binder phase in the XRD investigations of hard alloys) [3693]; a6) 25 % HNO3 solution in ethanol C2H5OH at –20 °C for 15 s (for electrochemical polishing of δ-WC1±x containing composites) [3134]; a7) mixture of 30 % HNO3 and HClO4 aqueous solutions (for electrochemical polishing of δ-WC1±x containing hard alloys and super-hard composites) [2411, 4386]

2.6 Chemical Properties and Materials Design

579

Table 2.29 The interaction of near-stoichiometric tungsten semicarbide materials with some common chemical reagents in aqueous (or organic) solutions and/or molten (fused) conditions [6, 11, 41, 45, 48, 68, 86, 118, 151, 153, 251, 1278, 2416, 3706, 3957, 4008, 4511, 4607, 46744675] (see also Table 2.22) Reagent, formula (density or concentration of aqueous solution) a

Treatment conditions Tempera- Exposure ture, °C time, h

Character of interaction b

20

24

Decomposes up to 3 % c

130

2

Decomposes up to 1 %

20

24

No decomposition

130

2

Decomposes up to 1 %

HF (1:1)

20

24

Decomposes completely

H2SO4 (1:4)

20

24

Decomposes up to 10 %

110

2

Decomposes up to 11 %

20

24

Decomposes up to 1 %

280

2

Decomposes up to 82 % d

20

24

Decomposes up to 5 % c

110

2

Decomposes up to 60 % d

20

24

No decomposition

110

2

Decomposes up to 40 % d

20

24

Decomposes up to 2 %

200

2

Decomposes up to 1 %

H3PO4 (d = 1.75)

20

24

Decomposes up to 1 % d

H2C2O4 e (saturated solution)

20

24

Decomposes up to 1 %

HCl (1:1) HCl (d = 1.19)

H2SO4 (d = 1.84) HNO3 (1:1) HNO3 (d = 1.43) H3PO4 (1:3)

105-110 3HCl (d = 1.19) + HNO3 (d = 1.43) 20 120 H2SO4 (d = 1.84) + HNO3 (d = 1.43) 20

2

Decomposes up to 1 %

24

Decomposes up to 33 %

2

Decomposes up to 50 % d

24

Decomposes up to 1 %

150

2

Decomposes up to 4 %

20

24

Decomposes up to 10 %

H2SO4 (d = 1.84) + H3PO4 (d = 1.75) 20

H2SO4 (1:4) + H3PO4 (1:3)

24

Decomposes up to 5 %

250

2

Decomposes completely

H2SO4 (1:4) + H2C2O4 (saturated solution)

20

24

Decomposes up to 13 %

250

2

Decomposes up to 2 %

H2SO4 (d = 1.84) + H2C2O4 e (saturated solution)

20

24

Decomposes up to 1 %

180

20

Decomposes up to 27 %

HNO3 (1:4) + HF (1:1)

20

e

–

Decomposes completely

4HNO3 (d = 1.43) + HF (d = 1.15) f 20

24

Decomposes completely

NaOH (10 %)

20

24

Decomposes up to 14 %

100

2

Decomposes up to 1 %

(continued)

580

2 Tungsten Carbides

Table 2.29 (continued) NaOH (20 %)

20 105

4NaOH (20 %) + Br2 (HBrO, HBr) 20 4NaOH (20 %) + H2O2 (30 %) 4NaOH (20 %) + K3[Fe(CN)6] (10 %) f

24

Decomposes up to 3 %

2

No decomposition

24

Decomposes up to 6 %

105

2

Decomposes up to 26 %

20

24

Decomposes up to 66 %

110

2

Decomposes up to 66 %

20

24

Decomposes up to 10 %

110 2 Decomposes up to 23 % All the ratios are given in volume fractions and percents in mass (weight) b When it is not indicated specially, the characteristics reported are related to the common powders of near-stoichiometric tungsten semicarbide with mean particle size of about 40-50 μm c Salt/oxide precipitation and partial hydrolysis are observed d Salt/oxide precipitation is observed e Oxalic acid f Recommended chemical etching (dissolving) and polishing agents for tungsten semicarbide materials: a) mixture of 1 g K3[Fe(CN)6], 1 g KOH and 10-100 ml H2O at room temperature for ~ 0.3-1 s (Murakami’s reagent, for metallographic phase analysis of hot-pressed and sintered materials containing various amounts of tungsten semicarbide phase; the reagent reacts more rapidly with semicarbide phases than with δ-WC1±x) [3875, 3957, 4008, 4674]; b) 10 % KOH and 10 % K3[Fe(CN)6] (warm or hot) aqueous solutions (for metallographic phase analysis of arc-melted materials containing tungsten semicarbide phase) [86]; c) mixture of 10-20 % NaOH and 20-30 % K3[Fe(CN)6] aqueous solutions in the ratio of 1:1 for ~ 3-5 min (Murakami’s reagent, for metallographic phase analysis of tungsten semicarbide containing materials) [41, 68, 3706]; d) mixture of HF (d = 1.15) and HNO3 (d = 1.43) in the ratio of (3÷4):1 at room temperature for 30 min using an ultrasonic bath (for metallographic phase analysis of plasmachemical synthesized materials and various tungsten semicarbide containing materials) [153, 2416, 3957]; e) 10 % NaOH aqueous solution (current density – 0.95 A cm–2) for 5 min (for electrochemical etching of layers) [4607]; f) 0.5 % oxalic acid H2C2O4 aqueous solution (for electrochemical etching of tungsten semicarbide containing materials) [48]; g) mixture of NaOH, NaNO3, ethylene glycol monoethyl ether CH2OHCH2OC2H5 and H2O in the mass ratio of 1:1:10:8 at 0 °C (for electropolishing preparation of thin foils for transmission electron microscopy (TEM)) [251] a

within the various ranges of temperatures are presented in the Table 2.27. The characters of chemical interaction of tungsten carbide phases with some common chemicals (acids, alkalis and salts in aqueous solutions and molten media) are summarized in Tables 2.28 and 2.29. In comparison with other ultra-high temperature materials the data on the chemical behaviour of tungsten carbides are given in Addendum.

References

581

References 1. Kosolapova TYa, ed (1990) Handbook of high-temperature compounds: properties, production and applications. Hemisphere, New York 2. Kurlov AS, Gusev AI (2013) Tungsten carbides. Structure, properties and application in hardmetals. Springer, Heidelberg 3. Samsonov GV, Vitryanyuk VK, Chaplygin FI (1974) Karbidy volframa (Tungsten carbides). Naukova Dumka, Kyiv (in Russian) 4. Kieffer R, Schwarzkopf P (1953) Hartstoffe und Hartmetalle (Refractory hard metals). Springer, Vienna (in German) 5. Goldschmidt HJ (1967) Interstitial alloys. Butterworths, London 6. Storms EK (1967) The refractory carbides. Academic Press, New York, London 7. Toth LE (1971) Transition metal carbides and nitrides. Academic Press, New York, London 8. Samsonov GV, Upadhyaya GS, Neshpor VS (1974) Fizicheskoe materialovedenie karbidov (Physical materials science of carbides). Naukova Dumka, Kyiv (in Russian) 9. Upadhyaya GS (1996) Nature and properties of refractory carbides. Nova Science, Commack, New York 10. Upadhyaya GS (1998) Cemented tungsten carbides. Production, properties and testing. Noyes Publications, Westwood, New Jersey 11. Shaffer PTB (1964) Handbooks of high-temperature materials: No. 1 – Materials index. Plenum Press, Springer, New York 12. Samsonov GV (1964) Handbooks of high-temperature materials: No. 2 – Properties index. Plenum Press, Springer Science, New York 13. Kotelnikov RB, Bashlykov SN, Galiakbarov ZG, Kashtanov AI (1968) Osobo tugoplavkie elementy i soedineniya (Extra-refractory elements and compounds). Metallurgiya, Moscow (in Russian) 14. Krawitz AD, Reichel DG, Hitterman R (1989) Thermal expansion of tungsten carbide at low temperature. J Am Ceram Soc 72(3):515-517 15. Parthé E, Sadagopan V (1962) Neutronen- und Röntgenbeugungsuntersuchungen über die Struktur des Wolframcarbides WC und Vergleich mit älteren Elektronenbeugungsdaten (Neutron and X-ray diffraction studies on the structure of tungsten carbide WC and comparison of it with earlier electron diffraction data). Monatsh Chem 93(1):263-270 (in German) 16. Coffman JA, Kibler GM, Lyon TF, Acchione BD (1963) Carbonization of plastics and refractory materials research. Technical Report WADD-TR-60-646, Contract USAF 33(616)6841, Part 2, pp. 1-183. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 17. Metcalfe AE (1947) The mutual solid solubility of tungsten carbide and titanium carbide. J Inst Met 73:591-607 18. Schuster J, Rudy E, Nowotny H (1976) Die “MoC”-Phase mit WC-Struktur (The “MoC” phase with WC structure). Monatsh Chem 107(5):1167-1176 (in German) 19. Bukatov VG, Knyazev VI, Korostin OS, Baranov VM (1975) Temperature dependence of the Young’s modulus of metal-like carbides. Inorg Mater 11(2):310-312 20. Roehrig FK, Wright TR (1972) Carbide synthesis by freeze-drying. J Am Ceram Soc 55(1):58 21. Stuart H, Ridley N (1970) Thermal expansion of some carbides and tessellated stresses in steels. J Iron Steel Inst 208(12):1087-1092 22. Rudy Er, Rudy El, Benesovsky F (1962) Untersuchungen in den Systemen Thorium – Wolfram – Kohlenstoff und Uran – Wolfram – Kohlenstoff (Investigations in the thorium – tungsten – carbon and uranium – tungsten – carbon systems). Monatsh Chem 93(2):522-535 (in German)

582

2 Tungsten Carbides

23. Rudy Er, Benesovsky F, Rudy El (1962) Untersuchungen im System Vanadin – Wolfram – Kohlenstoff (Investigations in the vanadium – tungsten – carbon system). Monatsh Chem 93(3):693-707 (in German) 24. Rudy Er, Rudy El, Benesovsky F (1962) Untersuchungen in System Tantal – Wolfram – Kohlenstoff (Investigations in the tantalum – tungsten – carbon system). Monatsh Chem 93(5):1176-1195 (in German) 25. Leciejewicz J (1961) A note on structure of tungsten carbide. Acta Crystallogr 14(2):200 26. Rudy E, Benesovsky F, Toth L (1963) Untersuchung der Dreistoffsysteme der Va-Metalle und VIa-Metalle mit Bor und Kohlenstoff (An investigation of the ternary systems of the Va metals and VIa metals with boron and carbon). Z Metallkd 54(6):345-353 (in German) 27. Schönberg N (1954) The tungsten carbide and nickel arsenide structures. Acta Metall 2(3):427-432 28. Nowotny HN, Kieffer R (1947) Röntgenographische Untersuchungen von Karbidsystemen (Radiographic analyses of carbide systems). Z Metallkd 38(2):257-265 (in German) 29. Butorina LN (1960) An electron diffraction study of the tungsten carbide WC. Sov Phys Crystallogr 5(2):216-220 30. Meinhardt D, Krisement O (1962) Strukturuntersuchungen an Karbiden des Eisens, Wolframs und Chroms mit thermischen Neutronen (Structure investigations on the carbides of iron, tungsten and chromium with thermal neutrons). Arch Eisenhuttenwes 33(7):493-499 (in German) 31. Deshpande VT, Pawar RR, Suryanarayana SV (1968) Thermal expansion of tungsten monocarbide. Curr Sci 37(19):543-545 32. Page K, Li J, Savinelli R, Szumila HN, Zhang J, Stalick JK, Proffen T, Scott SL, Seshadri R (2008) Reciprocal-space and real space neutron investigation of nanostructured Mo2C and WC. Solid State Sci 10:1499-1510 33. Suetin GD, Shein IR, Ivanovskii AL (2009) Electronic structure of tungsten aluminium carbides W2AlC and WAlC2. Russ J Inorg Chem 54(9):1433-1439 34. Fang Q, Bai W, Yang J, Xu X, Li G, Shi N, Xiong M, Rong H (2009) Qusongite (WC): a new mineral. Am Mineral 94(2-3):387-390 35. Yang J, Gao F (2010) Hardness calculations of 5d transition metal monocarbides with tungsten carbide structure. Phys Stat Sol B 247(9):2161-2167 36. Li Y, Gao Y, Xiao B, Min T, Fan Z, Ma S, Xu L (2010) Theoretical study on the stability, elasticity, hardness and electronic structures of W-C binary compounds. J Alloys Compd 502(1):28-37 37. Kavitha M, Priyanga GS, Rajeswarapalanichamy R, Iyakutti K (2015) First principles study of the structural, electronic, mechanical and superconducting properties of WX (X = C, N). J Phys Chem Solids 77:38-49 38. He ZJ, Fu ZH, Legut D, Yu XH, Zhang QF, Ivashchenko VI, Vepřek S, Zhang RF (2016) Tuning lattice stability and mechanical strength of ultra-incompressible tungsten carbides by varying the stacking sequence. Phys Rev B 93(18):184104 (8 pp.) 39. Kim J, Suh YJ, Kang I (2016) First principles calculations of the phase stability and the elastic and mechanical properties of η-phases in the WC-Co system. J Alloys Compd 656:213-217 40. Kim J, Suh YJ (2016) Temperature dependent elastic and thermal expansion properties of W3Co3C, W6Co6C and W4Co2C ternary carbides. J Alloys Compd 666:262-269 41. Sara RV (1965) Phase equilibria in the system tungsten-carbon. J Am Ceram Soc 48(5):251257 42. Litasov KD, Shatskiy A, Fei Y, Suzuki A, Ohtani E, Funakoshi K (2010) Pressure-volumetemperature equation of state of tungsten carbide to 32 GPa and 1673 K. J Appl Phys 108(5):053513 (7 pp.) 43. Kieffer R, Benesovsky F (1963) Hartstoffe (Hard materials). Springer, Vienna (in German) 44. Hansen M, Anderko K (1958) Constitution of binary alloys, 2nd ed. McGraw-Hill, New York, London

References

583

45. Pierson HO (1996) Handbook of refractory carbides and nitrides. Noyes Publications, Westwood, New Jersey 46. Rudy E, Windisch S, Hoffman JR (1965) W-C system. Supplemental information on the MoC system. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFML-TR-65-2, Contract USAF 33(615)-1249, Part 1, Vol. 6, pp. 1-79. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 47. Rudy E (1969) Compendium of phase diagram data. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFML-TR-65-2, Contracts USAF 33(615)-1249 and USAF 33(615)-67-C-1513, Part 5, pp. 1-689. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 48. Rudy E (1973) Constitution of ternary titanium-tungsten-carbon alloys. J Less-Common Met 33(2):245-273 49. Gupta DK, Seigle LL (1975) Free energies of formation of WC and W2C and the thermodynamic properties of carbon in solid tungsten. Metall Trans A 6(10):1939-1944 50. Gebhardt E, Fromm E, Roy U (1966) Solubility of carbon in molybdenum, tungsten and rhenium. Z Metallkd 57(10):732-736 51. Hultgren R, Desai PD, Hawkins DT, Gleiser M, Kelley KK (1973) Selected values of the thermodynamic properties of binary alloys. National Standard Reference Data System, The American Society for Metals, Metals Park, Ohio 52. Nagakura S, Oketani S (1968) Structure of transition metal carbides. Trans Iron Steel Inst Jpn 8(5):265-294 53. Holleck H (1984) Binäre und ternäre Carbid- und Nitridsysteme der Übergangsmetalle (Binary and ternary carbide and nitride systems of the transition metals). Gebrüder Bornträeger, Berlin, Stuttgart (in German) 54. Goldschmidt HJ, Brand JA (1963) The tungsten-rich region of the system tungsten-carbon. J Less-Common Met 5(2):181-194 55. Gleiser M, Chipman J (1962) Free energy of formation of tungsten carbide WC. Trans Metall Soc AIME 224(6):1278-1279 56. Coltters RG, Belton GR (1983) High-temperature thermodynamic properties of the tungsten carbide WC determined using a galvanic cell technique. Metall Trans A 14(9):1915-1919 57. Gustafson P (1986) Thermodynamic evaluation of C-W system. Mater Sci Technol 2(7):653658 58. Rudy E, Windisch S (1967) Evidence for zeta Fe2N-type sublattice order in W2C at intermediate temperatures. J Am Ceram Soc 50(5):272-273 59. Filimonenko VN, Pivovarov LKh (1968) Tungsten carbide with an fcc lattice. Met Sci Heat Treat 10(9):732 60. Epicier T (1990) Crystal chemistry of transition metal hemicarbides. In: Freer R (ed) The physics and chemistry of carbides, nitrides and borides, pp. 215-248. Kluwer Academic, Dordrecht 61. Uhrenius B (1984) Calculation of the Ti-C, W-C and Ti-W-C phase diagrams. Calphad 8(2):101-119 62. Uhrenius B (1991) Contribution to the knowledge of phase equilibria in tungsten-carbon based systems. In: Proc. Mats Hillert symp. in materials science on formation of microstructures, Stockholm, Sweden, 22-23 Oct 1990. Scand J Metall 20(1):93-98 63. Uhrenius B (1992) Phase diagrams as a tool for production and development of cemented carbides and steels. Powder Metall 35(3):203-210 64. Yao Z, Stiglich JJ, Sudarshan TS (1998) WC-Co enjoys proud history and bright future. Met Powder Rep 53(2):32-36 65. Demetriou MD, Ghoniem NM, Lavine AS (2002) Kinetic modeling of phase selection during non-equilibrium solidification of a tungsten-carbon system. Acta Mater 50:1421-1432 66. Demetriou MD, Ghoniem NM, Lavine AS (2002) Modeling of graphitization kinetics during peritectic melting of tungsten carbide. Acta Mater 50:4995-5004

584

2 Tungsten Carbides

67. Kublii VZ, Velikanova TYa (2004) Ordering in the carbide W2C and phase equilibria in the tungsten-carbon system in the region of its existence. Powder Metall Met Ceram 43(1112):630-644 68. Kurlov AS, Gusev AI (2006) Phase equilibria in the W-C system and tungsten carbides. Russ Chem Rev 75(7):617-636 69. Kurlov AS, Gusev AI (2006) Tungsten carbides and W-C phase diagram. Inorg Mater 42(2):121-127 70. Liu AY, Wentzcovitch RM, Cohen ML (1988) Structural and electronic properties of WC. Phys Rev B 38(14):9483-9489 71. Yamada Y, Wang Y, Sasajima N (2006) Metal carbide – carbon peritectic systems as hightemperature fixed points in thermometry. Metrologia 43:L23-L27 72. Sasajima N, Yamada Y (2007) Investigation of WC-C peritectic high-temperature fixed point. In: Proc. SICE annual conf. (SICE 2007), Takamatsu, Japan, 17-20 Sep 2007, pp. 1382-1385. The Society of Instrument and Control Engineers, Tokyo, Japan 73. Sasajima N, Yamada Y (2008) Investigation of TiC-C eutectic and WC-C peritectic hightemperature fixed points. Int J Thermophys 29:944-957 74. Khlevnoy BB, Grigoryeva IA, Otryaskin DA (2012) Development and investigation of WCC fixed-points cells. Metrologia 49:S59-S67 75. Wang T, Sasajima N, Yamada Y, Bai C, Yuan Z, Dong W-W, Ara C, Lu X (2013) Realization of the WC-C peritectic fixed point at NIM and NMIJ. In: Meyer CW (ed) Proc. 9th Int. temperature symp. “Temperature: its measurement and control in science and industry” (ITS 2012), Vol. 8, Los Angeles, California, 19-23 Mar 2012. AIP Conf Proc 1552:791-796 76. Khlevnoy BB, Grigoryeva IA (2015) Long-term stability of WC-C peritectic fixed point. Int J Thermophys 36:367-373 77. Grigoryeva IA, Khlevnoy BB, Solodilov MV (2017) Reproducibility of WC-C hightemperature fixed point. Int J Thermophys 38:69 (8 pp.) 78. Khlevnoy B, Grigoryeva I, Anhalt K, Waehmer M, Ivashin E, Otryaskin D, Solodilov M, Sapritsky V (2018) Development of large-area high-temperature fixed-point blackbodies for photometry and radiometry. Metrologia 55:S43-S51 79. Sasajima N, Lu X, Khlevnoy B, Grigoryeva I, Yoo YS, Otryaskin D, Markin S, Wang T, Yamada Y (2019) Performance of WC-C peritectic and Ru-C eutectic fixed points. Metrologia 56:055010 (11 pp.) 80. Rudy E, Hoffman JR (1967) Phasengleichgewichte im Bereich der kubischen Karbidphase im System Wolfram – Kohlenstoff (Phase equilibria in the area of the cubic carbide phase in the tungsten – carbon system). Planseeber Pulvermetall 15(3):174-178 (in German) 81. Suetin DV, Shein IR, Ivanovskii AL (2008) Elastic and electronic properties of hexagonal and cubic polymorphs of tungsten monocarbide WC and mononitride WN from first principles calculations. Phys Stat Sol B 245(8):1590-1597 82. Suetin DV, Shein IR, Ivanovskii AL (2009) Structural, electronic properties and stability of tungsten mono- and semi-carbides: a first principles investigation. J Phys Chem Solids 70:6471 83. Suetin DV, Shein IR, Ivanovskii AL (2010) Tungsten carbides and nitrides and ternary systems based on them: the electronic structure, chemical bonding and properties. Russ Chem Rev 79(7):611-634 84. Andrievskii RA, Lanin AG, Rymashevskii GA (1974) Prochnost tugoplavkikh soedinenii (Strength of refractory compounds). Metallurgiya, Moscow (in Russian) 85. Andrievskii RA, Spivak II (1989) Prochnost tugoplavkikh soedinenii i materialov na ikh osnove (Strength of refractory compounds and materials based on them). Metallurgiya, Chelyabinsk (in Russian) 86. Velikanova TYa, Eremenko VN, Bondar AA, Artyukh LV, Kublii VZ (1981) Effect of alloying on the structure and properties of cast WC1–x materials. Powder Metall Met Ceram 20(2):121-125

References

585

87. Tretyakov VI (1976) Osnovy metallovedeniya i tekhnologii proizvodstva spechennykh tverdykh splavov (Fundamentals of metal science and production technology of sintered hard alloys). Metallurgiya, Moscow (in Russian) 88. Amulele GM, Manghnani MH, Marriappan S, Hong X, Li F, Qin X, Liermann HP (2008) Compression behaviour of WC and WC – 6% Co up to 50 GPa determined by synchrotron Xray diffraction and ultrasonic techniques. J Appl Phys 103(11):113522 (6 pp.) 89. Cheng XY, Zhou JH, Xiong X, Du Y, Jiang C (2012) First principles thermal equation of state of tungsten carbide. Comput Mater Sci 59:41-47 90. Chen PH, Nordlund K (2013) Modified embedded-atom method used to derive interatomic potentials for defects and phase formation in the W-C system. Phys Rev B 88(21):214101 (9 pp.) 91. Juslin N, Erhart P, Träskelin P, Nord J, Henriksson KOE, Nordlund K, Salonen E, Albe K (2005) Analytical interatomic potential for modeling nonequilibrium processes in the W-C-H system. J Appl Phys 98(12):123520 (12 pp.) 92. Mishra V, Chaturvedi S (2013) FP-LAPW calculations of equation of state and elastic properties of α and β phases of tungsten carbide at high pressure. J Phys Chem Solids 74(3):509-517 93. Telepa VT, Alymov MI, Shcherbakov VA, Shcherbakov AV, Kovalev ID (2019) Observation of phase transition in the W-C system during electrothermal explosion under pressure. Int J Self-Propag High-Temp Synth 28(3):204-206 94. Bhat DG, Holzl RA (1982) Microstructural evaluation of CM 500L, a new W-C alloy coating deposited by the controlled nucleation thermochemical deposition process. Thin Solid Films 95:105-112 95. Srivastava PK, Rao TV, Vankar VD, Chopra KL (1984) Synthesis of tungsten carbide films by r.f. magnetron sputtering. J Vac Sci Technol A 2(3):1261-1265 96. Srivastava PK, Vankar VD, Chopra KL (1985) High rate reactive magnetron sputtered tungsten carbide films. J Vac Sci Technol A 3(6):2129-2134 97. Li T, Lou Q, Dong J, Wei Y, Liu J (2001) Escape of carbon element in surface ablation of cobalt cemented tungsten carbide with pulsed UV laser. Appl Surf Sci 172:51-60 98. Zhang F (2019) Tungsten carbide phase transformation under non-equilibrium solidification of high-intensity pulsed ion and electron beams. Vacuum 159:254-260 99. Srivastava PK, Vankar VD, Chopra KL (1986) R.F. magnetron sputtered tungsten carbide thin films. Bull Mater Sci 8(3):379-384 100. Srivastava PK, Vankar VD, Chopra KL (1988) Mechanical properties of r.f. magnetron sputtered W-C films on stainless steel. Thin Solid Films 161:107-116 101. Archer NJ, Yee KK (1978) Chemical vapour deposited tungsten carbide wear-resistant coatings formed at low temperatures. Wear 48:237-250 102. Demyashev GM, Krasovskii AI, Kuzmin VP, Malandin MB, Chuzhko RK (1985) Electron microscopic study of the structure of W8C phase. Inorg Mater 21(7):1007-1012 103. Gall NR, Rutkov EV, Tontegode AYa (1998) Obrazovanie i svoistva poverkhnostnykh karbidov na W (100) (Formation and properties of surface carbide on W (100)). Izv AN SSSR Fiz 62(10):1980-1983 (in Russian) 104. Gall NR (2001) Surface carbides in the sequence of phase equilibria in a binary (tungstencarbon) system. Tech Phys Lett 27(7):589-591 105. Gall NR, Rutkov EV, Tontegode AYa (2003) Poverkhnostnye soedineniya i reaktsii nemetallov s tugoplavkimi metallami (The surface compounds and reactions of non-metals with refractory metals). Zh Ros Khim Obshchestva Im D I Mendeleev 47(2):13-22 (in Russian) 106. Andrievskii RA, Kogan VB, Dyakov VK (1979) Effect of carbidizing temperature on some properties of tungsten carbides. Powder Metall Met Ceram 18(10):752-755 107. Hibbs MK, Sinclair R (1981) Room-temperature deformation mechanisms and the defect structure of tungsten carbide. Acta Metall 29:1645-1654

586

2 Tungsten Carbides

108. Ramnath V, Jayaraman N (1987) Quantitative phase analysis by X-ray diffraction in the CoW-C system. J Mater Sci Lett 6:1414-1418 109. Tanaka T, Otani S, Ishizawa Y (1988) Floating-zone crystal growth of WC. J Mater Sci 23:665-669 110. Ribeiro FH, Betta RAD, Guskey GJ, Boudart M (1991) Preparation and surface composition of tungsten carbide powders with high specific surface area. Chem Mater 3(5):805-812 111. Telle R (1994) Boride and carbide ceramics. In: Swain MV (ed) Materials science and technology. Vol. 11 – Structure and properties of ceramics, pp. 173-266. Wiley-VCH, Weinheim 112. Cottrell AH (1995) Cohesion in tungsten carbide. Mater Sci Technol 11(3):209-212 113. Mari D, Krawitz AD, Richardson JW, Benoit W (1996) Residual stress in WC-Co measured by neutron diffraction. Mater Sci Eng A 209:197-205 114. Mauer FA, Bolz LH (1955) Measurement of thermal expansion of cermet components of high-temperature X-ray diffraction. Technical Report WADC-TR-55-473, Contracts USAF 33(616)56-5 and USAF 33(616)53-12, pp. 1-57. National Bureau of Standards, US Government Printing Office, Washington, DC 115. Reeber RR, Wang K (1999) Thermophysical properties of α-tungsten carbide. J Am Ceram Soc 82(1):129-135 116. Belikov AM, Umanskii YaS (1960) Studies of the anisotropic thermal vibrations of the atoms in several hexagonal carbides and diborides of transition group metals. Sov Phys Crystallogr 4(6):643-645 117. Rempel AA, Würschum R, Schaefer H-E (2000) Atomic defects in hexagonal tungsten carbide studied by positron annihilation. Phys Rev B 61(9):5945-5948 118. Samsonov GV, Umanskii YaS (1957) Tverdye soedineniya tugoplavkihkh metallov (Hard compounds of refractory metals). Metallurgizdat, Moscow (in Russian) 119. Viñes F, Sousa C, Liu P, Rodriguez JA, Illas F (2005) A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides. J Chem Phys 122:174709 (11 pp.) 120. Kalin BA (ed), Platonov PA, Chernov II, Shtrombakh YaI (2008) Fizicheskoe materialovedenie (Physical materials science). Vol. 6, Part 1 – Konstruktsionnye materially yadernoi tekhniki (Structural materials of nuclear engineering). National Research Nuclear University MEPhI, Moscow (in Russian) 121. Gusev AI, Kurlov AS (2008) Production of nanocrystalline powders by high-energy ball milling: model and experiment. Nanotechnol 19:265302 (8 pp.) 122. Ma J, Du Y (2008) Synthesis of nanocrystalline hexagonal tungsten carbide via coreduction of tungsten hexachloride and sodium carbonate with metallic magnesium. J Alloys Compd 448:215-218 123. Li Y, Gao Y, Xiao B, Min T, Fan Z, Ma S, Yi D (2011) Theoretical study on the electronic properties and stabilities of low-index surfaces of WC polymorphs. Comput Mater Sci 50:939-948 124. Reddy KM, Rao TN, Joardar J (2011) Stability of nanostructured W-C phases during carburization of WO3. Mater Chem Phys 128:121-126 125. Dash T, Nayak BB (2013) Preparation of WC-W2C composites by arc plasma melting and their characterizations. Ceram Int 39:3279-3292 126. Brown HL, Armstrong PE, Kempter CP (1966) Elastic properties of some polycrystalline transition metal monocarbides. J Chem Phys 45(2):547-549 127. Lin Z, Wang L, Zhang J, Mao H-K, Zhao Y (2009) Nanocrystalline tungsten carbide: as incompressible as diamond. Appl Phys Lett 95(21):211906 (3 pp.) 128. Massalski TB, Subramanian PR, Okamoto H, Kacprzak L, eds (1990) Binary alloy phase diagrams, 2nd ed. ASM International, Metals Park, Ohio 129. Bolokang S, Banganayi C, Phasha M (2010) Effect of C and milling parameters on synthesis of WC powders by mechanical alloying. Int J Refract Met Hard Mater 28:211-216

References

587

130. Christensen M, Dudiy S, Wahnström G (2002) First principles simulations of metal-ceramic interface adhesion: Co/WC versus Co/TiC. Phys Rev B 65(4):045408 (9 pp.) 131. Bilyk N, Yatsenko I, Poberezhska I, Stepanov V (2014) Persha znahidka kusongitu v eksplozyvnyh utvorennyah Ukrainy (The first occurrence of Qusongite in explosive formations of Ukraine). Mineral Rev 64(1):103-110 (in Ukrainian) 132. Kong X-S, You Y-W, Xia JH, Liu CS, Fang QF, Luo G-N, Huang Q-Y (2010) First principles study of intrinsic defects in hexagonal tungsten carbide. J Nucl Mater 406:323-329 133. Liu L, Bi Y, Xu J, Chen X (2013) Ab initio study of the structural, elastic and thermodynamic properties of tungsten monocarbide at high pressure and high temperature. Phys B 413:109-115 134. Pasquazzi A, Schubert WD, Halwax E, Kremser G (2013) Incorporation of titanium, tantalum and vanadium into the hexagonal WC lattice. In: Sigl L, Kestler H, Wagner J (eds) Proc. 18th Int. Plansee seminar, Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 3-7 June 2013, Vol. 2 – P/M hard materials, pp. HM108/1-HM108/7. Plansee Metal AG, Reutte, Austria 135. Li X, Zhang X, Qin J, Zhang S, Ning J, Jing R, Ma M, Liu R (2014) First principles calculations of structural stability of tungsten carbide under high pressure. J Phys Chem Solids 75:1234-1239 136. Trosnikova IYu, Loboda PI, Bilyi OI (2014) Effect of molybdenum additions on the microstructure and properties of WC-W2C alloys. Powder Metall Met Ceram 53(3-4):219224 137. Chen W-T, Meredith CH, Dickey EC (2015) Growth and microstructure-dependent hardness of directionally solidified WC- W2C eutectoid ceramics. J Am Ceram Soc 98(7):2191-2196 138. Lucović J, Babić B, Bučevac D, Prekajski M, Pantić J, Baščarević Z, Matović B (2015) Synthesis and characterization of tungsten carbide fine powders. Ceram Int 41:1271-1277 139. Guo J, Liu L, Liu S, Zhou Y, Qi X, Ren X, Yang Q (2016) Stability of eutectic carbide in Fe-Cr-Mo-W-V-C alloy by first principles calculation. Mater Design 106:355-362 140. Kim H-C, Kim D-K, Ko I-Y, Shon I-J (2007) Sintering behaviour and mechanical properties of binderless WC-TiC produced by pulsed current activated sintering. J Ceram Process Res 8(2):91-97 141. Connétable D (2016) First principles study of transition metal carbides. Mater Res Express 3:126502 (13 pp.) 142. Pitschke W, Hermann H, Mattern N (1993) The influence of surface roughness on diffracted X-ray intensities in Bragg-Brentano geometry and its effect on the structure determination by means of Rietveld analysis. Powder Diffract 8(2):74-83 143. Willens RH, Buehler E (1965) The superconductivity of the monocarbides of tungsten and molybdenum. Appl Phys Lett 7(1):25-26 144. Willens RH, Buehler E, Matthias BT (1967) Superconductivity of the transition metal carbides. Phys Rev 159(2):327-330 145. Krainer E, Robitsch J (1967) Röntgenographischer Nachweis des kubischen Wolframkarbides in funkenerosiv bearbeiteten Hartmetallen und in reinen Wolframschmelzkarbiden (X-ray investigation of cubic tungsten carbide in spark-machined hard metals and pure fused tungsten carbides). Planseeber Pulvermetall 15(1):46-56 (in German) 146. Krainer E, Robitsch J (1967) Zur Frage des kubischen Wolframkarbides (On the problem of cubic tungsten carbide). Planseeber Pulvermetall 15(3):179-180 (in German) 147. Ronsheim P, Toth LE, Mazza A, Pfender E, Mitrofanov B (1981) Direct current arc-plasma synthesis of tungsten carbides. J Mater Sci 16(10):2665-2674 148. Gromilov SA, Kinelovskii SA (2003) X-ray investigation of tungsten carbides synthesized by cumulative explosion. J Struct Chem 44(3):434-440 149. Orton GW (1964) Phase transitions in the system tungsten-carbon. Trans Metall Soc AIME 230:600-602

588

2 Tungsten Carbides

150. Kieffer R, Kölbl F (1949) Tungsten carbide – free hard metals. Powder Metall Bull 4(1):417 151. Samsonov GV, Vinitskii IM (1980) Handbook on refractory compounds. IFI/Plenum, New York 152. Savitskii EM, Povarova KB, Makarov PB (1978) Metallovedenie volframa (Metal science of tungsten). Nauka, Moscow (in Russian) 153. Kong PC, Suzuki M, Young R, Pfender E (1983) Synthesis of β-WC1–x in an atmosphericpressure thermal jet reactor. Plasma Chem Plasma Process 3(1):115-133 154. Volpe L, Boudart M (1985) Compounds of molybdenum and tungsten with high specific surface area. II. Carbides. J Solid State Chem 59:348-356 155. McHale AE, ed (1994) Phase equilibria diagrams. Phase diagrams for ceramists. Vol. 10. The American Ceramic Society, Westerville, Ohio 156. Lyakishev NP, ed (1996) Diagrammy sostoyaniya dvoinykh metallicheskikh sistem (Phase diagrams of binary metal systems), Vol. 1. Mashinostroenie, Moscow (in Russian) 157. Fuchs K, Rödhammer P, Bertel E, Netzer FP, Gornik E (1987) Reactive and non-reactive high rate sputter deposition of tungsten carbide. Thin Solid Films 151(3):383-395 158. Cavaleiro A, Vieira MT, Lemperière G (1991) Structure and chemical composition of W-C(Co) sputtered films. Thin Solids Films 197(1-2):237-255 159. Singh M, Wiedemeier H (1997) Estimation of thermal expansion behaviour of some refractory carbides and nitrides. J Mater Sci 32(21):5749-5751 160. Babad-Zakhryapin AA, Lysenko LT, Gert LM (1966) Poluchenie i rentgenograficheskoe izuchenie faz s kubicheskoi reshetkoi v sistemakh volfram-uglerod i molibden-uglerod (Preparation and X-ray study of the phases with cubic lattice in the tungsten-carbon and molybdenum-carbon systems. Fiz Met Metalloved 21(5):782-785 (in Russian) 161. Babad-Zakhryapin AA, Gert LM, Valyavko LR (1968) Possibility of forming tungsten oxycarbide with a fcc lattice. Inorg Mater 4(8):1200-1201 162. Grossman JC, Mizel A, Côte M, Cohen ML, Louie SG (1999) Transition metals and their carbides and nitrides: trends in electronic and structural properties. Phys Rev B 60(9):63436347 163. Isaev EI, Simak SI, Abrikosov IA, Ahuja R, Vekilov YuKh, Katsnelson MI, Lichtenstein AI, Johansson B (2007) Phonon related properties of transition metals, their carbides and nitrides: a first principles study. J Appl Phys 101:123519 (18 pp) 164. Nartowski AM, Parkin IP, MacKenzie M, Craven AJ, MacLeod I (1999) Solid state metathesis routes to transition metal carbides. J Mater Chem 9(6):1275-1281 165. Vojvodic A, Ruberto C (2010) Trends in bulk electron-structural features of rock salt early transition-metal carbides. J Phys Condens Matter 22(37):375501 (10 pp) 166. Gao Y, Song X, Liu X, Wei C, Wang H, Guo G (2013) On the formation of WC1–x in nanocrystalline cemented carbides. Scripta Mater 68:108-110 167. Sivkov AA, Pak AYa, Rakhmatullin IA, Shatrova KN (2014) Production of ultra-fine tungsten carbide in a discharge plasma jet. Nanotechnol Russ 9(11-12):682-687 168. Pak A, Sivkov A, Shanenkov I, Rakhmatullin I, Shatrova K (2015) Synthesis of ultra-fine cubic tungsten carbide in a discharge plasma jet. Int J Refract Met Hard Mater 48:51-55 169. Shatrova KN, Sivkov AA, Shanenkov II, Saigash AS (2017) Effect of precursor mass on product phase composition in plasma dynamic synthesis of tungsten carbide. In: Proc. 5th Int. congress on energy fluxes and radiation effects (EFRE 2016), Tomsk, Russian Federation, 02-07 Oct 2016. J Phys Conf Series 830:012119 (5 pp.) 170. Kolel-Veetil MK, Goswami R, Fears KP, Qadri SB, Lambrakos SG. Laskoski M, Keller TM, Saab AP (2015) Formation and stability of metastable tungsten carbide nanoparticles. J Mater Eng Perform 24:2060-2066 171. Córdoba R, Ibarra A, Mailly D, De Teresa JM (2018) Vertical growth of superconducting crystalline hollow nanowires by He+ focused ion beam induced deposition. Nano Lett 18:1379-1386

References

589

172. Tanaka S, Bataev I, Oda H, Hokamoto K (2018) Synthesis of metastable cubic tungsten carbides by electrical explosion of tungsten wire in liquid paraffin. Adv Powder Technol 29:2447-2455 173. Liu AY, Cohen ML (1988) Theoretical study of the stability of cubic WC. Solid State Commun 67(10):907-910 174. Koverga AA, Flórez E, Dorkis L, Rodriguez JA (2019) CO, CO2 and H2 interactions with (0001) and (001) tungsten carbides surfaces: importance of carbon and metal sites. J Phys Chem C 123:8871-8883 175. Kremlev KV, Obedkov AM, Semenov NM, Kaverin BS, Ketkov SYu, Vilkov IV, Andreev PV, Gusev SA, Aborkin AV (2019) Synthesis of hybrid materials based on multi-walled carbon nanotubes decorated with WC1–x nanocoatings of various morphologies. Tech Phys Lett 45(4):348-351 176. Sivkov A, Shanenkov I, Ivashutenko A, Nikitin D, Shanenkova Yu, Rakhmatullin I (2019) Deposition of cubic tungsten carbide coating on metal substrates at sputtering of electric discharge plasma. In: Proc. 14th Int. conf. “Gas discharge plasmas and their applications” (GDP 2019), Tomsk, Russian Federation, 15-21 Sep 2019. J Phys Conf Series 1393:012133 (7 pp.) 177. Shanenkov I, Nikitin D, Ivashutenko A, Rakhmatullin I, Shanenkova Yu, Nassyrbayev A, Han W, Sivkov A (2020) Hardening the surface of metals with WC1–x coatings deposited by high-speed plasma spraying. Surf Coat Technol 389:125639 (8 pp.) 178. Lander JJ, Germer LH (1948) Plating molybdenum, tungsten and chromium by thermal decomposition of their carbonyls. Trans Metall Soc AIME 175:648-692 179. Lautz G, Schneider D (1961) Über die Supraleitung in den Wolframkarbiden W2C und WC (On the superconductivity in the tungsten carbides W2C and WC). Z Naturforsch A 16(12):1368-1372 (in German) 180. Yvon K, Nowotny H, Benesovsky F (1968) Zur Kristallstruktur von W2C (The crystal structure of W2C). Monatsh Chem 99(2):726-729 (in German) 181. Hårsta A, Rundqvist S, Thomas JO (1978) A neutron powder diffraction study of W2C. Acta Chem Scand A 32(9):891-892 182. Lönnberg B, Lundström T, Tellgren R (1986) A neutron powder diffraction study of Ta2C and W2C. J Less-Common Met 120(2):239-245 183. Epicier T, Dubous J, Esnouf C, Fantozzi G (1983) Identification de la phase β-W2C, type ε-Fe2N dans l’hémicarbure de tungstène (Identification of the β-W2C, type ε-Fe2N in tungsten hemicarbide). C R Hebd Séanc Acad Sci II 297(3):215-218 (in French) 184. Dubous J, Epicier T, Esnouf C, Fantozzi G (1988) Neutron powder diffraction studies of transition metal hemicarbides M2C1–x – I. Motivation for a study on W2C and Mo2C and experimental background for an in situ investigation at elevated temperature. Acta Metall 36(8):1891-1901 185. Epicier T, Dubous J, Esnouf C, Fantozzi G (1988) Neutron powder diffraction studies of transition metal hemicarbides M2C1–x – II. In situ high-temperature study on W2C1–x and Mo2C1–x. Acta Metall 36(8):1903-1921 186. Telegus VS, Gladyshevskii EI, Kripyakevich PI (1968) Orthorhombic modifications of the compounds W2C and Mo2C. Sov Phys Crystallogr 12(5):813-815 187. Lönnberg B (1986) Thermal expansion studies on the subcarbides of group V and VI transition metals. J Less-Common Met 120(1):135-146 188. Giorgi AL (1985) Superconductivity in the W-Tc and W2C-Tc systems. Phys B+C 135(13):420-422 189. Kuzma YuB, Lakh VI, Markiv VYa, Stadnyk BI, Gladyshevskii EI (1963) X-ray diffraction study of the system tungsten-rhenium-carbon. Powder Metall Met Ceram 2(4):286-292 190. Butorina LN, Pinsker ZG (1960-61) An electron diffraction study of W2C. Sov Phys Crystallogr 5(4):560-563 191. Swalin RA (1957) Orientation relationships involved in the formation of α-W2C on tungsten. Acta Crystallogr 10(7):473-474

590

2 Tungsten Carbides

192. Valvoda V (1984) X-ray Debye temperatures of HfC and α-W2C. Phys Stat Sol A 83(2):K123-K125 193. Stecher P, Benesovsky F, Nowotny H (1964) Untersuchungen im System Chrom – Wolfram – Kohlenstoff (Investigations in the chromium – tungsten – carbon system). Planseeber Pulvermetall 12(2):89-95 (in German) 194. Kurlov AS, Gusev AI (2007) Neutron and X-ray diffraction study and symmetry analysis of phase transformations in lower tungsten carbide W2C. Phys Rev B 76(17):174115 (16 pp.) 195. Yang J, Gao F (2012) First principles calculations of mechanical properties of cubic 5d transition metal monocarbides. Phys B 407:3527-3534 196. Abderrahim FZ, Faraoun HI, Ouahrani T (2012) Structure, bonding and stability of semicarbides M2C and sub-carbides M4C (M = V, Cr, Nb, Mo, Ta, W): a first principles investigation. Phys B 407:3833-3838 197. Bokii GB (1954) Vvedenie v kristallokhimiyu (Introduction to crystal chemistry). Moscow State University Publishing House, Moscow (in Russian) 198. Evans RC (1948) Crystal chemistry. University Press, Cambridge, UK 199. Nowotny H, Parthé E, Kieffer R, Benesovsky F (1954) Untersuchungen im System Titan – Wolfram – Kohlenstoff (Investigations in the titanium – tungsten – carbon system). Z Metallkd 45(1):97-101 (in German) 200. Kosolapova TYa (1971) Carbides: properties, production and applications. Plenum Press, New York 201. Grønvold F, Stølen S, Westrum EF, Jr, Labban AK, Uhrenius B (1988) Heat capacity and thermodynamic properties of ditungsten carbide W2C1–x from 10 to 1000 K. Thermochim Acta 129:115-125 202. Dolloff RT, Sara RV (1961) Research study to determine the phase equilibrium relations of selected metal carbides at high temperatures. Technical Report WADD-TR-60-143, Contract USAF 33(616)-6286, Part 2, pp. 1-24. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 203. Lee JS (1989) The topotactic transformation of tungsten oxide to a cubic tungsten carbide. Korean J Chem Eng 6(3):196-199 204. Khizhun OYu, Zhurakovskii EA, Zaulichnyi YaV (1990) The electronic structure of W2Cx nonstoichiometric tungsten carbides. Powder Metall Met Ceram 29(9):732-737 205. Bowman AL, Arnold GP (1971) High-temperature neutron diffraction studies. In: Eyring L (ed) Advances in high-temperature chemistry, Vol. 4, pp. 243-264. Academic Press, New York, London 206. Morton N, James BW, Wostenholm GH, Pomfret DG, Davies MR, Dykins JL (1971) Superconductivity of molybdenum and tungsten carbides. J Less-Common Met 25(1):97-106 207. Morton N, James BW, Wostenholm GH, Hepburn DCB (1972) Superconductivity and the structure of W2C. J Less-Common Met 29(4):423-426 208. Kublii VZ, Velikanova TYa, Gnitetskii OA, Makhovitskaya SI (2000) Structural parameters of the low-temperature metastable form of the carbide W2C. Powder Metall Met Ceram 39(34):151-156 209. Telegus VS, Kuzma YuB, Markov MA (1971) Phase equilibria in the systems molybdenum-manganese-carbon and tungsten-manganese-carbon. Powder Metall Met Ceram 10(11):898-903 210. Nozik YuZ, Linik YuV, Kuvaldin BV (1968) Neitronograficheskoe issledovanie rombicheskoi modifikatsii W2C (Neutron diffraction study of W2C rhombic modification). Latv PSR Zinat Akad Vestis Fiz Techn Ser (6):30-33 (in Russian) 211. Kublii VZ, Velikanova TYa, Khaenko BV (2001) Single crystal X-ray study of the W2C carbide with structure of the ε-Fe2N type. Met Phys Adv Technol 19(9):1163-1168 212. Liang C, Tian F, Li Z, Feng Z, Wei Z, Li C (2003) Preparation and adsorption properties for thiophene of nanostructured W2C on ultra-high surface area carbon materials. Chem Mater 15:4846-4853

References

591

213. Khaenko BV, Velikanova TYa, Kublii VZ, Makhovitskaya SI (1993) Uporyadochenie tipa ε-Fe2N v karbide W2C (Ordering of the ε-Fe2N type in the carbide W2C). In: Skorokhod VV (ed) Diagrammy sostoyaniya, stabilnost faz i metastabilnye sostoyaniya v metallicheskikh sistemakh (Phase equilibria, stability of phases and metastable states in metallic systems), pp. 119-124. Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kyiv (in Russian) 214. Gusev AI, Kurlov AS (2007) Ordering of the lowest tungsten carbide W2C. JETP Lett 85(1):34-39 215. Kurlov AS, Gusev AI (2007) Atomic-vacancy ordering in the lowest tungsten carbide W2C. J Exp Theor Phys 105(4):710-721 216. Kurlov AS, Gusev AI (2007) Phase transitions in the lowest tungsten carbide W2C. Dokl Phys 52(12):656-662 217. Huang W, Selleby M (1997) Thermodynamic assessment of the Nb-W-C system. Z Metallkd 88(1):55-62 218. Huang W (1997) Thermodynamic properties of the Nb-W-C-N system. Z Metallkd 88(1):63-68 219. Suetin DV, Shein IR, Kurlov AS, Gusev AI, Ivanovskii AL (2008) Band structure and properties of polymorphic modifications of lower tungsten carbide W2C. Phys Solid State 50(8):1420-1426 220. Oliveira FAC, Fernandes JC, Badie J-M, Granier B, Rosa LG, Shohoji N (2007) High metastability of tungsten subcarbide W2C formed from tungsten/carbon powder mixture during eruptive heating in a solar furnace. Int J Refract Met Hard Mater 25:101-106 221. Oliveira FAC, Granier B, Badie J-M, Fernandes JC, Rosa LG, Shohoji N (2007) Synthesis of tungsten subcarbide W2C from graphite/tungsten powder mixtures by eruptive heating in a solar furnace. Int J Refract Met Hard Mater 25:351-357 222. Kurlov AS, Gusev AI (2009) Ordering of nonstoichiometric hexagonal compounds M2X: a sequence of special figures. Phys Solid State 51(10):2051-2057 223. Kurlov AS, Rempel SV, Gusev AI (2011) Symmetry analysis of ordered phases of the lower tungsten carbide W2C. Phys Solid State 53(1):175-181 224. Eckerlin P, Kandler H (1971) Structural data for elements and intermetallic phases. Springer, Berlin 225. Morris MC (1985) Standard X-ray diffraction powder patterns. Section 21. Data for 92 substances. JCPDS – International Centre for Diffraction Data, National Bureau of Standards, US Government Printing Office, Washington, DC 226. Becker K (1928) Die Kristallstruktur und der lineare Wärmeausdehnungskoeffizient der Wolframcarbide (The crystal structure and the linear expansion coefficient of tungsten carbide). Z Phys 51(7-8):481-489 (in German) 227. Becker K (1928) Die Konstitution der Wolframcarbide (The structure of tungsten carbide). Z Elektrochem 34(9):640-642 (in German) 228. Touloukian YS, Kirby RK, Taylor RE, Lee TYR (1977) Thermophysical properties of matter. Vol. 13 – Thermal expansion – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington, DC 229. Takahashi T, Freise EJ (1965) Determination of the slip systems in single crystals of tungsten monocarbide. Philos Mag 12(115):1-8 230. French DN, Thomas DA (1965) Hardness anisotropy and slip in WC crystals. Trans Metall Soc AIME 233(5):950-952 231. Pons L (1968) Plastic properties in tungsten monocarbide. In: Vahldiek FW, Mersol SA (eds) Anisotropy in single-crystal refractory compounds. Proc. Int. symp., Dayton, Ohio, 1315 June 1967, Vol. 2, pp. 393-444. Springer, New York 232. Luyckx SB (1970) Slip system of tungsten carbide crystals at room temperature. Acta Metall 18:233-236 233. Andrievskii RA, Rymashevskii GA, Sinelnikova VS (1972) Single crystals of refractory compounds – a review. I. Powder Metall Met Ceram 11(3):207-215

592

2 Tungsten Carbides

234. Andrievskii RA, Rymashevskii GA, Sinelnikova VS (1972) Single crystals of refractory compounds – a review. II. Powder Metall Met Ceram 11(10):796-809 235. Vahldiek FW, Mersol SA (1977) Slip and microhardness of IVa to VIa refractory materials. J Less-Common Met 55(2):265-278 236. Greenwood RM, Loretto MH, Smallman RE (1982) The defect structure of tungsten carbide in deformed tungsten carbide – cobalt composites. Acta Metall 30:1193-1196 237. Johannesson T, Lehtinen B (1971) The analysis of dislocation structures in tungsten carbide by electron microscopy. Philos Mag 24(191):1079-1085 238. Johannesson T, Lehtinen B (1973) Dislocation networks in tungsten carbide studied by the weak-beam technique. J Microsc 98(2):226-228 239. Johannesson T, Lehtinen B (1973) On the plasticity of tungsten carbide. Phys Stat Sol A 16(2):615-622 240. Jayaram V, Sinclair R, Rowcliffe DJ (1983) Intergranular cracking in WC – 6% Co: an application of the von Mises criterion. Acta Metall 31(3):373-378 241. Hibbs MK, Sinclair R, Rowcliffe DJ (1984) Defect interactions in deformed WC. Acta Metall 32(6):941-947 242. Rowcliffe DJ (1984) Plastic deformation of transition metal carbides. In: Tressler RE, Bradt RC (eds) Deformation of ceramic materials II. Proc. Int. symp. on plastic deformation of ceramic materials, University Park, Pennsylvania, 20-22 July 1983, pp. 49-71. Plenum Press, New York, London 243. Nabarro FRN, Luyckx SB, Waghmare UV (2008) Slip in tungsten monocarbide. I. Some experimental observations. Mater Sci Eng A 483-484:139-142 244. Nabarro FRN, Luyckx SB, Waghmare UV (2008) Slip in tungsten monocarbide. II. A first principles study. Mater Sci Eng A 483-484:9-12 245. French DN, Thomas DA (1968) Crystallographic polarity of WC. In: Vahldiek FW, Mersol SA (eds) Anisotropy in single-crystal refractory compounds. Proc. Int. symp., Dayton, Ohio, 13-15 June 1967, Vol. 1, pp. 55-66. Springer, New York 246. Lewis D, Porter LJ (1969) Plastic deformation in tungsten carbide. J Appl Crystallogr 2(6):249-252 247. Dubois J, Orange G, Mai C, Fantozzi G (1978) Comportement plastique à température ambiante de l’hémicarbure de tungsténe (Plastic behaviour of tungsten hemicarbide at room temperature). C R Hebd Séanc Acad Sci B 287(4):53-56 (in French) 248. Dubois J, Fantozzi G, Orange G, Esnouf C (1981) Plastic deformation of tungsten hemicarbide up to 2200 °C. In: Carlsson R, Karlsson S (eds) Science of ceramics. Proc. 11th Int. conf., Stenungsund, Sweden, 14-17 June 1981, Vol. 11, pp. 413-418. Swedish Ceramic Society, Göteborg, Sweden 249. Epicier T, Esnouf C, Dubous J, Fantozzi G (1981) Observations of dislocations in tungsten hemicarbide deformed at high temperatures. Scripta Metall 15:1279-1283 250. Epicier T, Dubous J, Esnouf C, Fantozzi G (1982) Mécanismes de déformation des carbures métalliques: exemple de l’hémicarbure de tungstène (Deformation mechanisms of metal carbides: an example of tungsten hemicarbide). Rev Int Hautes Temp Refract 19(4):345-357 (in French) 251. Dubois J, Epicier T, Esnouf C, Fantozzi G (1983) Mechanical behaviour and electron microscopy analysis of W2C. In: Viswanadham RK, Rowcliffe DJ, Gurland J (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Jackson Hole, Wyoming, 23-28 Aug 1981, pp. 201-218. Plenum Press, New York, London 252. Dubois J, Fantozzi G, Epicier T, Esnouf C (1984) Determination experimentale d’une loi de comportement dans le cas de la deformation plastique à hautes températures de l’hémicarbure de tungstène (Experimental determination of a behaviour law for the case of the hightemperature plastic deformation of tungsten semicarbide). In: Vincenzini P (ed) Science of ceramics. Proc. 12th Int. conf., Saint-Vincent, Italy, 27-30 June 1983, Vol. 12, pp. 551-556. Research Institute for Ceramics Technology, Faenza, Italy (in French)

References

593

253. Epicier T, Esnouf C, Dubous J, Fantozzi G (1984) Dislocation structures in polycrystalline tungsten hemicarbide W2C deformed at high temperatures. In: Tressler RE, Bradt RC (eds) Deformation of ceramic materials II. Proc. Int. symp. on plastic deformation of ceramic materials, University Park, Pennsylvania, 20-22 July 1983, pp. 73-86. Plenum Press, New York, London 254. Epicier T, Esnouf C (1984) Observations de l’hémicarbure de tungstène W2C par microscopie électronique en transmission (Observations of tungsten carbide W2C by transmission electron microscopy). J Microsc Spectrosc Electron 9(1):17-28 (in French) 255. Dubois J, Fantozzi G, Epicier T, Esnouf C (1986) Deformation mechanisms of polycrystalline tungsten hemicarbide W2C. In: Almond EA, Brookes CA, Warren R (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Rhodes, Greece, 2328 Sep 1984. IOP Conf Series (75):265-278 256. Epicier T (1988) Contribution à l’étude des phénomènes d’ordre et des mécanismes de plasticité dans les carbures métalliques (Contribution to the study of ordering phenomena and plasticity mechanisms in metallic carbides). PhD thesis, Institut National des Sciences Appliquées de Lyon, France (in French) 257. Epicier T, Esnouf C (1988) High-resolution electron microscopy in transition metal carbides. II. Study of the hexagonal hemicarbide W2C. In: Dickinson HG, Goodhew PJ (eds) Proc. 9th European congress on electron microscopy (EUREM 88), York, England, 4-9 Sep 1988. IOP Conf Series 2(93):323-324 258. Epicier T, Dubous J, Esnouf C, Fantozzi G, Convert P (1984) High-temperature powder neutron diffraction studies of structural transformations in transition metal hemicarbides M2C1–x. II. Compounds of the VIth group (Mo2C1–x and W2C1–x). Phys B 156-157(C):44-46 259. Kameyama T, Tsunoda T, Motoe A, Uematsu T, Fukuda K (1991) The preparation of ultrafine WC1–x powder in a r.f. thermal plasma and its properties. J Jpn Soc Powder Powder Metall 38(2):109-113 (in Japanese) 260. Andrievskii RA (1993) Properties of nanocrystalline refractory compounds (review). Powder Metall Met Ceram 32(11-12):935-941 261. Andrievskii RA (1994) Review. Nanocrystalline high-melting point compound based materials. J Mater Sci 29:614-631 262. Andrievskii RA (2005) Nanomaterials based on high-melting carbides, nitrides and borides. Russ Chem Rev 74(12):1061-1072 263. Andrievskii RA (2012) Osnovy nanostrukturnogo materialovedeniya (Fundamentals of nanostructural materials science). BINOM, Moscow (in Russian) 264. Ishizaki K, Egashira T, Tanaka K, Celis PB (1989) Direct production of ultra-fine nitrides (Si3N4 and AlN) and carbides (SiC, WC and TiC) powders by the arc-plasma method. J Mater Sci 24:3553-3559 265. Gao L, Kear BH (1996) Synthesis of nanophase W and WC powders from ammonium metatungstate. In: Bose A, Dowding RJ (eds) Tungsten and refractory metals – 3. Proc. 3rd Int. conf. on tungsten and refractory metals, McLean, Virginia, 15-16 Nov 1995, pp. 247-256. Metal Powder Industries Federation, Princeton, New Jersey 266. Kear BH, Gao L, Seegopaul P (1997) Synthesis of nanophase WC powder by displacement reaction. Particul Sci Technol 15(2):173 267. Saito Y, Matsumoto T, Nishikubo K (1997) Encapsulation of carbides of chromium, molybdenum and tungsten in carbon nanocapsules by arc discharge. J Cryst Growth 172:163170 268. Goren-Muginstein GR, Berger S, Rosen A (1998) Sintering study of nanocrystalline tungsten carbide powders. Nanostruct Mater 10(5):795-804 269. Gusev AI (1998) The effects of the nanocrystalline state in solids. Phys Usp 41(1):49-76 270. Li ZQ, Zhang HF, Zhang XB, Wang YQ, Wu XJ (1998) Nanocrystalline tungsten carbide encapsulated in carbon shells. Nanostruct Mater 10(2):179-184 271. Tan G-L, Wu X-J (1998) Mechano-chemical synthesis of nanocrystalline tungsten carbide powders. Powder Metall 41(4):300-302

594

2 Tungsten Carbides

272. Nichols WT, Malyavanatham G, Beam MP, Henneke DE, Brock JR, Becker MF, Keto JW (2000) Synthesis of nanostructured WC films by supersonic impaction of nanoparticle aerosols. In: Komarneni S, Parker JC, Hahn H (eds) Nanophase and nanocomposite materials III. Proc. MRS Fall meeting symp. F, Boston, Massachusetts, 29 Nov – 3 Dec 1999. Mater Res Soc Symp Proc 581:193-198 273. Tan G-L, Wu X-J, Zhao M-H, Zhang H-F (2000) Synthesis of nanocrystalline cubic substoichiometric WC1–z powders by mechano-chemical technology. J Mater Sci 35:31513154 274. Yang X-G, Zhang X-B, Tan G-L, Zhang W-K, Lei Y-Q, Wang Q-D, Wu X-J (2000) Electrochemical investigation on hydride electrode with tungsten carbide additive. Trans Nonferr Met Soc China 10(1):60-63 275. Narayan J (2002) Novel nanocrystalline composites. In: Proc. ASME Int. mechanical engineering congress and exposition (IMECE 2002), New Orleans, Louisiana, 17-22 Nov 2002, pp. 297-301. The American Society of Mechanical Engineers, New York 276. Kim BK, Ha GH, Ka MD (2003) Synthesis of nanostructured WC powders by vapour phase reaction. In: Ahn JH, Hahn YD (eds) Proc. 9th Int. symp. on metastable, mechanically alloyed and nanocrystalline materials (ISMANAM-2002), Seoul, South Korea, 8-12 Sep 2002. J Metastable Nanocryst Mater 15-16:295-300 277. Liang C, Tian F, Wei Z, Xin Q, Li C (2003) The synthesis of nanostructured W2C on ultrahigh surface area carbon materials via carbothermal hydrogen reduction. Nanotechnol 14(9):955-958 278. Borovinskaya IP, Ignateva TI, Vershinnikov VI, Sachkova NV (2004) Preparation of tungsten carbide nanopowders by self-propagating high-temperature synthesis. Inorg Mater 40(10):1043-1048 279. Kim JC, Kim BK (2004) Synthesis of nanosized tungsten carbide powder by the chemical vapour condensation process. Scripta Mater 50:969-972 280. Li J, Wu X, Tan H, Liu J (2004) The preparation and thermal stability study of nanocrystalline tungsten carbide powder. Rare Met Mater Eng 33(7):736-739 (in Chinese) 281. Kurlov AS, Nazarova SZ, Gusev AI (2005) Magnetic susceptibility and thermal stability of nanocrystalline tungsten carbide. Dokl Phys Chem 405(1):229-234 282. Kwon YS, Andreev VM, Lomovsky OI, Bokhonov BB (2005) Synthesis of tungsten carbide nanoparticles encapsulated with graphite shell. J Alloys Compd 386:115-118 283. Maheshwari P, Wang X, Fang ZZ, Sohn HY (2005) Effect of particle size on sintering of WC-Co powders. In: Proc. conf. on materials science and technology, Pittsburgh, Pennsylvania, 25-28 Sep 2005. Mater Sci Technol 4:71-78 284. Tan GL, Wu XJ, Li ZQ (2005) Carburization of WC – carbon nanotube composite using C2H2 gas. In: Lu SW, Hu MZ, Gogotsi Yu (eds) Proc. 106th annual meeting of the American Ceramic Society, Indianapolis, Indiana, 18-21 Apr 2004. Ceram Trans 159:209-216 285. Temuujin J, Senna M, Jadambaa T, Byambasuren D (2005) Direct synthesis of tungsten carbide nanoparticles by mechanically assisted carbothermic reduction of natural wolframite. J Am Ceram Soc 88(4):983-985 286. Guo C, Liu Y, Ma X, Qian Y, Xu L (2006) Synthesis of tungsten carbide nanocrystal via a simple reductive reaction. Chem Lett 35(11):1210-1211 287. Lee JD, Lee D-H, Park N-K. Ryu SO, Lee TJ (2006) The preparation of nanophase tungsten carbide powder with zeolite-X catalysts. Curr Appl Phys 6:1040-1043 288. Meng H, Xie F, Shen PK (2006) Preparation and characterization of tungsten carbides as alkaline fuel cell catalysts. ECS Trans 1(32):1-9 289. Zhang L, Yang GB, Liu G, Chen S, Huang BY, Zhang CF (2006) Ultra-fine and nanoscaled tungsten carbide synthesis from colloidal carbon coated nano tungsten precursor. Powder Metall 49(4):369-373 290. Butler BG, Lu J, Fang ZZ, Rajamani RK (2007) Production of nanometric tungsten carbide powders by planetary milling. Int J Powder Metall 43(1):35-43

References

595

291. Kurlov AS, Gusev AI (2007) Determination of the particle sizes, microstrains and degree of inhomogeneity in nanostructured materials form X-ray diffraction data. Glass Phys Chem 33(3):276-282 292. Kurlov AS, Nazarova SZ, Gusev AI (2007) Magnetic susceptibility and thermal stability of particle size of nanocrystalline tungsten carbide WC. Phys Solid State 49(9):1780-1786 293. Lee S-S, Joo D, Jung Y-G, Choi C-J (2007) Synthesis of WC nanosized powder by the plasma-arc discharge process. In: Pan W, Gong JH (eds) High-performance ceramics IV. Proc. 4th China Int. conf. on high-performance ceramics (CICC-4), Chengdu, China, 23-26 Oct 2005. Key Eng Mater 336-338:2086-2088 294. Panov VS (2007) Nanotechnologies in production of solid alloys (review). Russ J Non-Ferr Met 48(2):148-152 295. Shimojima K, Hosokawa H, Nakajima T, Mizukami M, Yamamoto Y (2007) Binder-free tungsten carbide fabricated by pulsed electric current sintering. In: Proc. powder metallurgy world congress and exhibition (PM 2006), Busan, South Korea, 24-28 Sep 2006. Mater Sci Forum 534-536(2):1153-1156 296. Shimojima K, Hosokawa H, Nakajima T, Mizukami M, Yamamoto Y (2007) Binder-free tungsten carbide fabricated by pulsed current sintering. In: Proc. 5th Int. conf. on processing and manufacturing of advanced materials (THERMEC’2006), Vancouver, Canada, 4-8 July 2006. Mater Sci Forum 539-543(1):907-912 297. Borovinskaya IP, Ignateva TI, Vershinnikov VI, Miloserdova OM, Semenova VN (2008) Self-propagating high-temperature synthesis of ultra-fine and nanosized WC and TiC powders. Powder Metall Met Ceram 47(9-10):505-511 298. Burakov VS, Butsen AV, Brüser V, Harnish F, Misakov PY, Nevar EA, Rosenbaum M, Savatenko NA, Tarasenko NV (2008) Synthesis of tungsten carbide nanopowder via submerged discharge method. J Nanopart Res 10:881-886 299. Cahen S, Furdin G, Marêché JF, Albiniak A (2008) Synthesis and characterization of carbon-supported nanoparticles for catalytic applications. Carbon 46:511-517 300. Du Y, Lei M, Yang H, Wang X (2008) Facile route to prepare TaC, NbC and WC nanoparticles. J Wuhan Univ Technol Mater Sci Ed 23(6):779-782 301. Giordano C, Erpen C, Yao W, Antonietti M (2008) Synthesis of Mo and W carbide and nitride nanoparticles via a simple “urea glass” route. Nano Lett 8(12):4659-4663 302. Gusev AI, Kurlov AS (2008) Kharakterystyka nanokrystalichnykh materialiv za rozmirom chastinok (zeren) (Charactrization of nanocrystalline materials by the size of particles (grains)). Metallofiz Nov Tekhnol 30(5):679-694 (in Ukrainian) 303. Li PG, Lei M, Tang WH (2008) Route to transition metal carbide nanoparticles through cyanamide and metal oxides. Mater Res Bull 43:3621-3626 304. Liu J-Y, Xu Z-X, Xu Z-H, Sun J, Zhao T-L, Zhao G (2008) In situ synthesis of nano-WC particles by ion implantation. Nanotechnol Precision Eng 6(3):180-184 (in Chinese) 305. Luo J, Guo Z, Gao Y, Lin T (2008) Synthesis of nanosized tungsten carbide from phenol formaldehyde resin coated precursors. Rare Met 27(2):201-204 306. Pakransky N, Glikman L, Beilis II, Alterkop B, Boxman RL, Rosenberg Yu, Barkay Z (2008) W-C synthesis in a pulsed arc submerged in liquid. Plasma Chem Plasma Process 28(3):365-375 307. Ryu T, Hwang KS, Sohn HY, Fang ZZ (2008) Synthesis of nanosized tungsten carbide by a thermal plasma process. In: Proc. TMS 2008 annual meeting and exhibition / extraction and processing division (EPD) congress, New Orleans, Louisiana, 9-13 Mar 2008, pp. 385-391. The Minerals, Metals and Materials Society, Pittsburgh, Pennsylvania 308. Ryu T, Sohn HY, Hwang KS, Fang ZZ, Kim Y-U (2008) Plasma synthesis of tungsten carbide nanopowder from tungsten hexachloride. High Temp Mater Process 27(2):91-96 309. Ryu T, Sohn HY, Hwang KS, Fang ZZ (2008) Tungsten carbide nanopowder by plasmaassisted chemical vapour synthesis from WCl6-CH4-H2 mixtures. J Mater Sci 43(15):51855192

596

2 Tungsten Carbides

310. Ryu T, Sohn HY, Hwang KS, Fang ZZ (2009) Plasma synthesis of tungsten carbide nanopowder from ammonium paratungstate. J Am Ceram Soc 92(3):655-660 311. Ryu T, Hwang KS, Sohn HY, Fang ZZ (2009) Synthesis of tungsten and tungsten carbide nanopowders from ammonium paratungstate in a thermal plasma reactor. In: Proc. 3rd Int. conf. on processing materials for properties (PMP III), Bangkok, Thailand, 7-10 Dec 2008, Vol. 2, pp. 916-922. The Minerals, Metals and Materials Society, Pittsburgh, Pennsylvania 312. Gusev AI, Kurlov AS (2009) Mechanical milling process modelling and making WC nanocrystalline powder. Inorg Mater 45(1):35-42 313. Kim J, Jang J-H, Lee Y-H, Kwon Y-U (2009) Enhancement of electrocatalytic activity of platinum for hydrogen oxidation reaction by sonochemically synthesized WC1–x nanoparticles. J Power Sources 193:441-446 314. Liang C, Ding L, Wang A, Ma Z, Qiu J, Zhang T (2009) Microwave-assisted preparation and hydrazine decomposition properties of nanostructured tungsten carbides on carbon nanotubes. Indust Eng Chem Res 48:3244-3248 315. Tan GL (2009) Synthesis of metastable tungsten carbide nanoparticles by mechanochemical alloying process. In: Proc. 1st Int. symp. on advanced synthesis and processing technology for materials (ASPT08), Wuhan, China, 14-17 Nov 2008. Adv Mater Res 66:135138 316. Zhang C-H, Guo H-Q, Wang G-L, Song Z-H, Wu C-H, Wu Q-S (2009) Research of thermal stability of nanocrystalline tungsten carbide powder. J Funct Mater 40(3):486-489 (in Chinese) 317. Zhao J, Holland T, Unuvar C, Munir ZA (2009) Sparking-plasma sintering of nanometric tungsten carbide. Int J Refract Met Hard Mater 27:130-139 318. Chen D, Wen H, Zhai H, Wang H, Li X, Zhang R, Sun J, Gao L (2010) Novel synthesis of hierarchical tungsten carbide micro-/nanocrystals from a single-source precursor. J Am Ceram Soc 93(12):3997-4000 319. Debalina B, Kamaraj M, Murthy BS, Chakravarthi SR, Sarathi R (2010) Generation and characterization of nano tungsten carbide particle by wire explosion process. J Alloys Compd 496:122-128 320. Dvornik MI (2010) Nanostructured WC-Co particles produced by carbonization of spark eroded powder: synthesis and characterization. Int J Refract Met Hard Mater 28:523-528 321. Essaki K, Rees EJ, Burstein GT (2010) Synthesis of nanoparticulate tungsten carbide under microwave irradiation. J Am Ceram Soc 93(3):692-695 322. Kumar A, Singh K, Pandey OP (2010) Optimization of processing parameters for the synthesis of tungsten carbide (WC) nanoparticles through solvothermal route. Phys E 42:2477-2483 323. Kurlov AS, Gusev AI (2010) Particle size effects on the oxidation of tungsten carbide nanopowders. Russ J Phys Chem A 84(12):2095-2101 324. Polyakov EV, Maksimova LG, Krasilnikov VN, Zhilyaev VA, Timoshchuk TA, Ermakova ON, Shveikin GP, Nikolaenko IV (2010) Thermally stimulated transformation of micellar tungsten glycolate into nanodisperse tungsten carbide. Dokl Phys Chem 434(1):154-157 325. Reddy KM, Rao TN, Radha K, Joardar J (2010) Nanostructured tungsten carbides by thermochemical processing. J Alloys Compd 494:404-409 326. Ryu T, Olivas-Martinez M, Sohn HY, Fang ZZ, Ring TA (2010) Computational fluid dynamics simulation of chemical vapour synthesis of WC nanopowder from tungsten hexachloride. Chem Eng Sci 65:1773-1780 327. Shen PK, Yin S, Li Z, Chen C (2010) Preparation and performance of nanosized tungsten carbides for electrocatalysis. Electrochim Acta 55:7969-7974 328. Shon I-J, Kim B-R, Doh J-M, Yoon J-K, Woo K-D (2010) Properties and rapid consolidation of ultra-hard tungsten carbide. J Alloys Compd 489(1):L4-L8 329. Sohn HY, Ryu T (2010) Chemical vapour synthesis (CVS) of inorganic nanopowders. In: Cotler VF (ed) Nanopowders and nanocoatings: production, properties and applications, 147178. Nova Science, Hauppauge, New York

References

597

330. Sun S-K, Kan Y-M, Zhang G-J, Wang P-L (2010) Ultra-fine tungsten carbide powder prepared by a nitridation-carburization method. J Am Ceram Soc 93(11):3565-3568 331. Won HI, Nersisyan HH, Won CW (2010) Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides. J Nanopart Res 12:493-500 332. Yamashita Y, Harada T, Makino T, Fujiyoshi K, Ueno S, Koga M (2010) Fabrication of high-purity and nanosized tungsten carbide particles using chemical complex solution. J Jpn Soc Powder Powder Metall 57(5):348-351 (in Japanese) 333. Zaikovskii AV, Maltsev VA, Novopashin SA (2010) Plasma-chemical synthesis of carbon and composite nanostructured materials in an electric arc. J Eng Thermophys 19(2):94-101 334. Cetinkaya S, Eroglu S (2011) Comparative kinetic and structural analyses of nanocrystalline WC powder synthesis from pre-reduced W under pure and diluted CH4 atmospheres. Int J Refract Met Hard Mater 29:214-220 335. Giordano C, Antonietti M (2011) Synthesis of crystalline metal nitride and metal carbide nanostructures by sol-gel chemistry. Nano Today 6:366-380 336. Hu C, Zhou D-L, Xiong R-J, Luo Y-Z, He Y (2011) Synthesis of nano tungsten carbide and electrocatalytic activity of Pt/WC. J Inorg Mater 26(11):1152-1156 (in Chinese) 337. Kumar A, Singh K, Pandey OP (2011) Direct conversion of wolframite ore to tungsten carbide nanoparticles. Int J Refract Met Hard Mater 29:555-558 338. Luo J, Pang C-S, Guo Z-M, Shao H-P (2011) Thermodynamic analysis and experiment of carbonization process of nanosized W powder added V2O3 and Cr2O3. Trans Mater Heat Treat 32(2):26-29 (in Chinese) 339. Razavi M, Rahimipour MR, Yazdani-Rad R (2011) A novel technique for production of nanocrystalline tungsten monocarbide single phase via mechanical alloying. J Alloys Compd 509:6683-6688 340. Sherman AJ, Doud B, Hardy D (2011) Properties of nanocrystalline fluidized-bed-reduced tungsten, tungsten carbide and tungsten – rare-earth alloy powders. Int J Powder Metall 47(5):41-47 341. Yang R, Luo F, Xu R (2011) A novel method for preparing W2C nanopowders in molten salt. Mater Trans Jpn Inst Met 52(1):124-126 342. Zalite I, Angerer P, Yu LG, Khor KA (2011) Spark-plasma sintering (SPS) of tungsten carbide and titanium carbonitride nanopowders. In: Sternberg A, Muzikante I, Zicans J (eds) Proc. Int. annual conf. on functional materials and nanotechnologies (FM&NT 2011), Riga, Latvia, 5-8 Apr 2011. IOP Conf Series Mater Sci Eng 23:012039 (4 pp.) 343. Aravinth S, Sankar B, Kamaraj M, Chakravarthy SR, Sarathi R (2012) Synthesis and characterization of hexagonal tungsten carbide nanopowder using multi-walled carbon nanotubes. Int J Refract Met Hard Mater 33:53-57 344. Dopita M, Salomon A, Chmelik D, Reichelt B, Rafaja D (2012) Field assisted sintering technique compaction of ultra-fine grained binderless WC hard metals. In: Proc. 12th Int. symp. on physics of materials, Prague, Czech Republic, 4-8 Sep 2011. Acta Phys Polon A 122(3):639-642 345. He C, Meng H, Yao X, Shen PK (2012) Rapid formation of nanoscale tungsten carbide on graphitized carbon for electrocatalysis. Int J Hydrogen Energy 37:8154-8160 346. Huang Y, Deng F, Ni C, Chen JG, Vlachos DG (2012) Synthesis of mesoporous silica nanobamboo with highly dispersed tungsten carbide nanoparticles. Dalton Trans 43(23):6914-6918 347. Hugot N, Desforges A, Fontana S, Marêché JF, Hérold C, Albiniak A, Furdin G (2012) Solid-state chemistry route for supported tungsten and tungsten carbide nanoparticles. J Solid State Chem 194:23-31 348. Ilyin AP, Nazarenko OB, Tikhonov DV (2012) Synthesis and characterization of metal carbides nanoparticles produced by electrical explosion of wires. J Nanosci Nanotechnol 12(10):8137-8142 349. Kurlov AS, Gusev AI (2012) Vacuum annealing of nanocrystalline WC powders. Inorg Mater 48(7):680-690

598

2 Tungsten Carbides

350. Kurlov AS, Gusev AI (2012) Peculiarities of vacuum annealing of nanocrystalline WC powders. Int J Refract Met Hard Mater 32:51-60 351. Onoki T, Ikeda J, Ishii K, Sakamoto H, Tohgoh M, Hayashi M, Fukui T, Kumadani K (2012) Nanocrystalline tungsten monocarbide synthesis from tungstic acid and polyacrylonitrile mixed powder. J Ceram Soc Jpn 120(6):262-264 352. Zhao X, Wang J, Wang X, Zhao Y (2012) The progress in the preparation and catalytic application of WC nanopowders. Powder Metall Technol 30(4):307-312 (in Chinese) 353. Zhu W, Ignaszak A, Song C, Baker R, Hui R, Zhang J, Nan F, Botton G, Ye S, Campbell S (2012) Nanocrystalline tungsten carbide (WC) synthesis/characterization and its possible application as a PEM fuel cell catalyst support. Electrochim Acta 61:198-206 354. Abdullaeva Z, Omurzak E, Iwamoto C, Okudera H, Koinuma M, Takebe S, Sulaimankulova S, Mashimo T (2013) High-temperature stable WC1−x@C and TiC@C coreshell nanoparticles by pulsed plasma in liquid. RSC Adv 3(2):513-519 355. Debalina B, Kamaraj M, Chakravarthi SR, Vasa NJ, Sarathi R (2013) Understanding the mechanism of nanoparticle formation in a wire explosion process by adopting the optical emission technique. Plasma Sci Technol 15(6):562-569 356. Garcia-Esparza AT, Cha D, Ou Y, Kubota J, Domen K, Takanabe K (2013) Tungsten carbide nanoparticles as efficient co-catalysts for photocatalytic overall water splitting. ChemSuSChem 6(1):168-181 357. Gavrilov NM, Pašti IA, Krstić J, Mitrić M, Ćirić-Marjanović G, Mentus S (2013) The synthesis of single phase WC nanoparticles / C composite by solid state reaction involving nitrogen-rich carbonized polyaniline. Ceram Int 39:8761-8765 358. Kato S, Yamaki T, Yamamoto S, Hakoda T, Kawaguchi K, Kobayashi T, Suzuki A, Terai T (2013) Preparation of tungsten carbide nanoparticles by ion implantation and electrochemical etching. Nucl Instrum Meth B 314:149-152 359. Isaeva NV, Blagoveshchenskii YuV, Blagoveshchenskaya NV, Melnik YuI, Samokhin AV, Alekseev NV, Astashov AG (2014) Preparation of nanopowders of carbides and hard alloy mixtures applying low-temperature plasma. Russ J Non-Ferr Met 55(6):585-591 360. Khvostantsev LG, Borovskii GV, Brazhkin VV, Laitsan LA, Borovskii VG (2013) Effective introduction of tungsten carbide nanoparticles into a hard alloy. Nanotechnol Rus 8(9-10):659-663 361. Kurlov AS (2013) Effect of vacuum annealing on the particle size and phase composition of nanocrystalline tungsten carbide powders. Russ J Phys Chem A 87(4):654-661 362. Lin H, Tao B, Xiong J, Li Q, Li Y (2013) Tungsten carbide (WC) nanopowders synthesized via novel core-shell structured precursors. Ceram Int 39:2877-2881 363. Meng H, Zhang Z, Zhao F, Qiu T (2013) Preparation of WC nanoparticles by twice ball milling. Int J Refract Met Hard Mater 41:191-197 364. Samokhin AV, Alekseev NV, Kornev SA, Sinaiskii MA, Blagoveshchenskii YuV, Kolesnikov AV (2013) Tungsten carbide and vanadium carbide nanopowders synthesis in DC plasma reactor. Plasma Chem Plasma Process 33:605-616 365. Singla G, Singh K, Pandey OP (2013) Williamson-Hall study on synthesized nanocrystalline tungsten carbide (WC). Appl Phys A 113:237-242 366. Zaikovskii AV, Maltsev VA, Novopashin SA (2013) Synthesis of tungsten carbide nanoparticles in WO3 pyrolysis in a plasma arc. J Eng Thermophys 22(1):77-85 367. Zhao SQ, Jin SW, Wang YX (2013) The preparation of ultra-fine tungsten carbide nanoparticles by DC arc discharge plasma process. Mod Phys Lett B 27(19):1341003 (8 pp.) 368. Chen W-H, Nayak PK, Lin H-T, Chang M-P, Huang J-L (2014) Synthesis of nanostructured tungsten carbide via metal-organic chemical vapour deposition and carburization process. Int J Refract Met Hard Mater 47:44-48 369. Hunt ST, Nimmanwudipong T, Román-Leshkov Yu (2014) Engineering non-sintered metal-terminated tungsten carbide nanoparticles for catalysis. Angew Chem Int Ed 53:51315136

References

599

370. Nikolaenko I, Kedin N, Shveikin G, Polyakov E (2014) Microwave synthesis of ultra-fine and nanosized powders of tungsten oxide and carbide. Int J Mater Res 105(3):314-317 371. Nikolaenko I, Kedin N, Shveikin G (2014) Synthesis of ultra-fine powder (W,Ti)C by microwave heating in a stream of argon. Int J Mater Res 105(12):1232-1235 372. Novoselova IA, Nakoneshnaja EP, Karpushin NA, Bykov VN, Dovbeshko GI, Rynder AD (2014) Elektrokhimichnyi syntez kompozytsiinykh materialiv na osnovi nanorozmirnykh poroshkiv karbidiv volframu v rozplavi soli (Electrochemical synthesis of composite materials based on the nanoscale powders of tungsten carbides in salt melt). Metallofiz Nov Tekhnol 36(4):491-508 (in Ukrainian) 373. Onoki T, Shinoda Y, Akatsu T, Wakai F (2014) New processing method for tungsten carbide nanocrystalline particles and nanostructural carbon via polyacrylonitrile gasification. J Ceram Soc Jpn 122(7):570-573 374. Polyakov EV, Krasilnikov VN, Tyutyunnik AP, Khlebnikov NA, Shveikin GP (2014) Precursor-based synthesis of nanosized tungsten carbide WC and WC:nCo nanocomposites. Dokl Phys Chem 457(1):104-107 375. Rahsepar M, Pakshir M, Nikolaev P, Piao Y, Kim H (2014) A combined physicochemical and electrocatalytic study of microwave synthesized tungsten monocarbide nanoparticles on multi-walled carbon nanotubes as a co-catalyst for a proton-exchange membrane fuel cell. Int J Hydrogen Energy 39:15706-15717 376. Shabgard MR, Najafabadi AF (2014) The influence of dielectric media on nanostructured tungsten carbide (WC) powder synthesized by electro-discharge process. Adv Powder Technol 25:937-945 377. Xia M, Yan Q, Guo H, Lang S, Ge C (2014) Tunable carbon nanotube – tungsten carbide nanoparticles heterostructures by vapour deposition. J Appl Phys 115(18):184307 (4 pp.) 378. Abdelkader EM, Jelliss PA, Buckner SW (2015) Metal and metal carbide nanoparticle synthesis using electrical explosion of wires coupled with epoxide polymerization capping. Inorg Chem 54:5897-5906 379. Burakov VS, Nevar EA, Nedelko MI, Tarasenko NV (2015) Synthesis and modification of molecular nanoparticles in electrical discharge plasma in liquids. Russ J Gen Chem 85(5):1222-1237 380. Chuvildeev VN, Blagoveshchenskii YuV, Nokhrin AV, Sakharov NV, Boldin MS, Isaeva NV, Shotin SV, Lopatin YuG, Smirnova ES, Popov AA, Belkin OA, Semenycheva AV (2015) Sparking-plasma sintering of tungsten carbide nanopowders. Nanotechnol Russ 10(56):434-448 381. El-Eskandarany MS, Mahday AA, Ahmed HA, Amer AH (2000) Synthesis and characterizations of ball-milled nanocrystalline WC and nanocomposite WC-Co powders and subsequent consolidations. J Alloys Compd 312(1-2):315-325 382. El-Eskandarany MS (2015) Mechanical alloying: nanotechnology, materials science and powder metallurgy, 2nd ed. Elsevier, London, New York 383. Kanerva U, Lagerbom J, Karhu M, Kronlöf A, Laitinen T, Turunen E (2015) Synthesis of nano-WC from water soluble raw materials: effects of tungsten source and synthesis atmosphere on chemical and phase evolution. Int J Refract Met Hard Mater 50:65-71 384. Krasovskii PV, Malinovskaya OS, Samokhin AV, Blagoveshchenskii YuV, Kazakov VA, Ashmarin AA (2015) XPS study of surface chemistry of tungsten carbides nanopowders produced through DC thermal plasma / hydrogen annealing process. Appl Surf Sci 339:46-54 385. Perezhogin IA, Kulnitskii BA, Grishtaeva AE, Perfilov SA, Lomakin RL, Blank VD (2015) Transformations in WC lattice and polytype formation in the process of sintering of W/C60 mixture. Int J Refract Met Hard Mater 48:115-119 386. Wen J, Li Y, Meng X, Yin G, Yao Y (2015) Fabrication of tungsten carbide nanoparticles from refluxing derived precursor. J Wuhan Univ Technol Mater Sci Ed 30(2):231-234 387. Xie M, Zhang M, Wei W, Jiang Z, Xu Y (2015) Angstrom-sized tungsten carbide promoted platinum electrocatalyst for effective oxygen reduction reaction and resource saving. RSC Adv 5(117):96488-96494

600

2 Tungsten Carbides

388. Yan Q, Lu Y, To F, Li Y, Yu F (2015) Synthesis of tungsten carbide nanoparticles in biochar matrix as a catalyst for dry reforming of methane to syngas. Catal Sci Technol 5(6):3270-3280 389. Gong Q, Wang Y, Hu Q, Zhou J, Feng R, Duchesne PN, Zhang P, Chen F, Han N, Li Yaf, Jin C, Li Yan, Lee S-T (2016) Ultra-small and phase-pure W2C nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution. Nature Commun 7(1):13216 (8 pp.) 390. Guo J, Mao Z, Yan X, Su R, Guan P, Xu B, Zhang X, Qin G, Pennycook SJ (2016) Ultrasmall tungsten carbide catalysts stabilized in graphitic layers for high-performance oxygen reduction reaction. Nano Energy 28:261-268 391. Ishii T, Yamada K, Osuga N, Imashiro Y, Ozaki J-I (2016) Single-step synthesis of W2C nanoparticle – dispersed carbon electrocatalysts for hydrogen evolution reactions utilizing phosphate groups on carbon edge sites. ACS Omega 1:689-695 392. Jiang Y, Shi M-Q, Tong X, Chu Y, Ma C-A (2016) Nanostructure architectures of tungsten carbide for methanol electrooxidation catalyst. Chin J Chem 34:624-630 393. Mitran R-A, Radulescu M-C, Buhalteanu L, Tanase LC, Dumitrescu DG, Matei C (2016) Formation of pure-phase W2C nanoparticles through carbothermal reduction in the presence of Pd(0) nanoparticles. J Alloys Compd 682:679-685 394. Aleshin NP, Linnik AA, Kobernik NV, Mikheev RS, Pankratov AS, Samokhin AV, Alekseev NV, Shtokolov SA (2017) The influence of nanosized particles introduced into molten-pool tail on the impact toughness of weld metal. Nanotechnol Russ 12(7-8):409-415 395. Cheong Y-K, Calvo-Castro J, Ciric L, Edirisinghe M, Cloutman-Green E, Illangakoon UE, Kang Q, Mahalingam S, Matharu RK, Wilson RM, Ren G (2017) Characterization of the chemical composition and structural features of novel antimicrobial nanoparticles. Nanomater 7:152 (16 pp.) 396. Krasilnikov VN, Polyakov EV, Khlebnikov NA, Tarakina NV, Kuznetsov MV (2017) Precursor synthesis and properties of nanodispersed tungsten carbide and nanocomposites WC:nC. Ceram Int 43:4131-4138 397. Ma R, Song E, Zhou Y, Zhou Z, Liu G, Liu Q, Liu J, Zhu Y, Wang J (2017) Ultra-fine WC nanoparticles anchored on co-encased N-doped carbon nanotubes for efficient hydrogen evolution. Energy Storage Mater 6:104-111 398. Nokhrin AV, Chuvildeev VN, Blagoveshchenskii YuV, Boldin MS, Sakharov NV, Isaeva NV, Popov AA, Lantsev EA, Belkin OA, Smirnova ES (2017) Spark-plasma sintering of high-strength ultra-fine grained tungsten carbide. In: Olevsky EA, Grigoryev EG (eds) Proc. 5th Int. scientific workshop on advanced technologies of materials field-assisted consolidation (Consolidation2016), Moscow, Russian Federation, 28-31 Aug 2016. IOP Conf Series Mater Sci Eng 218:012012 (7 pp.) 399. Sagadevan S, Das I, Singh P, Podder J (2017) Synthesis of tungsten carbide nanoparticles by hydrothermal method and its characterization. J Mater Sci Mater Electron 28:1136-1141 400. Tian H, Zhang H, Wang C, Guo M, Cui Y, Gao J (2017) Morphology and in situ growth process of nano tungsten carbide on the surface of oxide graphene. Heat Treat Met 42(6):196200 (in Chinese) 401. Xu Y-T, Xiao X, Ye Z-M, Zhao S, Shen R, He C-T, Zhang J-P, Li Y, Chen X-M (2017) Cage-confinement pyrolysis route to ultra-small tungsten carbide nanoparticles. J Am Chem Soc 139:5285-5288 402. Ye N, Tang J, Wei X, Zhang J (2017) Process and mechanism of WC nanopowders prepared from W nanopowders by two-stage carbonization method. Chin J Rare Met 41(7):775-782 (in Chinese) 403. Zheng W, Wang L, Deng F, Giles SA, Prasad AK, Advani SG, Yan Y, Vlachos DG (2017) Durable and self-hydrating tungsten carbide – based composite polymer electrolyte membrane fuel cells. Nature Commun 8:418 (8 pp.)

References

601

404. Emin S, Altinkaya C, Semerci A, Okuyucu H, Yildiz A, Stefanov P (2018) Tungsten carbide electrocatalysts prepared from metallic tungsten nanoparticles for efficient hydrogen evolution. Appl Catal B 236:147-153 405. Kim CH, Hur YG, Lee SH, Lee K-Y (2018) Hydrocracking of vacuum residue using nanodispersed tungsten carbide catalyst. Fuel 233:200-206 406. Malyshev V, Gab A, Shakhnin D, Lukashenko T, Ishtvanik O, Gaune-Escard M (2018) High-temperature electrochemical synthesis of nanopowders of tungsten carbide in ionic melts. In: Fesenko O, Yatsenko L (eds) Proc. 5th Int. science and practice conf. on nanotechnology and nanomaterials (NANO 2017), Chernivtsi, Ukraine, 23-26 Aug 2017. Springer Proc Phys 214:311-321 407. Grigoryan RR, Aloyan SG, Harutyunyan VR, Arsentev SD, Tavadyan LA (2019) Dry reforming of methane over nanosized tungsten carbide powders obtained by mechanochemical and plasma-mechano-chemical methods. Petrol Chem 59(11):1256-1263 408. Mounfield WP, III, Harale A, Román-Leshkov Yu (2019) Impact of morphological effects on the activity and stability of tungsten carbide catalysts for dry methane reforming. Energy Fuels 33:5544-5550 409. Pfaff F, Glück B, Hoyer T, Rohländer D, Sauerbrei A, Zell R (2019) Tungsten carbide nanoparticles show a broad spectrum virucidal activity against enveloped and non-enveloped model viruses using a guideline-standardized in vitro test. Lett Appl Microbiol 69:302-309 410. Wu Y, Zhu X, Li P, Zhang T, Li M, Deng J, Huang Y, Ding P, Wang S, Zhang R, Lu J, Lu G, Li Yaf, Li Yan (2019) Ultra-dispersed WxC nanoparticles enable fast polysulfide interconversion for high-performance Li-S batteries. Nano Energy 59:636-643 411. Pan F, Du Z, Li S, Li J, Zhang M, Xiang M, Zhu Q (2020) Preparation of nanosized tungsten carbide via fluidized bed. Chin J Chem Eng 28(3):923-932 412. Liu D, Chang Q, Gao Y, Huang W, Sun Z, Yan M, Guo C (2020) High performance of microbial fuel cell afforded by metallic tungsten carbide decorated carbon cloth anode. Electrochim Acta 330:135243 (8 pp.) 413. Ranjan P, Kurosaki T, Suematsu H, Jayaganthan R, Sarathi R (2020) Formation of tungsten nanoparticles by wire explosion process. Int J Appl Ceram Technol 17:304-310 414. Wu Y-C, Yang Y, Tan X-Y, Luo L, Zan X, Zhu X-Y, Xu Q, Cheng J-G (2020) Preparation technology of ultra-fine tungsten carbide powders: an overview. Front Mater 7:94 (11 pp.) 415. Sakthivel K, Akilarasan M, Chen S-M, Ye Y-T, Chen T-W, Ali MA (2019) A novel synthetic approach to tungsten carbide polyhedrons. An effective electrocatalyst for the detection of organophosphate pesticide (fenitrothion) residues in environmental samples. Mater Chem Phys 233:52-59 416. Ling Y, Luo F, Zhang Q, Qu K, Guo L, Hu H, Yang Z, Cai W, Cheng H (2019) Tungsten carbide hollow microspheres with robust and stable electrocatalytic activity toward hydrogen evolution reaction. ACS Omega 4:4185-4191 417. Pan Y-X, Zhuang H-Q, Ma H, Cheng J, Song J (2019) Tungsten carbide hollow spheres flexible for charge separation and transfer for enhanced visible-light-driven photocatalysis. Chem Eng Sci 194:71-77 418. Wang Y, Zhang L, Meng X, Feng L, Wang T, Zhang W, Yang N (2019) Scalable processing hollow tungsten carbide spherical superstructure as an enhanced electrocatalyst for hydrogen evolution reaction over a wide pH range. Electrochim Acta 319:775-782 419. Wang Y, Zhang L, Meng X, Feng L, Wang T, Zhang W, Yang N (2020) Corrigendum to “Scalable processing hollow tungsten carbide spherical superstructure as an enhanced electrocatalyst for hydrogen evolution reaction over a wide pH range” [Electrochim Acta 319:775-782]. Electrochim Acta 331:135351 (2 pp.) 420. Shanmugam S, Jacob DS, Gedanken A (2005) Solid-state synthesis of tungsten carbide nanorods and nanoplatelets by a single-step pyrolysis. J Phys Chem B 109:19056-19059 421. Keller N, Pietruszka B, Keller V (2006) A new one-dimensional tungsten carbide nanostructured material. Mater Lett 60:1774-1777

602

2 Tungsten Carbides

422. Zheng HJ, Ma C-A, Wang W, Huang JG (2006) Nanorod tungsten carbide thin film and its electrocatalytic activity for nitromethane electroreduction. Electrochem Commun 8(6):977981 423. Yan Y, Zhang L, Qi X, Song H, Wang J-Y, Zhang H, Wang X (2012) Template-free pseudomorphic synthesis of tungsten carbide nanorods. Small 8(21):3350-3356 424. Jiang AM, Jiang XQ, Yang J, Yang RJ, Yu R (2014) Research progress of tungsten carbide nanorods and nanoplatelets. In: Proc. 4th Int. conf. on materials science and information technology (MSIT 2014), Tianjin, China, 14-15 June 2014. Adv Mater Res 989-994:552-555 425. Li N, Yan Y, Xia B-Y, Wang J-Y, Wang X (2014) Novel tungsten carbide nanorods: an intrinsic peroxidase mimetic with high activity and stability in aqueous and organic solvents. Biosens Bioelectron 54:521-527 426. Vijayakumar P, Pandian MS, Lim SP, Pandikumar A, Huang NM, Mukhopadhyay S, Ramasamy P (2015) Facile synthesis of tungsten carbide nanorods and its application as counter electrode in dye sensitized solar cells. Mater Sci Semicond Process 39:292-299 427. Paranthaman V, Muthu SP, Alagarsamy P, Ming HN, Perumalsamy R (2016) Influence of zirconium dioxide and titanium dioxide binders on the photovoltaic performance of dye sensitized solar cell tungsten carbide nanorods based counter electrode. Electrochim Acta 211:375-384 428. Liu R, Pang M, Chen X, Li C, Xu C, Liang C (2017) W2C nanorods with various amounts of vacancy defects: determination of catalytic active sites in the hydrodeoxygenation of benzofuran. Catal Sci Technol 7(6):1333-1341 429. Lv C, Wu G, Liu KX, Zhu YS, Yin YH, Hu YY, Li YS, Liu XB, Wu ZP (2017) Preparation of small-sized tungsten carbide nanorods for loading Pt with promoted electrocatalytic activity and stable anti-poisoning performance. RSC Adv 7:56713-56720 430. Vijayakumar P, Pandian MS, Ramasamy P (2017) Tungsten carbide nanorods with titanium dioxide composite counter electrode: effect of NMP to enhanced efficiency in dye sensitized solar cell (DSSC). In: Singh S, Basu S, Bhattacharya S, Das A (eds) Proc. 1st DAE solid state physics symp., Bhubaneswar, Odisha, India, 26-30 Dec 2016. AIP Conf Proc 1832:0500026 (4 pp.) 431. Kim D, Yong K (2020) Metal hydroxide hybridized tungsten carbide nanorod arrays for enhancing hydrogen evolution in alkaline media. Appl Surf Sci 509:144912 (7 pp.) 432. Teng F, Wang J, An X, Lu B, Su Y, Gong C, Zhang P, Zhang Z, Xie E (2012) Single-phase tungsten carbide nanopillar arrays prepared by chemical vapour deposition. RSC Adv 2(19):7403-7405 433. Han N, Liu K, Zhang X, Wang M, Du P, Huang Z, Zhou D, Zhang Q, Gao T, Jia Y, Luo L, Wang J, Sun X (2019) Highly efficient and stable solar-powered desalination by tungsten carbide nanoarray film with sandwich wettability. Sci Bull 64:391-399 434. Wang S-J, Chen C-H, Chang S-C, Uang K-M, Juan C-P, Cheng H-C (2004) Growth and characterization of tungsten carbide nanowires by thermal annealing of sputter-deposited WCx films. Appl Phys Lett 85(12):2358-2360 435. Wang S-J, Chen C-H, Chang S-C, Wong C-H, Uang K-M, Chen T-M, Ko R-M, Liou B-W (2005) On the thermal annealing conditions for self-synthesis of tungsten carbide nanowires from WCx films. Nanotechnol 16:273-277 436. Sun Y, Cui H, Jin SX, Wang CX (2012) Eutectic solidification applied to nanofabrication: a strategy to prepare large-scale tungsten carbide nanowalls. J Mater Chem 22(32):1656616571 437. Dai J, Onomitsu K, Kometani R, Krockenberger Y, Yamaguchi H, Ishihara S, Warisawa S (2013) Superconductivity in tungsten carbide nanowires deposited from the mixtures of W(CO)6 and C14H10. Jpn J Appl Phys 52:075001 (5 pp.) 438. Namazu T, Morikaku T, Akamine H, Fujii T, Kuroda K, Takami Y (2015) Mechanical reliability of FIB-fabricated WC-Co cemented carbide nanowires evaluated by MEMS tensile testing. Eng Fract Mech 150:126-134

References

603

439. Xiao P, Ge X, Wang H, Liu Z, Fisher A, Wang X (2015) Novel molybdenum carbide – tungsten carbide composite nanowires and their electrochemical activation for efficient and stable hydrogen evolution. Adv Funct Mater 25:1520-1526 440. Ren B, Li D, Jin Q, Cui H, Wang C (2017) Novel porous tungsten carbide hybrid nanowires on carbon cloth for high-performance hydrogen evolution. J Mater Chem A 5(25):1319613203 441. Ren X-N, Xia M, Yan Q-Z, Ge C-C (2017) Controllable preparation of tungsten / tungsten carbide nanowires or nanodots in nanostructured carbon with hollow macroporous core / mesoporous shell. Chin Phys B 26(3):038103 (4 pp.) 442. Ren X-N, Xia M, Yan Q-Z, Ge C-C (2017) Large scale and controllable preparation of W2C nanorods or WC nanodots with peroxidase-like catalytic activity. Chin Phys B 26(4):048103 (5 pp.) 443. Sun Y, Chen Y, Cui H, Wang J, Wang C (2017) Ultra-large bending strain and fracture resistance investigation of tungsten carbide nanowires. Small 13:1700389 (10 pp.) 444. Zheng H, Guo Y, Zhang Y, Geng D, Banis MN, Li R, Cai M, Sun X, Liu J, Wu Y (2019) Hierarchical hybrid of few-layer graphene upon tungsten monocarbide nanowires: controlled synthesis and electrocatalytic performance for methanol oxidation. ACS Appl Energy Mater 2:328-337 445. Bolton JD, Redington M (1980) Plastic deformation mechanisms in tungsten carbide. J Mater Sci 15:3150-3156 446. Takahashi T, Sugiyama K, Ito H (1971) Fibrous growth of tungsten carbide and molybdenum carbide by discharge method. J Soc Chem Indust Jpn 74(8):1606-1611 (in Japanese) 447. Zhou X, Qiu Y, Yu J, Yin J, Gao S (2011) Tungsten carbide nanofibers prepared by electrospinning with high electrocatalytic activity for oxygen reduction. Int J Hydrogen Energy 36:7398-7404 448. Ishikawa T, Abdelkareem MA, Tsujiguchi T, Nakagawa N (2014) Tungsten carbide nanofiber prepared by electrospinning for methanol oxidation reaction. In: Proc. 4th Int. conf. on advanced micro-device engineering (AMDE 2012), Kiryu, Japan, 7 Dec 2012. Key Eng Mater 596:55-59 449. Jeong I, Lee J, Joseph KLV, Lee HI, Kim JK, Yoon S, Lee J (2014) Low-cost electrospun WC/C composite nanofiber as a powerful platinum-free counter electrode for dye sensitized solar cell. Nano Energy 9:392-400 450. Oh Y, Kim S-K, Peck D-H, Jang J-S, Kim J, Jung D-H (2014) Improved performance using tungsten carbide / carbon nanofiber based anode catalysts for alkaline direct ethanol fuel cells. Int J Hydrogen Energy 39:15907-15912 451. Hollak SAW, Gosselink RW, Van Es DS, Bitter JH (2013) Comparison of tungsten and molybdenum carbide catalysts for the hydrodeoxygenation of oleic acid. ACS Catal 3:28372844 452. Pol SV, Pol VG, Gedanken A (2006) Synthesis of WC nanotubes. Adv Mater 18(15):20232027 453. Remskar M (2011) Inorganic nanotubes. In: Hayden O, Nielsch K (eds) Molecular- and nano-tubes, pp. 391-412. Springer Science, New York 454. Maiyalagan T, Kannan P, Jönsson-Niedziolka M, Niedziolka-Jönsson J (2014) Tungsten carbide nanotubes supported platinum nanoparticles as a potential sensing platform for oxalic acid. Anal Chem 86:7849-7857 455. Pan H, Feng YP, Lin J (2007) Hydrogen adsorption by tungsten carbide nanotube. Appl Phys Lett 90(22):223104 (3 pp.) 456. Ganji MD (2008) Theoretical study of the adsorption of CO2 on tungsten carbide nanotubes. Phys Lett A 372:3277-3282 457. Arie T, Akita S, Nakayama Y (1998) Growth of tungsten carbide nanoneedle and its application as a scanning tunnelling microscope tip. J Phys D Appl Phys 31:L49-L51

604

2 Tungsten Carbides

458. Mohapatra DR, Lee H-J, Sahoo S, Lee W-S (2012) A novel structure of tungsten carbide nanowalls grown on nanocrystalline diamond film. CrystEngComm 14(6):2222-2228 459. Ko A-R, Lee Y-W, Moon J-S, Han S-B, Cao G, Park K-W (2014) Ordered mesoporous tungsten carbide nanoplates as non-Pt catalysts for oxygen reduction. Appl Catal A 477:103108 460. Wu ZP, Zhao M, Hu JW, Zhang WB, Yin YH, Hu YY, Li YS, Yang JG, Xu QF, Krishamurthy A (2014) Preparation of tungsten carbide nanosheets with large surface area using an in situ DWCNT template. RSC Adv 4(88):47414-47420 461. Yang W, Sun H-B, Yu Y, Tong M-X, Xie W-M, Li G-H (2015) Preparation and electrocatalytic property of tungsten carbide nanoplate with mesoporosity. Chin J Nonferr Met 25(10):2770-2776 (in Chinese) 462. Ko Y-J, Cho J-M, Kim I, Jeong DS, Lee K-S, Park J-K, Baik Y-J, Choi H-J, Lee W-S (2017) Tungsten carbide nanowalls as electrocatalyst for hydrogen evolution reaction: new approach to durability issue. Appl Catal B 203:684-691 463. Boopathy G, Govindasamy M, Nazari M, Wang S-F, Umapathy MJ (2019) Facile synthesis of tungsten carbide nanosheets for trace level detection of toxic mercury ions in biological and contaminated sewage water samples: an electrocatalytic approach. J Electrochem Soc 166(10):B761-B770 464. Taylor KA (1977) Ancillary properties of vapour-deposited carbide coating. In: Bunshah RF (ed) Proc. 2nd Int. conf. on metallurgical coatings, San Francisco, California, 28 Mar – 1 Apr 1977. Thin Solid Films 40:201-209 465. Srivastava PK, Vankar VD, Chopra KL (1986) Very hard W-C coatings on stainless steel by r.f. reactive magnetron sputtering. J Vac Sci Technol A 4(6):2819-2826 466. Machida K, Enyo M, Toyoshima I (1988) Preparation of W-C thin films by reactive r.f. sputtering and Auger electron spectroscopy surface characterization. Thin Solid Films 161:L91-L95 467. Keller G, Erz R, Barzen I, Weiler M, Jung K, Ehrhardt H (1990) Mechanical properties, structure and composition of ion-plated tungsten carbide films. Vacuum 41(4-6):1294-1296 468. Machida K, Enyo M (1990) Preparation of WCx thin films by r.f. sputtering and their electrocatalytic property for anodic methanol oxidation. J Electrochem Soc 137(3):871-876 469. Keller G, Barzen I, Erz R, Dötter W, Ulrich S, Jung K, Ehrhardt H (1991) Crystal structure, morphology and composition of magnetron sputtered tungsten carbide films. Fresenius J Anal Chem 341:349-352 470. Keller G, Barzen I, Dötter W, Erz R, Ulrich S, Jung K, Ehrhardt H (1991) Correlation of particle flux parameters with the properties of thin tungsten carbide films. Mater Sci Eng A 139:137-143 471. Slimani T, Goudeau Ph, Naudon A, Farges G, Dereep JL (1991) Grazing incidence X-ray scattering study of the microstructure of tungsten-carbon films. In: Proc. 8th Int. conf. on small angle scattering, Leuven, Belgium, 6-9 Aug 1990. J Appl Crystallogr 24(5):638-644 472. Wagh BG, Godbole VP, Ogale SB (1991) Ion implantation effects in pulsed laser deposited tungsten carbide films. Surf Coat Technol 49:439-442 473. Xue Z, Caulton KG, Chisholm MH (1991) Low-pressure chemical vapour deposition of tungsten carbide thin films. Chem Mater 3:384-386 474. Zhang N, Wang Y (1992) Dislocations and hardness of hard coatings. Thin Solid Films 214:4-5 475. Teng Z, Teng F-E, Wang Y (1995) Some applications of the Hall-Petch relationship for single-phase imperfect polycrystals. Mater Charact 34:237-240 476. Chitica N, Gyorgy E, Lita A, Marin G, Mihailescu IN, Pantelica D, Petrascu M, Hatziapostolou A, Grivas C, Broll N, Cornet A, Mirica C, Andrei A (1997) Synthesis of tungsten carbide thin films by reactive pulsed laser deposition. Thin Solid Films 301:71-76 477. Monteiro OR, Delplancke-Ogletree M-P, Lo RY, Winand R, Brown I (1997) Synthesis and characterization of thin films of WCx produced by mixing W and C plasma streams. Surf Coat Technol 94-95:220-225

References

605

478. Nakajima T, Shirasaki T (1997) Chemical vapour deposition of tungsten carbide, molybdenum carbide nitride and molybdenum nitride films. J Electrochem Soc 144(6):20962100 479. Mihailescu IN, Gyorgy E, Marin G, Popescu M, Teodorescu VS, Van Landuyt J, Grivas C, Hatziapostolou A (1999) Crystalline structure of very hard tungsten carbide thin films obtained by reactive pulsed laser deposition. J Vac Sci Technol A 17(1):249-255 480. Voevodin AA, O’Neill JP, Prasad SV, Zabinski JS (1999) Nanocrystalline WC and WC/a-C composite coatings produced from intersected plasma fluxes at low deposition temperatures. J Vac Sci Technol A 17(3):986-992 481. Esteve J, Zambrano G, Rincon C, Martinez E, Galindo H, Prieto P (2000) Mechanical and tribological properties of tungsten carbide sputtered coatings. Thin Solid Films 373:282-286 482. Lundberg N, Östling M, Zetterling C-M, Tägtström P, Jansson U (2000) CVD-based tungsten carbide Schottky contacts to 6H-SiC for very high-temperature operation. J Electron Mater 29(3):372-375 483. Veldman S, Lemonds AM, Kershen K, Sun Y-M, Emesh I, Pfeifer K, White JM, Ekerdt JG (2000) Growth of tungsten carbide thin films as diffusion barriers for Cu metallization. In: Edelstein D, Dixit G, Yasuda Y, Ohba T (eds) Proc. advanced metallization conf. (AMC 2000), San Diego, California, 2-5 Oct 2000 and Tokyo, Japan, 19-20 Oct 2000, pp. 307-312. Materials Research Society, Warrendale, Pennsylvania 484. Tsai HY, Wang SJ, Sun SC (2001) Investigation of sputtered TaCx and WCx films as diffusion barriers for Cu metallization. In: Proc. Int. symp. on VLSI technology, systems and applications, Hsinchu, Taiwan, Republic of China, 18-20 Apr 2001, pp. 267-270. Industrial Technology Research Institute, Zhudong, Hsinchu, Republic of China 485. Sun Y-M, Lee SY, Lemonds AM, Engbrecht ER, Veldman S, Lozano J, White JM, Ekerdt JG, Emesh I, Pfeifer K (2001) Low-temperature chemical vapour deposition of tungsten carbide for copper diffusion barriers. Thin Solid Films 397:109-115 486. Wang SJ, Tsai HY, Sun SC (2001) Characterization of tungsten carbide as diffusion barrier for Cu metallization. Jpn J Appl Phys 40(1/4B):2642-2649 487. Wang SJ, Tsai HY, Sun SC, Shiao MH (2001) Thermal stability of sputtered tungsten carbide as diffusion barrier for copper metallization. J Electrochem Soc 148(9):G500-G506 488. Wang SJ, Tsai HY, Sun SC (2001) A comparative study of sputtered TaCx and WCx films as diffusion barriers between Cu and Si. Thin Solid Films 394:180-188 489. Dubček P, Radić N, Milat O, Bernstorff S (2002) Grazing incidence small angle X-ray scattering investigation of tungsten-carbon films produced by reactive magnetron sputtering. Surf Coat Technol 151-152:218-221 490. He J, Liu Y, Qiao Y, Fischer TE, Lavernia EJ (2002) Near-nanostructured WC – 18 % Co coating with low amounts of non-WC carbide phase. Part I. Synthesis and characterization. Metall Mater Trans A 33(1):145-157 491. Liu Y, Qiao Y, He J, Lavernia EJ, Fischer TE (2002) Near-nanostructured WC – 18 % Co coating with low amounts of non-WC carbide phase. II. Hardness and resistance to sliding and abrasive wear. Metall Mater Trans A 33(1):159-164 492. Rumaiz AK, Shah IS, Ni C, Demaree DJ, Hirvonen JK (2002) Reactive sputtering of nanostructured WCx. In: Kumar A, Meng WJ, Cheng Y, Zabinski JS, Doll Gl, Vepřek S (eds) Proc. symp. on surface engineering: synthesis, characterization and applications, Boston, Massachusetts, 2-5 Dec 2002. Mater Res Soc Symp Proc 750:319-324 493. Sun J-P, Zhang Z-X, Hou S-M, Zhang G-M, Zhao X-Y, Liu W-M, Xue Z-Q (2002) Work function of tungsten carbide thin film calculated using field emission microscopy. Acta Electron Sin 30(5):655-657 (in Chinese) 494. Cheng YH, Tay BK (2003) Structure and mechanical properties of tungsten carbide films deposited by off-plane double bend filtered cathodic vacuum arc. J Vac Sci Technol A 21(2):411-415 495. Hoffmann P, Galindo H, Zambrano G, Rincón C, Prieto P (2003) FTIR studies of tungsten carbide in bulk material and thin film samples. Mater Charact 50:255-259

606

2 Tungsten Carbides

496. Kim D-H, Kim YJ, Song YS, Lee B-T, Kim JH, Suh S, Gordon R (2003) Characteristics of tungsten carbide films prepared by plasma-assisted ALD using bis(tert-butylimido) bis(dimethylamido) tungsten. J Electrochem Soc 150(10):C740-C744 497. Palmquist J-P, Czigány Zs, Hultman L, Jansson U (2003) Epitaxial growth of tungsten carbide films using C60 as carbon precursor. J Cryst Growth 259:12-17 498. Palmquist J-P, Czigány Zs, Odén M, Neidhart J, Hultman L, Jansson U (2003) Magnetron sputtered W-C films with C60 as carbon source. Thin Solid Films 444:29-37 499. Rincón C, Romero J, Esteve J, Martínez E, Lousa A (2003) Effects of carbon incorporation in tungsten carbide films deposited by r.f. magnetron sputtering: single layers and multilayers. Surf Coat Technol 163-164:386-391 500. Wittkowski T, Distler G, Jung K, Hillebrands B, Comins JD (2004) The use of guided surface acoustic resonances in the determination of the thin film elastic tensor. Appl Phys Lett 84(26):5356-5358 501. Wittkowski T, Distler G, Jung K, Hillebrands B, Comins JD (2004) General methods for the determination of the stiffness tensor and mass density of thin films using Brillouin light scattering: study of tungsten carbide films. Phys Rev B 69(20):205401 (9 pp.) 502. Zellner MB, Chen JG (2004) Synthesis, characterization and surface reactivity of tungsten carbide (WC) PVD films. Surf Sci 569:89-98 503. Gubisch M, Liu Y, Krischok S, Ecke G, Spiess L, Schaefer JA, Knedlik C (2005) Tribological characteristics of WC1–x, W2C and WC tungsten carbide films. Tribol Interface Eng Ser 48:409-417 504. Park Y, Lim J, Lee C (2005) Effects of process parameters on the deposition rate, hardness and corrosion resistance of tungsten carbide coatings deposited by reactive sputtering. Jpn J Appl Phys 44(5A):3196-3199 505. Zheng HJ, Huang JG, Ma C-A (2005) Preparation of nanocrystalline tungsten carbide thin films by magnetron sputtering and their electrocatalytic property for PNP reduction. Chin Chem Lett 16(11):1539-1542 506. Zheng HJ, Huang JG, Wang W, Ma C-A (2005) Preparation of nanocrystalline tungsten carbide thin film electrode and its electrocatalytic activity for hydrogen evolution. Electrochem Commun 7:1045-1049 507. Zheng HJ, Ma C-A, Huang JG (2005) Preparation of nanocrystalline tungsten carbide thin film electrode and its electrocatalytic activity for oxidation of methanol. J Chem Indust Eng 56(5):947-951 (in Chinese) 508. Zheng HJ, Ma C-A, Huang JG, Li G (2005) Plasma enhanced chemical vapour deposition nanocrystalline tungsten carbide thin film and its electrocatalytic activity. J Mater Sci Technol 21(4):545-548 509. Abdelouahdi K, Sant C, Legrand-Buscema C, Aubert P, Perrière J, Renou G, Houdy Ph (2006) Microstructural and mechanical investigations of tungsten carbide films deposited by reactive r.f. sputtering. Surf Coat Technol 200:6469-6473 510. Abdelouahdi K, Sant C, Miserque F, Aubert P, Zheng Y, Legrand-Buscema C, Perrière J (2006) Influence of CH4 partial pressure on the microstructure of sputter-deposited tungsten carbide thin films. J Phys Condens Matter 18:1913-1925 511. Liao M, Koide Y, Alvarez J (2006) Crystallographic and electrical characterization of tungsten carbide thin films for Schottky contact of diamond photodiode. J Vac Sci Technol B 24(1):185-189 512. Ma C-A, Huang JG, Zheng HJ (2006) PECVD nanostructured tungsten carbide thin films at low temperature. Heat Treat Met 31(2):20-23 (in Chinese) 513. Suda Y, Yukimura K, Nakamura K, Takaki K, Sakai Y (2006) Deposition of tungsten carbide thin films by simultaneous r.f. sputtering. Jpn J Appl Phys 45(10B):8449-8452 514. Wittkowski T, Jung K, Hillebrands B, Comins JD (2006) Structural and chemical phase transitions in tungsten carbide films evidenced by the analysis of their stiffness tensors. J Appl Phys 100(7):073513 (11 pp.)

References

607

515. Da Cunha AP, Walker TD, Sims RA, Chhay B, Muntele CI, Muntele I, Elsamadicy A, Ila D (2007) Characterization of W1Cx electrical contacts on silicon carbide using RBS and AFM/SEM. Nucl Instrum Meth B 261:561-565 516. Kushkhov KhB, Adamokova MN (2007) Electrodeposition of tungsten and molybdenum metals and their carbides from low-temperature halide-oxide melts. Russ J Electrochem 43(9):997-1006 517. Sun J (2007) Field emission properties of tungsten carbide thin films formed on tungsten tips. In: Proc. Asia Display 2007 (AD’07), Shanghai, China, 12-16 Mar 2007, Vol. 2, pp. 1328-1332. The Society for Information Display, East China Normal University, Shanghai 518. Beadle KA, Gupta R, Mathew A, Chen JG, Willis BG (2008) Chemical vapour deposition of phase-rich WC thin films on silicon and carbon substrates. Thin Solid Films 516:38743854 519. Lakhotkin YuV (2008) Chemical deposition of nanostructured tungsten and tungsten alloy coatings from gas phase. Protect Met 44(4):319-332 520. Weigert EC, Humbert MP, Mellinger ZJ, Ren Q, Beebe TP, Jr, Bao L, Chen JG (2008) Physical vapour deposition synthesis of tungsten monocarbide (WC) thin films on different carbon substrates. J Vac Sci Technol A 26(1):23-28 521. Yang BQ, Wang XP, Zhang HX, Wang ZB, Feng PX (2008) Effect of substrate temperature variation on nanostructured WC films prepared using HFCVD technique. Mater Lett 62:1547-1550 522. Liu Y, Gubisch M, Spiess L, Schaefer J (2009) Sliding of nanocomposite WC1–x/C coatings: transfer film and its influence on tribology. J Nanosci Nanotechnol 9(6):3499-3505 523. El-Mrabet S, Abad MD, López-Cartes C, Martínez-Martínez D, Sánchez-López JC (2009) Thermal evolution of WC/C nanostructured coatings by Raman and in situ XRD analysis. Plasma Process Polym 6:S444-S449 524. Raekelboom E, Abdelouahdi K, Legrand-Buscema C (2009) Structural investigation by the Rietveld method of sputtered tungsten carbide thin films. Thin Solid Films 517:1555-1558 525. Sauter PA, Balden M (2009) Deuterium retention in tungsten-doped carbon films. Phys Scripta T 138:014044 (4 pp.) 526. Sánchez-López JC, Martínez-Martínez D, Abad MD, Fernández A (2009) Metal carbide / amorphous C – based nanocomposite coatings for tribological applications. Surf Coat Technol 204:947-954 527. Abad MD, Muñoz-Márquez MA, El Mrabet S, Justo A, Sánchez-López JC (2010) Tailored synthesis of nanostructured WC/a-C coatings by dual magnetron sputtering. Surf Coat Technol 204:3490-3500 528. Moskalewicz T, Wendler B, Czyrska-Filemonowicz A (2010) Microstructural characterization of nanocomposite nc-MeC/a-C coatings on oxygen hardened Ti-6Al-4V alloy. Mater Charact 61:959-968 529. Moskalewicz T, Wendler B, Zimowski S, Dubiel B, Czyrska-Filemonowicz A (2010) Micro-structure, micro-mechanical and tribological properties of the nc-WC/a-C nanocomposite coatings magnetron sputtered on non-hardened and oxygen hardened Ti-6Al4V alloy. Surf Coat Technol 205:2668-2677 530. Ospina-Ospina R, Jurado JF, Vélez JM, Arango PJ, Salazar-Enríquez C, Restrepo-Parra E (2010) Structural and morphological characterization WCxNy thin films grown by pulsed vacuum arc discharge in an argon-nitrogen atmosphere. Surf Coat Technol 205:2191-2196 531. El Mrabet S, Abad MD, Sánchez-López JC (2011) Identification of the wear mechanism on WC/C nanostructured coatings. Surf Coat Technol 206:1913-1920 532. De Bonis A, Teghil R, Santagata A, Galasso, Rau JV (2012) Thin films deposited by femtosecond pulsed laser ablation of tungsten carbide. Appl Surf Sci 258:9198-9201 533. Lungu CP, Marcu A, Porosnicu C, Jepu I, Kovac J, Nemanic V (2012) Carbon-tungsten thin film deposition by a dual thermionic vacuum arc. IEEE Trans Plasma Sci 40(12):3546-3551 534. Jansson U, Lewin E (2013) Sputter deposition of transition metal carbide films – a critical review from a chemical perspective. Thin Solid Films 536:1-24

608

2 Tungsten Carbides

535. Ramírez MNT, Ardila VAM, García VJ, Zambrano G (2013) Composite nanoestructurado del sistema binario W-C en películas obtenidas por pulverzación catódica (Nanostructured composite of the binary system W-C in films obtained by sputtering). Rev Colomb Fis 45(1):92-95 (in Spanish) 536. Tang XH, Zhang WZ, Shi LQ, Qi Q, Zhang B, Zhang WY, Wang K, Hu JS (2013) Characteristic of the carbon-tungsten co-deposition layers prepared by r.f. magnetron sputtering in a D2/Ar plasma. Nucl Instrum Meth B 305:55-60 537. Teng F, Zhang P, Zhang G, Gong C, Gao C, Fu X, Wang J, Zhang Z, Pan X, Xie E (2014) One-step synthesis porous tungsten carbide films with excellent hydrophilicity. Mater Lett 115:9-12 538. Jinga V, Mateescu AO, Cristea D, Mateescu G, Burducea I, Ionescu C, Crӑciun LS, Ghiuţӑ I, Samoilӑ C, Ursuţiu D, Munteanu D (2015) Compositional, morphological and mechanical investigations of monolayer type coatings obtained by standard and reactive magnetron sputtering from Ti, TiB2 and WC. Appl Surf Sci 358:579-585 539. Nazon J, Herbst M, De Lucas MCM, Bourgeois S, Domenichini B (2015) WC-based thin films obtained by reactive radio-frequency magnetron sputtering using W target and methane gas. Thin Solid Films 591:119-125 540. Pawlak W, Kubiak KJ, Wendler BG, Mathia TG (2015) Wear-resistant multilayer nanocomposite WC1–x/C coating on Ti-6Al-4V titanium alloy. Tribol Int 82:400-406 541. He D, Pu J, Wang L, Zhang G, Wang Y, Xue Q (2016) Investigation of post-deposition annealing effects on microstructure, mechanical and tribological properties of WC/a-C nanocomposite coatings. Tribol Lett 63(2):14 (14 pp.) 542. Jiang J, Guan X, Lattimer J, Friend C, Verma A, Tsuchiya M, Ramanathan S (2016) Experimental investigation into tungsten carbide thin films as solid oxide fuel cell anodes. J Mater Res 31(19):3050-3059 543. Kim JB, Kim S-H, Han WS, Lee D-J (2016) Atomic layer deposited nanocrystalline tungsten carbides thin films as a metal gate and diffusion barrier for Cu metallization. J Vac Sci Technol A 34(4):041504 (6 pp.) 544. Kim JB, Jang B, Lee H-J, Han WS, Lee D-J, Lee H-B-R, Hong TE, Kim S-H (2016) A controlled growth of WNx and WCx thin films prepared by atomic layer deposition. Mater Lett 168:218-222 545. Kushkhov KhB, Kuchmezova FYu, Adamokova MN, Asanov AM (2016) Electrodeposition of coatings of double carbides of tungsten and molybdenum from tungstate-molybdatecarbonate solutions. Russ J Non-Ferr Met 57(5):515-520 546. Lofaj F, Kvetková L, Hviščová P, Gregor M, Ferdinandy M (2016) Reactive processes in the high target utilization sputtering (HiTUS) W-C based coatings. J Eur Ceram Soc 36(12):3029-3040 547. Lofaj F, Hviščová P, Zubko P, Németh D, Kabátová M (2019) Mechanical and tribological properties of the high target utilization sputtering W-C coatings on different substrates. Int J Refract Met Hard Mater 80:305-314 548. Larsen KR (2017) Nanostructured tungsten carbide coatings protect against corrosion. Mater Perform 56(10):17-19 549. Saravanan M, Venkateshwaran N, Devaraju A, Krishnakumari A (2018) Tribological behaviour of thin nano tungsten carbide film deposited on 316L stainless steel surface. Surf Rev Lett 25(8):1950027 (10 pp.) 550. Dushik VV, Rozhanskii NV, Lifshits VO, Rybkina TV, Kuzmin VP (2018) The formation of tungsten and tungsten carbides by CVD synthesis and proposed mechanism of chemical transformations and crystallization processes. Mater Lett 228:164-167 551. Gabhale B, Jadhawar A, Bhorde A, Nair S, Borate H, Waykar R, Aher R, Sharma P, Pawbake A, Jadkar S (2018) High band gap nanocrystalline tungsten carbide (nc-WC) thin films grown by hot wire chemical vapour deposition (HW-CVD) method. J Nano Electron Phys 10(3):03001 (6 pp.)

References

609

552. Zhu F, Chen Z-L, Liu K-Z, Liang W, Zhang Z (2018) Deposition of thin tungsten carbide films by dual ion beam sputtering. Vacuum 157:45-50 553. Phiri RR, Oladijo OP, Akinlabi ET (2019) Tungsten carbide thin films review: effect of deposition parameters on film microstructure and properties. In: Jen T-C, Akinlabi ET, Olubambi P, Augbavboa C (eds) Proc. 2nd Int. conf. on sustainable materials processing and manufacturing (SMPM 2019), Sun City, South Africa, 8-10 Mar 2019. Proc Manuf 35:522528 554. Wicher B, Chodun R, Kwiatkowski R, Trzcinski M, Nowakowska-Langier K, Lachowski A, Minikayev R, Rudnicki J, Naparty MK, Zdunek K (2019) Plasmochemical investigations of DLC/WCx nanocomposite coatings synthesized by gas injection magnetron sputtering technique. Diam Relat Mater 96:1-10 555. Ikenoue T, Yoshida T, Miyake M, Kasada R, Hirato T (2020) Fabrication and mechanical properties of tungsten carbide thin films via mist chemical vapour deposition. J Alloys Compd 829:154567 (7 pp.) 556. Novoselov KS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov SV, Geim AK (2005) Two-dimensional atomic crystals. Proc Nat Acad Sci USA 102(30):10451-10453 557. Butler SZ, Hollen SM, Cao L, Cui Y, Gupta JA, Gutiérrez HR, Heinz TF, Hong SS, Huang J, Ismach AF, Johnston-Halperin E, Kuno M, Plashnitsa VV, Robinson RD, Ruoff RS, Salahuddin S, Shan J, Shi L, Spencer MG, Terrones M, Windl W, Goldberger JE (2013) Progress, challenges and opportunities in two-dimensional materials beyond graphene. ACS Nano 7(4):2898-2926 558. Gogotsi Yu (2015) Not just graphene: the wonderful world of carbon and related nanomaterials. Mater Res Soc Bull 40:1110-1120 559. Gogotsi Yu (2015) Transition metal carbides go 2D. Nature Mater 14(11):1079-1080 560. Naguib M, Mashtalir O, Carle J, Presser V, Lu J, Niu J, Heon M, Hultman L, Gogotsi Yu, Barsoum MW (2012) Two-dimensional transition metal carbides. ACS Nano 6(2):1322-1331 561. Naguib M, Mochalin VN, Barsoum MW, Gogotsi Yu (2014) MXenes: a new family of twodimensional materials. Adv Mater 26(7):992-1005 562. Konyashin I, Ries B (2019) Microstructure, grain boundaries and properties of nanostructured hardmetals. Mater Lett 253:128-130 563. Nguyen TP, Kim SY, Lee TH, Jang HW, Le QV, Kim IT (2020) Facile synthesis of W2C@WS2 alloy nanoflowers and their hydrogen generation performance. Appl Surf Sci 504:144389 (7 pp.) 564. Anasori B, Gogotsi Yu (2019) Introduction to 2D transition metal carbides and nitrides (MXenes). In: Anasori B, Gogotsi Yu (eds) 2D Metal carbides and nitrides (MXenes), pp. 312. Springer Nature, Cham, Switzerland 565. Xu C, Wang L, Liu Z, Chen L, Guo J, Kang N, Ma X-L, Cheng H-M, Ren W (2015) Largearea high-quality 2D ultra-thin Mo2C superconducting crystals. Nature Mater 14(11):11351141 566. Meshkian R, Dahlqvist M, Lu J, Wickman B, Halim J, Thörnberg J, Tao Q, Li S, Intikhab S, Snyder J, Barsoum MW, Yildizhan M, Palisaitis J, Hultman L, Persson OÅ, Rosen J (2018) W-based atomic laminates and their 2D derivative W1,33C MXene with vacancy ordering. Adv Mater 30:1706409 (8 pp.) 567. Anasori B, Lu J, Rivin O, Dahlqvist M, Halim J, Voigt C, Rosen J, Hultman L, Barsoum MW, Caspi EN (2019) A tungsten-based nanolaminated ternary carbide: (W,Ti)4C4–x. Inorg Chem 58:1100-1106 568. Rosen J, Dahlqvist M, Tao Q, Hultman L (2019) In- and out-of-plane ordered MAX phases and their MXene derivatives. In: Anasori B, Gogotsi Yu (eds) 2D Metal carbides and nitrides (MXenes), pp. 37-52. Springer Nature, Cham, Switzerland 569. Guo Z, Zhu L, Zhou J, Sun Z (2015) Microscopic origin of MXenes derived from layered MAX phases. RSC Adv 5(32):25403-25408

610

2 Tungsten Carbides

570. Weng H, Ranjbar A, Liang Y, Song Z, Khazaei M, Yunoki S, Arai M, Kawazoe Y, Fang Z, Dai X (2015) Large-gap two-dimensional topological insulator in oxygen functionalized MXene. Phys Rev B 92(7):075436 (7 pp.) 571. Pan H (2016) Ultra-high electrochemical catalytic activity of MXenes. Sci Rep 6:32531 (10 pp.) 572. Zhang Y (2017) First principles prediction of two-dimensional tungsten carbide (W2C) monolayer and its Li storage capability. Comput Condens Matter 10:35-38 573. Morales-García Á, Fernández-Fernández A, Viñes F, Illas F (2018) CO2 abatement using two-dimensional MXene carbides. J Mater Chem A 6(8):3381-3385 574. Wu D, Wang S, Zhang S, Yuan J, Yang B, Chen H (2018) Highly negative Poisson’s ratio in a flexible two-dimensional tungsten carbide monolayer. Phys Chem Chem Phys 20(28):18924-18930 575. Zou X, Li G, Wang Q, Tang D, Wu B, Wang X (2018) Energy storage properties of selectively functionalized Cr-group MXenes. Comput Mater Sci 150:236-243 576. Li L, Wang X, Guo H, Yao G, Yu H, Tian Z, Li B, Chen L (2019) Theoretical screening of single transition metal atoms embedded in MXene defects as superior electrocatalyst of nitrogen reduction reaction. Small Methods 3(11):1900337 (7 pp.) 577. Sabzi M, Anijdan SHM, Ghobeiti-Hasab M, Fatemi-Mehr M (2018) Sintering variables optimization, microstructural evolution and physical properties enhancement of nano-WC ceramics. J Alloys Compd 766:672-677 578. Lengauer W (2000) Transition metal carbides, nitrides and carbonitrides. In: Riedel R (ed) Handbook of ceramic hard materials, Vol. 1, pp. 202-252. Wiley-VCH, Weinheim, New York 579. Samsonov GV, Épik AP (1973) Tugoplavkie pokrytiya (Refractory coatings). Metallurgiya, Moscow (in Russian) 580. Zefirov AP (ed), Veryatin UD, Mashirev VP, Ryabtsev NG, Tarasov VI, Rogozkin BD, Korobov IV (1965) Termodinamicheskie svoistva neorganicheskikh veschestv (Thermodynamic properties of inorganic substances). Atomizdat, Moscow (in Russian) 581. Hague JR, Lynch JF, Rudnick A, Holden FC, Duckworth WH (1964) Refractory ceramics for aerospace. Battelle Memorial Institute, The American Ceramic Society, Columbus, Ohio 582. Lynch JF, Ruderer CG, Duckworth WH (1966) Engineering properties of selected ceramic materials. The American Ceramic Society, Columbus, Ohio 583. Lynch JF (1979) Engineering property data on selected ceramics, Vol. 2 – Carbides. Technical Report MCIC-HB-07, pp. 1-136. Metals and Ceramics Information Centre, Battelle Columbus Laboratories, Ohio 584. Krzhizhanovskii RE, Shtern ZYu (1977) Teplofizicheskie svoistva nemetallicheskikh materialov (karbidy) (Thermophysical properties of non-metallic materials (carbides)). Energiya, Leningrad (in Russian) 585. Portnoi KI, Chubarov VM (1967) Svoistva tugoplavkikh metallov i soedinenii (The properties of refractory metals and compounds). In: Tumanov AT, Portnoi KI (eds) Tugoplavkie materialy v mashinostroenii (Refractory materials in machinery construction), pp. 7-124. Mashinostroenie, Moscow (in Russian) 586. Sheipline VM, Runck RJ (1956) Carbides. In: Campbell IE (ed) High temperature technology, pp. 114-130. Wiley, New York, Chapman and Hall, London 587. Rother B, Vetter J (1992) Plasma-Beschichtungsverfahren und Hartstoffschichten (Plasma coating processes and hard coatings). Deutscher Verlag für Grundstoffindustrie, Leipzig (in German) 588. Simon H, Thoma M (1985) Angewandte Oberflächentechnik für metallische Werkstoffe (Applied surface jetting technology for metallic materials). Hanser, München (in German) 589. Schedler W (1988) Hartmetall für den Praktiker (Hardmetal for the practitioner). VDIVerlag, Düsseldorf (in German) 590. Holleck H (1986) Material selection for hard coatings. J Vac Sci Technol A 4(6):2661-2669

References

611

591. Dörre E (1986) Nichtmetallische Hartstoffe (Non-metallic hard materials). In: Uetz H (ed) Abrasion und erosion (Abrasion and erosion), pp. 433-437. Hanser, München (in German) 592. Lönnberg B (1988) Synthesis, structure and properties of some technologically important carbides, borides and silicides. PhD thesis, Uppsala Universitet, Sweden 593. Pearson WB (1958) Lattice spacings and structures of metals and alloys. Pergamon Press, London 594. Berg G, Friedrich C, Broszeit E, Berger C (2000) Data collection of properties of hard materials. In: Riedel R (ed) Handbook of ceramic hard materials, pp. 965-995. Wiley – VCH, Weinheim 595. Levinson LS (1964) High-temperature heat content of tungsten carbide and hafnium carbide. J Chem Phys 40(5):1437-1438 596. Turchanin AG, Turchanin MA (1991) Termodinamika tugoplavkikh karbidov i karbonitridov (Thermodynamics of refractory carbides and carbonitrides). Metallurgiya, Moscow (in Russian) 597. Mah AD (1963) Heats of combustion and formation of carbides tungsten and molybdenum. Technical Report BM-RI-6337, pp. 1-9. US Bureau of Mines, US Department of the Interior, Washington, DC 598. Bolgar AS, Turchanin AG, Fesenko VV (1973) Termodinamicheskie svoistva karbidov (Thermodynamic properties of carbides). Naukova Dumka, Kyiv (in Russian) 599. Glushko VP, Gurvich LV, eds (1982) Termodinamicheskie svoistva individualnukh veshchestv (Thermodynamic properties of individual substances), Vol. IV, Parts 1-2. Nauka, Moscow (in Russian) 600. Neel DS, Pears CD, Oglesby S (1963) The thermal properties of twenty-six solid materials to 5000 °F or their destruction temperatures. Technical Report ASD-TDR-62-765, Contract USAF 33(616)-7319, pp. 1-420. Southern Research Institute, University of Alabama, Birmingham, USA 601. McGraw LD, Seltz H, Snyder PE (1947) The heat of combustion of tungsten carbide WC. J Am Chem Soc 69(2):329-331 602. Huff G, Squitieri E, Snyder PE (1948) The heat of formation of tungstic oxide WO3. J Am Chem Soc 70(10):3380-3381 603. Krikorian OH (1955) High temperature studies. I. Reactions of the refractory silicides with carbon and with nitrogen. II. Thermodynamic properties of carbides. III. Heat of formation of the 3πu state of C2 from graphite. Technical Report UCRL-2888, Contract W-7405-eng-48, pp. 1-136. United States Atomic Energy Commission, University of California Radiation Laboratory, Berkeley, California 604. Ormont BF (1959) Energii atomizatsii i teploty obrazovaniya nekotorykh karbidov i nitridov i naibolee veroyatnye znacheniya dlya energii dissotsiatsii azota i energii sublimatsii ugleroda (Atomization energies and heats of formation of some carbides and nitrides and the most probable values for the dissociation energy of nitrogen and sublimation energy of carbon). Zh Fiz Khim 33(7):1455-1460 (in Russian) 605. Fujishiro S (1961) Thermodynamic properties of transition metal carbides and their periodicity. J Jpn Soc Powder Powder Metall 8(2):73-76 606. Oshcherin BN (1965) Nekotorye voprosy termodinamiki karbidnykh faz vnedreniya v oblastyakh gomogennosti (The certain problems of thermodynamics of carbide interstitial phases within the homogeneity ranges). In: Grigoreva VV, Eremenko VN, Nazarchuk TN, Samsonov GV, Fedorchenko IM, Frantsevich IN (eds) Vysokotemperaturnye neorganicheskie soedineniya (High-temperature inorganic compounds), pp. 157-165. Naukova Dumka, Kyiv (in Russian) 607. Krajewski A, D’Alessio L, De Maria G (1998) Physico-chemical and thermophysical properties of cubic binary carbides. Cryst Res Technol 33(3):341-374 608. Finlay GR (1952) Refractories for 4000 °F and higher. Chem Can 4:41-44 609. Cronin LJ (1951) Refractory cermets. Am Ceram Soc Bull 30(7):234-236

612

2 Tungsten Carbides

610. Kubaschewski O, Evans EL (1958) Metallurgical thermochemistry. Pergamon Press, Oxford 611. Nadler MR, Kempter CP (1960) Some solidus temperatures in several metal-carbon systems. J Phys Chem 64(10):1468-1471 612. Lvov SN, Nemchenko VF, Samsonov GV (1960) Nekotorye zakonomernosti elektricheskikh svoistv boridov, karbidov i nitridov perekhodnykh metallov IV-VI grup periodicheskoi sistemy (Some regularities in the electric properties of borides, carbides and nitrides of transition metals within IV-VI groups of the periodic system). Doklady AN SSSR 135(3):577-580 (in Russian) 613. Schick HL, ed (1966) Thermodynamics of certain refractory compounds, Vol. 1-2. Academic Press, New York, London 614. Brewer L, Bromley LA, Gilles PW, Lofgen NL (1950) Thermodynamics and physical properties of nitrides, carbides, sulphides, silicides and phosphides. In: Quill LL (ed) The chemistry and metallurgy of miscellaneous materials: thermodynamics, pp. 40-59. McGrawHill, New York 615. Alekseev VI, Shvartsman LA (1963) Termodinamika reaktsii obrazovaniya karbidov volframa (Thermodynamics of formation reactions of tungsten carbides). Izv AN SSSR OTN Metall Gornoe Delo (1):91-99 (in Russian) 616. Krikorian OH (1962) Estimation of high-temperature heat capacities of carbides. Technical Report UCRL-6785, Contract W-7405-eng-48, pp. 1-9. University of California Lawrence Radiation Laboratory, Livermore, California 617. Sara RV, Dolloff RT, Kroenke WJ, Ruggiero JD, Lowell CE, Forgeng WD, Shaler AJ, Beodray FJ, Weigel J (1962) Research study to determine the phase equilibrium relations of selected metal carbides at high temperatures. Technical Report WADD-TR-60-143, Contracts AF33(616)-6286 and AF33(657)-8025, Part 3, pp. 1-31. Research Laboratory of National Carbon Company, Union Carbide Corporation, Parma, Ohio 618. Barin I (1995) Thermochemical data of pure substances, 3rd ed., Vol. 1-2. VCH, Weinheim, New York 619. Chang YA (1965) Thermochemical calculations. Thermodynamic properties of group IV, V and VI binary transition metal carbides. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFML-TR-65-2, Contract USAF 33(615)-1249, Part 4, Vol. 1, pp. 1-114. Air Force Materials Laboratory, Wright Patterson Air Force Base, Ohio 620. Touloukian YS, Buyco EH (1970) Thermophysical properties of matter. Vol. 5 – Specific heat – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington, DC 621. Pfau H, Rix W (1954) Über die Kristallform des Wolframkarbides WC und die Verteilung der Kohlenstoffatome in seinem Gitter (On the crystal structure of tungsten carbide WC and the distribution of carbon atoms in its lattice). Z Metallkd 45(3):116-118 (in German) 622. Wicks CE, Block FE (1963) Thermodynamic properties of 65 elements – their oxides, halides, carbides and nitrides. Bulletin N 605, pp. 1-146. US Bureau of Mines, US Department of the Interior, Washington, DC 623. Iwai T, Takahashi I, Handa M (1986) Gibbs free energies of formation of molybdenum carbide and tungsten carbide from 1173 to 1573 K. Metall Trans A 17(11):2031-2034 624. Samsonov GV, Latysheva VP (1956) Issledovanie diffuzii bora i ugleroda v nekotorye metally perekhodnykh grupp (A study of the diffusion of boron and carbon into certain metals of transition groups). Fiz Met Metalloved 2(2):309-319 (in Russian) 625. Shunk FA (1969) Constitution of binary alloys, second supplement. McGraw-Hill, New York, London 626. Samsonov GV (1964) Refractory transition metal compounds. Academic Press, New York 627. Chirkin VS (1968) Teplofizicheskie svoistva materialov yadernoi tekhniki (Thermophysical properties of nuclear materials). Atomizdat, Moscow (in Russian) 628. Chang YA, Toth LE, Tyan YS (1971) On the elastic and thermodynamic properties of transition metal carbides. Metall Trans 2(1):315-320

References

613

629. Corteville J, Pons L (1963) Cristallographie – mise en evidence de la plasticité du monocarbure de tungstène (Crystallography – demonstration of the plasticity of tungsten monocarbide). C R Hebd Séanc Acad Sci 257(13):1915-1918 (in French) 630. Corteville J, Monier JC, Pons L (1965) Détermination des plans de glissement dans le tungstène monocarbure (Determination of the glide planes in tungsten monocarbide). C R Hebd Séanc Acad Sci 260:2773-2777 (in French) 631. Vereshchagin LF, Fateeva NS (1977) Melting temperatures of refractory metals at high pressures. High Temp High Press 9(6):619-628 632. Andon RJL, Martin JF, Mills KC, Jenkins TR (1975) Heat capacity and entropy of tungsten carbide. J Chem Thermodyn 7(11):1079-1084 633. Shatynski SR (1979) The thermochemistry of transition metal carbides. Oxid Met 13(2):105-118 634. Chang YA (1967) Thermal properties of tantalum monocarbide and tungsten monocarbide. Trans Metall Soc AIME 239(11):1685-1691 635. Chang YA (1968) Reply to the discussion of “Thermal properties of tantalum monocarbide and tungsten monocarbide” by C. P. Kempter and H. L. Brown. Trans Metall Soc AIME 242(12):1751-1752 636. Pankratz LB, Stuve JM, Gokcen NA (1984) Thermodynamic data for mineral technology. Bulletin N 677, pp. 1-355. US Bureau of Mines, US Department of the Interior, Washington, DC 637. Coltters RG (1985) Thermodynamics of binary metallic carbides: a review. Mater Sci Eng 76:1-50 638. Kubaschewski O, Alcock CB (1979) Metallurgical thermochemistry, 5th ed. Pergamon Press, Oxford 639. Vorobev YuP (2004) Karbidy v stalyakh (Carbides in steels). Izv Chelyabinsk Nauch Tsentr (2):34-60 (in Russian) 640. Hoch M, Blackburn PE, Dingledy DP, Johnston HL (1955) The heat of sublimation of carbon. J Phys Chem 59(2):97-99 641. Storms EK (1964) A critical review of refractories. Technical Report LA-TR-2942, Contract W-7405-eng-36, pp. 1-255. Los Alamos Scientific Laboratory, New Mexico 642. Kulikov IS (1988) Termodinamika karbidov i nitridov (Thermodynamics of carbides and nitrides). Metallurgiya, Chelyabinsk (in Russian) 643. Fesenko VV, Bolgar AS (1965) Isparenie tugoplavkikh soedinenii (Vaporization of refractory compounds). Metallurgiya, Moscow (in Russian) 644. Nesmeyanov AN (1963) Vapour pressure of the chemical elements. Elsevier, New York 645. Fesenko VV, Bolgar AS (1963) Evaporation rate and vapour pressures of carbides, silicides, nitrides and borides. Powder Metall Met Ceram 2(1):11-17 646. Ren JM, Salin ED (1994) Direct solid sample analysis using furnace vaporization with freon modification and industry coupled plasma atomic emission spectrometry. I. Vaporization of oxides and carbides. Spectrochim Acta B 49(6):555-566 647. Zhou X, Ma D, Wang L, Zhao Y, Wang S (2020) Large-volume cubic press produces high temperatures above 4000 K for study of the refractory materials at pressures. Rev Sci Instrum 91(1): 015118 (3 pp.) 648. Ortman BJ, Hauge RH, Margrave JL (1988) Chemical reactions of carbon atoms and molecules from laser-induced vaporization of graphite, TaC and WC. J Quant Spectrosc Radiat Transfer 40(3):439-447 649. Tsidulko AG, Rusanov VM, Bobrov GV, Dokukina IA, Timofeeva II, Shaposhnikova TI (1992) Loss of carbon during plasma-spraying of clad carbide powders. Powder Metall Met Ceram 31(10):883-885 650. Yamamoto A, Kusano T, Seki T, Okutomi T (1999) Vaporization of carbon from Cu-WC contact during arc discharge in vacuum. IEEE Trans Plasma Sci 27(4):915-922 651. Golubev OL, Loginov MV (2006) Effect of the emitter temperature and emitter atom ionization potential on field evaporation. Tech Phys 51(9):1215-1222

614

2 Tungsten Carbides

652. Sabor S, Benjelloun AT, Al Mogren MM, Hochlaf M (2014) Characterization of gas phase WC2+: a thermodynamically stable carbide dication. Phys Chem Chem Phys 16(39):2135621362 653. Sabor S, Fadili D, Benjelloun AT, Benzakour M, Mcharfi M (2020) Computational spectroscopy of diatomic tungsten carbide WC. J Mol Spectrosc 371:111305 (11 pp.) 654. Kulikov IS (1969) Termicheskaya dissotsiatsiya soedinenii (Thermal dissociation of compounds), 2nd ed. Metallurgiya, Moscow (in Russian) 655. Perecherla A, Williams WS (1988) Room-temperature thermal conductivity of cemented transition metal carbides. J Am Ceram Soc 71(12):1130-1133 656. Frandsen MV, Williams WS (1991) Thermal conductivity and electrical resistivity of cemented transition metal carbides at low temperatures. J Am Ceram Soc 74(6):1411-1416 657. Sakurai J, Hayashi J, Mekata M, Tsuchida T, Takagi H (1961) Thermal conductivities of monocarbides of transition metals. J Jpn Inst Met Mater 25(4):289-292 (in Japanese) 658. Lvov SN, Lesnaya MI, Vinitskii IM, Naumenko VYa (1972) Thermal conductivity of some refractory carbides and borides. High Temp 10(6):1196-1198 659. Karapetyants MKh, Karapetyants ML (1968) Osnovnye termodinamicheskie konstanty neorganicheskikh i organicheskikh veshchestv (General thermodynamic constants of inorganic and organic substances). Khimiya, Moscow (in Russian) 660. Touloukian YS, Powell RW, Ho CY, Klemens PG (1970) Thermophysical properties of matter. Vol. 2 – Thermal conductivity – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington, DC 661. Gubernat A, Rutkowski P, Grabowski G, Zientara D (2014) Hot-pressing of tungsten carbide with and without sintering additives. Int J Refract Met Hard Mater 43:193-199 662. Shackelford JF, Han Y-H, Kim S, Kwon S-H (2016) CRC materials science and engineering handbook, 4th ed. CRC Press, Boca Raton, London, New York 663. Schultrich B, Poeßnecker W (1988) Thermal conductivity of cemented carbides. J Therm Anal Calorim 33:305-310 664. Wang H, Webb T, Bitler JW (2015) Study of thermal expansion and thermal conductivity of cemented WC-Co composite. Int J Refract Met Hard Mater 49:170-177 665. Hajare AS, Gogte CL (2018) Comparative study of wear behaviour of thermal spray HVOF coating on 304 SS. In: Sivaprasad K (ed) Proc. Int. conf. on emerging trends in materials and manufacturing engineering (IMME17), Tiruchirappalli, India, 10-12 Mar 2017. Mater Today Proc 5:6924-6933 666. Sun J, Zhao J, Huang Z, Yan K, Shen X, Xing J, Gao Y, Jian Y, Yang H, Li B (2020) A review on binderless tungsten carbide: development and application. Nano-Micro Lett 12:13 (37 pp.) 667. Krikorian OH (1960) Thermal expansion of high-temperature materials. Technical Report UCRL-6132, Contract W-7405-eng-48, pp. 1-7. University of California Lawrence Radiation Laboratory, Livermore, California 668. Whittemore OJ, Jr (1959) Extreme temperature refractories. J Can Ceram Soc 28:43-48 669. Neshpor VS, Samsonov GV (1957) Brittleness in metallic compounds. Phys Met Metallogr 4(1):147-148 670. Bradshaw WG, Matthews CO (1959) Properties of refractory materials: collected data and references. Technical Report LMSD-2466, 2nd ed., pp. 1-91. Lockheed Aircraft Corporation Missile Systems Division, Sunnyvale, California 671. Gurland J, Norton JT (1952) Role of the binder phase in cemented tungsten carbide – cobalt alloys. J Met 4(10):1051-1056 672. Norton FH, Kingery WD (1953) The measurement of thermal conductivity of refractory materials. Technical Report NYO-3644, pp. 1-18. United States Atomic Energy Commission, Washington, DC 673. Bukatov VG (1979) Issledovanie fiziko-mekhanicheskikh svoistv karbidov tugoplavkikh metallov i nekotorykh splavov na ikh osnove (Studies of physico-mechanical properties of

References

615

refractory metal carbides and some alloys on their basis). PhD thesis, Moscow Institute of Steels and Alloys (in Russian) 674. Frantsevich IN, Zhurakovskii EA, Lyashchenko AB (1967) Elastic constants and characteristics of the electron structure of certain classes of refractory compounds obtained by the metal-powder method. Inorg Mater 3(1):6-12 675. Panov VS, Meerson GA (1968) Preparation and study of some properties of NbC-WC and TaC-WC. Powder Metall Met Ceram 7(5):375-381 676. Tumanov VI, Funke VF, Baskin ML, Novikova TA (1964) Vliyanie temperatury na fizicheskie svoistva tverdykh splavov karbid volframa – kobalt (Effect of temperature on the physical properties of tungsten carbide – cobalt hard metals). Izv AN SSSR OTN Metall Gornoe Delo (1):170-175 (in Russian) 677. Nowotny H, Laube E (1961) Die thermische Ausdehnung des hochschmelzenden Phasen (The thermal expansion of high-melting phases). Planseeber Pulvermetall 9:54-59 (in German) 678. Koenig JH (1958) New developments in ceramics. Mater Design Eng 47(5):121-123 679. Schwarzkopf P, Kieffer R (1960) Cemented carbides. Macmillan, New York 680. Berger J (1992) Beschihten mit Hartstoffen (Hard material coatings). VDI-Verlag, Düsseldorf (in German) 681. Samsonov GV, Grebenkina VG, Klimenko VS (1971) Coefficient of thermal expansion of refractory compounds. Powder Metall Met Ceram 10(8):643-647 682. Mai YW (1976) Thermal shock resistance and fracture strength behaviour of two tool carbides. J Am Ceram Soc 59(11-12):491-494 683. Kiernan JS (1985) Why tungsten carbide? Aircraft Eng 57(9):6-7 684. Schultrich B, Kreher W (1986) Influence of anisotropic thermal expansion on internal stresses in WC hardmetals. J Mater Sci Lett 5:389-390 685. Sayers CM (1987) Thermal contraction stresses in cemented tungsten carbide composites. Mater Sci Eng 91:195-199 686. Bachmann K, Williams WS (1971) Low-temperature electrical resistivity and Hall effect of single-crystal α-tungsten carbide. J Appl Phys 42(11):4406-4407 687. Grebenkina VG, Denbnovetskaya EN (1974) Thermal coefficient of the electrical resistivity of carbides and their solid solutions. In: Samsonov GV (ed) Refractory carbides, pp. 269-274. Consultants Bureau, New York, London 688. Denbnovetskaya EN, Lvov SN (1974) A study of some physical properties of alloys of the system TaC-WC. In: Samsonov GV (ed) Refractory carbides, pp. 275-282. Consultants Bureau, New York, London 689. Samsonov GV, Sinelnikova VS (1962) Vysokotemperaturnye metallokeramicheskie materialy (High-temperature sintered metal-powder materials). UkrSSR Academy of Sciences, Kyiv (in Russian) 690. Funke VF, Shurshakov AN, Yudkovskii SI, Kuznetsova KF, Shulepov VI, Yurkevich YuN (1960) Elektricheskoe soprotivlenie i struktura splavov WC-Co (Electrical resistance and structure of WC-Co alloys). Fiz Met Metalloved 10(2):207-215 (in Russian) 691. Kolomoets NV, Neshpor VS, Samsonov GV, Semenkovich SA (1958) Termoelektricheskie svoistva nekotorykh metallopodobnykh soedinenii (Thermoelectric properties of some metallike compounds) Zh Tekh Fiz 28(11):2382-2389 (in Russian) 692. Rudy E, Benesovsky F (1960) Über die elektrische Leitfähigkeit der sehr hohen Schmelzpunktcarbide und Carbidmischkristalle (On the electrical conductivity of the very high-melting point carbides and carbide mixed crystals). Planseeber Pulvermetall 8:66-72 (in German) 693. Goldsmith A, Waterman T, Hirschorn HJ (1961) Handbook of thermophysical properties of solid materials. Pergamon Press, Oxford, London 694. Samsonov GV (1956) Elektroprovodnost nekotorykh soedinenii perekhodnykh metallov s borom, uglerodom i azotom i ikh splavov (Electroconductivity of some compounds of

616

2 Tungsten Carbides

transition metals with boron, carbon and nitrogen and their alloys). Zh Tekh Fiz 26(4):716722 (in Russian) 695. Lvov SN, Nemchenko VF, Samsonov GV (1962) Effect of non-metallic atoms on the electric properties of high-melting compounds of transition metals. Powder Metall Met Ceram 1(4):231-236 696. Samsonov GV, Sinelnikova VS (1962) The resistivity of refractory compounds at high temperatures. Powder Metall Met Ceram 1(4):272-274 697. Neshpor VS, Samsonov GV (1964) O svyazi koeffitsienta termoelektricheskoi dobrotnosti monokarbidov i mononitridov perekhodnykh metallov s ikh atomnymi kharakteristikami (Thermoelectric efficiency of monocarbides and mononitrides of transition metals as related to their atomic characteristics). Doklady AN SSSR 157(4):834-836 (in Russian) 698. Clinard FW, Jr, Kempter CP (1968) Low-temperature electrical properties of some transition metals and transition metal carbides. J Less-Common Met 15:59-73 699. Samsonov GV, Grebenkina VG (1968) Temperature coefficient of electroresistance of some high-melting compounds. Powder Metall Met Ceram 7(2):107-111 700. Grebenkina VG, Sorokin VN, Yusov YuP, Perevezentsev AV (1973) Use of refractory carbides in resistors. Powder Metall Met Ceram 12(6):502-504 701. Weishart H, Heera V, Matz W, Skorupa W (1997) Ion beam assisted deposition of a tungsten compound layer on 6H-silicon carbide. Diam Relat Mater 6:1432-1435 702. Dy LC, Williams WS (1982) Resistivity, superconductivity and order-disorder transformations in transition metal carbides and hydrogen-doped carbides. J Appl Phys 53(12):89158927 703. Williams WS (1999) Electrical properties of hard materials. Int J Refract Met Hard Mater 17:21-26 704. Sun B, Sun Y, Wang C (2017) Anisotropic electrical transport of flexible tungsten carbide nanostructures: towards nanoscale interconnects and electron emitters. Nanotechnol 28:445707 (9 pp.) 705. Roberts BW (1963) Superconductive materials and some of their properties. Technical Report TR-63-RL-3252M, pp. 1-92. General Electric Company, Schenectady, New York 706. Roberts BW (1972) Properties of selected superconductive materials. NBS Technical Note NBS-TN-724, National Bureau of Standards, US Government Printing Office, Washington, DC 707. Roberts BW (1978) Properties of selected superconductive materials. Technical Report NBS-TN-983/NBS-TN-825, Accession PB-287013/7, N79-74281, pp. 1-103. National Technical Information Service, Washington, DC 708. Rajagopalan M, Saigeetha P, Kalpana G, Palanivel B (1994) Superconductivity of WC in the NaCl-type structure under pressure. Jpn J Appl Phys 33(1-4A):1847-1850 709. Miki H, Takeno T, Takagi T, Bozhko A, Shupegin M, Onodera H (2006) Superconducting property in tungsten containing amorphous carbon composite. In: Proc. IEEE conf. on nanoelectronics (NanoSingapore 2006), Singapore, 10-13 Jan 2006. Proc IEEE Conf Emerg Technol Nanoelectron 9(6):278-282 710. Hou X-Y, Wang Z, Gu Y-D, He J-B, Chen D, Zhu W-L, Zhang M-D, Zhang F, Xu Y-F, Zhang S, Yang H-X, Ren Z-A, Weng H-M, Hao N, Lv W-G, Hu J-P, Chen G-F, Shan L (2019) Superconductivity induced at a point contact on the topological semimetal tungsten carbide. Phys Rev B 100(23):235109 (7 pp.) 711. Zhu W-L, Hou X-Y, Li J, Huang Y, Zhang S, He J-B, Chen D, Wang Y, Dong Q, Zhang MD, Yang H-X, Ren Z-A, Hu J-P, Shan L, Chen G-F (2020) Interfacial superconductivity on the topological semimetal tungsten carbide induced by metal deposition. Adv Mater 1907970 (6 pp.) 712. He J-B, Chen D, Zhu W-L, Zhang S, Zhao L-X, Ren Z-A, Chen G-F (2017) Magnetotransport properties of the triply degenerate node topological semimetal tungsten carbide. Phys Rev B 95(19):195165 (4 pp.)

References

617

713. Wang C, Chen L, Liu Z, Liu Z, Ma X-L, Xu C, Cheng H-M, Ren W, Kang N (2019) Transport properties of topological semimetal tungsten carbide in the 2D limit. Adv Electron Mater 5(4):1800839 (5 pp.) 714. Kikoin IK (1976) Tablitsy fizicheskikh velichin (Tables of physical values). Atomizdat, Moscow (in Russian) 715. Klemm W, Schüth W (1931) Magnetochemische Untersuchungen. 3. Über den Magnetismus einiger Carbide und Nitride (Magnetochemical studies. 3. On the magnetism of some carbides and borides). Z Anorg Allg Chem 201(1):24-31 (in German) 716. Lin Z-D, Wang C-H, Shen D-H (1986) Studies of electron structure and magnetism of WC. Acta Phys Sin 35(1):98-103 (in Chinese) 717. Kanematsu K, Misawa S (1997) 4d and 5d elements, alloys and compounds between themselves or with main group elements. In: Wijn HPJ (ed) Magnetic properties of metals. Subvol. A – 3d, 4d and 5d elements, alloys and compounds, pp. 225-285. Springer, Berlin, Heidelberg 718. Kurlov AS, Nazarova SZ, Gusev AI (2005) Magnetic susceptibility of tungsten carbide: relaxation and impurity effects. JETP Let 82(8):509-514 719. Ramqvist L, Hamrin K, Johansson G, Fahlman A, Nordling C (1969) Charge transfer in transition metal carbides and related compounds studied by ESCA. J Phys Chem Solids 30(7):1835-1847 720. Williams WS (1971) Transition-metal carbides. Prog Solid State Chem 6:57-118 721. Kammori Ô, Sato K, Kurosawa F (1968) Infrared absorption spectra of metal carbides, nitrides and sulfides. Jpn Analyst 17(10):1270-1273 (in Japanese) 722. Xiong H (1984) Research on the infrared spectra of the interstitial TiC and WC, their bonding type and the metallization of non-metals. J Cent South Inst Min Metall (2):74-79 (in Chinese) 723. Yanagihara M, Niwano M, Koide T, Sato S, Miyahara T, Iguchi Y, Yamaguchi S, Sasaki T (1986) Soft X-ray reflection from SiC, TiC and WC mirrors. Appl Optics 25(24):4586-4590 724. Ivanchenko LA (1983) Optical properties of powders of some refractory compounds. Powder Metall Met Ceram 22(8):653-659 725. Qin D-Y, Gao Z (1990) XPS study of tungsten carbide. Chin J Chem 8(4):301-305 726. Katrib A, Hemming F, Hilaire L, Wehrer P, Maire G (1994) XPS studies of supported tungsten carbide(s). J Electron Spectrosc Relat Phenom 68(C):589-595 727. Yamada K, Kohzuki H, Takahashi T, Motoyama M (1999) Dependence of C K X-ray emission spectra of WC on crystalline size and observation angle. J Jpn Inst Met 63(4):417421 (in Japanese) 728. Sickafoose SM, Smith AW, Morse MD (2002) Optical spectroscopy of tungsten carbide (WC). J Chem Phys 116(3):993-1002 729. Smetyukhova TN, Druzhinin AV, Podgorny DA (2017) Features of the Auger spectra of Ti2C, SiC and WC. J Surf Investig X-Ray Synchrotron Neutron Tech 11(2):414-419 730. Samsonov GV, Fomenko VS, Paderno YuB (1962) Spectral emittance of the powders of some high-melting compounds. Refract Indust Ceram 3(1-2):35-37 731. Wickersham CE, Foster EL, Stickford GH (1981) Reactively sputter-deposited highemissivity tungsten carbide / carbon coatings. In: Proc. 27th Natl. symp. of the American Vacuum Society, Detroit, Michigan, 13-17 Oct 1980, Part 1. J Vac Sci Technol 18(2):223225 732. Ozaki Y, Zee RH (1995) Investigation of thermal and hydrogen effects on emissivity of refractory metals and carbides. Mater Sci Eng A 202:134-141 733. Samsonov GV, Podchernyaeva IA, Fomenko VS (1969) Emission coefficient of highmelting compounds. Powder Metall Met Ceram 8(5):374-379 734. Touloukian YS, DeWitt DP (1972) Thermophysical properties of matter. Vol. 8 – Thermal radiative properties – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington, DC

618

2 Tungsten Carbides

735. Juenke EF (1964) A review of recent research on refractory metal carbides and borides. Technical Report GEMT-267, Contract USAEC-AT(40-1)-2847, pp. 1-24. Nuclear Materials and Propulsion Operation Advanced Technology Services, General Electric, Cincinnati, Ohio 736. Riethof T, Acchione BD, Branyan ER (1962) High-temperature spectral emissivity studies on some refractory metals and carbides. In: Herzfeld CM, Dahl AI (eds) Temperature, its measurement and control in science and industry, Vol. 3, Part 2, p. 515-522. Reinholds, New York, Chapman and Hall, London 737. Samsonov GV (ed), Fomenko VS (1966) Handbook of thermionic properties. Plenum Press, New York 738. Fomenko VS (1981) Emissionnye svoistva materialov (The thermionic emission properties of materials). Naukova Dumka, Kyiv (in Russian) 739. Denbnovetskaya EN, Lavrenko VA, Podchernyaeva IA, Protsenko TG, Siman NI, Fomenko VS (1971) Electron work function and surface recombination of hydrogen for alloys of the system HfC-WC. Powder Metall Met Ceram 10(4):289-291 740. Mattheiss LF, Hamann DR (1984) Bulk and surface electronic structure of hexagonal WC. Phys Rev B 30(4):1731-1738 741. Podchernyaeva IA, Siman NI, Fomenko VS (1971) Termoemissionnye i adsorbtsionnye svoistva karbidov perekhodnykh metallov obrabotannykh nizkotemperaturnoi tsezievoi plazmoi (Thermionic emission and adsorption properties of transition metal carbides exposed to cesium low-temperature plasma) In: Nikolaev AV (ed) Nizkotemperaturnaya plasma v tekhnologii neorganicheskikh veshchestv (Low-temperature plasma in inorganic materials technology), pp. 54-57. Novosibirsk, Nauka Siberian Branch (in Russian) 742. Siman NI (1977) Emissionno-adsorbtsionnye svoistva tugoplavkikh uglerod-soderzhashchikh elektrodnykh materialov (Emission and adsorption properties of refractory carboncontaining electrode materials). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 743. Sumin LV (1975) Ionizing properties of non-metallic emitters (Ioniziruyushchie svoistva nemetallicheskikh emitterov). Zh Tekh Fiz 45(9):1896-1903 (in Russian) 744. Schneider P (1962) A contribution to the evaluation of some anti-emission materials for tubes with cathodes of thoriated tungsten. Vacuum 12(6):293-299 745. Dyubua BCh, Novikova TM, Stepanov LA (1965) Primenenie tugoplavkikh metallopodobnykh soedinenii v kachestve antiemissionnykh pokrytii dlya stabilizatsii raboty katodnogo uzla (The use of refractory metal-like compounds as anti-emission coatings to stabilize the operation of the cathode assembly). Vopr Radioelektron Ser Elektron (3):162172 (in Russian) 746. Zubenko YuV, Sokolskaya IL (1962) O rabote vykhoda karbida volframa (On the work function of tungsten carbide). Zh Tekh Fiz 32(3):378-380 (in Russian) 747. Golubev OL, Shrednik VN, Shaikhin BM (1975) Ob izobrazhaemosti karbidov volframa v ionnom proektore (On the imaginability of tungsten carbides in an ionic projector) Pisma Zh Tekh Fiz 1(15):714-718 (in Russian) 748. Elinson MI, Kudintseva GA (1962) Avtoelektronnye katody na osnove metallopodobnykh tugoplavkikh soedinenii (Field emission cathodes based on metal-like refractory compounds) Radiotekh Elektron 7(9):1511-1518 (in Russian) 749. Samsonov GV, Neshpor VS (1957) Superconductivity of borides, carbides, nitrides and silicides of transition metals. Sov Phys JETP 3(6):947-948 750. Neshpor VS, Novikov VI, Noskin VA, Shalyt SS (1968) Superconductivity of some alloys of tungsten-rhenium-carbon system. Sov Phys JETP 27(1):13-16 751. Matthias BT, Hulm JK (1952) A search for new superconducting compounds. Phys Rev 87(5):799-806 752. Ziegler WT, Young RA (1953) Studies of compounds for superconductivity. Phys Rev 90(1):115-119 753. Sadki ES, Ooi S, Hirata K (2004) Focused ion beam induced deposition of superconducting nanowires. Appl Phys Lett 85(25):6206-6208

References

619

754. Morita T, Nakamatsu K-I, Kanda K, Haruyama Y, Kondo K, Hoshino T, Kaito T, Fujita J-I, Ichihashi T, Ishida M, Ochiai Y, Tajima T, Matsui S (2004) Nanomechanical switch fabrication by focused ion beam chemical vapour deposition. J Vac Sci Technol B 22(6):3137-3142 755. Sadki ES, Ooi S, Hirata K (2005) Focused ion beam induced deposition of superconducting thin films. Phys C 426-431:1547-1551 756. Morita T, Kanda K, Haruyama Y, Matsui S (2005) Nanomechanical switch formed by focused ion beam chemical vapour deposition. Jpn J Appl Phys 44(5A):3341-3343 757. Li W, Fenton JC, Wang Y, McComb DW, Warburton PA (2008) Tunability of the superconductivity of tungsten films grown by focused ion beam direct writing. J Appl Phys 104(9):093913 (5 pp.) 758. Yang L, Carpenter FD (1961) Materials problems in cesium thermionic converters. J Electrochem Soc 108(11):1079-1086 759. Albert MJ, Atta MA, Gabor D (1967) A new type of composite all-metal electron emitter for valves and electron-optical devices. Brit J Appl Phys 18(5):627-634 760. Samsonov GV, Paderno YuB, Fomenko VS (1967) Thermionic emission characteristics of transition metals and their compounds. Sov Phys Tech Phys 11(8):1070-1083 761. Yada K, Masaoka H, Shoji Y, Tanji T (1989) Studies of refractory carbides, nitrides and borides as the thermionic emitters for electron microscopy. J Electron Microsc Tech 12:252261 762. Hugosson HW, Eriksson O, Jansson U, Ruban AV, Souvatzis P, Abrikosov IA (2004) Surface energies and work functions of the transition metal carbides. Surf Sci 557:243-254 763. Sun J (2008) Field emission from tungsten carbide on W tips. In: Proc. Int. conf. on advanced infocomm technology (ICAIT ’08), Shenzhen, China, 29-31 July 2008, 812008 (4 pp.) 764. Golubev OL (2009) Single nanodimensional emitting protrusion on a surface of a tungsten carbide field emitter. Tech Phys Lett 35(6):545-547 765. Golubev OL (2010) Formation of a single nanodimensional emitting protrusion on a surface of a tungsten carbide field emitter. In: Proc. 8th Int. conf. on vacuum electron sources and nano-carbon (IVESC 2010 / NANOcarbon 2010), Nanjing, China, 14-16 Oct 2010, 5644420, pp. 70-71. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 766. Golubev OL (2010) Growing of a single nanodimensional emitting protrusion on a surface of a tungsten carbide field emitter. In: Proc. 23rd Int. conf. on vacuum nanoelectronics (IVNC 2010), Palo Alto, California, 26-30 July 2010, 5563174, pp. 70-71. SRI International, Menlo Park, California 767. Golubev OL (2011) Modification of the tungsten carbide field emitter surface to localize the electron and ion emission. Tech Phys 56(6):859-864 768. Siegel DJ, Hector LG, Jr, Adams JB (2002) Adhesion, stability and bonding at metal / metal carbide interfaces: Al/WC. Surf Sci 498:321-336 769. Nguyen TP, Choi KS, Kim SY, Lee TH, Jang HW, Le QV, Kim IT (2020) Strategy for controlling the morphology and work function of W2C/WS2 nanoflowers. J Alloys Compd 829:154582 (9 pp.) 770. Quesne MG, Roldan A, De Leeuw NH, Catlow CRA (2018) Bulk and surface properties of metal carbides: implications for catalysis. Phys Chem Chem Phys 20:6905-6916 771. Yu ML, Lang ND, Hussey BW, Chang THP, Mackie WA (1996) New evidence for localized electronic states on atomically sharp field emitters. Phys Rev Lett 77(8):1636-1639 772. Almaksour K, Kirkpatrick MJ, Dessante Ph, Odic E, Simonin A, De Esch HPL, Lepetit B, Alamarguy D, Bayle F, Teste Ph (2014) Experimental study of the reduction of field emission by gas injection in vacuum for accelerator applications. Phys Rev ST Accel Beams 17(10):103502 (9 pp.) 773. Golubev OL (2014) Point sources of electrons and ions based on field emitters from refractory carbides. In: Proc. 10th Int. conf. on vacuum electron sources (IVESC 2014) and

620

2 Tungsten Carbides

2nd Int. conf. on emission electronics (ICEE 2014), Saint-Petersburg, Russian Federation, 30 June – 4 July 2014, 6891990 (1 p.) 774. Cherepin VT, Kosyachkov AA, Vasilev MA (1978) Secondary ion emission of transition metal carbides. Phys Stat Sol A 50:K113-K116 775. Meerson GA, Umanskii YaS (1953) O tverdosti tugoplavkih karbidov (On the hardness of refractory carbides). Izv Sektora Fiz Khim Analiza AN SSSR 22:104-110 (in Russian) 776. Williams AE (1951) Compacts of pure tungsten carbide. Met Treat Drop Forging 18:445447 777. Samsonov GV, Neshpor VS, Khrenova LM (1959) Tverdost i khrupkost metallopodobnykh soedinenii (Hardness and brittleness of metal-like compounds). Fiz Met Metalloved 8(4):622630 (in Russian) 778. Brookes CA, Atkins AG (1965) The friction and hardness of refractory compounds. In: Benesovsky F (ed) Metals for the space age. Proc. 5th Int. Plansee seminar, Reutte, Tyrol, Austria, 22-26 June 1964, pp. 712-720. Plansee Holding AG, Reutte, Austria 779. Samsonov GV, Neshpor VS (1958) Nekotorye fizicheskie kharakteristiki metallopodobnykh soedinenii (Certain physical properties of metal-like compounds). In: Frantsevich IN (ed) Voprosy poroshkovoi metallurgii i prochnosti materialov (Problems of powder metallurgy and strength of materials), Vol. 5, pp. 3-8. UkrSSR Academy of Sciences, Kyiv (in Russian) 780. Ivanko AA (1971) Handbook of hardness data. Keter, Jerusalem 781. Krushinskii AN (1974) The influence of production conditions on some physical properties of tungsten carbide and of a complex carbide based on it. In: Samsonov GV (ed) Refractory carbides, pp. 307-309. Consultants Bureau, New York, London 782. Pivovarov LKh, Yanshin SI, Semerchan AA, Baskin ML (1964) Vliyanie vysokikh davlenii i temperatur na monokarbid volframa (The effect of high pressures and temperatures on tungsten carbide). Fiz Met Metalloved 17(4):606-607 (in Russian) 783. Kovalchenko MS, Rogovoi YuI (1971) Microhardness anisotropy in polycrystalline carbides of the transition metals of group VI. Powder Metall Met Ceram 10(2):157-162 784. Nino A, Tanaka A, Sugiyama S, Taimatsu H (2010) Indentation size effect for the hardness of refractory carbides. Mater Trans Jpn Inst Met 51(9):1621-1626 785. Taimatsu H, Sugiyama S, Kodaira Y (2008) Synthesis of W2C by reactive hot-pressing and its mechanical properties. Mater Trans Jpn Inst Met 49(6):1256-1261 786. Skuratovskii VN (1969) Issledovanie mikrotverdosti materialov v shirokom diapazone temperatur (A study of the microhardness of materials in the wide range of temperatures). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 787. Skuratovskii VN, Tkachenko YuG, Borisenko VA (1969) A technique for investigating the microhardness of refractory compounds within a wide temperature range. Strength Mater 1(4):393-396 788. Kovalchenko MS, Dzhemelinskii VV, Skuratovskii VN, Tkachenko YuG, Yurchenko DZ, Alekseev VI (1971) Microhardness of some carbides at various temperatures. Powder Metall Met Ceram 10(8):665-668 789. Kovalchenko MS, Dzhemelinskii VV, Skuratovskii VN, Tkachenko YuG (1973) Temperaturnaya zavisimost mikrotverdosti karbidov perekhodnykh metallov (Temperature dependence of the microhardness of transition metal carbides). Izv AN SSSR Neorg Mater 9(10):1525-1528 (in Russian) 790. Borisenko VA (1984) Tverdost i prochnost tugoplavkikh materialov pri vysokikh temperaturakh (Hardness and strength of refractory materials at high temperatures). Naukova Dumka, Kyiv (in Russian) 791. Samsonov GV, Latysheva VP (1956) Diffuziya bora, ugleroda i azota v perekhodnye metally IV, V i VI grupp periodicheskoi tablitsy (The diffusion of boron, carbon and nitrogen into transition metals of the IV, V and VI groups of the periodic table). Doklady AN SSSR 109(3):582-585 (in Russian)

References

621

792. Foster LS, Forbes LW, Jr, Friar LB, Moody LS, Smith WH (1950) Sintering carbides by means of fugitive binders. J Am Ceram Soc 33(1):27-33 793. Thibault NW, Nyquist HL (1947) The measured Knoop hardness of hard substances and factors affecting its determination. Trans Am Soc Met 38:271-330 794. Rüdiger O (1953) Zur Kenntnis des Systems Wolframkarbid – Titankarbid – Chromkarbid (A notice on the system tungsten carbide – titanium carbide – chromium carbide). Metall 7:967-969 (in German) 795. Hibbs MK, Sinclair R, Rowcliffe DJ (1983) Defect structure of WC deformed at room and high temperatures. In: Viswanadham RK, Rowcliffe DJ, Gurland J (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Jackson Hole, Wyoming, 23-28 Aug 1981, pp. 121-135. Plenum Press, New York, London 796. Mott BW (1956) Micro indentation hardness testing. Butterworth, London 797. Kovalskii AE, Petrova LA (1951) Mikrotverdost dvoinykh tugoplavkikh karbidov (Microhardness of binary refractory carbides). In: Khrushchov MM (ed) Mikrotverdost (Microhardness), pp. 170-186. AN SSSR, Moscow (in Russian) 798. Luyckx S (2000) The hardness of tungsten carbide – cobalt hardmetal. In: Riedel R (ed) Handbook of ceramic hard materials, Vol. 2, pp. 946-964. Wiley-VCH, Weinheim, New York 799. Sigl LS, Exner HE (1989) The flow stress and hardness of metal-reinforced brittle composites. Mater Sci Eng A 108:121-129 800. Lee HC, Gurland J (1978) Hardness and deformation of cemented tungsten carbide. Mater Sci Eng 33:125-133 801. Warren R (1983) Indentation hardness of microstructures consisting of hard particles in a metallic matrix. In: Bilde-Sørensen JB, Hansen N, Horsewell A, Leffers T, Lilholt H (eds) Deformation of multi-phase and particle containing materials. Proc. 4th Risø Int. symp. on metallurgy and materials science, Roskilde, Denmark, 5-9 Sep 1983, pp. 572-582. Risø National Laboratory, Roskilde, Denmark 802. Habig K-H (1980) Verschleiß und Härte von Werkstoffen (Wear and hardness of materials). Hanser, München (in German) 803. Sundgren J-E (1986) A review of the present state of art in hard coatings grown from the vapour phase. J Vac Sci Technol A 4(5):2259-2279 804. Frey H, Kienel G (1987) Dünnschichttechnologie (Thin film technology). VDI-Verlag, Düsseldorf (in German) 805. Hornbogen E (1987) Werkstoffe: Aufbau und Eigenschaften von Keramik, Metallen, Polymer- und Verbundwerkstoffen (Materials: structure and properties of ceramics, metals, polymer and composite materials). Springer, Berlin (in German) 806. Bargel H-J, Schulze G (1988) Werkstoffe (Materials). CDI-Verlag, Düsseldorf (in German) 807. Reinhold R, Becker S (1982) Superharte Schneidwerkstoffe der Spanungstechnik (Superhard cutting materials for machining technology). VEB Verlag Technik, Berlin (in German) 808. Peters R-J (1992) Beschichten mit Hartstoffen (Hard materials coatings). VDI Technologiezentrum Physikalische Technologien, VDI-Verlag, Düsseldorf (in German) 809. Popov VS, Nagornyi PL (1971) Disintegration of carbides during abrasive wear. Inorg Mater 7(2):196-200 810. Powell CF, Oxley JH, Blocher JM, eds (1966) Vapour deposition. Wiley, New York 811. Kelly A (1966) Strong solids. Clarendon Press, London 812. Fitzgerald LM (1960) Measurement of hardness at very high temperatures. Brit J Appl Phys 11:551-554 813. Fitzgerald LM (1963) The hardness at high temperatures of some refractory carbides and borides. J Less-Common Met 5:356-364 814. Atkins AG, Tabor D (1965) Mutual indentation hardness apparatus for use at very high temperatures. Brit J Appl Phys 16:1015-1021

622

2 Tungsten Carbides

815. Miyoshi A, Hara A (1965) High-temperature hardness of WC, TiC, TaC, NbC and their mixed carbides. J Jpn Soc Powder Powder Metall 12(2):78-84 816. Atkins AG, Tabor D (1966) Hardness and deformation properties of solids at very high temperatures. Proc Royal Soc Lond A 292(1431):441-459 817. Bartolucci S, Schlössin HH (1966) Plastic deformation preceding fracture in tungsten carbide – cobalt alloys. Acta Metall 14:337-339 818. Kushtalova IP, Ivanov AN (1967) Plastic deformation and recrystallization of refractory compounds. Powder Metall Met Ceram 6(2):97-98 819. Bazhenova LN, Ivanko AA (1969) Microhardness of carbides of certain transition metals. Inorg Mater 5(12):1763-1767 820. Ivanko AA (1974) The microhardness of transition metal carbides. In: Samsonov GV (ed) Refractory carbides, pp. 367-370. Consultants Bureau, New York, London 821. Artamonov AYa, Bovkun GA (1974) Some aspects of the abrasive wear of transition metal carbides. In: Samsonov GV (ed) Refractory carbides, pp. 371-376. Consultants Bureau, New York, London 822. Dzhemelinskii VV, Kovalchenko MS, Borisenko VA, Makarenko GN (1974) Indentors for measuring the hardness of materials at high temperatures. In: Samsonov GV (ed) Refractory carbides, pp. 403-407. Consultants Bureau, New York, London 823. Rice RW (1971) The compressive strength of ceramics. In: Kriegel WW, Palmour H, III (eds) Ceramics in severe environments. Proc. 6th university conf. on ceramic science, North Carolina State University, Raleigh, 7-9 Dec 1970, pp. 195-229. Plenum Press, New York 824. Lee M (1983) High temperature hardness of tungsten carbide. Metall Trans A 14(8):16251629 825. Tkachenko YuG, Bovkun GA, Berdikov VF (1977) Behaviour of specimens of transition metal carbides during micromechanical tests. Powder Metall Met Ceram 16(5):366-369 826. Chatfield Ch (1985) Influence of carbide grain size on the hot hardness of polycrystalline tungsten carbide and WC-Co cemented carbides. Powder Metall Int 17(3):113-115 827. Moriyoshi Y, Akaishi M, Fukunaga O (1986) The microstructure of WC and WC – 4.3 wt% Co sintered at high pressure. J Mater Sci 21:4250-4256 828. Iskhakova GA, Marusina VI, Rakhimyanov KhM (1987) Determination of the microhardness of tungsten carbide particles produced in the spark discharge. Powder Metall Met Ceram 26(10):852-854 829. Smith EN (1988) Tungsten carbide: crystals by the ton. J Cryst Growth 89:75-79 830. Milman YuV (1991) Characteristic temperature of deformation of materials and cold brittleness of bcc metals and ceramics. In: Cocks ACF, Ponter ARS (eds) Mechanics of creep brittle materials – 2. Proc. Int. colloquium, University of Leicester, UK, 2-4 Sep 1991, pp. 124-133. Elsevier Applied Science, London, New York 831. Luyckx SB, Nabarro FRN, Wai S-W, James MN (1992) The anisotropic work-hardening of WC crystals. Acta Metall Mater 40(7):1623-1627 832. Bangert H, Wagendristel A (1985) Ultra-low load hardness tester for use in a scanning electron microscope. Rev Sci Instrum 56(8):1568-1572 833. Gee MG, Roebuck B, Lindahl P, Andrén H-O (1996) Constituent phase nanoindentation of WC/Co and Ti(C,N) hard metals. Mater Sci Eng A 209:128-136 834. Iizuka T, Hirata A, Takatsu S, Yoshikawa M (1998) Mechanical strength of cobaltless sintered tungsten carbide body. J Jpn Soc Precision Eng 64(12):1811-1815 (in Japanese) 835. Luyckx S, Demanet CM, Shrivastava S (1999) The effect of elastic relaxation on the indentation size effect in tungsten carbide. J Mater Sci Lett 18:705-706 836. Wang HL, Hon MH (1999) Temperature dependence of ceramics hardness. Ceram Int 25(3):267-271 837. Mukhopadhyay A, Raju GB, Basu B (2013) Ultra-high temperature ceramics: processing, properties and applications. In: Low IM, Sakka Y, Hu CF (eds) MAX phases and ultra-high temperature ceramics for extreme environments, pp. 49-99. IGI Global, Hershey, Pennsylvania

References

623

838. Koester RD, Moak DP (1967) Hot hardness of selected borides, oxides and carbides to 1900 °C. J Am Ceram Soc 50(6):290-296 839. Acchar W, Martinelli AE, Cairo CAA (2000) Reinforcing Al2O3 with W-Ti mixed carbides. Mater Lett 46(4):209-211 840. Kramer BM, Judd PK (1985) Computational design of wear coatings. J Vac Sci Technol A 3(6):2439-2444 841. Srivatsan TS, Woods R, Petraroli M, Sudarshan TS (2002) An investigation of the influence of powder particle size on microstructure and hardness of bulk samples of tungsten carbide. Powder Technol 122:54-60 842. Czyzniewski A (2003) Deposition and some properties of nanocrystalline WC and nanocomposite WC/a-C:H coatings. Thin Solid Films 433:180-185 843. Nayak BB (2003) Enhancement in the microhardness of arc-plasma melted tungsten carbide. J Mater Sci 38:2717-2721 844. Pauleau Y, Gouy-Pailler Ph, Païdassi S (1992) Structure and mechanical properties of hard W-C coatings deposited by reactive magnetron sputtering. Surf Coat Technol 54-55:324-328 845. Gouy-Pailler Ph, Pauleau Y (1993) Tungsten and tungsten-carbon thin films deposited by magnetron sputtering. J Vac Sci Technol A 11(1):96-102 846. Drábik M, Truchlý M, Ballo V, Roch T, Kvetková L, Kúš P (2018) Influence of substrate material and its plasma pre-treatment on adhesion and properties of WC/a-C:H nanocomposite coatings deposited at low temperature. Surf Coat Technol 333:138-147 847. Kim H-C, Shon I-J, Garay JE, Munir ZA (2004) Consolidation and properties of binderless submicron tungsten carbide by field-activated sintering. Int J Refract Met Hard Mater 22:257-264 848. Kim H-T, Kim J-S, Kwon Y-S (2005) Mechanical properties of binderless tungsten carbide by spark-plasma sintering. In: Proc. 9th Russian-Korean Int. symp. on science and technology (KORUS-2005), Novosibirsk, Russian Federation, 26 June – 2 July 2005, pp. 458-461. Novosibirsk State University, Russian Federation 849. Kwon Y-S, Kim H-T, Choi D-W, Kim J-S (2005) Mechanical properties of binderless WC produced by SPS process. In: Miyake S (ed) Novel materials processing by advanced electromagnetic energy sources. Proc. Int. symp. on novel materials (MAPEES’04), Osaka, Japan, 19-22 Mar 2004, pp. 275-279. Elsevier Science, Amsterdam, London 850. Kim H-C, Yoon J-K, Doh J-M, Ko I-Y, Shon I-J (2006) Rapid sintering process and mechanical properties of binderless ultra-fine tungsten carbide. Mater Sci Eng A 435436:717-724 851. Shao GQ, Xiong Z, Wang TG, Shi XL, Duan XL (2007) Consolidation and properties of tungsten carbide target with low cobalt content by hot-press sintering. In: Zhang D, Guo J, Tsao CYA (eds) Composite Materials V. Proc. 5th China Cross-Strait conf. on composite materials, Shanghai, China, 23-25 Oct 2006. Key Eng Mater 351:98-102 852. Girardini L, Zadra M, Casari F, Molinari A (2007) Bulk fine-grained and nanostructured binderless WC consolidated by spark-plasma sintering. In: Proc. European Int. powder metallurgy congress and exhibition (Euro PM 2007), Toulouse, France, 15-17 Oct 2007, Vol. 3, pp. 77-82. The European Powder Metallurgy Association, Shrewsbury, UK 853. Girardini L, Zadra M, Casari F, Molinari A (2008) SPS, binderless WC powders and the problem of subcarbide. Met Powder Rep 63(4):18-22 854. Suzuki S (1996) Fabrication of hard metal. In: Proc. 1st symp. on spark-plasma sintering, pp. 14-18. Tohoku University, Sendai, Japan (in Japanese) 855. Omori M, Kakita T, Okubo A, Hirai T (1998) Preparation of a WC/Mo functionally graded material. J Jpn Inst Met 62(11):986-991 (in Japanese) 856. Omori M (2000) Sintering, consolidation, reaction and crystal growth by the spark-plasma system (SPS). Mater Sci Eng A 287:183-188 857. Huang SG, Vanmeensel K, Van Der Biest O, Vleugels J (2008) Binderless WC and WCVC materials obtained by pulsed electric current sintering. Int J Refract Met Hard Mater 26(1):41-47

624

2 Tungsten Carbides

858. Kornaus K, Rączka M, Gubernat A, Zientara D (2017) Pressureless sintering of binderless tungsten carbide. J Eur Ceram Soc 37:4567-4576 859. Huang B, Chen LD, Bai SQ (2006) Bulk ultra-fine binderless WC prepared by sparkplasma sintering. Scripta Mater 54:441-445 860. Kim H-C, Shon I-J, Ko I-Y, Yoon J-K, Doh J-M, Lee G-W (2006) Fabrication of ultra-fine binderless WC and WC-Ni hard materials by a pulsed current activated sintering method. J Ceram Process Res 7(3):224-229 861. Kim H-C, Shon I-J, Yoon J-K, Lee G-W, Munir ZA (2006) One step synthesis and densification of ultra-fine WC by high-frequency induction combustion. Int J Refract Met Hard Mater 24:202-209 862. Kim H-C, Shon I-J, Jeong I-K, Ko I-Y, Yoon J-K, Doh J-M (2007) Rapid sintering of ultrafine WC and WC-Co hard materials by high-frequency induction-heated sintering and their mechanical properties. Met Mater Int 13(1):39-45 863. Kim H-C, Shon I-J, Yoon J-K, Doh J-M (2007) Consolidation of ultra-fine WC and WC-Co hard materials by pulse current activated sintering and its mechanical properties. Int J Refract Met Hard Mater 25:46-52 864. Kim H-C, Kim D-K, Woo K-D, Ko I-Y, Shon I-J (2008) Consolidation of binderless WCTiC by high-frequency induction-heating sintering. Int J Refract Met Hard Mater 26:48-54 865. Kim H-C, Park H-K, Jeong I-K, Ko I-Y, Shon I-J (2008) Sintering of binderless WC-Mo2C hard materials by rapid sintering process. Ceram Int 34:1419-1423 866. Sugiyama S, Kudo D, Taimatsu H (2008) Preparation of WC-SiC whisker composites by hot-pressing and their mechanical properties. Mater Trans Jpn Inst Met 49(7):1644-1649 867. Sugiyama S, Sato S, Taimatsu H (2008) Synthesis of WC-W2C-TiC ceramics by resistanceheated hot-pressing and their mechanical properties. J Jpn Soc Powder Powder Metall 55(8):588-592 (in Japanese) 868. Zalite I, Grabis J, Angerer P (2008) Sintering of nanosized tungsten carbide produced by gas phase synthesis. Powder Metall Met Ceram 47(11-12):669-673 869. Grasso S, Sakka Y, Maizza G, Hu C (2009) Pressure effect on the homogeneity of sparkplasma sintered tungsten carbide powder. J Am Ceram Soc 92(10):2418-2421 870. Wang X, Fang ZZ (2009) Sintering and properties of ultra-fine binderless WC. In: Advances in powder metallurgy and particulate materials – 2009. Proc. Int. conf. on powder metallurgy and particulate materials (PowderMet 2009), Las Vegas, Nevada, 28 June – 1 July 2009, pp. 86-91. Metal Powder Industries Federation, Princeton, New Jersey 871. Zhang J, Zhang G, Zhao S, Song X (2009) Binder-free WC bulk synthesized by sparkplasma sintering. J Alloys Compd 479:427-431 872. Bonache V, Rayón E, Salvador MD, Busquets D (2010) Nanoindentation study of WC12Co hardmetals obtained from nanocrystalline powders: evaluation of hardness and modulus on individual phases. Mater Sci Eng A 527:2935-2941 873. Milman YuV, Chugunova SI (1999) Mechanical properties, indentation and dynamic yield stress of ceramic targets. Int J Impact Eng 23:629-638 874. Buchheit TE, Vogler TJ (2010) Measurement of ceramic powders using instrumented indentation and correlation with their dynamic response. Mech Mater 42:599-614 875. Teter DM (1998) Computational alchemy: the search for new superhard materials. Mater Res Soc Bull 23(1):22-27 876. Brazhkin VV, Lyapin AG, Hemley RJ (2002) Harder than diamond: dreams and reality. Philos Mag A 82(2):231-253 877. Dubrovinsky LS, Dubrovinskaia NA, Swamy V, Muscat J, Harrison NM, Ahuja R, Holm B, Johansson B (2001) The hardest known oxide. Nature 410(6829):653-654 878. Zou H-W, Ye J-W, Liu Y, Xia S, Li P-P (2010) The influence of quality of ultra-fine powder on microstructure and properties of binderless tungsten carbide. J Funct Mater 41(1):90-93 (in Chinese) 879. Armstrong RW (2011) The hardness and strength properties of WC-Co composites. Materials 4(7):1287-1308; doi:10.3390/ma4071287

References

625

880. Iskhakova GA, Marusina VI (1989) Structural state and phase composition of tungsten carbide particles synthesized in spark discharge. Powder Metall Met Ceram 28(10):749-753 881. Corteville J, Pons L (1965) Macles et fautes d’empliment dans le monocarbure de tungstène (Twinned crystals and defects in tungsten monocarbide). C R Hebd Séanc Acad Sci 260(17):4477-4480 (in French) 882. Corteville J (1966) Plasticité, dureté et fragilité du carbure de tungstène (Plasticity, hardness and fragility of tungsten carbide). Rev Inst Fr Petrol 21(9):1355-1359 (in French) 883. Kohn JA, Cotter PG, Potter RA (1955) Directional hardness variation in tungsten carbide (WC) monocrystals. Am Mineralogist 4(5-6):522-526 884. Rüdiger O (1967) Herstellung und Eigenschaften von WC-Einkristallen (Production and properties of WC single crystals). In: Czesc I, Stolarz S, Missol W, Zolkowski W, Kurzeja J, Cyunczyk A (eds) II Konferencja metalurgii proszkow (Proc. 2nd conf. on powder metallurgy, Krakow, Poland, 20-23 Sep 1967), Vol. 1, pp. 196-215. Zakladzie Graficznym Politechniki Slaskiej, Gliwice (in German) 885. Hidnert P (1937) Thermal expansion of cemented tungsten carbide. J Res Nat Bur Stand 18:47-52 886. Samsonov GV, Portnoi KI (1961) Splavy na osnove tugoplavlikh soedinenii (The alloys based on refractory compounds). Oborongiz, Moscow (in Russian) 887. Malli M, Hillnhagen E (1967) Metallographische Untersuchungen an WC-Einkristallen (Metallographic investigations on WC single crystals). Prakt Metallogr 4:16-27 (in German) 888. Rogovoi YuI (1973) Issledovanie vliyaniya neitronnogo oblucheniya na strukturu i svoistva karbidov perekhodnyh metallov IV-VI grupp (A study of the effect of neutron irradiation on the structure and properties of transition metal carbides of IV-VI groups). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 889. Chen X-Q, Niu H, Li D, Li Y (2011) Modelling hardness of polycrystalline materials and bulk metallic glasses. Intermetallics 19:1275-1281 890. Gao F, He J, Wu E, Liu S, Yu D, Li D, Zhang S, Tian Y (2003) Hardness of covalent crystals. Phys Rev Lett 91(1):015502 (4 pp.) 891. Šimůnek A, Vackář J (2006) Hardness of covalent and ionic crystals: first principles calculations. Phys Rev Lett 96(8):085501 (4 pp.) 892. Li K, Wang X, Zhang F, Xue D (2008) Electronegativity identification of novel superhard materials. Phys Rev Lett 100(23):235504 (4 pp.) 893. Chuvildeev VN, Moskvicheva AV, Lopatin YuG, Blagoveshchenskii YuV, Isaeva NV, Melnik YuI (2011) Sintering of WC and WC-Co nanopowders with different inhibitor additions by the SPS method. Dokl Phys 56(2):114-117 894. Friedrich A, Winkler B, Juarez-Arellano EA, Bayarjargal L (2011) Synthesis of binary transition metal nitrides, carbides and borides from the elements in the laser-heated diamond anvil cell and their structure – property relations. Materials 4(10):1648-1692; doi: 10.3390/ma4101648 895. Nino A, Nakaibayashi Y, Sugiyama S, Taimatsu H (2011) Microstructure and mechanical properties of WC-SiC composites. Mater Trans Jpn Inst Met 52(8):1641-1645 896. Shon I-J, Na K-I, Kim B-R, Ko I-Y, Doh J-M, Yoon J-K (2011) Mechanical properties and consolidation of nanostructured WC-CNT composites by high-frequency induction-heated sintering. Rev Adv Mater Sci 28:9-12 897. Sun S-K, Kan Y-M, Zhang G-J (2011) Fabrication of nanosized tungsten carbide ceramics by reactive spark-plasma sintering. J Am Ceram Soc 94(10):3230-3233 898. Tsai K-M (2011) The effect of consolidation parameters on the mechanical properties of binderless tungsten carbide. Int J Refract Met Hard Mater 29:188-201 899. Staia MH, Torres IJ, Castillo C, Sudarshan TS, Lesage J, Chicot D (2006) Tribological study of WC produced by plasma pressure compaction. Int J Refract Met Hard Mater 24:183188

626

2 Tungsten Carbides

900. Li K, Yang P, Xue D (2012) Anisotropic hardness prediction of crystalline hard materials from the electronegativity. Acta Mater 60:35-42 901. Lide DR, ed (2010) CRC handbook of chemistry and physics, 90th ed. CRC Press, Boca Raton, New York 902. Nino A, Takahashi K, Sugiyama S, Taimatsu H (2012) Effects of carbon addition on microstructures and mechanical properties of binderless tungsten carbide. Mater Trans Jpn Inst Met 53(8):1475-1480 903. Cuadrado N, Casellas D, Llanes L, Gonzalez I, Caro J (2011) Effect of crystal anisotropy on the mechanical properties of WC embedded in WC-Co cemented carbides. In: Castro F, Molins C (eds) Proc. Int. powder metallurgy congress and exhibition (Euro PM 2011), Barcelona, Spain, 9-12 Oct 2011. Hard materials, pp.215-220. The European Powder Metallurgy Association, Shrewsbury, UK 904. Roebuck B, Klose P, Mingard KP (2012) Hardness of hexagonal tungsten carbide crystals as a function of orientation. Acta Mater 60:6131-6143 905. Sun S-K, Kan Y-M, Ni D-W, Zou J, Zhang G-J (2012) Synthesis mechanism and sintering behaviour of tungsten carbide powder produced by a novel solid state reaction of W2N. Int J Refract Met Hard Mater 35:202-206 906. Li K, Xue D (2009) Hardness of materials: studies at levels from atoms to crystals. Chin Sci Bull 54(1):131-136 907. Tian Y, Xu B, Zhao Z (2012) Microscopic theory of hardness and design of novel superhard crystals. Int J Refract Met Hard Mater 33:93-106 908. Duszová A, Haglaš R, Bl’anda M, Hvizdoš P, Lofaj F, Dusza J, Morgiel J (2013) Nanoindentation of WC-Co hardmetals. J Eur Ceram Soc 33:2227-2232 909. Grasso S, Poetschke J, Richter V, Maizza G, Sakka Y, Reece MJ (2013) Low-temperature spark-plasma sintering of pure nano WC powder. J Am Ceram Soc 96(6):1702-1705 910. Jiang Y, Yang JF, Zhuang Z, Liu R, Zhou Y, Wang XP, Fang QF (2013) Characterization and properties of tungsten carbide coatings fabricated by SPS technique. J Nucl Mater 433:449-454 911. Liu X, Wang Lim, Wang Lig, Guo Z (2013) Hardmetals: consolidation and wear resistance of binderless cemented carbide by high-frequency induction-heated pressing. In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2013), Gothenburg, Sweden, 15-18 Sep 2013, 110976 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 912. Zhang X, Wang Y, Lv J, Zhu C, Li Q, Zhang M, Li Q, Ma Y (2013) First principles structural design of superhard materials. J Chem Phys 138(11):114101 (9 pp.) 913. Agudelo-Morimitsu LC, De La Roche J, Ruden A, Escobar D, Restrepo-Parra E (2014) Effect of substrate temperature on the mechanical and tribological properties of W/WC produced by DC magnetron sputtering. Ceram Int 40:7037-7042 914. Bl’anda M, Duszová A, Csanádi T, Hvizdoš P, Lofaj F, Dusza J (2014) Indentation fatigue of WC grains in WC-Co composite. J Eur Ceram Soc 34:3407-3412 915. Csanádi T, Bl’anda M, Duszová A, Chinh NQ, Szommer P, Dusza J (2014) Deformation characteristics of WC micropillars. J Eur Ceram Soc 34:4099-4103 916. Csanádi T, Bl’anda M, Duszová A, Hvizdoš P, Dusza J (2014) Nanoindentation and AFM studies on tungsten carbide crystals in WC-Co hardmetal. In: Proc. 10th Int. conf. on local mechanical properties (LMP 2013), Kutna Hora, Czech Republic, 6-8 Nov 2013. Key Eng Mater 606:107-110 917. Liu YZ, Jiang YH, Zhou R, Feng J (2014) Mechanical properties and chemical bonding characteristics of WC and W2C compounds. Ceram Int 40:2891-2899 918. Sun S-K, Zhang G-J, Wu W-W, Liu J-X, Zou J, Suzuki T, Sakka Y (2014) Reactive sparkplasma sintering of binderless WC ceramics at 1500 °C. Int J Refract Met Hard Mater 43:4245 919. Yu R, Zhang Q, Zhan Q (2014) Softest elastic mode governs materials hardness. Chin Sci Bull 59(15):1747-1754

References

627

920. Bl’anda M, Duszová A, Csanádi T, Hvizdoš P, Lofaj F, Dusza J (2015) Indentation hardness and fatigue of WC-Co composites. Int J Refract Met Hard Mater 49:178-183 921. Chuvildeev VN, Blagoveshchenskii YuV, Sakharov NV, Boldin MS, Nokhrin AV, Isaeva NV, Shotin SV, Lopatin YuG, Smirnova ES (2015) Preparation and investigation of ultrafine grained tungsten carbide with high hardness and fracture toughness. Dokl Phys 60(7):288-291 922. Chuvildeev VN, Blagoveshchenskii YuV, Boldin MS, Sakharov NV, Nokhrin AV, Isaeva NV, Shotin SV, Lopatin YuG, Belkin OA, Smirnova ES (2015) High-strength ultra-fine grained tungsten carbide based materials obtained. Tech Phys Lett 41(4):397-400 923. Csanádi T, Novák M, Naughton-Duszová A, Dusza J (2015) Anisotropic nanoscratch resistance of WC grains in WC-Co composite. Int J Refract Met Hard Mater 51:188-191 924. Csanádi T, Bl’anda M, Chinh NQ, Hvizdoš P, Dusza J (2015) Orientation-dependent hardness and nanoindentation-induced deformation mechanisms of WC crystals. Acta Mater 83:397-407 925. Li SK, Li JQ, Li Y, Liu FS, Ao WQ (2015) Dense pure binderless WC bulk material prepared by spark-plasma sintering. Mater Sci Technol 31(14):1749-1756 926. Ren X, Peng Z, Wang C, Miao H (2015) Influence of nanosized La2O3 addition on the sintering behaviour and mechanical properties of WC-La2O3 composites. Ceram Int 41:14811-14818 927. Roa JJ, Jiménez-Piqué E, Verge C, Tarragó JM, Mateo A, Fair J, Llanes L (2015) Intrinsic hardness of constitutive phases in WC-Co composites: nanoindentation testing, statistical analysis, WC crystal orientation effects and flow stress for the constrained metallic binder. J Eur Ceram Soc 35:3419-3425 928. Kwak B-W, Song J-H, Kim B-S, Shon I-J (2016) Mechanical properties and rapid sintering of nanostructured WC and WC-TiAl3 hard materials by the pulsed current activated heating. Int J Refract Met Hard Mater 54:244-250 929. Kwak B-W, Oh S-J, Kim B-S, Yoon J-K, Shon I-J (2016) Properties and rapid sintering of nanostructured WC and WC-TiAl by the high-frequency induction-heating. Korean J Met Mater 54(3):180-186 (in Korean) 930. Ma D-J, Kou Z-L, Liu Y-J, Wang Y-K, Gao S-P, Luo X, Li W-T, Wang Y-H, Du Y-C, Lei L (2016) Submicron binderless tungsten carbide sintering behaviour under high pressure and high temperature. Int J Refract Met Hard Mater 54:427-432 931. Oh S-J, Kim B-S, Shon I-J (2016) Mechanical properties and rapid consolidation of nanostructured WC and WC-Al2O3 composites by high-frequency induction-heated sintering. Int J Refract Met Hard Mater 58:189-195 932. Shon I-J (2016) High-frequency induction-heated sintering of nanostructured WC and WCTiAl3 hard materials and their mechanical properties. J Ceram Process Res 17(9):919-924 933. Chuvildeev VN, Blagoveshchenskii YuV, Nokhrin AV, Boldin MS, Sakharov NV, Isaeva NV, Shotin SV, Belkin OA, Popov AA, Smirnova ES, Lantsev EA (2017) Spark-plasma sintering of tungsten carbide based nanopowders obtained through DC arc plasma synthesis. J Alloys Compd 708:547-561 934. Chi J, Li H-Q, Wang S-F, Li M, Wu J, Li J-N, Zhao J (2017) In situ growth mechanism and hardness of W2C under non-equilibrium solidification conditions. Chin J Nonferr Met 27(3):555-562 (in Chinese) 935. Deng H, Zhang X, Liu K, Yamamura K, Sato H (2017) Polishing of tungsten carbide by combination of anodizing and silica slurry polishing. J Electrochem Soc 164(12):E352-E359 936. Dong Y, Zhang L, Wang C, Shen Q (2017) In situ reactive synthesis and plasma-activated sintering of binderless WC ceramics. Adv Appl Ceram 116(5):267-271 937. Ishii T, Yamazaki D, Tsujino N, Xu F, Liu Z, Kawazoe T, Yamamoto T, Druzhbin D, Wang L, Higo Y, Tange Y, Yoshino T, Katsura T (2017) Pressure generation to 65 GPa in a Kawaitype multi-anvil apparatus with tungsten carbide anvils. High Press Res 37(4):507-515

628

2 Tungsten Carbides

938. Nino A, Izu Y, Sekine T, Sugiyama S, Taimatsu H (2017) Effects of ZrC and SiC addition on the microstructures and mechanical properties of binderless WC. Int J Refract Met Hard Mater 69:259-265 939. Poetschke J, Richter V, Michaelis A (2014) Influence of small additions of MeC on properties of binderless tungsten carbide. In: Proc. Int. conf. and exhibition on powder metallurgy (Euro PM 2014), Salzburg, Austria, 21-24 Sep 2014, 117821 (10 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 940. Shon I-J (2017) High-frequency induction-heated consolidation of nanostructured WC and WC-Al hard materials and their mechanical properties. Int J Refract Met Hard Mater 64:242247 941. Tang W, Zhang L, Chen Y, Zhang H, Zhou L (2017) Corrosion and strength degradation behaviours of binderless WC material and WC-Co hardmetal in alkaline solution: a comparative investigation. Int J Refract Met Hard Mater 68:1-8 942. Tang W, Zhang L, Zhu J-F, Chen Y, Tian W, Liu T (2017) Effect of direct current patterns on densification and mechanical properties of binderless tungsten carbides fabricated by the spark-plasma sintering system. Int J Refract Met Hard Mater 64:90-97 943. Zhang H, Tan C, Yu X, Ma H, Cai H, Wang F (2017) Microstructure and properties of atmospheric pressure chemical vapour deposition of tungsten carbide. In: Xiao J, You Z, Tan Z (eds) Proc. 1st Int. conf. on materials science, energy technology and power engineering (MEP 2017), Hangzhou, China, 15-16 Apr 2017. AIP Conf Proc 1839:020074 (5 pp.) 944. Zhang Z, Chen Y, Zuo L, Zhang Y, Qi Y, Gao K (2017) The effect of volume fraction of WC particles on wear behaviour of in situ WC/Fe composites by spark-plasma sintering. Int J Refract Met Hard Mater 69:196-208 945. Fox RT, Nilsson R (2018) Binderless tungsten carbide carbon control with pressureless sintering. Int J Refract Met Hard Mater 76:82-89 946. Savinykh AS, Mandel K, Razorenov SV, Krüger L (2018) The influence of the cobalt content on the strength properties of tungsten carbide ceramics under dynamic loads. Tech Phys 63(3):357-362 947. Lee J-H, Oh I-H, Jang J-H, Hong S-K, Park H-K (2019) Mechanical properties and microstructural evolution of WC-binderless and WC-Co hard materials by the heat treatment process. J Alloys Compd 786:1-10 948. Nino A, Izu Y, Sekine T, Sugiyama S, Taimatsu H (2019) Effects of TaC and TiC addition on the microstructures and mechanical properties of binderless WC. Int J Refract Met Hard Mater 82:167-173 949. Park H-K, Lee J-H, Jang J-H, Oh I-H (2019) Property evaluation of binderless-WC hard materials as a function of sintering temperature. Korean J Met Mater 57(5):304-309 (in Korean) 950. Savinykh AS, Cherepanov IA, Razorenov SV, Mandel K, Krüger L (2019) Elastic precursor decay and spallation in non-porous tungsten carbide ceramics. Tech Phys 64(3):356-360 951. Telepa VT, Alymov MI, Shcherbakov VA, Shcherbakov AV, Vershinnikov VI (2018) Synthesis of the WC-W2C composite by electrothermal explosion under pressure. Lett Mater 8(2):119-122 952. Zhang Y, Kou Z, Wang Z, Yang M, Lu J, Liang H, Guan S, Hu Q, Gong H, He D (2019) Magic high-pressure strengthening in tungsten carbide system. Ceram Int 45:8721-8726 953. Augustine AM, Ravindran P (2020) Role of W-site substitution on mechanical and electronic properties of cubic tungsten carbide. J Phys Condens Matter 32(14):145701 (16 pp.) 954. Swab JJ, Tice J (2005) Evaluation of tungsten carbide (WC) for armour applications. Technical Report ARL-TR-3523 (FMTR-1827-2003-35-001-05), pp. 1-44. United States Army Research Laboratory, Aberdeen Proving Ground, Maryland 955. Silvestroni L, Gilli N, Migliori A, Sciti D, Watts J, Hilmas GE, Fahrenholtz WG (2020) Binderless WC with high strength and toughness up to 1500 °C. J Eur Ceram Soc 40:22872294

References

629

956. Dopita M, Sriram CR, Chmelik D, Salomon A, Seifert HJ (2010) Spark-plasma sintering of nanocrystalline binderless WC hard metals. In: Zbořil R, Shrbená J (eds) Proc. 2nd Int. conf. NANOCON 2010, Olomouc, Czech Republic, 12-14 Oct 2010, pp.133-139. Tanger Ltd., Ostrava, Czech Republic 957. Gridneva IV, Milman YuV, Trefilov VI (1969) On the mechanical properties of crystals with covalent bond. Phys Stat Sol B 36(1):59-67 958. Westbrook JH, Stover ER (1967) Carbides for high-temperature materials. In: Campbell IE, Sherwood EM (eds) High-temperature materials and technology, pp. 312-348. Wiley, New York 959. Zavodinsky VG (2010) Small tungsten carbide nanoparticles: simulation of structure, energetics and tensile strength. Int J Refract Met Hard Mater 28:446-450 960. Zavodinsky VG (2010) Tungsten carbide on the subnanoscale level: atomic structure, electronic states and mechanical properties. Nanotechnol Russ 5(11-12):837-843 961. Samsonov GV, Kharchenko VK, Struk LI (1968) Static strength of refractory compounds at high temperatures. Powder Metall Met Ceram 7(3):206-209 962. Struk LI (1969) Issledovanie protsessa pressovaniya i nekotorykh fiziko-mekhanicheskikh svoistv tugoplavkikh soedinenii (A study of pressing procedure and some physicomechanical properties of refractory compounds). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 963. Porter HB (1955) Rocket refractories. Technical Report 4893, Note 1191, pp. 1-54. United States Naval Ordnance Test Station, Inyokern, California 964. Agte C, Vacek J (1953) Výroba a vlastnosti hustých tĕl vyrobených z karbidu wolframu (Production and properties of dense bodies made from tungsten carbide). Hutnické Listy 8(5):249-252 (in Czech) 965. Pisarenko GS, Rudenko VN, Tretyachenko GN, Troshchenko VT (1966) Prochnost materialov pri vysokikh temperaturakh (Strength of materials at high temperatures). Naukova Dumka, Kyiv (in Russian) 966. Whitney ED, Niesse JE, Murata Y (1963) Development of improved cutting tool materials. Interim Progress Technical Report IR-7-724(IV), Contract USAF 33(657)-9789, pp. 1-43. The Carborundum Company, Niagara Falls, New York 967. Kelly A, Rowcliffe DJ (1967) Deformation of polycrystalline transition metal carbides. J Am Ceram Soc 50(5):253-256 968. Kharchenko VK, Struk LI (1962) Some data on the effect of temperature on the strength and plasticity of high melting point materials. Powder Metall Met Ceram 1(2):128-130 969. Every AG, McCurdy AK (1992) Second and higher order elastic constants. Subvol. A. In: Nelson DF (ed) High and low frequency properties of dielectric crystals. Springer, Berlin, Heidelberg 970. Lee M, Gilmore RS (1982) Single-crystal elastic constants of tungsten monocarbide. J Mater Sci 17:2657-2660 971. Hauk V, Kockelmann H (1979) Bewertung von Einkristall-Elastizitätskonstanten aus mechanischen und Röntgenelastizitätskonstanten des Polykristalls (Evaluation of singlecrystal elastic constants from mechanical and X-ray elastic constants of the polycrystal). Z Metallkd 70(8):500-502 (in German) 972. Kreimer GS (1968) Strength of hard alloys. Consultants Bureau, New York 973. Zhukov VP, Gubanov VA (1985) Energy band structure and thermo-mechanical properties of tungsten and tungsten carbides as studied by the LMTO-ASA method. Solid State Commun 56(1):51-55 974. Zhukov VP, Gubanov VA (1985) Study of energy band structures, some thermo-mechanical properties and chemical bonding for a number of refractory metal carbides by the LMTOASA method. J Phys Chem Solids 46(10):1111-1116 975. Hugosson HW, Engqvist H (2003) The connection between the electronic structure and the properties of binderless tungsten carbides. Int J Refract Met Hard Mater 21:55-61

630

2 Tungsten Carbides

976. Exner HE (1979) Physical and chemical nature of cemented carbides. Int Met Rev 24(1):149-173 977. Rahim-Garzon GPA, Rodríguez JAM (2011) Un estudio sobre la dureza y su correlación con las propiedades del material WC a partir de primeros principios (A study on the hardness and its correlation with the WC material properties based on first principles). Rev Colomb Fis 43(3):779-782 (in Spanish) 978. Sahraoui T, Kellou A, Faraoun HI, Fenineche N, Aourag H, Coddet C (2004) Ab initio calculations and experimental studies of site substitution of ternary elements in WC. Mater Sci Eng B 107:1-7 979. Su YD, Hu CQ, Wang C, Wen M, Zheng WT (2009) Relatively low temperature synthesis of hexagonal tungsten carbide films by N doping and its effect on the preferred orientation, phase transition and mechanical properties. J Vac Sci Technol 27(2):167-173 980. Golovchan VT, Bondarenko VP, Litoshenko NV (2003) Strength of polycrystalline tungsten monocarbide under tension. Strength Mater 35(4):387-394 981. Frantsevich IN, Lyashchenko AB (1966) Young’s moduli of the carbides of some transition metals. Powder Metall Met Ceram 5(7):573-574 982. Köster W, Rauscher W (1948) Beziehungen zwischen dem Elastizitätsmodul von Zweistofflegierungen und ihrem Aufbau (Relationships between the modulus of elasticity of binary alloys and their structure). Z Metallkd 39:111-120 (in German) 983. Doi H, Fujiwara Y, Miyake K, Oosawa Y (1970) A systematic investigation of elastic moduli of WC-Co alloys. Metall Trans 1(5):1417-1425 984. Doi H, Fujiwara Y, Miyake K, Oosawa Y (1972) Corrections to Metall. Trans., 1970, Vol. 1, “A systematic investigation of elastic moduli of WC-Co alloys” by Doi H., Fujiwara Y., Miyake K. and Oosawa Y., pp. 1417-1425. Metall Trans 3(2):602 985. Voronov FF, Balashov DB (1960) Adiabaticheskie moduli uprugosti metallokeramicheskikh volframovykh tverdykh splavov (Adiabatic elastic moduli of cermet tungsten hard alloys) Fiz Met Metalloved 9(4):616-620 (in Russian) 986. Jaensson BO, Sundström BO (1972) Determination of Young’s modulus and Poisson’s ratio for WC-Co alloys by the finite element method. Mater Sci Eng 9:217-222 987. Warren R (1978) Measurement of the fracture properties of brittle solids by Hertzian indentation. Acta Metall 26:1759-1769 988. Dubois J, Orange G, Fantozzi G (1980) Comportement mecanique entre 800 °C et 2200 °C de l’hémicarbure de tungstene (Mechanical behaviour of tungsten semicarbide at 800-2200 °C). Scripta Metall 14(1):107-111 (in French) 989. Kovalchenko MS, Bovkun GA, Tkachenko YuG, Ragozin IP (1983) Deformation properties of monocarbides of transition metals by the method of continuous impression of an indenter. Powder Metall Met Ceram 22(12):1034-1037 990. Lay S, Osterstock F (1984) High-temperature creep of pure tungsten carbide and WC-Co alloys with low cobalt volumic ratios. In: Tressler RE, Bradt RC (eds) Deformation of ceramic materials II. Proc. Int. symp. on plastic deformation of ceramic materials, University Park, Pennsylvania, 20-22 July 1983, pp. 463-471. Plenum Press, New York, London 991. Lay S, Chermant J-L, Vicens J (1984) Plasticity of WC materials by TEM investigations. In: Tressler RE, Bradt RC (eds) Deformation of ceramic materials II. Proc. Int. symp. on plastic deformation of ceramic materials, University Park, Pennsylvania, 20-22 July 1983, pp. 87-96. Plenum Press, New York, London 992. Lay S, Delavignette P, Vicens J (1985) Analysis of subgrain boundaries in tungsten carbide deformed at high temperature. Phys Stat Sol A 90(1):53-68 993. Luyckx SB, Cassuto Y, Sellschop JPF (1987) Ductile-to-brittle transition induced by nitrogen ion implantation into WC single crystals. Mater Sci Eng 90:339-341 994. Pezzotti G, Nishida T, Kleebe H-J, Ota K, Muraki N, Sergo V (1999) Effect of interface chemistry on the mechanical properties of Si3N4-matrix composites. J Mater Sci 34(7):16671680

References

631

995. Dandekar DP, Grady DE (2002) Shock equation of state and dynamic strength of tungsten carbide. In: Furnish MD, Thadhani NN, Horie Y (eds) Shock compression of condensed matter – 2001, pp. 783-786. American Institute of Physics, New York 996. Gooch WA, Burkins MS, Palicka R (2000) Ballistic development of US high density tungsten carbide ceramics. J Phys IV 10:735-741 997. Dandekar DP (2004) Spall strength of tungsten carbide. Technical Report ARL-TR-3335, pp. 1-20. United States Army Research Laboratory, Aberdeen Proving Ground, Maryland 998. Pujada BR, Janssen GCAM (2006) Density, stress, hardness and reduced Young’s modulus of W-C:H coatings. Surf Coat Technol 201:4284-4288 999. Kawakami Y, Enjoji T, Mouri S, Tanaka H, Takashima K (2007) Development of binderless WC hard alloy prepared by pulsed current sintering. J Jpn Inst Met 71(2):195-198 (in Japanese) 1000. Shein IR, Suetin DV, Ivanovskii AL (2008) Elastic properties of carbide, nitride and boride ceramics with WC-type structures. Tech Phys Lett 34(10):841-844 1001. Golovchan VT (2009) On bending strength of superhard composite materials based on WC-Co hardmetals. Strength Mater 41(6):603-612 1002. Golovchan VT (2010) On the strength of polycrystalline tungsten monocarbide. Int J Refract Met Hard Mater 28:250-253 1003. Golovchan VT (1998) Elastic moduli of a tungsten monocarbide crystal. Int Appl Mech 34(8):755-757 1004. Baek ER, Kim HT, Kim JS, Kwon YS (2005) Sintering and mechanical properties of binderless WC sintered by spark-plasma sintering method. In: Kneringer G, Rödhammer P, Wildner H (eds) Powder metallurgical high-performance materials. Proc. 16th Int. Plansee seminar, Reutte, Tyrol, Austria, 30 May – 3 June 2005, Vol. 2 – Plenary lectures & P/M hard materials, pp. 277-286. Plansee Metal AG, Reutte, Austria 1005. Chermant J-L, Osterstock FE (1979) Elastic and plastic characteristics of WC-Co composite materials. Powder Metall Int 11(3):106-109 1006. Imasato S, Tokumoto K, Kitada T, Sakaguchi S (1995) Properties of ultra-fine grain binderless cemented carbide “RCCFN”. Int J Refract Met Hard Mater 13(5):305-312 1007. Kang H-S, Doh J-M, Hong K-T, Ko I-K, Shon I-J (2010) Rapid sintering of nanostructured tungsten carbide by high-frequency induction heating and its mechanical properties. Korean J Met Mater 48(11):1009-1013 (in Korean) 1008. Li X, Xiao Z, Yang C, Qu S (2010) Research on binderless tungsten carbide prepared by spark-plasma sintering. In: Proc. Int. conf. on engineering design and optimization (ICEDO 2010), Ningbo, China, 28-30 Oct 2010. Appl Mech Mater 37-38:980-984 1009. Shon I-J, Kim B-R, Doh J-M, Yoon J-K, Woo K-D (2010) Properties of nanostructured tungsten carbide and their rapid consolidation by pulsed current activated sintering. Phys Scripta T 139:014043 (4 pp.) 1010. Ferreira JAM, Amaral MAP, Antunes FV, Costa JDM (2009) A study on the mechanical behaviour of WC/Co hardmetals. Int J Refract Met Hard Mater 27:1-8 1011. Zavodinsky VG, Kulik MA, Gnidenko AA (2012) Quantum-mechanical simulation of the elastic properties of titanium carbide and tungsten carbide nanoparticles. Int J Nanomech Sci Technol 3(4):283-295 1012. Price DL, Cooper BR (1989) Total energies and bonding for crystallographic structures in titanium-carbon and tungsten-carbon systems. Phys Rev B 39(8):4945-4957 1013. Christensen M, Wahnström G (2003) Co-phase penetration of WC (1010) / WC (1010) grain boundaries from first principles. Phys Rev B 67(11):115415 (11 pp.) 1014. Yang W, Sun M, Yang Z, Xu C, Xia Y, Xiong Z (2020) Dielectric and electromagnetic attenuated properties of WC/wax composite. Front Mater 7:177 (6 pp.) 1015. Eriksson M, Radwan M, Shen Z (2013) Spark-plasma sintering of WC, cemented carbide and functional graded materials. Int J Refract Met Hard Mater 36:31-37 1016. Wheeler JM, Michler J (2013) Indenter materials for high-temperature nanoindentation. Rev Sci Instrum 84(10):101301 (11 pp.)

632

2 Tungsten Carbides

1017. Gao Z, Kang S (2013) First principles investigation of the elastic, electronic and thermodynamic properties of a nitrogen-doped (Ti0.75W0.25)C solid solution. Solid State Commun 156:25-30 1018. Sobol OV (2016) The influence of nonstoichiometry on elastic characteristics of metastable β-WC1–x phase in ion plasma condensates. Tech Phys Lett 42(9):909-911 1019. Feng Q, Song X, Liu X, Liang S, Wang H, Nie Z (2017) Compression deformation of WC: atomistic description of hard ceramic material. Nanotechnol 28:475709 (8 pp.) 1020. Liu X, Zhang J, Hou C, Wang H, Song X, Nie Z (2018) Mechanisms of WC plastic deformation in cemented carbide. Mater Design 150:154-164 1021. Humphry-Baker SA, Smith GDW, Pintsuk G (2019) Thermal shock of tungsten carbide in plasma-facing conditions. J Nucl Mater 524:239-246 1022. Mejbel MK, Allawi MK, Oudah MH (2019) Effects of WC, SiC, iron and glass fillers and their high percentage content on adhesive bond strength of an aluminium alloy butt joint: an experimental study. J Mech Eng Res Devel 42(5):224-231 1023. Kashtalyan YuA (1970) Kharakteristiki uprugosti materialov pri vysokikh temperaturakh (Elasticity characteristics of materials at high temperature). Naukova Dumka, Kyiv (in Russian) 1024. Frantsevich IN, Voronov FF, Bakuta SA (1982) Uprugie postoyannye i moduli uprugosti metallov i nemetallov (The elastic constants and elasticity moduli of metals and non-metals). Naukova Dumka, Kyiv (in Russian) 1025. Dzhemelinskii VV (1970) Issledovanie temperaturnoi zavisimosti tverdosti nekotorykh tugoplavkikh soedinenii (Study of the temperature dependence of hardness of some refractory compounds). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 1026. Trefilov VI, Milman YuV, Firstov SA (1975) Fizicheskie osnovy prochnosti tugoplavkikh metallov (Fundamentals of strength physics of refractory metals). Naukova Dumka, Kyiv (in Russian) 1027. Chermant J-L, Deschanvres A, Osterstock FE (1978) Toughness and fractography of TiC and WC. In: Bradt RC, Hasselman DPH, Lange FF (eds) Proc. Int. symp. on the fracture mechanics of ceramics, University Park, Pennsylvania, 27-29 July 1977. Fracture mechanics of ceramics. Vol. 4 – Crack growth and microstructure, pp. 891-901. Plenum Press, New York, London 1028. Prantskyavichyus GA (1986) Relationship between the strength and crack resistance of refractory ceramics. Refract Indust Ceram 27(5-6):254-258 1029. Tumanov VI, Yudkovskii SI, Chernyshev VV (1968) Relationship between the physical and mechanical properties of carbides of groups IV-VI metals and their electron structure and thermodynamic parameters. Russ Metall (4):134-137 1030. Tumanov VI, Yudkovskii SI, Chernyshev VV (1969) Svyaz fiziko-mekhanicheskikh svoistv karbidov metallov IV-VI grupp periodicheskoi sistemy s ikh elektronnym stroeniem i termodinamicheskimi parametrami (The relation of physico-mechanical properties of metal carbides of IV-VI groups of the periodic system with their electronic structure and thermodynamic parameters). In: Tumanov VI (ed) Tverdye splavy. Trudy Vsesoyuznogo nauchno-issledovatelskogo i proektnogo instituta tverdykh splavov i tugoplavkikh metallov (VNIITS). (Hard alloys. Proc. of All-Union Scientific Research and Design Institute of Hard Alloys and Refractory Metals (VNIITS)), Vol. 6, pp. 187-195. Metallurgiya, Moscow (in Russian) 1031. Warde JM (1956) Refractories for nuclear energy. Technical Bulletin N 94. Refractories Institute, Pittsburgh, Pennsylvania 1032. Graeve OA, Kelly JP (2014) High-temperature materials processing. In: Bar-Cohen Y (ed) High-temperature materials and mechanisms, pp. 163-191. CRC Press, Boca Raton, London, New York

References

633

1033. Kovalchenko MS, Ogorodnikov VV, Rogovoi YuI, Krainii AG (1979) Radiatsionnoe povrezhdenie tugoplavkikh soedinenii (The radiation damage of refractory compounds). Atomizdat, Moscow (in Russian) 1034. Gubanov VA, Ivanovskii AL, Zhukov VP (1994) Electronic structure of refractory carbides and nitrides. Cambridge University Press, Cambridge, New York 1035. Suzuki H, Ohta J-I, Shimada H, Watanabe R (1986) Determination of Young’s moduli of some sintered hard materials by speckle photography. J Jpn Soc Powder Powder Metall 33(8):418-421 (in Japanese) 1036. Wachtman JB, Jr (1969) Elastic deformation of ceramics and other refractory materials. In: Wachtman JB, Jr (ed) Mechanical and thermal properties of ceramics. Proc. symp. on mechanical and thermal properties of ceramics, Gaithersburg, Maryland, 1-2 Apr 1968, Special Publication 303, pp. 139-168. National Bureau of Standards, US Government Printing Office, Washington, DC 1037. Tumanov VI, Goldberg ZA, Chernyshev VV, Pavlova ZI (1966) Thermal shock resistance of tungsten carbide – cobalt alloys. Powder Metall Met Ceram 5(10):818-822 1038. Mai YW, Atkins AG (1975) Fracture strength behaviour of tool carbides subjected to thermal shock. Am Ceram Soc Bull 54(6):593 1039. Mai YW, Atkins AG (1975) Fracture toughness and thermal shock of tool and turbine ceramics. J Mater Sci 10(11):1904-1919 1040. Merten CW (1983) Response of a WC-Co alloy to thermal shock. In: Viswanadham RK, Rowcliffe DJ, Gurland J (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Jackson Hole, Wyoming, 23-28 Aug 1981, pp. 757-774. Plenum Press, New York, London 1041. Han D (1990) Fracture analysis and thermal shock behaviour of WC-Co and Mo/Nb metallic particulate reinforced WC-Co pseudo-matrix composites. PhD thesis, Pennsylvania State University, University Park, Pennsylvania 1042. Han D, Mecholsky JJ, Jr (1990) Strength and toughness degradation of tungsten carbide – cobalt due to thermal shock. J Am Ceram Soc 73(12):3692-3695 1043. Yamamoto T, Kouno S, Miyatake K (2000) Evaluation on thermal shock resistance of WC-Co based alloys YAG laser machining. J Jpn Soc Powder Powder Metall 47(5):553-558 (in Japanese) 1044. Hasselman DPH (1978) Figures-of-merits for the thermal stress resistance of hightemperature brittle materials: a review. Ceramurg Int 4(4):147-150 1045. Shabalin IL, Wang Y, Krynkin AV, Umnova OV, Vishnyakov VM, Shabalin LI, Churkin VK (2010) Physico-mechanical properties of ultra-high temperature hetero-modulus ceramics based on group 4 transition metal carbides. Adv Appl Ceram 109(7):405-415 1046. Shabalin IL (2014) TSR of hetero-modulus ceramics. In: Hetnarski RB (ed) Encyclopedia of thermal stresses, Vol. 11, pp. 6250-6255. Springer, Dordrecht, New York, London 1047. Keilholtz GW, Moore RE, Osborne MF (1968) Fast neutron effects on the carbides of titanium, zirconium, tantalum, niobium and tungsten. Nucl Appl 4:330-336 1048. Keilholtz GW, Moore RE (1969) Fast neutron stability of refractory metal carbides at high temperatures. Trans Am Nucl Soc 12(1):101-103 1049. Keilholtz GW, Moore RE, Dyslin DA (1969) Behaviour of refractory materials under irradiation. Technical Report ORNL-4390, Contract W-7405-eng-26, pp. 1-195. Oak Ridge National Laboratory, Tennessee 1050. Keilholtz GW, Dyslin DA, Moore RE, Robertson HE (1969) Behaviour of refractory materials under irradiation. Technical Report ORNL-4420, Contract W-7405-eng-26, pp. 1285. Oak Ridge National Laboratory, Tennessee 1051. Patriarca P, Harms WO, Rucker DJ, eds (1969) Fuels and materials development program. Quarterly Progress Technical Report ORNL-4350, Contract W-7405-eng-26, pp.1-320. Oak Ridge National Laboratory, Tennessee

634

2 Tungsten Carbides

1052. Keilholtz GW, Dyslin DA, Moore RE, Robertson HE (1970) Behaviour of refractory materials under irradiation. Technical Report ORNL-4440, Contract W-7405-eng-26, pp. 1355. Oak Ridge National Laboratory, Tennessee 1053. Keilholtz GW, Moore RE, Robertson HE (1970) The effects of neutron irradiation on carbides of refractory metals. In: Grimes WR, Bohlmann EG, McDuffie HF, Watson GM, Blankenship FF (eds) Reactor chemistry division. Annual Progress Technical Report ORNL4586, Contract W-7405-eng-26, p. 129. Oak Ridge National Laboratory, Tennessee 1054. Kovalchenko MS, Rogovoi YuI (1973) Radiation effects in tungsten monocarbide. Phys Met Metallogr 35(1):55-61 1055. Ogorodnikov VV, Kovalchenko MS, Krainii AG, Épik AP (1969) Influence of neutron bombardment of diffused carbide and boride coatings on refractory metals. Mater Sci 4(1):24-26 1056. Karditsas PJ, Edwards JEG (2000) Blanket and first wall conceptual design issues of the spherical tokamak power plant. Fusion Eng Design 48:379-387 1057. Dolan TJ, Waganer LM, Merola M (2013) First wall, blanket and shield. In: Dolan TJ (ed) Magnetic fusion technology, pp.233-311. Springer, London 1058. Liu N, Huang J, Sato K, Xu Q, Shi LQ, Wang YX (2014) Hydrogen trapping under the effect of W-C mixed layers. Nucl Fusion 54:033013 (6 pp.) 1059. Dash T, Nayak BB, Abhangi M, Makwana R, Vala S, Jakhar S, Rao CVS, Basu TK (2014) Preparation and neutronic studies of tungsten carbide composite. Fusion Sci Technol 65(2):241-247 1060. Šestan A, Jenuš P, Krmpotič SN, Zavašnik J, Čeh M (2018) The role of tungsten phases formation during tungsten metal powder consolidation by FAST: implications for hightemperature applications. Mater Charact 138:308-314 1061. Tejado E, Dias M, Correia JB, Palacios T, Carvalho PA, Alves E, Pastor JY (2018) New WC-Cu thermal barriers for fusion applications: high temperature mechanical behaviour. J Nucl Mater 498:355-361 1062. Windsor CG, Marshall JM, Morgan JG, Fair J, Smith GDW, Rajczyk-Wryk A, Tarragó JM (2018) Design of cemented tungsten carbide and boride – containing shields for a fusion power plant. Nucl Fusion 58(7):076014 (12 pp.) 1063. Humphry-Baker SA, Smith GDW (2019) Shielding materials in the compact spherical tokamak. Philos Trans Royal Soc A 377(2141):20170443 (18 pp.) 1064. Oliver SX, Jackson ML, Burr PA (2020) Radiation-induced evolution of tungsten carbide in fusion reactors: accommodation of defect clusters and transmutation elements. ACS Appl Energy Mater 3:868-878 1065. Burr PA, Oliver SX (2019) Formation and migration of point defects in tungsten carbide: unveiling the sluggish bulk self-diffusivity of WC. J Eur Ceram Soc 39(2-3):165-172 1066. Dubček P, Radić N, Milat O (2003) Characterization of grains in tungsten-carbon films. Nucl Instrum Meth B 200:329-332 1067. Olsher RH, Hsu H-H (1994) A new neutron dose equivalent meter. In: Lampo E (ed) Proc. IEEE nuclear science symp. and medical imaging conf. (NSS-MIC ‘93), San Francisco, California, 2-6 Nov 1993, pp.741-745. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 1068. Olsher RH, Hsu H-H, Beverding A, Kleck JH, Casson WH, Vasilik DG, Devine RT (2000) WENDI: an improved neutron REM meter. Health Phys 79(2):170-181 1069. Evans BR, Lian J, Ji W (2018) Evaluation of shielding performance for newly developed composite materials. Ann Nucl Energy 116:1-9 1070. Rybin VV, Trushin YuV, Fedorov FYu, Kharlamov VS (2000) Special features of the effect of oversized impurities on the cascade development in α-iron alloys containing special carbides. Tech Phys Lett 26(10):876-878 1071. Kharlamov VS, Trushin YuV, Rybin VV, Fedorov FYu (2001) Computer simulation of the special carbides (WC and MoC) destruction by collision cascades in Fe matrix. In: Melker AI (ed) Proc. 4th SPIE Int. workshop on nondestructive testing and computer

References

635

simulations in science and engineering, St. Petersburg, Russian Federation, 12-17 June 2000. Proc SPIE 4348:254-256 1072. Hershkowitz N, Wender SA, Oberley LW (1970) Radiation damage in tungsten carbide. Phys Lett A 33(2):89-90 1073. Soylu HM, Lambrecht FY, Ersöz OA (2015) Gamma radiation shielding efficiency of a new lead-free composite material. J Radioanal Nucl Chem 305:529-534 1074. Gual MR, Mesquita AZ, Pereira C (2018) Evaluation of an alternative shielding materials for F-127 transport package. Radiat Phys Chem 144:29-33 1075. Remanan M, Bhowmik S, Varshney L, Jayanarayanan K (2018) Poly(aryl ether ketone) based individual, binary and ternary nanocomposites for nuclear waste storage: mechanical, rheological and thermal analysis. Mater Res Express 5:105306 (18 pp.) 1076. Chesters MA, Hopkins BJ, Jones AR, Nathan R (1974) Some electron beam effects on CO / W (100), C2H4 / W (100) and tungsten carbide. J Phys C Solid State Phys 7:4486-4492 1077. Petrenko PV, Grabovskii YuE, Gritskevich AL, Kulish NP, Melnikova NA (2003) Strukturno-fazovye prevrashcheniya v tverdykh splavakh WC-Co pri obluchenii nizkopotokovym elektronnym puchkom (Structure and phase transformations in WC-Co hard alloys irradiated with low-flux electron beam). Fiz Khim Obrabotki Mater (3):29-39 (in Russian) 1078. Ivanov Yu, Ovcharenko V, Belyi A, Teresov A (2014) The structure and properties of hard metals irradiated by high-energy electron beam. Adv Mater Res 872:214-218 1079. Zhang FG, Zhu XP, Lei MK (2017) Surface characterization and tribological properties of WC-Ni cemented carbide irradiated by high-intensity pulsed electron beam. Vacuum 137:119-124 1080. Peng W, Hao S, Zhao L, Li Z, Chen J, Lan J, Wang X, Wang K (2020) Thermal stability of modified surface microstructure on WC-Co cemented carbide after high current pulsed electron beam irradiation. J Alloys Compd 829:154545 (7 pp.) 1081. Migge H (1986) Thermodynamic stability of structural materials in a fusion reactor environment. J Nucl Mater 141-143:448-452 1082. Wang W, Alimov VKh, Scherzer BMU, Roth J (1997) Deuterium trapping in and release from tungsten carbide. J Nucl Mater 241-243:1087-1092 1083. Anderl RA, Pawelko RJ, Schuetz ST (2001) Deuterium retention in W, W 1 % La, Ccoated W and W2C. J Nucl Mater 290-293:38-41 1084. Alimov VKh, Komarov DA (2003) Deuterium retention in carbon and tungsten-carbon mixed films deposited by magnetron sputtering in D2 atmosphere. J Nucl Mater 313-316:599603 1085. Ogorodnikova OV, Roth J, Mayer M (2003) Deuterium retention in tungsten in dependence of the surface conditions. J Nucl Mater 313-316:469-477 1086. Alimov VKh (2004) Deuterium retention in pure and mixed plasma facing materials. Phys Scripta T 108:46-56 1087. Kimura H, Nishikawa Y, Nakahata T, Oyaidzu M, Oya Y, Okuno K (2006) Chemical behaviour of energetic deuterium implanted into tungsten carbide. Fusion Eng Design 81:295-299 1088. Nordlund K, Salonen E, Krasheninnikov AV, Keinonen J (2006) Swift chemical sputtering of covalently bonded materials. Pure Appl Chem 78(6):1203-1211 1089. Igarashi E, Nishikawa Y, Nakahata T, Yoshikawa A, Oyaidzu M, Oya Y, Okuno K (2007) Dependence of implantation temperature on chemical behaviour of energetic deuterium implanted into tungsten carbide. J Nucl Mater 363-365:910-914 1090. Träskelin P, Juslin N, Erhart P, Nordlund K (2007) Molecular dynamics simulations of hydrogen bombardment of tungsten carbide surfaces. Phys Rev B 75(17):174113 (7 pp.) 1091. Träskelin P, Björkas C, Juslin N, Vörtler K, Nordlund K (2007) Radiation damage in WC studied with MD simulations. Nucl Instrum Meth B 257:614-617

636

2 Tungsten Carbides

1092. Gorelick S, Whitlow HJ (2009) Aperture edge scattering in focused MeV ion beam lithography and nuclear microscopy: an application for the GEANT4 toolkit. Nucl Instrum Meth B 267:2050-2053 1093. Vörtler K, Nordlund K (2007) Molecular dynamics simulations of deuterium trapping and re-emission in tungsten carbide. J Phys Chem C 114(12):5382-5390 1094. Kong X-S, You Y-W, Liu CS, Fang QF, Chen J-L, Luo G-N (2011) First principles study of hydrogen behaviours in hexagonal tungsten carbide. J Nucl Mater 418:233-238 1095. Ou XD, Shi LQ, Sato K, Xu Q, Wang YX (2012) Effect of carbon on hydrogen behaviour in tungsten: first principles calculations. Nucl Fusion 52:123003 (6 pp.) 1096. Wang P, Jacob W (2014) Deuterium diffusion and retention in a tungsten-carbon multilayer system. Nucl Instrum Meth B 329:6-13 1097. Oya Y, Sato M, Li X, Yuyama K, Fujita H, Sakurada S, Uemura Y, Hatano Y, Yoshida N, Ashikawa N, Sagara A, Chikada T (2016) Impact of temperature during He+ implantation on deuterium retention in tungsten, tungsten with carbon deposit and tungsten carbide. Phys Scripta T 167:014037 (5 pp.) 1098. Weinberg WH, Merrill RP (1970) Atomic and molecular diffraction of helium and deuterium from a tungsten carbide surface characterized by low-energy electron diffraction. Phys Rev Lett 25(17):1198-1201 1099. Weinberg WH, Merrill RP (1972) Atomic and molecular diffraction and scattering from a tungsten carbide surface characterized by LEED. J Chem Phys 56(6):2903-2911 1100. Weinberg WH (1972) Application of the Debye-Waller theory to atomic and molecular scattering from solid surfaces. J Chem Phys 57(12):5467-5474 1101. Fremlin JH, Askouri NA (1974) Hardening of tungsten carbide by irradiation. Nature 249(5453):137 1102. Dearnaley G, Goode PD, Hartley NEW, Proctor GW, Turner JF, Watkins REJ (1979) The ion implantation of steel and cemented carbides. In: Hurley R (ed) Ion plating and allied technique – 1979. Proc. Int. conf. on ion plating and allied techniques (IPAT 79), London, 35 July 1979, 243-254. CEP Consultants Ltd, Edinburgh, UK 1103. Hartley NEW (1979) Friction and wear of ion-implanted metals – a review. Thin Solid Films 64:177-190 1104. Hartley NEW (1979) Applications for ion implantation as a surface treatment process in production engineering. In: Proc. 2nd Int. conf. on ion implantation and equipment, Povo, Trento, Italy, 28-31 Aug 1978. Radiat Eff 44(1-4):19-29 1105. Dearnaley G (1981) The effects of ion implantation upon the mechanical properties of metals and cemented carbides. In: Proc. Int. workshop on ion implantation, laser treatment and ion beam analysis of materials, Bombay, India, 9-13 Feb 1981. Radiat Eff 63(1-4):1-15 1106. Dearnaley G (1981) Applications of ion implantation in metals & alloys. IEEE Trans Nucl Sci 28(2):1808-1811 1107. Kolitsch A, Richter E (1983) Change of microhardness on ion implanted tungsten carbide. Cryst Res Technol 18(1):K5-K7 1108. Oblas DW (1984) Characterization of nitrogen implanted WC/Co. In: Hubler GK, Holland OW, Clayton CR, White CW (eds) Proc. symp. on ion implantation and ion beam processing of materials, Boston, Massachusetts, 14-17 Nov 1983. Mater Res Soc Symp Proc 27:631-636 1109. Robelet M, Barnavon T, Tousset J, Faveulle S, Treheux D, Guiraldenq P (1984) Amelioration des proprietes mecaniques des materiaux par implantation ionique (Improvement of materials properties by ion implantation). In: 26eme Colloq. de metallurgie de Saclay: effets d’irradiation dans les materiaux (metaux, alliages, verres) (26th Saclay colloq. on metallurgy: effects of irradiation in materials (metals, alloys, glasses)), pp. 229233. Institut National des Sciences et Techniques Nucléaires, Centre d’Etudes Nucléaires de Saclay, Masson, Paris (in French) 1110. Dearnaley G, Minter FJ, Rol PK, Saint A, Thompson V (1985) Microhardness and nitrogen profiles in ion implanted tungsten carbide and steels. Nucl Instrum Meth B 78(1):188-194

References

637

1111. Dearnaley G (1985) Adhesive, abrasive and oxidative wear in ion-implanted metals. Mater Sci Eng 69:139-147 1112. Fayeulle S, Treheux D, Guiraldenq P, Dubois J, Fantozzi G (1986) Nitrogen implantation in tungsten carbides. J Mater Sci 21:1814-1818 1113. McHargue CJ (1986) Ion implantation in metals and ceramics. Int Met Rev 31(1):49-76 1114. Anderson AD, Loretto MH, Dearnaley G (1988) Microstructural study of ion-implanted WC-Co. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:503-507 1115. Anderson AD, Loretto MH, Dearnaley G (1989) Microstructural study of ion-implanted WC-Co. Int J Refract Met Hard Mater 8(3):189-191 1116. Platonov GL, Leonov EYu, Anikin VN, Anikeev AI (1988) Examination of the variation of the phase composition and stress state of surface layers of VK20 hard alloy after ion bombardment. Powder Metall Met Ceram 27(2):167-169 1117. Guzman L, Ciaghi L, Giacomozzi F, Voltolini E, Peacock A, Dearnaley G, Gardner P (1989) Ion implantation in WC-Co: analysis of treated surfaces and testing of industrial tools. Mater Sci Eng A 116:183-191 1118. Didenko AN, Ligachev AE, Kurakin IB, Sipailo MG, Kozlov EV, Sharkeev JB (1992) Structural changes of materials modified by ion beams and the nature of their hardening. Surf Coat Technol 51:186-189 1119. Walter JL, Skelly DW, Minnear WP (1993) Ion implantation of cobalt – tungsten carbide tools for machining titanium. Wear 170:79-92 1120. Choi BN, Kim W, Han JG, Atamanov MV, Guseva MI, Gordeeva GV, Neumoin VE (1994) Issledovanie svoistv poverkhnosti ionno-implantirovannogo WC-Co (Study of surface properties of ion-implanted WC-Co). Mashinoved (5):69-76 (in Russian) 1121. Choi BN, Kim W, Atamanov MV, Guseva MI, Popkov NG (1995) Issledovanie temperatur ionnoi implantatsii WC-Co i bystrorezhushchei stali i ikh vliyanie na mikrotverdost (Studying temperatures of WC-Co and high-speed steel ion-implantation and their effect on microhardness). Mashinoved (1):69-73 (in Russian) 1122. Poleshchenko KN, Nikolaev AV, Vershinin GA (1995) Thermally activated processes in the surface of a WC-Co bombarded with high-energy ions. Phys Chem Mech Surf 11(11):1227-1233 1123. Poleshchenko KN, Poletika MF, Gering GI, Vershinin GA, Tajlashev AS (1995) WC-Co hard alloy treated with gas-metal ion beams: phase composition and wear resistance of the near-surface layer. Phys Met Metallogr 80(1):75-78 1124. Poleshchenko KN, Poletika MF, Gering GI, Vershinin GA (1995) Vliyanie kombinirovannogo ionnogo oblucheniya na khimicheskii sostav i iznosostoikost splava WC-Co (Effect of combined ion irradiation on the chemical composition and wear resistance of WC-Co alloy). Fiz Khim Obrabotki Mater (3):29-33 (in Russian) 1125. Poleshchenko KN, Poletika MF, Vershinin GA (1995) Vliyanie modifikatsii tverdogo splava ionnym puchkom na kontaktnye effekty v usloviyakh rezaniya (The influence of hard alloy ion beam modification on contact effects under cutting conditions). Fiz Khim Obrabotki Mater (4):21-26 (in Russian) 1126. Povoroznyuk SN, Poleshchenko KN, Kulkov SN, Vershinin GA (1995) Ion-beam – induced structural changes and distribution of implanted atoms in a WC-Co alloy. Phys Chem Mech Surf 11(11):1211-1215 1127. Gering GI, Poleshchenko KN, Vershinin GA, Kulkov SN, Povoroznyuk SN, Orlov PV (1998) Influence of diffusion on the wear resistance of modified hard alloys. J Frict Wear 19(4):23-27 1128. Poleshchenko KN, Orlov PV, Mashkov YuK, Ivanov YuF, Povoroznyuk SN, Vershinin GA (1998) Friction-induced structural transformations in sub-surface layers of modified hard alloys. J Frict Wear 19(4):28-33 1129. Poleshchenko KN, Povoroznyuk SN, Vershinin GA, Orlov PV (1998) Wear resistance of hard alloys WC-Co modified by ion beams of different intensity. J Frict Wear 19(4):42-45

638

2 Tungsten Carbides

1130. Povoroznyuk SN, Poleshchenko KN, Vershinin GA, Orlov PV (2000) Variation of surface properties of hard alloys exposed to ion beams of various intensity. J Surf Investig X-Ray Synchrotron Neutron Tech 15(5):791-796 1131. Guseva MI, Atamanov MV, Gordeeva GV, Neumoin VE, Choi BN, Kim W, Han JG (1996) Hardening of WC-Co alloys by ion implantation. Radiat Eff Defect Solids 138(12):57-62 1132. Plank H, Eckstein W (1997) Preferential sputtering of carbides under deuterium irradiation – a comparison between experiment and computer simulation. Nucl Instrum Meth B 124:2330 1133. Mrochek I, Günzel R, Matz W, Möller W, Anishchik V (1999) Implantation of boron ions into hard metals. Nukleonika 44(2):217-224 1134. Lin WL, Sang JM, Ding XJ, Xu J, Yuan XM (2002) Microchemical and microstructural changes of Co cemented WC induced by ion implantation. Nucl Instrum Meth B 188:201-204 1135. Tsareva IN, Romanov IG, Ovsyannikov MYu, Kutuzov VL (2005) Vliyanie parametrov moshchnogo ionnogo puchka na izmenenie poverkhnostnykh svoistv naplavlennogo splava T14K8 (Influence of powerful ion beam parameters on the changing of surface properties of hard-facing alloy T14K8). Poverkhnost Rentgen Sinkhrotron Neitron Issled (9):84-89 (in Russian) 1136. Uglov VV, Anishchik VM, Astashinski VM, Cherenda NN, Gimro IG, Kovyazo AV (2005) Modification of WC hard alloy by compressive plasma flow. Surf Coat Technol 200:245-249 1137. Uglov VV, Remnev GE, Kuleshov AK, Astashinski VM, Saltymakov MS (2010) Formation of hardened layer in WC-TiC-Co alloy by treatment of high-intensity pulse ion beam and compression plasma flows. Surf Coat Technol 204:1952-1956 1138. Baik S-I, Choi E-G, Jun J-H, Kim Y-W (2008) Defect structure induced by ion injection in WC-Co. Scripta Mater 58:614-617 1139. Belbah A, Mkaddem A, Ladaci N, Mebarki N, Mansori ME (2014) Low energy implantation to inhibit wear in N+ ions implanted WC-Co composite. Mater Design 53:202208 1140. Zhang F-G, Zhu X-P, Lei M-K (2014) Tribological behaviour of WC-Ni cemented carbide irradiated by high-intensity pulsed ion beam. Surf Coat Technol 258:78-85 1141. Zhang F-G, Zhu X-P, Lei M-K (2016) Tribological properties of WC-Ni cemented carbide irradiated by high-intensity pulsed ion beam. China Surf Eng 29(1):96-102 (in Chinese) 1142. Luyckx SB, Sellschop JPF (1988) Wear mechanisms modification induced by ion implantation in cemented tungsten carbide. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:509-512 1143. Luyckx SB, Sellschop JPF (1988) Effects of ion implantation on the abrasive wear of WCCo. J Mater Sci Lett 7:265-266 1144. Luyckx SB, Cassuto Y, Derry TE, Sellschop JPF (1987) Sub-surface modification of WC single crystals by nitrogen implantation. Nucl Instrum Meth B 19-20(1):158-161 1145. Karioris FG, Özkan H, Luyckx SB, Cartz L (1990) The stability of WC to ion bombardment. Nucl Instrum Meth B 46(1-4):176-179 1146. Makhele-Lekala L, Luyckx SB, Derry TE (1997) Inhibition of stress corrosion cracking in WC-Co by means of ion implantation. Nucl Instrum Meth B 127-128:770-774 1147. Wolf GK, Spiegel R, Zucholl K (1987) The catalytic activity of tungsten carbide modified by ion implantation and ion beam mixing. Nucl Instrum Meth B 19-20(2):1030-1033 1148. Dorigoni C, Laidani N, Miotello A, Calliari L (1998) Ar+-implantation effects on the interfacial properties of the WC/Ti-6Al-4V system. Surf Coat Technol 100-101:358-361 1149. Laidani N, Dorigoni C, Miotello A, Calliari L, Scarel G, Sancrotti M (1998) Depthprofiling via X-ray photoemission and Auger spectroscopies of N+-implanted tungsten carbides grown on the Ti6-6Al-4V alloy. Thin Solid Films 317:477-480

References

639

1150. Döbeli M, Dommann A, Maeder X, Neels A, Passerone D, Rudigier H, Scopece D, Widrig B, Ramm J (2014) Surface layer evolution caused by the bombardment with ionized metal vapour. Nucl Instrum Meth B 332:337-340 1151. Vlcak P (2016) The effect of ion irradiation and elevated temperature on the microstructure and the properties of C/W/C/B multilayer coating. Appl Surf Sci 365:306-313 1152. Vörtler K, Björkas C, Nordlund K (2011) The effect of plasma impurities on the sputtering of tungsten carbide. J Phys Condens Matter 23:085002 (8 pp.) 1153. Lasa A, Björkas C, Vörtler K, Nordlund K (2012) MD simulations of low energy deuterium irradiation on W, WC, W2C surfaces. J Nucl Mater 429:284-292 1154. Ono T, Kawamura T, Kenmotsu T, Yamamura Y (2001) Simulation study on retention and reflection from tungsten carbide under high fluence of helium ions. J Nucl Mater 290293:140-143 1155. Husmann OK, Jamba DM, Denison DR (1966) Influence of residual gas atmosphere in space chambers on neutral efflux and critical temperature of tungsten ionizers. AIAA J 4(2):273-282 1156. Suzuki K, Fujiwara T, Usui S (1976) Effect of WC grain size on oxidation and thermal shock resistance of WC – 20 % Co sintered alloys. J Jpn Inst Met 40(3):211-218 (in Japanese) 1157. Zucholl K, Wolf GK, Schmiedel H (1985) Electrochemical hydrogen evolution and formic acid oxidation on ion-bombarded catalysts. Mater Sci Eng 69:327-328 1158. Zucholl K, Wolf GK (1986) Ionenbestrahites Wolframcarbid als Elektrokatalysator (Ionirradiated tungsten carbide as electrocatalyst). In: Schultze JW (ed) Grundlagen von Elektrodenreaktionen. Vorträge von der Tagung der Fachgruppe Angewandte Elektrochemie der GDCH, Düsseldorf, Bundesrepublik Deutschland, 8-10 Okt 1986 (Fundamentals of electrode reactions. Proc. conf. on applied electrochemistry of the GDCH, Düsseldorf, Federal Republic of Germany, 8-10 Oct 1986). Dechema Monograph (Deut Gesell Chem Apparat) 102:413-417 (in German) 1159. Singh A, Derry TE, Luyckx SB, Sellschop JPF (1990) X-ray photoelectron spectroscopy of nitrogen-implanted cemented tungsten carbide (WC-Co). J Mater Sci Lett 9:1101-1102 1160. Zeng D, Hampden-Smith MJ (1992) Room-temperature synthesis of molybdenum and tungsten carbides Mo2C and W2C via chemical reduction methods. Chem Mater 4:968-970 1161. Zheng H, Gu Z, Zhong J, Wang W (2007) Preparation and electrocatalytic activity of tungsten carbide nanorod arrays. J Mater Sci Technol 23(5):591-594 1162. Kovač J, Panjan P, Zalar A (2007) XPS analysis of WxCy thin films prepared by sputter deposition. Vacuum 82(2):150-153 1163. Xu Y, Zhang Y, Hao SZ, Perroud O, Li MC, Wang HH, Grosdidier T, Dong C (2013) Surface microstructure and mechanical property of WC – 6 % Co hard alloy irradiated by high current pulsed electron beam. Appl Surf Sci 279:137-141 1164. Bazarjani MS, Müller MM, Kleebe H-J, Fasel C, Riedel R, Gurlo A (2014) In situ formation of tungsten oxycarbide, tungsten carbide and tungsten nitride nanoparticles in micro- and mesoporous polymer-derived ceramics. J Mater Chem A 2(27):10454-10464 1165. Zhu XP, Zhang FG, Song TK, Lei MK (2014) Nonlinear wear response of WC-Ni cemented carbides irradiated by high-intensity pulsed ion beam. J Tribol 136(1):011603 (5 pp.) 1166. Yan Z, Gu Y, Wei W, Jiang Z, Xie J, Shen PK (2015) Tungsten carbide synthesized by polystyrene sphere template method promoting Pd electrocatalyst for alcohol oxidation in alkaline media. Fuel Cells 15(2):256-261 1167. Hunt ST, Milina M, Wang Z, Román-Leshkov Y (2016) Activating earth-abundant electrocatalysts for efficient low-cost hydrogen evolution/oxidation: sub-monolayer platinum coatings on titanium tungsten carbide nanoparticles. Energy Environ Sci 9(10):3290-3301 1168. Pawbake A, Waykar R, Jadhavar A, Kulkarni R, Waman V, Date A, Late D, Pathan H, Jadkar S (2016) Wide band gap and conducting tungsten carbide (WC) thin films prepared by hot wire chemical vapour deposition (HW-CVD) method Mater Lett 183:315-317

640

2 Tungsten Carbides

1169. Si G, Xi X, Nie Z, Zhang L, Ma L (2016) Preparation and characterization of tungsten nanopowders from WC scrap in molten salts. Int J Refract Met Hard Mater 54:422-426 1170. Begum M, Yurukcu M, Yurtsever F, Ergul B, Kariuki NN, Myers DJ, Karabacak T (2017) Pt-Ni/WC alloy nanorods arrays as ORR catalyst for PEM fuel cells. In: Shirvan PA, Ramani V, Kim Y-T, Gasteiger HA, Shinohara K et al. (eds) Proc. 232nd ECS meeting – symp. on polymer electrolyte fuel cells (PEFC 2017), National Harbor, Maryland, 1-5 Oct 2017. ECS Trans 80(8):919-925 1171. Cho JH, Lee HK, Kim MS, Rhim JD, Park YJ (2018) Development of a new nanocrystalline alloy for X-ray shielding. Radiat Eff Defect Solids 173(7-8):643-656 1172. Cui X-Z, Zhang L-L, Zeng L-M, Zhang X-H, Chen H-R, Shi J-L (2018) Fabrication of tungsten carbide nanoparticle – encased graphite-like mesoporous carbon as a precious metal – free electrocatalyst for oxygen reduction. J Inorg Mater 33(2):213-220 (in Chinese) 1173. Ekvall MT, Hedberg J, Wallinder OI, Hansson L-A, Cedervall T (2018) Long-term effects of tungsten carbide (WC) nanoparticles in pelagic and benthic aquatic ecosystems. Nanotoxicol 12(1):79-89 1174. Giménez MAN, Lopasso EM (2018) Tungsten carbide compact primary shielding for small medium reactor. Ann Nucl Energy 116:210-223 1175. Han N, Yang KR, Lu Z, Li Y, Xu W, Gao T, Cai Z, Zhang Y, Batista VS, Liu W, Sun X (2018) Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. Nature Commun 9:924 (10 pp.) 1176. Jafari A, Fayaz V, Meshkani S, Terohid SAA (2018) Interaction between plasma and tungsten carbide thin films coated on stainless steel as tokamak reactor first wall. Philippine J Sci 147(3):537-543 1177. Huang W, Meng H, Gao Y, Wang J, Yang C, Liu D, Liu J, Guo C, Yang B, Cao W (2019) Metallic tungsten carbide nanoparticles as a near-infrared-driven photocatalyst. J Mater Chem A 7(31):18538-18546 1178. Novotný J, Lysoňková I, Svobodová J, Michna Š (2019) Technology of preparing coatings with nanoparticles. In: Machado JM, Soares F, Veiga G (eds) Innovation, engineering and entrepreneurship. Selected proc. 3rd Int. conf. on innovation, engineering and entrepreneurship (HELIX 2018), Guimaraes, Portugal, 27-29 June 2018, pp. 561-567. Springer International, Cham, Switzerland 1179. Song DH, Shin JW, Lee Y, Kwon YK, Lim JH, Kim E-J, Oh SK, Kim MJ, Cho EA (2019) Thin nickel layer with embedded WC nanoparticles for efficient oxygen evolution. ACS Appl Energy Mater 2:3452-3460 1180. Voitovich RF, Pugach ÉA (1973) High-temperature oxidation characteristics of the carbides of the group VI transition metals. Powder Metall Met Ceram 12(4):314-318 1181. Voitovich RF, Pugach ÉA (1975) Vysokotemperaturnoe okislenie karbidov perekhodnykh metallov IV-VI grupp (High-temperature oxidation of transition metals IV-VI groups carbides). In: Samsonov GV (ed) Vysokotemperaturnye karbidy (High-temperature carbides), pp. 143-156. Naukova Dumka, Kyiv (in Russian) 1182. Voitovich RF, Pugach ÉA (1976) Nekotorye osobennosti protsessa okisleniya karbidov metallov IV-VI grupp (The certain features of the oxidation process of metals IV-VI groups carbides). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 233-234. Naukova Dumka, Kyiv (in Russian) 1183. Voitovich RF, Pugach ÉA (1968) Okislenie tugoplavkikh soedinenii (Oxidation of refractory compounds). Naukova Dumka, Kyiv (in Russian) 1184. Voitovich RF (1981) Okislenie karbidov i nitridov (Oxidation of carbides and nitrides). Naukova Dumka, Kyiv (in Russian) 1185. Shabalin IL (2008) “Ridge effect” in oxidation kinetics of hetero-modulus ceramics based on titanium carbide. Powder Metall Met Ceram 47(1-2):137-150

References

641

1186. Shabalin IL (2008) Mechanism of ridge effect phenomenon in high-temperature oxidation of TiC-graphite particulate composites. In: Proc. 214th Electrochemical Society meeting, Honolulu, Hawaii, 12-17 Oct 2008. Meet Abstr Electrochem Soc 802:1758 (1 p.) 1187. Shabalin IL (2009) Oxidation behaviour of hetero-modulus ceramics based on titanium carbide. In: Lin H-T, Koumoto K, Kriven WM, Norton DP, Garsia E, Reimanis IE (eds) Developments in strategic materials. Ceramic engineering and science proceedings, Vol. 29, N 10, pp. 261-278. Wiley, New York 1188. Schulz-Ekloff G, Baresel D, Sarholz W (1976) Crystal face specificity in ammonia synthesis on tungsten carbide. J Catal 43(1-3):353-355 1189. Bystrikov AS, Radzikhovskii LA (1975) Vliyanie dobavok karbida wolframa na sintez kordierita (Effect of tungsten carbide additions on the synthesis of cordierite). Izv AN SSSR Neorg Mater 11(8):1481-1485 (in Russian) 1190. Tsirlina GA (1985) Elektrokhimicheskoe i adsorbtsionnoe povedenie nekotorykh karbidnykh materialov (Electrochemical and adsorption behaviour of some carbide materials). PhD thesis, Lomonosov Moscow State University (in Russian) 1191. Horányi G, Rizmayer EM (1976) Catalytic reduction of sulphuric acid by molecular hydrogen in the presence of tungsten carbide and platinum catalysts. J Electroanal Chem 70(3):377-379 1192. Samsonov GV, Zhidkova TG, Klimak ZA (1975) O kataliticheskikh svoistvakh karbidov perekhodnykh metallov (On the catalytic properties of transition metal carbides). In: Samsonov GV (ed) Vysokotemperaturnye karbidy (High-temperature carbides), pp. 76-81. Naukova Dumka, Kyiv (in Russian) 1193. Kharlamov AI, Rafal AN, Samsonov GV, Belov AS (1977) Catalytic activities of hafnium, tantalum and tungsten carbides in the high-temperature para/ortho conversion of hydrogen. Theor Exp Chem 13(1):92-94 1194. Chebotareva NP, Ilchenko NI, Golodets GI (1976) Kinetics and mechanism of oxidation of hydrogen on carbides of transition metals of groups IV-VI. Theor Exp Chem 12(2):154-162 1195. Chebotareva NP, Ilchenko NI, Golodets GI (1976) General relationships in the catalytic oxidation of hydrogen over carbides of the groups IV-VI transition metals. Theor Exp Chem 12(3):277-281 1196. Ilchenko NI, Pyatnitsky YuI (1996) Carbides of transition metals as catalysts for oxidation reactions. In: Oyama ST (ed) The chemistry of transition metal carbides and nitrides, pp. 311327. Chapman & Hall, London, Glasgow 1197. Ilchenko NI (1973) Kataliticheskaya aktivnost i promotiruyushchie svoistva karbida volframa v reaktsii okisleniya vodoroda (Catalytic activity and promoting properties of tungsten carbide in the hydrogen oxidation reaction). Kinet Catal 14(4):976-980 (in Russian) 1198. Schulz-Ekloff G, Baresel D (1972) Zum Mechanismus der Zersetzung und anodischen Oxidation von Hydrazin an Platin und Wolframcarbid (On the mechanism of the decomposition and anodic oxidation of hydrazine on platinum and tungsten carbide). J Electroanal Chem 35(1):73-76 (in German) 1199. Samsonov GV (1965) Kataliticheskie svoistva tugoplavkikh soedinenii i printsipy sozdaniya tugoplavkikh materialov s zaranee zadannymi kataliticheskimi svoistvami (Catalytic properties of refractory compounds and the principles of creating refractory materials with predetermined catalytic properties). Kinet Catal 6(3):421-432 (in Russian) 1200. Sokolskii DV, Dalikhanova A (1981) Katalizatory na osnove karbida volframa v reaktsii gidrogenizatsii pod davleniem vodoroda (Catalysts based on tungsten carbide in the hydrogenation reaction under hydrogen pressure). Zh Fiz Khim 55(11):2799-2801 (in Russian) 1201. Böhm H, Pohl FA (1968) Wolframcarbid, ein Elektrokatalysator für saure Brennstoffzellen (Tungsten carbide, an electrocatalyst for acid fuel cells). Wiss Ber AEGTelefunken 41(2):46-49 (in German) 1202. Binder H, Köhling A, Kuhn W, Lindner W, Sandstede G (1970) Das verhalten von Wolframcarbid in Elektroden für Brennstoffzellen mit saurem Elektrolyten (The behaviour of

642

2 Tungsten Carbides

tungsten carbide in electrodes for fuel cells with acidic electrolytes). Energy Conversion 10(1):25-28 (in German) 1203. Mareček V, Svatá M, Weber J (1977) Sedimented electrode for studying the properties of tungsten carbide catalysts. Collect Czech Chem Commun 42(12):3363-3366 1204. Baresel D, Heidermeier J, Schulz-Ekloff G (1972) Hartstoffe als Electrokatalysatoren (Hard materials as electrocatalysts). Bosch Techn Ber 4(1):35-39 (in German) 1205. McAlister AJ, Cohen MJ (1980) Electro-oxidation of hydrogen on Mo-W carbide alloy catalysts in acid electrolyte. Electrochim Acta 25(12):1685-1688 1206. Nguen DH, Rudolf S, Rademacher O, Wiesener K (1976) Beitrag zur Herstellung eines aktiven Wolframcarbid-Electrokatalysatoren für Brennstoffzellen mit Sauren Elektrolyten (Contribution to the production of active tungsten carbide electrocatalysts for fuel cells with acid electrolytes). Z Chem 16(1):30-32 (in German) 1207. Svatá M, Zabransky Z (1974) Preparation of WC catalysts with carbon deficient crystal lattice. Collect Czech Chem Commun 39(4):1015-1019 1208. Böhm H, Diemer W (1971) Der Einfluß der elektrokatalytischen Eigenschaften von Wolframcarbid auf die anodische Oxidation von Wasserstoff (The influence of the electrocatalytic properties of tungsten carbide on the anodic oxidation of hydrogen). Angew Chem 83(22):894 (in German) 1209. Wiesener K, Rudolf S, Nguen DH (1974) Elektrokatalytische Wirksamkeit von Wolframcarbid (Electrocatalytic effectiveness of tungsten carbide). Z Chem 14(3):117 (in German) 1210. Mazulevskii EA, Palanker VSh, Baibatyrov EN, Khisametdinov AM, Domanovskaya EI (1977) Optimizatsiya izgotovleniya katalizatora iz karbida volframa (Optimizing the fabrication of a tungsten carbide catalyst). Kinet Catal 18(3):767-772 (in Russian) 1211. Binder H, Köhling A, Kuhn W, Lindner W, Sandstede G (1969) Tungsten carbide electrodes for fuel cells with acid electrolyte. Nature 224(5226):1299-1300 1212. Binder H, Köhling A, Kuhn W, Sandstede G (1969) Electrochemical oxidation of aldehydes, formic acid and carbon monoxide at tungsten carbide electrodes in 2 N sulfuric acid. Angew Chem Int Ed 8(10):757-758 1213. Böhm H (1970) New non-noble metal anode catalysts for acid fuel cells. Nature 227(5257):483-484 1214. Böhm H (1970) Adsorption und anodische Oxidation von Wasserstoff an Wolframcarbid (Adsorption and anodic oxidation on tungsten carbide). Electrochim Acta 15(7):1273-1280 (in German) 1215. Baresel D, Gellert W, Heidemeyer J, Scharner P (1971) Tungsten carbide as anode material for fuel cells. Angew Chem Int Ed 10(3):194-195 1216. Klimak ZA, Podchernyaeva IA, Samsonov GV, Fomenko VS (1971) Catalytic effect of hafnium, tantalum and tungsten carbide powders on the reduction of nickel oxide. Powder Metall Met Ceram 10(5):356-358 1217. Voïnov M, Bühler D, Tannenberger H (1971) Oxygen reduction on tungsten carbide. J Electrochem Soc 118(7):1137-1138 1218. Armstrong RD, Douglas AF (1972) The anodic oxidation of the binary compounds of the transition elements in sulphuric acid. J Appl Electrochem 2(2):143-149 1219. Levy RB, Boudart M (1973) Platinum-like behaviour of tungsten carbide in surface catalysis. Science 181(4099):547-549 1220. Fézler G (1973) Tungsten carbide as catalyst for liquid (aqueous) phase heterogeneous catalytic hydrogenation. Z Phys Chem 83(5-6):322-324 1221. Jindra J (1973) On the catalytic activity of tungsten carbide in anodic oxidation of CHO compounds in acid electrolyte. Chem Zvesti 27(6):766-769 1222. Vértes G, Horányi G, Szakács S (1973) Selective catalytic behaviour of tungsten carbide in the liquid-phase hydrogenation of organic compounds. J Chem Soc Perkin Trans 2 (10):14001402

References

643

1223. Bennett LH, Cuthill JR, McAlister AJ, Erickson NE, Watson RE (1974) Electron structure and catalytic behaviour of tungsten carbide. Science 184(4136):563-565 1224. Houston JE, Laramore GE, Park RL (1974) Surface electronic properties of tungsten, tungsten carbide and platinum. Science 185(4147):258-260 1225. Horányi G, Vértes G (1974) Reduction of perchlorate ions by molecular hydrogen in the presence of tungsten carbide. Inorg Nucl Chem Lett 10(9):767-770 1226. Vértes G, Horányi G (1974) On the reduction of perchlorate ions at tungsten carbide electrodes. J Electroanal Chem 54(2):454-446 1227. Bennett LH, Cuthill JR, McAlister AJ, Erickson NE, Watson RE (1975) Electronic and catalytic properties of tungsten carbide. Science 187(4179):858-859 1228. Colton RJ, Huang J-TJ, Rabalais JW (1975) Electronic structure of tungsten carbide and its catalytic behaviour. Chem Phys Lett 34(2):337-339 1229. Horányi G, Vértes G (1975) Kinetics of the liquid-phase hydrogenation of aromatic nitrocompounds in the presence of tungsten carbide catalyst. J Chem Soc Perkin Trans 2 (8):827829 1230. Horányi G, Vértes G (1975) Experimental study of the electrocatalytic behaviour of tungsten carbide. Reduction of perchlorate ions. J Electroanal Chem 63(3):359-364 1231. Ross PN, Jr, Stonehart P (1975) Surface characterization of catalytically active tungsten carbide. J Catal 39(2):298-301 1232. Ross PN, Jr, Macdonald J, Stonehart P (1975) Surface composition of catalytically active tungsten carbide (WC). J Electroanal Chem 63(3):450-455 1233. Palanker VSh, Sokolskii DV, Mazulevskii EA, Baibatyrov EN (1976-1977) Highly dispersed tungsten carbide for fuel cells with acidic electrolyte. J Power Sources 1(2):169176 1234. Svatá M, Rudolf S (1976-1977) Influence of bonding and filling agents on the activity of tungsten carbide hydrogen electrodes. J Power Sources 1(3):277-284 1235. Baehr HD, Schmidt EF (1977) Zur thermodynamik eines Brennstoffzellen-Aggregats mit thermisch-katalytischer Methanolspaltung (Thermodynamic properties of fuel cells with thermal-catalytic methanol decomposition). Brennstoff Wärme Kraft 29(10):393-400 (in German) 1236. Fleischmann R, Böhm H (1977) Wasserstoffoxidation an verschiedenen Wolframcarbidmaterialen (Hydrogen oxidation on various tungsten carbide materials). Electrochim Acta 22(10):1123-1128 (in German) 1237. Palanker VSh, Sokolskii DV, Mazulevskii EA, Baibatyrov EN (1977) Catalytic activity and capacitance of tungsten carbide as a function of its dispersity and surface state. Electrochim Acta 22(6):661-667 1238. Palanker VSh, Gajyev RA, Sokolskii DV (1977) On adsorption and electro-oxidation of some compounds on tungsten carbide; their effect on hydrogen electro-oxidation. Electrochim Acta 22(2):133-136 1239. Ross PN, Jr (1977) Relation of surface structure to the electrocatalytic activity of tungsten carbide. In: Proc. conf. on role of solid state chemistry in catalysis, New Orleans, Louisiana, 20-25 Mar 1977. Am Chem Soc Div Petrol Chem Preprints 22(2):535-542 1240. Ross PN, Jr, Stonehart P (1977) The relation of surface structure to the electrocatalytic activity of tungsten carbide. J Catal 48(1-3):42-59 1241. Armstrong RD, Bell MF (1978) Tungsten carbide catalysts for hydrogen evolution. Electrochim Acta 23(11):1111-1115 1242. Nikolov I, Svatá M, Grigorov L, Vitanov T, Zabransky Z (1978) Influence of composition on the activity of tungsten carbide gas diffusion hydrogen electrodes. J Power Sources 3(3):237-244 1243. Leclercq L, Imura K, Yoshida S, Barbee T, Boudart M (1979) Synthesis of new catalytic materials: metal carbides of the group VIB elements. Studies Surf Sci Catal 3(C):627-639 1244. Nikolov I, Nikolova V, Vitanov T, Svatá M (1979) The effect of method of preparation on the catalytic activity of tungsten carbide. J Power Sources 4(1):65-75

644

2 Tungsten Carbides

1245. Horányi G, Rizmayer EM (1980) Novel evidence for the selective behaviour of tungsten carbide in liquid-phase heterogeneous catalytic hydrogenation. React Kinet Catal Lett 13(1):21-26 1246. Miles R (1980) Characterization and evaluation of highly dispersed tungsten carbide electrocatalysts. J Chem Technol Biotechnol 30(2):35-43 1247. Nikolov I, Vitanov T (1980) The effect of method of preparation on the corrosion resistance and catalytic activity during corrosion of tungsten carbide. I. Corrosion resistance of tungsten carbide in sulphuric acid. J Power Sources 5(3):273-281 1248. Nikolov I, Vitanov T (1980) The effect of method of preparation on the corrosion resistance and catalytic activity during corrosion of tungsten carbide. II. Changes in the catalytic activity of tungsten carbides during the corrosion process. J Power Sources 5(3):283-290 1249. Nikolov I, Vitanov T, Nikolova V (1980) The effect of the method of preparation on the catalytic activity of tungsten carbide for hydrogen evolution. J Power Sources 5(2):197-206 1250. Stortnik H, Stockmeyer R, Monkenbusch M (1980) Motion of hydrogen and water adsorbed on fuel cell catalysts examined by neutron scattering. J Mol Struct 60(C):443-448 1251. Nikolov I, Nikolova V (1981-1982) Preparation of the white tungstic acid modification and its use for the synthesis of highly active tungsten carbide. J Power Sources 7(1):83-94 1252. Nikolov I, Nikolova V, Vitanov T (1981-1982) The preparation of the white tungstic acid modification and its use for the synthesis of highly active tungsten carbide. J Power Sources 7(1):95-102 1253. Bashtavelova E, Nikolov I, Vitanov T (1982) Adsorption behaviour in the gas phase of carbides prepared from different starting materials. J Power Sources 7(3):257-266 1254. Horányi G, Rizmayer EM (1982) Catalytic activity of a tungsten carbide electrocatalyst in the reduction of HNO3, HNO2 and NH2OH by molecular hydrogen. J Electroanal Chem 132(C):119-128 1255. Kharlamov AI, Kirillova NV (1983) Catalytic properties of powdered refractory compounds of transition elements. Carbides and nitrides – a review. Powder Metall Met Ceram 22(2):123-134 1256. Mund K, Richter G, Sturm VF (1971) Aktivitätsvergleich an Katalysatoren für saure Brennstoffzellen und Entwicklung einer Ag-WC-Electrode für die H2-Oxidation (Activity comparison on catalysts for acidic fuel cells and development of an Ag-WC electrode for the oxidation of H2). Collect Czech Chem Commun 36(2):439-453 (in German) 1257. Ilchenko NI (1977) Okislitelnyi kataliz na karbidakh perekhodnykh metallov (Oxidizing catalysis on transition metal carbides). Kinet Catal 18(1):153-163 (in Russian) 1258. Kudo T, Kawamura G, Okamoto H (1983) A new (W,Mo)C electrocatalyst synthesized by a carbonyl process: its activity in relation to H2, HCHO and CH3OH electro-oxidation. J Electrochem Soc 130(7):1491-1497 1259. Nikolov I, Petrov K, Vitanov T, Guschev A (1983) Tungsten carbide cathodes for electrolysis of sulphuric acid solutions. Int J Hydrogen Energy 8(6):437-440 1260. Struck BD, Neumeister H, Schirbach A, Triefenbach D, Naoumidis A (1983) Tungsten carbide cathodes for hydrogen production. In: Proc. 34th meeting of the International Society of Electrochemistry, Erlangen, Federal Republic of Germany, 18-23 Sep 1983. Extended abstracts, 3935 (3 pp.). International Society of Electrochemistry, Graz, Austria 1261. Vijh AK, Jacques R, Bélanger G (1983) The electrochemical reduction of oxygen on cobalt-cemented tungsten carbide. J Power Sources 9(1):1-10 1262. Vijh AK, Bélanger G, Jacques R (1983) Electrocatalysis on some cemented metal carbides. New Mater New Processes 2:502-507 1263. Hojo J, Nakahara K, Matsumoto M, Kato A (1984) Hydrogen oxidation behaviour and structure of gas-diffusion electrodes consisting of WC-PTFE system. J Jpn Soc Powder Powder Metall 31(2):45-50 (in Japanese) 1264. Nikolova V, Nikolov I, Vitanov T, Yotova L (1984) Corrosion resistance and catalytic activity of tungsten carbide in phosphoric acid. J Power Sources 12(1):1-8

References

645

1265. Okamoto H, Ishikawa A, Kawamura G, Kudo T (1984) WC catalysed anodic oxidation of methanol. In: Proc. 165th spring meeting of the Electrochemical Society, Cincinnati, Ohio, 611 May 1983. Electrochem Soc Ext Abstr 84(1):578 1266. Schneider W, Winkler E, Wiesener K (1984) Mechanism of hydrogen oxidation on tungsten carbide electrodes. In: Proc. 35th meeting of the International Society of Electrochemistry, Berkeley, California, 5-10 Aug 1984. Extended abstracts, p. 408. International Society of Electrochemistry, Graz, Austria 1267. Struck BD, Neumeister H, Schirbach A, Triefenbach D, Naoumidis A (1984) Tungsten carbide cathodes for hydrogen production. In: Veziroğlu TN, Taylor JB (eds) Advances in hydrogen energy. Hydrogen energy progress V: Proc. 5th World hydrogen energy conf., Toronto, Ontario, Canada, 15-20 July 1983, Vol. 2, pp. 943-946. Pergamon Press, New York 1268. Yang RT, Wong C (1984) Catalysis of carbon oxidation by transition metal carbides and oxides. J Catal 85(1):154-168 1269. Ilchenko NI, Dolgikh LYu, Golodets GL (1985) Factors determining the activity of catalysts of different chemical types in the oxidation of hydrogen. III. Oxidation and isotopic exchange of hydrogen on tungsten carbide. Kinet Catal 26(3/1):550-554 1270. Kojima I, Miyazaki E, Inoue Y, Yasumori I (1985) Catalysis by transition metal carbides. VI. Hydrogenation of carbon monoxide over WC, W2C and W powder catalysts. Bull Chem Soc Jpn 58:611-617 1271. Kudo T, Ishikawa A, Kawamura G, Okamoto H (1985) A new (W,Mo)C electrocatalyst synthesized by a carbonyl process activity enhancement resulting from water vapour treatment in the synthesizing process. J Electrochem Soc 132(8):1814-1819 1272. Miyazaki E, Kojima I, Orita M (1985) Synthesis of methyl formate from methanol over metal carbide catalysts. J Chem Soc Chem Commun (3):108-109 1273. Nakazawa M, Okamoto H (1985) Surface composition of prepared tungsten carbide and its catalytic activity. Appl Surf Sci 24:75-86 1274. Nikolov I, Nikolova V, Vitanov T (1985) The preparation of the white tungstic acid modification and its use for the synthesis of highly active tungsten carbide. J Power Sources 16(3):233-239 1275. Lemaître J, Vidick B, Delmon B (1986) Control of the catalytic activity of tungsten carbides. I. Preparation of highly dispersed tungsten carbides. J Catal 99(2):415-427 1276. Orita M, Kojima I, Miyazaki E (1986) Catalysis by transition metal carbides. VII. Kinetic and XPS studies of the decomposition of methanol on TiC, TaC, Mo2C, WC and W2C. Bull Chem Soc Jpn 59:689-695 1277. Struck BD, Neumeister H, Naoumidis A (1986) Tungsten carbide cathodes for hydrogen production in acidic electrolytes. Int J Hydrogen Energy 11(8):541-548 1278. Tsirlina GA, Petrii OA, Koloskova EF (1986) Dissolution of ditungsten carbide electrodes in acidic media. Russ J Electrochem 23(3):395-397 1279. Vidick B, Lemaître J, Delmon B (1986) Control of the catalytic activity of tungsten carbides. II. Physico-chemical characterizations of tungsten carbides. J Catal 99(2):428-438 1280. Vidick B, Lemaître J, Leclercq L (1986) Control of the catalytic activity of tungsten carbides. III. Activity for ethylene hydrogenation and cyclohexane dehydrogenation. J Catal 99(2):439-448 1281. Anoshchenko IP, Tulenov AN, Androsov AV (1987) Corrosion and electrochemical behaviour of tungsten carbide in phosphoric acid at high temperature. In: Armanios EA (ed) Proc. 10th Int. conf. on metallic corrosion, Madras, India, 7-11 Nov 1987. Key Eng Mater 2028(1-4):593-595 1282. Boudart M, Lee JS, Imura K, Yoshida S (1987) The effect of surface composition on the chemisorption of hydrogen on tungsten carbide. J Catal 103(1):30-36 1283. Boikova GV, Zhutaeva GV, Tarasevich MR (1987) Electrochemical reaction mechanisms for hydrogen at highly disperse tungsten carbide. Russ J Electrochem 23(7):822-828

646

2 Tungsten Carbides

1284. Boikova GV, Schneider W, Wiesener K, Zhutaeva GV, Tarasevich MR (1987) Influence of chemical composition of tungsten carbide catalysts on their electrocatalytic properties in hydrogen reactions. Russ J Electrochem 22(8):1073-1076 1285. Kawamura G, Okamoto H, Ishikawa A, Kudo T (1987) Tungsten molybdenum carbide for electrocatalytic oxidation of methanol. J Electrochem Soc 134(7):1653-1658 1286. Leclercq L, Prigent M, Daubrege F, Gengembre L, Leclercq G (1987) Tungsten carbide and tungsten molybdenum carbides as automobile exhaust catalysts. Studies Surf Sci Catal 30(C):417-426 1287. Nakamura O, Ogino I, Yamamoto Y, Ashimura S (1987) Hydrogen electrode catalysts in a molybdophosphoric acid solid electrolyte fuel cell: admixing effect of tungsten carbides with platinum black. Chem Express 2(10):635-638 1288. Okamoto H, Kawamura G, Ishikawa A, Kudo T (1987) Characterization of oxygen in WC catalysts and its role in electrocatalytic activity for methanol oxidation. J Electrochem Soc 134(7):1645-1649 1289. Tsirlina GA, Petrii OA (1987) Hydrogen evolution on smooth stoichiometric tungsten and chromium carbides. Electrochim Acta 32(4):649-657 1290. Archakov OV, Lyutikova EK, Fateev VN, Kushkhov KhB, Shapoval VI (1988) Electrocatalytic properties of highly dispersed tungsten carbide in electrolysis of water with a solid polymeric electrolyte. Sov Prog Chem 54(7):40-43 1291. Oyama ST, Schlatter JC, Metcalfe JE, III, Lambert JM, Jr (1988) Preparation and characterization of early transition metal carbides and nitrides. Indust Eng Chem Res 27:1639-1648 1292. Leclercq L, Provost M, Pastor H, Grimblot J, Hardy AM, Gengembre L, Leclercq G (1989) Catalytic properties of transition metal carbides. I. Preparation and physical characterization of bulk mixed carbides of molybdenum and tungsten. J Catal 117(2):371-383 1293. Leclercq L, Provost M, Pastor H, Leclercq G (1989) Catalytic properties of transition metal carbides. II. Activity of bulk mixed carbides of molybdenum and tungsten in hydrocarbon conversion. J Catal 117(2):384-395 1294. Volynsky AB, Sedykh EM (1989) Principal processes in graphite atomisers modified by high-melting carbides. J Anal Atom Spectrometry 4:71-75 1295. Zoltowski P (1989) An immitance study of the mechanism of hydrogen reactions on a tungsten carbide electrode. Part I. Experiment and analysis in terms of a linear model. J Electroanal Chem 260(2):269-285 1296. Zoltowski P (1989) An immitance study of the mechanism of hydrogen reactions on a tungsten carbide electrode. Part II. Analysis in terms of a non-linear model. J Electroanal Chem 260(2):287-301 1297. Gao Z, Qin D-Y (1990) Catalytic properties of tungsten oxycarbide and carbide in hydrocarbon conversion. Chin J Chem 8(3):207-214 1298. Möbius A, Wiesener K (1990) Tungsten carbide catalyzed hydrogen anodes for electrochemical processes. Phys Chem Chem Phys 94(9):1039-1042 1299. Nikolov I, Papazov G, Pavlov D, Vitanov T, Naidenov V (1990) Tungsten carbide electrodes for gas recombination in lead/acid batteries. J Power Sources 31(1-4):69-77 1300. Papazov G, Nikolov I, Pavlov D, Vitanov T, Andreev P, Bojinov M (1990) Sealed lead/acid battery with auxiliary tungsten carbide electrodes. J Power Sources 31(1-4):79-88 1301. Bronoel G, Museux E, Leclercq G, Leclercq L, Tassin N (1991) Study of hydrogen oxidation on carbides. Electrochim Acta 36(10):1543-1547 1302. Iglesia E, Baumgartner JE, Ribeiro FH, Boudart M (1991) Bifunctional reactions of alkanes on tungsten carbides modified by chemisorbed oxygen. J Catal 131(2):523-544 1303. Keller V, Cheval M, Vayer M, Ducros R, Maire G (1991) Tungsten carbides as substitutes of platinoids in heterogeneous catalysis. I. The effect of surface composition on the reactivity of methyl cyclopentane on tungsten carbides. Catal Lett 10:137-148 1304. Lee JS, Boudart M (1991) Reactivity of tungsten carbides. I. Catalytic and temperatureprogrammed reactions of methanol. Catal Lett 8:107-114

References

647

1305. Nikolova V, Nikolov I, Vitanov T, Möbius A, Wiesener K, Schab D (1991) Gas-diffusion electrodes catalysed with tungsten carbide as anodes for nickel electrowinning. J Appl Electrochem 21:313-316 1306. Qin D-Y, Fan K-N, Gao Z (1991) Electronic structure and catalytic behaviour of tungsten carbides. Chin J Chem 9(2):97-101 1307. Ribeiro FH, Dalla-Betta RA, Boudart M, Baumgartner JE, Iglesia E (1991) Reactions of neopentane, methyl cyclohexane and 3,3-dimethylpentane on tungsten carbides: the effect of surface oxygen on reaction pathways. J Catal 130(1):86-105 1308. Ribeiro FH, Boudart M, Dalla-Betta RA, Iglesia E (1991) Catalytic reactions of n-alkanes on β-W2C and WC: the effect of surface oxygen on reaction pathways. J Catal 130(1):498513 1309. Dietz H, Dittmar L, Ohms D, Radwan M, Wiesener K (1992) Noble metal – free catalysts for the hydrogen/oxygen recombination in sealed lead/acid batteries using immobilized electrolytes. J Power Sources 40(1-2):175-186 1310. Dubois JL, Sayama K, Arakawa H (1992) CO2 hydrogenation over carbide catalysts. Chem Lett 21(1):5-8 1311. Gazaryan KG, Nersesyan GA, Mkrtchyan DzhS, Mnatsakanyan RA (1992) Transition metal carbides as catalysts for n-heptane conversion. Petrol Chem 32(6):486-491 1312. Iglesia E, Ribeiro FH, Boudart M, Baumgartner JE (1992) Synthesis, characterization and catalytic properties of clean and oxygen-modified tungsten carbides. Catal Today 15(2):307337 1313. Iglesia E, Ribeiro FH, Boudart M, Baumgartner JE (1992) Tungsten carbides modified by chemisorbed oxygen. A new class of bifunctional catalysts. Catal Today 15(3-4):455-458 1314. Keller V, Cheval M, Garin F, Ducros R, Maire G (1992) Effect of surface composition on the activity and selectivity in skeletal rearrangement of hydrocarbons on bulk and model tungsten carbides and oxycarbides. In: Proc. symp. on octane and cetane enhancement processes for reduced emissions motor fuels, San Francisco, California, 5-10 Apr 1992. Am Chem Soc Div Petrol Chem Preprints 37(3):766-767 1315. Ledoux MJ, Huu CP (1992) High specific surface area carbides of silicon and transition metals for catalysis. Catal Today 15(2):263-284 1316. Ledoux MJ, Huu CP, Guille J, Dunlop H (1992) Compared activities of platinum and high specific surface area Mo2C and WC catalysts for reforming reactions. I. Catalyst activation and stabilization: reaction of n-hexane. J Catal 134(2):383-398 1317. Oyama ST (1992) Preparation and catalytic properties of transition metal carbides and nitrides. Catal Today 15:179-200 1318. Qin D-Y, Gao Z, Qiu Y-M, Dong S-Z (1992) Hydrogenation of CO over carbides of tungsten. Chin J Chem 10(1):5-9 1319. Ribeiro FH, Iglesia E, Boudart M, Baumgartner JE (1992) Carbides modified by chemisorbed oxygen a new class of bifunctional catalysts. In: Proc. symp. on octane and cetane enhancement processes for reduced emissions motor fuels, San Francisco, California, 5-10 Apr 1992. Am Chem Soc Div Petrol Chem Preprints 37(3):762-765 1320. Frennet A, Leclercq G, Leclercq L, Maire G, Ducros R, Jardinier-Offergeld M, Bouillon F, Bastin J-M, Löfberg A, Blehen P, Dufour M, Kamal M, Feigenbaum L, Giraudon J-M, Keller V, Wehrer P, Cheval M, Garin F, Kons P, Delcambe P, Binst L (1993) Bulk tungsten carbide as catalyst in hydrocarbon reactions: association of selectivity differences with surface composition as compared to the selectivity of Pt series metals. Studies Surf Sci Catal 75(C):927-939 1321. Keller V, Cheval M, Garin F, Ducros R, Maire G (1993) The effect of surface composition on the activity and selectivity in skeletal rearrangement of hydrocarbons on bulk and model tungsten carbides. Catal Today 17(3):493-504 1322. Curry KE, Thompson LT (1994) Carbon-hydrogen bond activation over tungsten carbide catalysts. Catal Today 21(1):171-184

648

2 Tungsten Carbides

1323. Katrib A, Hemming F, Wehrer P, Hilaire L, Maire G (1994) The multi-structure of oxidized-reduced tungsten carbide surface(s). Catal Lett 29:397-408 1324. Katrib A, Hemming F, Wehrer P, Hilaire L, Maire G (1994) Surface characterization and catalytic properties of supported tungsten and platinum – tungsten carbide and oxycarbides. Topics Catal 1:75-85 1325. Ramanathan S, Da Silva TVLS, Oyama ST (1994) New catalysts for hydroprocessing: transition metal carbides and nitrides. In: Proc. 208th Natl. meeting of the American Chemical Society, Washington, DC, 21-26 Aug 1994. Am Chem Soc Div Petrol Chem Preprints 39(4):618-620 1326. Bi X-X, Chowdhury KD, Ochoa R, Lee WT, Bandow S, Dresselhaus MS, Eklund PC (1995) Structural characterization of nanocrystalline Mo and W carbide and nitride catalysts produced by CO2 laser pyrolysis. In: Proc. MRS Fall meeting, Boston, Massachusetts, 28 Nov – 2 Dec 1994. Mater Res Soc Symp Proc 368:69-74 1327. Keller V, Wehrer P, Garin F, Ducros R, Maire G (1995) Catalytic activity of bulk tungsten carbides for alkane reforming. I. Characterization and catalytic activity for reforming of hexane isomers in the absence of oxygen. J Catal 153:9-16 1328. Leclercq G, Kamal M, Lamonier J-F, Feigenbaum L, Malfoy P, Leclercq L (1995) Treatment of bulk group VI transition metal carbides with hydrogen and oxygen. Appl Catal A 121:169-190 1329. Löfberg A, Seyfried L, Blehen P, Decker S, Bastin J-M, Frennet A (1995) Post structure tungsten carbide powder catalysts. Catal Lett 33:165-173 1330. Muller A, Keller V, Ducros R, Maire G (1995) Catalytic activity and XPS surface determination of tungsten carbide for hydrocarbon reforming. Influence of the oxygen. Catal Lett 35:65-74 1331. Leclercq G, Kamal M, Giraudon JM, Devassine P, Feigenbaum L, Leclercq L, Frennet A, Bastin J-M, Löfberg A, Decker S, Dufour M (1996) Study of the preparation of bulk powder tungsten carbides by temperature programmed reaction with CH4 + H2 mixtures. J Catal 158:142-169 1332. Barnett CJ, Burstein GT, Kucernak ARJ, Williams KR (1997) Electrocatalytic activity of some carburised nickel, tungsten and molybdenum compounds. Electrochim Acta 42(15):2381-2388 1333. Bodoardo S, Maja M, Penazzi N, Henn FEG (1997) Oxidation of hydrogen on WC at low temperature. Electrochim Acta 42(17):2603-2609 1334. Choi S, Thompson LT (1997) Comparison between the structural and catalytic properties of supported W2C, WC and WC1–x. In: Cammarata RC, Chason EH, Einstein TL, Williams ED (eds) Proc. MRS Fall meeting, Boston, Massachusetts, 2-5 Dec 1996. Mater Res Soc Symp Proc 454:41-46 1335. Decker S, Löfberg A, Bastin J-M, Frennet A (1997) Study of the preparation of bulk tungsten carbide catalysts with C2H6/H2 and C2H4/H2 carburizing mixtures. Catal Lett 44:229239 1336. Garin F, Keller V, Ducros R, Muller A, Maire G (1997) Catalytic activity of bulk tungsten carbides for alkane reforming. III. Reaction mechanisms and the kinetic model. J Catal 166:136-147 1337. Hemming F, Wehrer P, Katrib A, Maire G (1997) Reactivity of hexanes (2MP, MCP and CH) on W, W2C and WC powders. Part II. Approach to the reaction mechanisms using concepts of organometallic chemistry. J Mol Catal A 124:39-56 1338. Keller V, Touroude R, Maire G (1997) Mechanism of but-1-ene hydrogenation and isomerization on oxygen-modified bulk tungsten carbides using deuterium tracer studies. Effect of oxygen treatment on hydrogen dissociation. Catal Lett 47:63-69 1339. Keller V, Wehrer P, Garin F, Ducros R, Maire G (1997) Catalytic activity of bulk tungsten carbides for alkane reforming. II. Catalytic activity of tungsten carbides modified by oxygen. J Catal 166:125-135

References

649

1340. York APE, Claridge JB, Brungs AJ, Tsang SC, Green MLH (1997) Molybdenum and tungsten carbides as catalysts for the conversion of methane to synthesis gas using stoichiometric feedstocks. Chem Commun (1):39-40 1341. York APE, Claridge JB, Márquez-Alvarez C, Brungs AJ, Tsang SC, Green MLH (1997) Synthesis of early transition metal carbides and their application for the reforming of methane to synthesis gas. Studies Surf Sci Catal 110:711-720 1342. Zhuang Y, Löfberg A, Frennet A (1997) Effect of pre-treatment of tungsten carbide on alkane reactions. Chin J Catal 18(1):60-63 (in Chinese) 1343. Claridge JB, York APE, Brungs AJ, Márquez-Alvarez C, Sloan J, Tsang SC, Green MLH (1998) New catalysts for the conversion of methane to synthesis gas: molybdenum and tungsten carbide. J Catal 180:85-100 1344. Gobbo-Ferreira J, Rodrigues JAJ, Hinckel JN, Migueis CE, Dacruz GM (1998) Controlled porosity carbides used as hydrazine decomposition catalysts. In: Proc. 34th AIAA / ASME / SAE / ASEE joint propulsion conf. and exhibit, Cleveland, Ohio, 13-15 July 1998, 152439 (6 pp.). American Institute of Aeronautics and Astronautics, Reston, Virginia 1345. Lukashenko TA, Tikhonov KI, Sher ÉM (1999) Corrosion resistance and electrocatalytic activity of some refractory compounds of transition metals. Refract Indust Ceram 40(1-2):1013 1346. Neylon MK, Choi S, Kwon H, Curry KE, Thompson LT (1999) Catalytic properties of early transition metal nitrides and carbides: n-butane hydrogenolysis, dehydrogenation and isomerization. Appl Catal A 183:253-263 1347. Shohoji N, Rosa LG, Fernandes JC, Martínez D, Rodríguez J (1999) Catalytic acceleration of graphitisation of amorphous carbon during synthesis of tungsten carbide from tungsten and excess amorphous carbon in a solar furnace. Mater Chem Phys 58:172-176 1348. Keller V, Garin F, Maire G (2000) Study of the isomerization of 13C labelled methyl pentanes on oxygen modified bulk tungsten carbides. Phys Chem Chem Phys 2(13):28932902 1349. Naito S, Tsuji M, Sakamoto Y, Miyao T (2000) Marked difference of catalytic behaviour by preparation methods in CH4 reforming with CO2 over Mo2C and WC catalysts. Studies Surf Sci Catal 143:415-423 1350. York APE, Claridge JB, Williams VC, Brungs AJ, Sloan J, Hanif A, Al-Megren H, Green MLH (2000) Synthesis of high surface area transition metal carbide catalysts. Studies Surf Sci Catal 130(B):989-994 1351. Da Costa P, Lemberton J-L, Potvin C, Manoli J-M, Perot G, Breysse M, DjégaMariadassou G (2001) Tetralin hydrogenation catalyzed by Mo2C/Al2O3 and WC/Al2O3 in the presence of H2S. Catal Today 65:195-200 1352. Da Costa P, Potvin C, Manoli J-M, Djéga-Mariadassou G (2001) Novel phosphorus-doped alumina-supported molybdenum and tungsten carbides: synthesis, characterization and hydrogenation properties. Catal Lett 72(1-2):91-97 1353. Hwu HH, Chen JG, Kourtakis K, Lavin JG (2001) Potential application of tungsten carbides as electrocatalysts. 1. Decomposition of methanol over carbide-modified W (111). J Phys Chem B 105:10037-10044 1354. Liu N, Chen JG (2001) Synergistic effect in the dehydrogenation of cyclohexene on C / W (111) surfaces modified by sub-monolayer coverage Pt. Catal Lett 77(1-3):35-40 1355. Moreno-Castilla C, Alvarez-Merino MA, Carrasco-Marín F, Fierro JLG (2001) Tungsten and tungsten carbide supported on activated carbon: surface structures and performance for ethylene hydrogenation. Langmuir 17:1752-1756 1356. Vieira R, Cruz GM, Rodrigues JAJ (2001) Decomposition of hydrazine by tungsten oxycarbides: the influence of macroporosity and mechanical strength on a 2 N microthruster engine. Braz J Chem Eng 18(4):359-365 1357. Wang G, Liu R, Chang J (2001) New type catalysts – molybdenum carbide and tungsten carbide. J Qingdao Univ Eng Technol Ed 16(3):51-53 (in Chinese)

650

2 Tungsten Carbides

1358. Zhang M, Hwu HH, Buelow MT, Chen JG, Ballinger TH, Andersen PJ (2001) Decomposition of NO on tungsten carbide and molybdenum carbide surfaces. Catal Lett 77(1-3):29-34 1359. Delannoy L, Giraudon J-M, Granger P, Leclercq L, Leclercq G (2002) Chloropentafluoroethane hydrodechlorination over tungsten carbides: influence of surface stoichiometry. J Catal 206:358-362 1360. Hanif A, Suhartanto T, Green MLH (2002) Possible utilization of CO2 on Natuna’s gas field using dry reforming of methane to syngas (CO & H2). In: Proc. SPE Asia Pacific oil and gas conf. and exhibition, Melbourne, Victoria, Australia, 8-10 Oct 2002, pp. 833-840. The Society of Petroleum Engineers, Kuala Lumpur, Malaysia 1361. Ma C-A, Zhang W-K, Cheng D-H, Zhou B-X (2002) Preparation and electrocatalytic properties of tungsten carbide electrocatalysts. Trans Nonferr Met Soc China 12(6):10151019 1362. McIntyre DR, Burstein GT, Vossen A (2002) Effect of carbon monoxide on the electrooxidation of hydrogen by tungsten carbide. J Power Sources 107:67-73 1363. Nagai M, Kunieda K, Izuhal S, Omi S (2002) Preparation of carburized WO3/FSM-16 and Al-FSM-16 and its catalytic activity. Studies Surf Sci Catal 146:733-736 1364. Santos JBO, Valença GP, Rodrigues JAJ (2002) Catalytic decomposition of hydrazine on tungsten carbide: the influence of adsorbed oxygen. J Catal 210:1-6 1365. Xiao T, Wang H, York APE, Williams VC, Green MLH (2002) Preparation of nickel – tungsten bimetallic carbide catalysts. J Catal 209:318-330 1366. Chen JG, Hwu HH, Zellner MB (2003) Tungsten carbides as potential electrocatalysts. ACS Div Fuel Chem Preprints 48(2):891-892 1367. Hwu HH, Chen JG (2003) Potential application of tungsten carbides as electrocatalysts. J Vac Sci Technol A 21(4):1488-1493 1368. Hwu HH, Chen JG (2003) Potential application of tungsten carbides as electrocatalysts: 4. Reactions of methanol, water and carbon monoxide over carbide-modified W (110). J Phys Chem B 107:2029-2039 1369. Ensinger W, Müller HR (2003) Surface treatment of aluminium oxide and tungsten carbide powders by ion beam sputter deposition. Surf Coat Technol 163-164:281-285 1370. Liu N, Kourtakis K, Figueroa JC, Chen JG (2003) Potential application of tungsten carbides as electrocatalysts. III. Reactions of methanol, water and hydrogen on Pt-modified C / W (111) surfaces. J Catal 215:254-263 1371. Nguen TH, Yue EMT, Lee YJ, Khodakov A, Adesina AA, Brungs MP (2003) Synthesis of bimetallic Mo-W carbide from its sulphide precursor via propane carburization: statistical correlation of the physico-chemical properties with preparation conditions. Catal Commun 4:353-359 1372. Patterson PM, Das TK, Davis BH (2003) Carbon monoxide hydrogenation over molybdenum and tungsten carbides. Appl Catal A 251:449-455 1373. Xue H-X, Song G-X, Wang L, Chen J-M (2003) Studies of n-pentane reaction on tungsten carbides promoted S2O82–/ZrO2 solid super-acid catalysts. Acta Chim Sin 61(2):208-212 (in Chinese) 1374. Iyer MV, Norcio LP, Punnoose A, Kugler EL, Seehra MS, Dadyburjor DB (2004) Catalysis for synthesis gas formation from reforming of methane. Topics Catal 29(3-4):197200 1375. Lee K, Ishihara A, Mitsushima S, Kamiya N, Ota K-I (2004) Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst. Electrochim Acta 49:3479-3485 1376. Ma C-A, Gan Y-P, Chu Y-Q, Huang H, Cheng D-H, Zhou B-X (2004) Electro-oxidation behaviour of tungsten carbide electrode in different electrolytes. Trans Nonferr Met Soc China 14(1):11-14 1377. Medvedev IG (2004) To a theory of electrocatalysis for the hydrogen evolution reaction: the hydrogen chemisorption energy on the transition metal alloys within the Anderson-Newns model. Russ J Electrochem 40(11):1123-1131

References

651

1378. Oxley JD, Mdleleni MM, Suslick KS (2004) Hydrodehalogenation with sonochemically prepared Mo2C and W2C. Catal Today 88:139-151 1379. Rumaiz AK, Shah SI, Lin HY, Baldytchev I, Chen JG (2004) Stability of WC nanoparticles for NOx reduction. In: Proc. MRS Fall meeting, Boston, Massachusetts, 29 Nov – 3 Dec 2004. Mater Res Soc Symp Proc 854:149-153 1380. Xue H-X, Chen J-M (2004) Preparation, characterization and catalytic properties of S2O82– /ZrO2 supported by tungsten carbide. Chem Res Chin Univ 20(1):68-72 1381. Zhu Q, Yang J, Ji S, Wang J, Wang H (2004) Progress of transition metal carbides in heterogenous catalysis. Prog Chem 16(3):382-385 (in Chinese) 1382. Ganesan R, Lee JS (2005) Tungsten carbide microspheres as a noble-metal-economic electrocatalyst for methanol oxidation. Angew Chem Int Ed 44:6557-6560 1383. Li G-H, Ma C-A, Zheng Y-F, Zhang W-M (2005) Preparation and electrocatalytic activity of hollow global tungsten carbide with mesoporosity. Micropor Mesopor Mater 85:234-240 1384. Ma C-A, Zhang W-M, Li G-H, Zheng Y-F, Zhou B-K, Cheng D-H (2005) Preparation of hollow global tungsten carbide (WC) catalysts with mesoporosity and its characterization. Acta Chim Sin 63(12):1151-1154 (in Chinese) 1385. Ma C-A, Huang Y, Tong S-P, Zhang W-M (2005) The catalytic behaviour of tungsten carbide for the electroreduction of p-nitrophenol. Acta Phys Chim Sin 21(7):721-724 (in Chinese) 1386. Park H, Kim M-H, Hwang YK, Chang J-S, Kwon Y-U (2005) Sonochemical synthesis and catalytic properties of oxide and carbide nanocomposites on carbon nanotubes. Chem Lett 34(2):222-223 1387. Shao H, Kugler EL, Ma W, Dadyburjor DB (2005) Effect of temperature on structure and performance of in-house cobalt – tungsten carbide catalyst for dry reforming of methane. Indust Eng Chem Res 44:4914-4921 1388. Yang XG, Wang CY (2005) Nanostructured tungsten carbide catalysts for polymer electrolyte fuel cells. Appl Phys Lett 86:224104 (3 pp.) 1389. Zellner MB, Chen JG (2005) Surface science and electrochemical studies of WC and W2C PVD films as potential electrocatalysts. Catal Today 99:299-307 1390. Zellner MB, Chen JG (2005) Potential application of tungsten carbides as electrocatalysts: synergistic effect by supporting Pt on C / W (110) for the reactions of methanol, water and CO. J Electrochem Soc 152(8):A1483-A1494 1391. De La Torre RAI, Melo-Banda JA, Sandoval-Robles G, Terrés-Rojas E, Domínguez JM, López-Pérez L, Torres-Rodríguez M (2006) Molybdenum and tungsten carbides supported on mesostructured MCM-41 material with polymeric carbon. Studies Surf Sci Catal 162:47-54 1392. Meng H, Shen PK (2006) Novel Pt-free catalyst for oxygen electroreduction. Electrochem Commun 8:588-594 1393. Meng H, Shen PK, Wei Z, Jiang SP (2006) Improved performance of direct methanol fuel cells with tungsten carbide promoted Pt/C composite cathode electrocatalyst. Electrochem Solid State Lett 9(7):A368-A372 1394. Nie M, Shen PK, Wu M, Wei Z, Meng H (2006) A study of oxygen reduction on improved Pt-WC/C electrocatalysts. J Power Sources 162:173-176 1395. Pansare SS, Torres W, Goodwin JG, Jr, Gangwal SK (2006) WC catalyzed NH3 decomposition for clean production of H2 from biomass gasification. In: Proc. 231st Natl meeting of the ACS, Atlanta, Georgia, 26-30 Mar 2006. ACS Natl Meet Book Abstr, Vol. 231 (1 p.). The American Chemical Society, Washington, DC 1396. Pansare SS, Torres W, Goodwin JG, Jr (2006) Kinetic study of ammonia decomposition on tungsten carbide for cleaner production of hydrogen from biomass gasification. In: Proc. 2006 AIChE annual meeting, San Francisco, California, 12-17 Nov 2006, 380A (1 p). The American Institute of Chemical Engineers, New York https://www.aiche.org/conferences/aiche-annual-meeting/2006/proceeding/paper/380akinetic-study-ammonia-decomposition-on-tungsten-carbide-cleaner-production-hydrogenbiomass Accessed 2 October 2020

652

2 Tungsten Carbides

1397. Pietron JJ, Laberty C, Swider-Lyons KE (2006) Metal carbide – based hydrodesulphurization catalysts as sulphur-tolerant electrocatalysts for PEMFC anodes. In: Proc. 210th Electrochemical Society meeting, Cancun, Mexico, 29 Oct – 3 Nov 2006. Proton exchange membrane fuel cells – 6. ECS Trans 3(1):471-477 1398. Rosenbaum M, Zhao F, Schröder U, Scholz F (2006) Interfacing electrocatalysis and biocatalysis with tungsten carbide: a high-performance noble-metal-free microbial fuel cell. Angew Chem Int Ed 45:6658-6661 1399. Sheng J, Ma C-A, Zhang C, Li G, Zhang W (2006) Electrochemical reduction behaviour of α-nitronaphthalene on tungsten carbide catalysts with mesoporosity. J Chem Indust Eng 57(10):2355-2360 1400. Wu M, Shen P-K, Wei Z-D, Song S-Q, Nie M (2006) Hydrogen evolution reaction on PtPd-WC/C electrocatalyst. J Wuhan Univ Technol 28(S2):87-92 (in Chinese) 1401. Yoo SJ, Sung Y-E (2006) Electrocatalytic enhancement of methanol oxidation at WCPtRu nanophase electrodes as an anode catalyst for direct methanol fuel cells. In: Proc. 232nd ACS meeting and exposition, San Francisco, California, 10-14 Sep 2006. ACS Natl Meet Book Abstr, Vol. 232 (1 p.). The American Chemical Society, Washington, DC 1402. Yoo SJ, Sung Y-E (2006) High electrocatalytic properties of WC-PtRu as anode catalyst of DMFC. In: Proc. 232nd ACS meeting and exposition, San Francisco, California, 10-14 Sep 2006. ACS Natl Meet Book Abstr, Vol. 232 (1 p.). The American Chemical Society, Washington, DC 1403. Zheng H-J, Huang J-G, Wang W, Ma C-A (2006) Electrocatalytic properties of nanocrystal-line tungsten carbide thin film as cathode electrode for p-nitrophenol electroreduction. J Chem Eng Chin Univ 20(1):57-62 (in Chinese) 1404. Zheng H-J, Gu Z-H, Zhao F-M, Huang J-G, Wang W, Ma C-A (2006) Electrocatalytic properties of nanocrystalline tungsten carbide thin film electrode for nitromethane electroreduction. Chem J Chin Univ 27(9):1742-1745 (in Chinese) 1405. Zheng H-J, Wang W, Huang J-G, Ma C-A (2006) Electrocatalytic activity of nanocrystalline tungsten carbide thin film electrode for hydrogen evolution. J Inorg Mater 21(2):481-487 (in Chinese) 1406. Chhina H, Campbell S, Kesler O (2007) Thermal and electrochemical stability of tungsten carbide catalyst supports. J Power Sources 164:431-440 1407. Ganesan R, Ham DJ, Lee JS (2007) Platinized mesoporous tungsten carbide for electrochemical methanol oxidation. Electrochem Commun 9:2576-2579 1408. Hara Y, Minami N, Itagaki H (2007) Synthesis and characterization of high-surface area tungsten carbides and application to electrocatalytic hydrogen oxidation. Appl Catal A 323:86-93 1409. Hara Y, Minami N, Matsumoto H, Itagaki H (2007) New synthesis of tungsten carbide particles and the synergistic effect with Pt metal as a hydrogen oxidation catalyst for fuel cell applications. Appl Catal A 332:289-296 1410. Hu FP, Shen PK (2007) Ethanol oxidation on hexagonal tungsten carbide single nanocrystal – supported Pd electrocatalyst. J Power Sources 173:877-881 1411. Hu Z, Wu M, Wei Z, Song S, Shen PK (2007) Pt-WC/C as a cathode electrocatalyst for hydrogen production by methanol electrolysis. J Power Sources 166:458-461 1412. Li G-H, Tian W, Tang J-Y, Ma C-A (2007) Preparation and electrocatalytic property for methanol oxidation of WC/CNT nanocomposites. Acta Phys Chim Sin 23(9):1370-1374 (in Chinese) 1413. Li G-H, Ma C-A, Tang J-Y, Sheng J-F (2007) Preparation and electrocatalytic property of WC / carbon nanotube composite. Electrochim Acta 52:2018-2023 1414. Ma C-A, Sheng J-F, Brandon N, Zhang C, Li G-H (2007) Preparation of tungsten carbide – supported nano platinum catalyst and its electrocatalytic activity for hydrogen evolution. Int J Hydrogen Energy 32:2824-2829

References

653

1415. Ma N, Ji S-F, Wu P-Y, Hu L-H, Nie P-Y (2007) Preparation, characterization and catalytic performance for hydrodesulphurization of WxC/SBA-16 catalysts. Acta Phys Chim Sin 23(8):1189-1194 (in Chinese) 1416. Nagai M, Yoshida M, Tominaga H (2007) Tungsten and nickel tungsten carbides as anode electrocatalysts. Electrochim Acta 52:5430-5436 1417. Nagai M, Kakinuma T, Matsuda K (2007) Temperature-programmed reduction and oxidation of tungsten carbide catalyst for low-temperature water-gas shift reaction. J New Mater Electrochem Systems 10(4):217-220 1418. Nie M, Tang H, Wei Z, Jiang SP, Shen PK (2007) Highly efficient AuPd-WC/C electrocatalyst for ethanol oxidation. Electrochem Commun 9:2375-2379 1419. Nie M, Shen PK, Wei Z (2007) Nanocrystalline tungsten carbide supported Au-Pd electrocatalyst for oxygen reduction. J Power Sources 167:69-73 1420. Nie P-Y, Ji S-F, Hu L-H, Wu P-Y, Ma N (2007) Synthesis, characterization and hydrodesulphurization catalytic performance of WxC-MCM-48 catalysts. Chin J Inorg Chem 23(6):987-993 (in Chinese) 1421. Pansare SS, Torres W, Goodwin JG, Jr (2007) Ammonia decomposition on tungsten carbide. Catal Commun 8:649-654 1422. Rosenbaum M, Zhao F, Quaas M, Wulff H, Schröder U, Scholz F (2007) Evaluation of catalytic properties of tungsten carbide for the anode of microbial fuel cells. Appl Catal B 74:261-269 1423. Rumaiz AK, Lin HY, Baldytchev I, Shah SI (2007) Nanosized tungsten carbide for NOx reduction. J Vac Sci Technol B 25(3):893-898 1424. Santos LGRA, Freitas KS, Ticianelli EA (2007) Electrocatalysis of oxygen reduction and hydrogen oxidation in platinum dispersed on tungsten carbide in acid medium. J Solid State Electrochem 11:1541-1548 1425. Sheng J-F, Ma C-A, Zhang C, Li G-H (2007) Preparation of tungsten carbide – supported nano platinum catalyst and its electrocatalytic activity for hydrogen evolution. Acta Phys Chim Sin 23(2):181-186 (in Chinese) 1426. Szymańska-Kolasa A, Lewandowski M, Sayag C, Djéga-Mariadassou G (2007) Comparison of molybdenum carbide and tungsten carbide for the hydrodesulphurization of dibenzo-thiophene. Catal Today 119:7-12 1427. Szymańska-Kolasa A, Lewandowski M, Sayag C, Brodzki D, Djéga-Mariadassou G (2007) Comparison between tungsten carbide and molybdenum carbide for the hydrodenitrogenation of carbazole. Catal Today 119:35-38 1428. Weigert EC, Zellner MB, Stottlemyer AL, Chen JG (2007) A combined surface science and electrochemical study of tungsten carbides as anode electrocatalysts. Topics Catal 46(34):349-357 1429. Weigert EC, Stottlemyer AL, Zellner MB, Chen JG (2007) Tungsten monocarbide as potential replacement of platinum for methanol electroreduction. J Phys Chem C 111(40):14617-14620 1430. Wu M, Shen PK, Wei Z, Song S, Nie M (2007) High activity PtPd-WC/C electrocatalyst for hydrogen evolution reaction. J Power Sources 166:310-316 1431. Zhang S, Zhu H, Yu H, Hou J, Yi B, Ming P (2007) The oxidation resistance of tungsten carbide as catalyst support for proton exchange membrane fuel cells. Chin J Catal 28(2):109111 1432. Angelucci CA, Deiner LJ, Nart FC (2008) On-line mass spectrometry of the electrooxidation of methanol in acidic media on tungsten carbide. J Solid State Electrochem 12(12):1599-1603 1433. Brady CDA, Rees EJ, Burstein GT (2008) Electrocatalysis by nanocrystalline tungsten carbides and the effects of co-deposited silver. J Power Sources 179:17-26 1434. Chhina H, Campbell S, Kesler O (2008) High surface area synthesis, electrochemical activity and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells. J Power Sources 179:50-59

654

2 Tungsten Carbides

1435. Cui X, Li H, Guo L, He D, Chen H, Shi J (2008) Synthesis of mesoporous tungsten carbide by an impregnation-compaction route and its NH3 decomposition catalytic activity. Dalton Trans (45):6435-6440 1436. Ham DJ, Kim YK, Han SH, Lee JS (2008) Pt/WC as an anode catalyst for PEMFC: activity and CO tolerance. Catal Today 132:117-122 1437. Hu F, Cui G, Wei Z, Shen PK (2008) Improved kinetics of ethanol oxidation on Pd catalysts supported on tungsten carbides / carbon nanotubes. Electrochem Commun 10:13031306 1438. Hu X, Zeng Z, Hu F, Wang J, Shen PK (2008) Alcohol oxidation on Pd catalyst supported on tungsten carbides / carbon nanotubes. Chin J Catal 29(10):1027-1031 (in Chinese) 1439. Jang JS, Ham DJ, Lakshminarasimhan N, Choi WY, Lee JS (2008) Role of platinum-like tungsten carbide as co-catalyst of CdS photocatalyst for hydrogen production under visible light irradiation. Appl Catal A 346:149-154 1440. Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, Chen JG (2008) Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts. Angew Chem Int Ed 47:8510-8513 1441. Joo JB, Kim JS, Kim P, Yi J (2008) Simple preparation of tungsten carbide supported on carbon for use as a catalyst support in a methanol electro-oxidation. Mater Lett 62:3497-3499 1442. Kirakosyan KhG, Manukyan KhV, Kharatyan SL, Mnatsakanyan RA (2008) Synthesis of tungsten carbide – carbon nanomaterials by combustion reaction. Mater Chem Phys 110:454456 1443. Kim Y-H, Irie H, Hashimoto K (2008) A visible light-sensitive tungsten carbide – tungsten trioxide composite photocatalyst. Appl Phys Lett 92(18):182107 (3 pp.) 1444. Lee K, Zhang L, Zhang J (2008) Non-noble electrocatalysts for the PEM fuel cell oxygen reduction reaction. In: Zhang J (ed) PEM fuel cell electrocatalysts and catalyst layers: fundamental and applications, pp. 715-757. Springer, London 1445. Mellinger ZJ, Weigert EC, Stottlemyer AL, Chen JG (2008) Enhancing CO tolerance of electrocatalysts: electro-oxidation of CO on WC and Pt-modified WC. Electrochem Solid State Lett 11(5):B63-B67 1446. Obradović MD, Babić BM, Kowal A, Panić VV, Gojković SLJ (2008) Electrochemical properties of mixed WC and Pt-black powders. J Serb Chem Soc 73(12):1197-1209 1447. Pansare SS, Goodwin JG, Jr (2008) Ammonia decomposition on tungsten-based catalysts in the absence and presence of syngas. Indust Eng Chem Res 47:4063-4070 1448. Pansare SS, Goodwin JG, Jr, Gangwal S (2008) Toluene decomposition in the presence of hydrogen on tungsten-based catalysts. Indust Eng Chem Res 47:4077-4085 1449. Pansare SS, Goodwin JG, Jr, Gangwal S (2008) Simultaneous ammonia and toluene decomposition on tungsten-based catalysts for hot gas clean-up. Indust Eng Chem Res 47:8602-8611 1450. Rees EJ, Essaki K, Brady CDA, Burstein GT (2008) Synthesis of electrocatalytic carbides. In: Proc. 214th Electrochemical Society meeting, Honolulu, Hawaii, 12-17 Oct 2008. Proton exchange membrane fuel cells (PEMFC) – 8. ECS Trans 16(2/1):147-158 1451. Shanmugam S, Gedanken A (2008) An easy single step route to synthesize open-ended carbon nanotubes. Carbon 46:1611-1625 1452. Sun J, Wang Xi, Wang X, Zheng M, Wang A, Zhang T (2008) Hydrazine decomposition and CO adsorption microcalorimetry on tungsten carbide catalysts with different phases. Chin J Catal 29(8):710-714 (in Chinese) 1453. Sun J, Zheng M, Wang X, Wang A, Cheng R, Li T, Zhang T (2008) Catalytic performance of activated carbon supported tungsten carbide for hydrazine decomposition. Catal Lett 123:150-155 1454. Wang X, Ma C-A, Li G, Shen T (2008) Preparation and electrocatalytic activity of WC/CNT nanocomposite for nitrobenzene electro-reduction. J Chem Indust Eng 59(11):2904-2909 (in Chinese)

References

655

1455. Wang Z-B, Zuo P-J, Liu B-S, Yin G-P, Shi P-F (2008) Stable PtNiPb/WC catalyst for direct methanol fuel cells. Electrochem Solid State Lett 12(1):A13-A15 1456. Weigert EC, Arisetty S, Advani SG, Prasad AK, Chen JG (2008) Electrochemical evaluation of tungsten monocarbide (WC) and platinum-modified WC as alternative DMFC electrocatalysts. J New Mater Electrochem Systems 11(4):243-251 1457. Chen JG, Stottlemyer AL, Ji N, Zheng M, Wang A, Zhang T (2009) Conversion of biomass-derived molecules using carbide and bimetallic catalysts. In: Proc. 238th Natl meeting and exposition of the American Chemical Society, Washington, DC, 16-20 Aug 2009. ACS Natl Meet Book Abstr 2009, 82479 (1 p.) 1458. Essaki K, Rees EJ, Burstein GT, Haslam GE (2009) Synthesis and characterization of nano-particulate WC electrocatalysts. In: Proc. 216th Electrochemical Society meeting, Vienna, Austria, 4-9 Oct 2009. Proton exchange membrane fuel cells (PEMFC) – 9. ECS Trans 25(1/1):141-153 1459. Gaston N, Hendy S (2009) Hydrogen adsorption on model tungsten carbide surfaces. Catal Today 146:223-229 1460. Harnisch F, Schröder U, Quaas M, Scholz F (2009) Electrocatalytic and corrosion behaviour of tungsten carbide in near-neutral pH electrolytes. Appl Catal B 87:63-69 1461. Harnisch F, Sievers G, Schröder U (2009) Tungsten carbide as electrocatalyst for the hydrogen evolution reaction in pH neutral electrolyte solutions. Appl Catal B 89:455-458 1462. Hinckel JN, Jorge JAR, Neto TGS, Zacharias MA, Palandi JAL (1998) Low cost catalysts for hydrazine monopropellant thrusters. In: Proc. 45th AIAA / ASME / SAE / ASEE joint propulsion conf. and exhibit, Denver, Colorado, 2-5 Aug 2009, 81720 (6 pp.). American Institute of Aeronautics and Astronautics, Reston, Virginia 1463. Ingham B, Brady CDA, Burstein GT, Gaston N, Ryan MP (2009) EXAFS analysis of electrocatalytic WC materials. J Phys Chem C 113(40):17407-17410 1464. Izhar S, Yoshida M, Nagai M (2009) Characterization and performances of cobalt-tungsten and molybdenum-tungsten carbides as anode catalyst for PEFC. Electrochim Acta 54:12551262 1465. Jang J-H, Kim J, Lee Y-H, Pak C, Kwon Y-U (2009) Sonochemical synthesis of tungsten carbide – palladium nanocomposites and their electrocatalytic activity for hydrogen oxidation reaction. Electrochim Acta 55:485-490 1466. Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, Shu Y, Stottlemyer AL, Chen JG (2009) Catalytic conversion of cellulose into ethylene glycol over supported carbide catalysts. Catal Today 147:77-85 1467. Lu H, Yan T (2009) Electrocatalytic activity of tungsten trioxide microspheres, tungsten carbide microspheres and multi-walled carbon nanotube – tungsten carbide composites. J Wuhan Univ Technol Mater Sci Ed 24(20):229-234 1468. Ma C-A, Huang Y, Zhu Y, Chen Z, Lin W (2009) Preparation and characterization of Pt/WC catalyst for oxygen reduction at gas-diffusion electrode. CIESC J 60(10):2633-2639) (in Chinese) 1469. Rees EJ, Essaki K, Brady CDA, Burstein GT (2009) Hydrogen electrocatalysts from microwave-synthesized nanoparticulate carbides. J Power Sources 188:75-81 1470. Shao H, Kugler EL, Dadyburjor DB, Rykov SA, Chen JG (2009) Correlating NEXAFS characterization of Co-W and Ni-W bimetallic carbide catalysts with reactivity for dry reforming of methane. Appl Catal A 356:18-22 1471. Shao Y, Liu J, Wang Y, Lin Y (2009) Novel catalyst support materials for PEM fuel cells: current status and future prospects. J Mater Chem 19(1):46-59 1472. Wang R, Tian C, Wang L, Wang B, Zhang H, Fu H (2009) In situ simultaneous synthesis of WC / graphitic carbon nanocomposite as a highly efficient catalyst support for DMFC. Chem Commun (21):3104-3106 1473. Wang Y, Song S, Shen PK, Guo C, Li CM (2009) Nanochain-structured mesoporous tungsten carbide and its superior electrocatalysis. J Mater Chem 19(34):6149-6153

656

2 Tungsten Carbides

1474. Wang Y, Song S, Maragou V, Shen PK, Tsiakaras P (2009) High surface area tungsten carbide microspheres as effective Pt catalyst support for oxygen reduction reaction. Appl Catal B 89:223-228 1475. Weigert EC, Esposito DV, Chen JG (2009) Cyclic voltammetry and X-ray photoelectron spectroscopy studies of electrochemical stability of clean and Pt-modified tungsten and molybdenum carbide (WC and Mo2C) electrocatalysts. J Power Sources 193:501-506 1476. Xiao T-C, Hanif A, York APE, Green MLH (2009) Methane partial oxidation to synthesis gas over bimetallic cobalt/tungsten carbide catalysts and integration with a Mn substituted hexaaluminate combustion catalyst. Catal Today 147:196-202 1477. Zeng J, Yuan D, Liu Y, Chen J, Tan S (2009) Synthesis of tungsten carbide nanocrystals and their electrochemical properties. Front Chem China 4(2):127-131 1478. Zhao Z, Fang X, Li Y, Wang Y, Shen PK, Xie F, Zhang X (2009) The origin of the high performance of tungsten carbides / carbon nanotubes supported Pt catalysts for methanol electrooxidation. Electrochem Commun 11:290-293 1479. Zheng M, Wang A, Ji N, Pang J, Zhang T (2009) Direct catalytic conversion of cellulose into ethylene glycol. In: Proc. 8th World congress of chemical engineering (WCCE8), Montreal, Canada, 23-27 Aug 2009, pp. 512-517. École Polytechnique de Montréal, The Canadian Society for Chemical Engineering, Montreal, Canada 1480. Zhu Q, Zhou S, Wang X, Dai S (2009) Controlled synthesis of mesoporous carbon modified by tungsten carbides as an improved electrocatalyst support for the oxygen reduction reaction. J Power Sources 193:495-500 1481. Bozzini B, De Gaudenzi GP, Busson B, Humbert C, Six C, Gayral A, Tadjeddine A (2010) In situ spectro-electrochemical measurements during the electro-oxidation of ethanol on WCsupported Pt-black based on sum-frequency generation spectroscopy. J Power Sources 195:4119-4123 1482. Awaad M, Kenawy SH, El-Kherbawi MA, Naga SM (2010) Microstructural evolution and catalytic activity of porous biomorphous tungsten carbide and silicon carbide ceramics. Int Ceram Rev 59(3):186-192 1483. Bosco JP, Sasaki K, Sadakane M, Ueda W, Chen JG (2010) Synthesis and characterization of three-dimensionally ordered macroporous (3DOM) tungsten carbide: application to direct methanol fuel cells. Chem Mater 22(3):966-973 1484. Cheng JG (2010) Tungsten carbides as alternative electrocatalysts: from surface science studies to fuel cell evaluation. In: Proc. 240th Natl meeting and exposition of the American Chemical Society, Boston, Massachusetts, 22-26 Aug 2010. ACS Natl Meet Book Abstr 2010, Vol. 240, 159-FUEL (1 p.) 1485. Chen Z-Y, Ma C-A, Zhao F-M, Qiao Y, Tu X (2010) Synthesis of mesoporous tungsten carbide with low carbon content and its electrocatalysis toward methanol oxidation. Acta Chim Sin 68(4):320-324 (in Chinese) 1486. Chen Z-Y, Zhao F-M, Ma C-A, Qiao Y (2010) Ultrasonic-assisted preparation of bimodal mesoporous hollow global tungsten carbide and its electrocatalytic performance. Acta Phys Chim Sin 26(9):2569-2574 (in Chinese) 1487. Esposito DV, Hunt ST, Stottlemyer AL, Dobson KD, McCandless BE, Birkmire RW, Chen JG (2010) Low-cost hydrogen-evolution catalysts based on monolayer platinum on tungsten monocarbide substrates. Angew Chem Int Ed 49:9859-9862 1488. Fu H (2010) Designed synthesis of WC / crystalline nanocarbon composites and their application exploration in DMFC. In: Proc. 239th Natl meeting and exposition of the American Chemical Society, San Francisco, California, 21-25 Mar 2010. ACS Natl Meet Book Abstr 2010, Vol. 239, 24-FUEL (1 p.) 1489. Glibin V, Svirko L, Bashtan-Kandybovich I, Karamanev D (2010) Synthesis, surface chemistry and electrocatalytic properties of oxygen-modified tungsten carbide in relation to the electrochemical hydrogen oxidation. Surf Sci 604:500-507

References

657

1490. Gregoire JM, Tague ME, Smith EH, Dale D, DiSalvo FJ, Abruña HD, Hennig RG, Van Dover RB (2010) Phase behaviour of pseudo-binary precious metal-carbide systems. J Phys Chem C 114(49):21664-21671 1491. Humbert MP, Menning CA, Chen JG (2010) Replacing bulk Pt in Pt-Ni-Pt bimetallic structures with tungsten monocarbide (WC): hydrogen adsorption and cyclohexene on Pt-NiWC. J Catal 271:132-139 1492. Jang JS, Ham DJ, Ramasamy E, Lee J, Lee JS (2010) Platinum-free tungsten carbides as an efficient counter electrode for dye sensitized solar cells. Chem Commun 46(45):86008602 1493. Joo JB, Kim J, Kim P, Yi J (2010) Molybdenum and tungsten promoted carbons for use as catalyst supports in methanol electro-oxidation. J Nanosci Nanotechnol 10(5):3397-3401 1494. Ko A-R, Kim J-Y, Oh J-K, Kim H-S, Lee Y-W, Han S-B, Park K-W (2010) Synergy effect of nanostructure electrodes supported by tungsten carbide and oxide for methanol electro-oxidation. Phys Chem Chem Phys 12(46):15181-15183 1495. Lewandowski M, Da Costa P, Benichou D, Sayag C (2010) Catalytic performance of platinum doped tungsten carbide in simultaneous hydrodenitrogenation and hydrodesulphurization. Appl Catal B 93:241-249 1496. Liang C, Ding L, Li C, Pang M, Su D, Li W, Wang Y (2010) Nanostructured WCx/CNTs as highly efficient support of electrocatalysts with low Pt loading for oxygen reduction reaction. Energy Environ Sci 3(8):1121-1127 1497. Shi B-B, Yao G-X, Li G-H, Zheng Y-F (2010) Preparation of tungsten carbide – titania nanocomposite and its electrocatalytic activity. Chin J Catal 31(4):466-470 (in Chinese) 1498. Stottlemyer AL, Liu P, Chen JG (2010) Comparison of bond scission sequence of methanol on tungsten monocarbide and Pt-modified tungsten monocarbide. J Chem Phys 133(10):104702 (8 pp.) 1499. Teng W, Mao X, Ma C-A (2010) Preparation and electrocatalytic activity of WC/C composite for p-nitrophenol electroreduction. CIESC J 61(5):1313-1318 (in Chinese) 1500. Wang H, Zhang H, Wang A, Zhang T (2010) Preparation of metal carbide imbedded ordered mesoporous carbon and its catalytic properties for N2H4 decomposition. Chin J Catal 31(9):1172-1176 (in Chinese) 1501. Xu R, Wang J, Guo Z (2010) Oxygen evolution kinetic parameters of electrodeposited composite inert electrodes. In: Proc. Int. conf. on manufacturing science and engineering (ICMSE 2009), Zhuhai, China, 26-28 Dec 2009. Adv Mater Res 97-101:1385-1388 1502. Yao G-X, Shi B-B, Li G-H, Zheng Y-F (2010) Preparation and electrocatalytic activity of tungsten carbide and zeolite nanocomposite. Acta Phys Chim Sin 26(5):1317-1322 (in Chinese) 1503. Zhang Y, Wang A, Zhang T (2010) A new 3D mesoporous carbon replicated from commercial silica as a catalyst support for direct conversion of cellulose into ethylene glycol. Chem Commun 46(6):862-864 1504. Zheng Y-F, Lu Y-P, Mo W-M, Li G-H, Zhao N (2010) Microstructure characterization and electrocatalytic properties of WC/TiO2 nanocomposites. J Inorg Mater 25(11):1139-1144 (in Chinese) 1505. Cui X, Zhou X, Chen H, Hua Z, Wu H, He Q, Zhang L, Shi J (2011) In situ carbonization synthesis and ethylene hydrogenation activity of ordered mesoporous tungsten carbide. Int J Hydrogen Energy 36:10513-10521 1506. D’Arbigny JB, Taillades G, Rozière J, Jones DJ, Marrony M (2011) High surface area tungsten carbide with novel architecture and high electrochemical stability. In: Proc. 11th polymer electrolyte fuel cell symp. (PEFC 11) at the 220th Electrochemical Society meeting, Boston, Massachusetts, 9-14 Oct 2011. ECS Trans 41(1):1207-1213 1507. Esposito DV, Chen JG (2011) Monolayer platinum supported on tungsten carbides as lowcost electrocatalysts: opportunities and limitations. Energy Environ Sci 4(10):3900-3912 1508. Hansgen DA, Vlachos DG, Chen JG (2011) Ammonia decomposition activity on monolayer Ni supported on Ru, Pt and WC substrates. Surf Sci 605:2055-2060

658

2 Tungsten Carbides

1509. Ham DJ, Pak C, Bae GH, Han S, Kwon K, Jin S-A, Chang H, Choi SH, Lee JS (2011) Palladium-nickel alloys loaded on tungsten carbide as platinum-free anode electrocatalysts for polymer electrolyte membrane fuel cells. Chem Commun 47(20):5792-5794 1510. Hsu IJ, Esposito DV, Mahoney EG, Black A, Chen JG (2011) Particle shape control using pulse electrodeposition: methanol oxidation as a probe reaction on Pt dendrites and cubes. J Power Sources 196:8307-8312 1511. Hu S, Shi B-B, Yao G-X, Li G-H, Ma C-A (2011) Preparation and electrocatalytic activity of tungsten carbide and titania nanocomposite. Mater Res Bull 46:1738-1745 1512. Hu X-C, Chen D, Shi B-B, Li G-H (2011) Preparation of tungsten carbide and titania nanocomposite and its electrocatalytic activity for methanol. Acta Phys Chim Sin 27(12):2863-2871 (in Chinese) 1513. Kelly TG, Chen JG (2011) Metal-modified tungsten carbide (WC) for catalytic and electrocatalytic conversion of alcohols. In: Proc. 2011 AIChE annual meeting, Minneapolis, Minnesota, 16-21 Oct 2011. Catalysis and reaction engineering division – core programming topic, Vol. 2, pp. 1126-1127. The American Institute of Chemical Engineers, New York 1514. Li G-H, Chen D, Yao G-X, Shi B-B, Ma C-A (2011) Preparation of WC@TiO2 core-shell nanocomposite and its electrocatalytic characteristics. Chin J Chem Eng 19(1):145-150 1515. Liu Y, Mustain WE (2011) Structural and electrochemical studies of Pt clusters supported on high surface area tungsten carbide for oxygen reduction. ACS Catal 1:212-220 1516. Manukyan KhV, Zurnachyan AR, Kharatyan SL, Mnatsakanyan RA (2011) WC-based catalyst for isopropyl alcohol dehydration as prepared by combustion synthesis. Int J SelfPropag High-Temp Synth 20(1):1-5 1517. Ma C-A, Chen Z, Zhao F (2011) Synthesis of ultra-fine mesoporous tungsten carbide by high-energy ball milling and its electrocatalytic activity for methanol oxidation. Chin J Chem 29:611-616 1518. Muroyama H, Katsukawa K, Matsui T, Eguchi K (2011) Tungsten based carbides as anode for intermediate-temperature fuel cells. J Electrochem Soc 158(9):B1072-B1075 1519. Pang J, Zheng M, Wang A, Zhang T (2011) Catalytic hydrogenation of corn stalk to ethylene glycol and 1,2-propylene glycol. Indust Eng Chem Res 50:6601-6608 1520. Ren H, Hansgen DA, Stottlemyer AL, Kelly TG, Chen JG (2011) Replacing platinum with tungsten carbide (WC) for reforming reactions: similarities in ethanol decomposition on Ni/Pt and Ni/WC surfaces. ACS Catal 1:390-398 1521. Shao M, Merzougui B, Shoemaker K, Stolar L, Protsailo L, Mellinger ZJ, Hsu IJ, Chen JG (2011) Tungsten carbide modified high surface area carbon as fuel cell catalyst support. J Power Sources 196:7426-7434 1522. Shi M, Lang X, Ma C-A, Chu Y, Chen Z, Yu B (2011) Microwave heated synthesis of Pt/WC and its electrocatalytic activity for methanol electrooxidation. Acta Chim Sin 69(9):1029-1034 (in Chinese) 1523. Stottlemyer AL, Weigert EC, Chen JG (2011) Tungsten carbides as alternative electrocatalysts: from surface science studies to fuel cell evaluation. Indust Eng Chem Res 50:16-22 1524. Wang L, Wu M, Gao Y, Ma T (2011) Highly catalytic electrodes for organic redox couple of thiolate/disulphide in dye-sensitized solar cells. Appl Phys Lett 98(22):221102 (3 pp.) 1525. Wu M, Lin X, Hagfeldt A, Ma T (2011) Low-cost molybdenum carbide and tungsten carbide counter electrodes for dye-sensitized solar cells. Angew Chem Int Ed 50:3520-3524 1526. Zheng HJ, Yu AM, Ma C-A (2011) Polyporous C@WC1–x composite and its electrocatalytic activity for p-nitrophenol reduction. Chin Chem Lett 22:497-500 1527. Zurnachyan AR, Manukyan KhV, Kharatyan SL, Matyshak VA, Mnatsakanyan RA (2011) New isopropanol dehydration catalyst based on tungsten carbide prepared by modified selfpropagating high-temperature synthesis. Kinet Catal 52(6):851-854 1528. Cao M, Guo Z, Xie X, He S (2012) Study on structure and properties of Ti/Pb-PANI-WC inert anodes. In: Proc. Int. conf. on emerging materials and mechanics applications (ICEMMA 2012), Hangzhou, China, 5-6 Feb 2012. Adv Mater Res 487:53-57

References

659

1529. Christensen JM, Duchstein LDL, Wagner JB, Jensen PA, Temel B, Jensen AD (2012) Catalytic conversion of syngas into higher alcohols over carbide catalysts. Indust Eng Chem Res 51:4161-4172 1530. Chen D, Zhai H, Chen H, Zhang Y, Fan B, Wang H, Lu H, Li Z, Zhang R, Sun J, Gao L (2012) Porous tungsten carbide nanoplates derived from tungsten trioxide nanoplates. J Am Ceram Soc 95(11):3370-3373 1531. Cheng Y, Xie W, Yao G, Hu S, Li G (2012) Electrocatalytic activity of tungsten carbide and natural zeolite composite in aqueous solution. Chin J Chem Eng 20(2):254-261 1532. Elezović NR, Babić BM, Gajić-Krstajić Lj, Ercius P, Radmilović VR, Krstajić NV, Vračar LjM (2012) Pt supported on nano-tungsten carbide as a beneficial catalyst for the oxygen reduction in alkaline solution. Electrochim Acta 69:239-246 1533. Esposito DV, Hunt ST, Kimmel YC, Chen JG (2012) A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides. J Am Chem Soc 134:3025-3033 1534. Fu Z, Huang QM, Xiang XD, Lin YL, Wu W, Hu SJ, Li WS (2012) Mesoporous tungsten carbide – supported platinum as carbon monoxide – tolerant electrocatalyst for methanol oxidation. Int J Hydrogen Energy 37:4704-4709 1535. Ham DJ, Han S, Pak C, Ji SM, Jin S-A, Chang H, Lee JS (2012) High electrochemical performance and stability of co-deposited Pd-Au on phase-pure tungsten carbide for hydrogen oxidation. Topics Catal 55:922-930 1536. Hsu IJ, Kimmel YC, Jiang X, Willis BG, Chen JG (2012) Atomic layer deposition synthesis of platinum – tungsten carbide core-shell catalysts for the hydrogen evolution reaction. Chem Commun 48(7):1063-1065 1537. Jiang K, Jia Q, Xu M, Wu D, Yang L, Yang G, Chen L, Wang G, Yang X (2012) A novel non-precious metal catalyst synthesized via pyrolysis of polyaniline-coated tungsten carbide particles for oxygen reduction reaction. J Power Sources 219:249-252 1538. Ji N, Zheng M, Wang A, Zhang T, Chen JG (2012) Nickel-promoted tungsten carbide catalysts for cellulose conversion: effect of preparation methods. ChemSusChem 5(5):939944 1539. Kimmel YC, Esposito DV, Birkmire RW, Chen JG (2012) Effect of surface carbon on the hydrogen evolution reactivity of tungsten carbide (WC) and Pt-modified WC electrocatalysts. Int J Hydrogen Energy 37:3019-3024 1540. Lausche AC, Okada K, Thompson LT (2012) Tungsten carbide – supported Pd electrocatalysts for triglyceride hydrogenation in a solid polymer electrolyte reactor. Electrochem Commun 15:46-49 1541. Li G-H, Chen D, Zheng X, Xie W-M, Cheng Y (2012) Preparation and electrocatalytic activity of WC/W2C nanocomposite with core-shell structure. Acta Phys Chim Sin 28(9):2077-2083 (in Chinese) 1542. Liu Y, Mustain WE (2012) Evaluation of tungsten carbide as the electrocatalyst support for platinum hydrogen evolution/oxidation catalysts. Int J Hydrogen Energy 37:8929-8938 1543. Lu JL, Li ZH, Jiang SP, Shen PK, Li L (2012) Nanostructured carbide – carbon composites synthesized by a microwave heating method as supports of platinum catalysts for methanol oxidation. J Power Sources 202:56-62 1544. Mellinger ZJ, Kelly TG, Chen JG (2012) Pd-modified tungsten carbide for methanol electro-oxidation: from surface science studies to electrochemical evaluation. ACS Catal 2:751-758 1545. Nie M, Shen PK, Wei Z, Li Q, Bi H, Liang C (2012) Preparation of pure tungsten carbide and catalytic activity of platinum on a tungsten carbide nanocrystalline support for oxygen reduction. ECS Electrochem Lett 1(3):H11-H13 1546. Nikiforov AV, Petrushina IM, Christensen E, Alexeev NV, Samokhin AV, Bjerrum NJ (2012) WC as a non-platinum hydrogen evolution electrocatalyst for high-temperature PEM water electrolysers. Int J Hydrogen Energy 37:18591-18597

660

2 Tungsten Carbides

1547. Nishanth KG, Sridhar P, Pitchumani S, Shukla AK (2012) Durable transition metal carbide – supported Pt-Ru anodes for direct methanol fuel cells. Fuel Cells 12(1):146-152 1548. Obradović MD, Babić BM, Radmilović VR, Krstajić NV, Gojković SLj (2012) Core-shell structured tungsten – tungsten carbide as a Pt catalyst support and its activity for methanol electrooxidation. Int J Hydrogen Energy 37:10671-10679 1549. Obradović MD, Gojković SLj, Elezović NR, Ercius P, Radmilović VR, Vračar LjD, Krstajić NV (2012) The kinetics of the hydrogen oxidation reaction on WC/Pt catalyst with low content of Pt nanoparticles. J Electroanal Chem 671:24-32 1550. Rahsepar M, Pakshir M, Nikolaev P, Safavi A, Palanisamy K, Kim H (2012) Tungsten carbide on directly grown multi-walled carbon nanotube as a co-catalyst for methanol oxidation. Appl Catal B 127:265-272 1551. Semin GL, Dubrovskii AR, Snytnikov PV, Kuznetsov SA, Sobyanin VA (2012) Using catalysts based on molybdenum and tungsten carbides in the water-gas shift reaction. Catal Indust 4(1):59-66 1552. Shi M-Q, Chen N, Ma C-A, Li Y, Wei A (2012) Catalytic performance of bifunctional WC/HZSM-5 catalysts for n-hexane aromatization. Chin J Catal 33(3):570-575 (in Chinese) 1553. Stottlemyer AL, Kelly TG, Meng Q, Chen JG (2012) Reaction of oxygen-containing molecules on transition metal carbides: surface science insight into potential applications in catalysis and electrocatalysis. Surf Sci Rep 67:201-232 1554. Wang R, Xie Y, Shi K, Wang J, Tian C, Shen PK, Fu H (2012) Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells. Chem Eur J 18:7443-7451 1555. Wang Y, He C, Brouzgou A, Liang Y, Fu R, Wu D, Tsiakaras P, Song S (2012) A facile soft-template synthesis of ordered mesoporous carbon / tungsten carbide composites with high surface area for methanol electrooxidation. J Power Sources 200:8-13 1556. Weidman MC, Esposito DV, Hsu Y-C, Chen JG (2012) Comparison of electrochemical stability of transition metal carbides (WC, W2C, Mo2C) over a wide pH range. J Power Sources 202:11-17 1557. Wei A, Shi M-Q, Ma C-A, Chen N (2012) Dehydroaromatization of n-hexane over zinc modified WC/HZSM-5 catalysts. In: Proc. 4th Int. conf. on mechanical and electrical technology (ICMET 2012), Kuala Lumpur, Malaysia, 24-26 July 2012. Appl Mech Mater 229-231:147-150 1558. Wirth S, Harnish F, Weinmann M, Schröder U (2012) Comparative study of IVB-VIB transition metal compound electrocatalysts for the hydrogen evolution reaction. Appl Catal B 126:225-230 1559. Xia L, Zhang M, Rong M, Guo K, Hu Y, Wu Y, Czigany T (2012) An easy soft-template route to synthesis of wormhole-like mesoporous tungsten carbide / carbon composites. Compos Sci Technol 72:1651-1655 1560. Yang X, Kimmel YC, Fu J, Koel BE, Chen JG (2012) Activation of tungsten carbide catalysts by use of an oxygen plasma pretreatment. ACS Catal 2:765-769 1561. Yan Z, Meng H, Shen PK, Wang R, Wang L, Shi K, Fu H (2012) A facile route to carbidebased electrocatalytic nanocomposites. J Mater Chem 22(11):5072-5079 1562. Yin M, Li Q, Jensen JO, Huang Y, Cleemann LN, Bjerrum NJ, Xing W (2012) Tungsten carbide promoted Pd and Pd-Co electrocatalysts for formic acid electrooxidation. J Power Sources 219:106-111 1563. Zheng Y-F, Zhao N, Zhang J, Yu X-Y, Mo W-M (2012) Microstructures and properties of WC / natural zeolite composites. J Inorg Mater 27(2):129-133 (in Chinese) 1564. Zhu A-J, Chu Y-Q, Ma C-A, Chen Z-Y (2012) Synthesis and characterization of PtSn/WC(O)/C catalyst for ethanol electrooxidation. In: Proc. 4th Int. conf. on mechanical and electrical technology (ICMET 2012), Kuala Lumpur, Malaysia, 24-26 July 2012. Appl Mech Mater 229-231:151-154 1565. Bozzini B, Abyaneh MK, Busson B, De Gaudenzi GP, Gregoratti L, Humbert C, Amati M, Mele C, Tadjeddine A (2013) Spectro-electrochemical study of the electro-oxidation of

References

661

ethanol on WC-supported Pt – Part III. Monitoring of electrodeposited – Pt catalyst ageing by in situ Fourier transform infrared spectroscopy, in situ sum frequency generation spectroscopy and ex situ photoelectron spectromicroscopy. J Power Sources 231:6-17 1566. Chen W-F, Muckerman JT, Fujita E (2013) Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem Commun 49(79):88968909 1567. Chen Z-Y, Shi M-Q, Ma C-A, Chu Y-Q, Zhu A-J (2013) Simple green self-construction approach for large-scale synthesis of hollow needle-like tungsten carbide. Powder Technol 235:467-474 1568. Chen Z-Y, Ma C-A, Chu Y-Q, Jin J-M, Lin X, Hardacre C, Lin W-F (2013) WC@meso-Pt core-shell nanostructures for fuel cells. Chem Commun 49(99):11677-11679 1569. Deng L-F, Xia L-Y, Hu Y-C, Wu Y-Q, Zhang M-Q, Rong M-Z (2013) Preparation of ordered mesoporous tungsten carbide / carbon composites by nanocasting method and its electrocatalysis. J Funct Mater 44(15):2262-2267 1570. Garcia AC, Ticianelli EA (2013) Investigation of the oxygen reduction reaction on PtWC/C electrocatalysts in alkaline media. Electrochim Acta 106:453-459 1571. Gong X-B, You S-J, Wang X-H, Gan Y, Zhang R-N, Ren N-Q (2013) Silver – tungsten carbide nanohybrid for efficient electrocatalysis of oxygen reduction reaction in microbial fuel cell. J Power Sources 225:330-337 1572. Hu X-C, Hu J-G, Sun J, Li G-H (2013) Mesoporous tungsten carbide supported Pt and their electrocatalytic activity for methanol electro-oxidation. J Inorg Mater 28(12):1286-1290 (in Chinese) 1573. Kelly TG, Hunt ST, Esposito DV, Chen JG (2013) Monolayer palladium supported on molybdenum and tungsten carbide substrates as low-cost hydrogen evolution reaction (HER) electrocatalysts. Int J Hydrogen Energy 38:5638-5644 1574. Lang X-L, Shi M-Q, Chu Y-Q, Liu W-M, Chen Z-Y, Ma C-A (2013) Microwave-assisted synthesis of Pt-WC/TiO2 in ionic liquid and its application for methanol oxidation. J Solid State Electrochem 17:2401-2408 1575. Liu Y, Kelly TG, Chen JG, Mustain WE (2013) Metal carbides as alternative electrocatalyst support. ACS Catal 3:1184-1194 1576. Ma C-A, Liu W-M, Shi M-Q, Lang X-L, Chu Y-Q, Chen Z-Y, Zhao D, Lin W-F, Hardacre C (2013) Low loading platinum nanoparticles on reduced graphene oxide – supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation. Electrochim Acta 114:133-141 1577. Ma C-A, Xu C-B, Shi M-Q, Song G-H, Lang X-L (2013) The high performance of tungsten carbides / porous bamboo charcoals supported Pt catalysts for methanol electrooxidation. J Power Sources 242:273-279 1578. Mellinger ZJ, Chen JG (2013) Metal-modified carbide anode electrocatalysts. In: Shao M (ed) Electrocatalysis in fuel cells, pp. 27-42. Springer-Verlag, London 1579. Mu G, Wang L, Yin J, Jiang B, Jiang L, Umar A, Fu H (2013) Synergetic effect of WC / porous graphite carbon supports on electrocatalytic reactivity of Pt for methanol electrooxidation. Sci Adv Mater 5(11):1709-1717 1580. Nikolić VM, Zugić DL, Perović IM, Saponjić AB, Babić BM, Pašti IA, Marčeta-Kaninski MP (2013) Investigation of tungsten carbide supported Pd or Pt as anode catalysts for PEM fuel cells. Int J Hydrogen Energy 38:11340-11345 1581. Obradović MD, Babić BM, Krstajić NV, Gojković SL (2013) Uticaj prisustva voframkarbida u ugljeničnom nosaču Pt nanočestica na elektrohemijsku redukciju kiseonika u kiselom rastvoru (Effect of tungsten carbide in carbon Pt catalyst support on electrochemical oxygen reduction in acid solution). Hemi Indust 67(2):303-311 (in Serbian) 1582. Perchthaler M, Ossiander T, Juhart V, Mitzel J, Heinzl C, Scheu C, Hacker V (2013) Tungsten materials as durable catalyst supports for fuel cell electrodes. J Power Sources 243:472-480

662

2 Tungsten Carbides

1583. Poh CK, Lim SH, Tian Z, Lai L, Feng YP, Shen Z, Lin J (2013) Pt-WxC nanocomposites as an efficient electrochemical catalyst for oxygen reduction reaction. Nano Energy 2:28-39 1584. Song G-H, Shi M-Q, Chu Y-Q, Ma C-A (2013) Synthesis and characterization of highly dispersed Pt-TiO2ǀWC/BC as anode catalyst for methanol oxidation. Electrochim Acta 112:53-58 1585. Vasić-Anićijević DD, Nikolić VM, Marčeta-Kaninski MP, Pašti IA (2013) Is platinum necessary for efficient hydrogen evolution? – DFT study of metal monolayers on tungsten carbide. Int J Hydrogen Energy 38:16071-16079 1586. Vasić DD, Pašti IA, Mentus SV (2013) DFT study of platinum and palladium overlayers on tungsten carbide: structure and electrocatalytic activity toward hydrogen oxidation / evolution reaction. Int J Hydrogen Energy 38:5009-5018 1587. Xu C-B, Shi M-Q, Kang L-Z, Ma C-A (2013) Novel core-shell Pt/WC@TiO2 electrocatalyst for methanol oxidation. Mater Lett 91:183-186 1588. Yang J, Xie Y, Wang R, Jiang B, Tian C, Mu G, Yin J, Wang B, Fu H (2013) Synergistic effect of tungsten carbide and palladium on graphene for promoted ethanol electrooxidation. ACS Appl Mater Interfaces 5:6571-6579 1589. Yan Y, Xia B, Qi X, Wang H, Xu R, Wang J-Y, Zhang H, Wang X (2013) Nano-tungsten carbide decorated graphene as co-catalysts for enhanced hydrogen evolution on molybdenum disulphide. Chem Commun 49(43):4884-4886 1590. Yan Z, He G, Cai M, Meng H, Shen PK (2013) Formation of tungsten carbide nanoparticles on graphitized carbon to facilitate the oxygen reduction reaction. J Power Sources 242:817-823 1591. Yan Z, Cai M, Shen PK (2013) Nanosized tungsten carbide synthesized by a novel route at low temperature for high performance electrocatalysis. Sci Rep 3:1646 (7 pp.) 1592. Zhang X, Shen PK (2013) Glycerol electrooxidation on highly active Pd supported / C aerogel composite catalysts. Int J Hydrogen Energy 38:2257-2262 1593. Zheng H-J, Chen Z, Li Y, Ma C-A (2013) Synthesis of ordered mesoporous carbon / tungsten carbides as a replacement of platinum-based electrocatalyst for methanol oxidation. Electrochim Acta 108:486-490 1594. Zhong G, Wang H, Yu H, Peng F (2013) A novel carbon-encapsulated cobalt – tungsten carbide as electrocatalyst for oxygen reduction reaction in alkaline media. Fuel Cells 13(3):387-391 1595. Zou L, Ren M, Zhang H, Zou Z, Yang H, Feng S (2013) Pd nanoparticles supported on tungsten carbide embedded onto ordered mesoporous carbons for electrocatalysis of formic acid oxidation. Int J Electrochem Sci 8:6180-6190 1596. Al-Alwan B, Sari E, Salley SO, Ng KYS (2014) Effect of metal ratio and preparation method on nickel – tungsten carbide catalyst for hydrocracking of distillers dried grains with solubles corn oil. Indust Eng Chem 53:6923-6933 1597. Berglund SP, He H, Chemelewski WD, Celio H, Dolocan A, Mullins CB (2014) p-Si/W2C and p-Si/W2C/Pt photocathodes for the hydrogen evolution reaction. J Am Chem Soc 136:1535-1544 1598. Borchardt L, Oschatz M, Graetz S, Lohe MR, Rümmeli MH, Kaskel S (2014) A hardtemplating route towards ordered mesoporous tungsten carbide and carbide-derived carbons. Micropor Mesopor Mater 186:163-167 1599. Chen H, Chen D, Xie W-M, Zheng X, Li G-H (2014) Preparation and electrocatalytic activity of tungsten carbide and tungsten-iron carbide composite with core-shell structure. Acta Phys Chim Sin 30(5):891-898 (in Chinese) 1600. Chen W-F, Schneider JM, Sasaki K, Wang C-H, Schneider J, Iyer Shi, Iyer Shw, Zhu Y, Muckerman JT, Fujita E (2014) Tungsten carbide-nitride on graphene nanoplatelets as a durable hydrogen evolution electrocatalyst. ChemSusChem 7(9):2414-2418 1601. Cui S-H, Li J-H, Luo J-L, Chuang KT, Qiao L-J (2014) Co-generation of energy and ethylene in hydrocarbon fuelled SOFCs with Cr3C2 and WC anode catalysts. Ceram Int 40:11781-11786

References

663

1602. He C, Shen PK (2014) Pt loaded on truncated hexagonal pyramid WC/graphene for oxygen reduction reaction. Nano Energy 8:52-61 1603. Jiang L, Fu H, Wang L, Mu G, Jiang B, Zhou W Wang R (2014) Nanocrystalline tungstic carbide / graphitic carbon composite: synthesis, characterization and its application as an effective Pt catalyst support for methanol oxidation. J Solid State Electrochem 18:2225-2232 1604. Jiang L, Fu H, Wang L, Mu G, Jiang B, Zhou W, Wang R (2014) Tungsten carbide / porous carbon composite as superior support for platinum catalyst toward methanol electrooxidation. Mater Res Bull 49:480-486 1605. Jin Y, Shi M-Q, Liu W, Chu Y, Xu Y, Ma C-A, Jia W, Zhao G, Yu J (2014) Pt/WC-CNTs electrocatalyst for oxygen reduction reaction. CIESC J 65(10):4015-4024 (in Chinese) 1606. Kelly TG, Stottlemyer AL, Yang X, Chen JG (2014) Theoretical and experimental studies of ethanol decomposition and electrooxidation over Pt-modified tungsten carbide. J Electrochem Soc 161(8):E3165-E3170 1607. Ko A-R, Lee Y-W, Moon J-S, Han S-B, Cao G, Park K-W (2014) Ordered mesoporous tungsten carbide nanoplates as non-Pt catalysts for oxygen reduction reaction. Appl Catal A 477:102-108 1608. Lewandowski M, Szymańska-Kolasa A, Sayag C, Beaunier P, Djéga-Mariadassou G (2014) Atomic level characterization and sulphur resistance of unsupported W2C during dibenzo-thiophene hydrodesulphurization. Classical kinetic simulation of the reaction. Appl Catal B 144:750-759 1609. Li P, Liu Z, Cui L, Zhai F, Wan Q, Li Z, Fang ZZ, Volinsky AA, Qu X-H (2014) Tungsten carbide synthesized by low-temperature combustion as gas diffusion electrode catalyst. Int J Hydrogen Energy 39:10911-10920 1610. Ma C-A, Kang L-Z, Shi M-Q, Lang X-L, Jiang Y (2014) Preparation of Pt-mesoporous tungsten carbide / carbon composites via a soft-template method for electrochemical methanol oxidation. J Alloys Compd 588:481-487 1611. Michalsky R, Zhang Y-J, Medford AJ, Peterson AA (2014) Departures from the adsorption energy scaling relations for metal carbide catalysts. J Phys Chem C 118:1302613034 1612. Moon J-S, Lee Y-W, Han S-B, Kwak D-H, Lee K-H, Park A-R, Sohn JI, Cha SN, Park KW (2014) Iron-nitrogen-doped mesoporous tungsten carbide nanostructures as oxygen reduction electrocatalysts. Phys Chem Chem Phys 16(28):14644-14650 1613. Moon J-S, Lee Y-W, Han S-B, Park K-W (2014) Pd nanoparticles on mesoporous tungsten carbide as a non-Pt electrocatalyst for methanol electrooxidation reaction in alkaline solution. Int J Hydrogen Energy 39:7798-7804 1614. Nie M, Zeng ZJ, He B, Li Q, Liu XW, Zheng CS (2014) Tungsten carbide promoted AuPd-Pt as methanol-tolerant electrocatalysts for oxygen reduction reaction. Mater Res Innov 18(4):255-258 1615. Nikolić VM, Perović IM, Gavrilov NM, Pašti IA, Saponjić AB, Vulić PJ, Karić SD, Babić BM, Marčeta-Kaninski MP, (2014) On the tungsten carbide synthesis for PEM fuel cell application – problems, challenges and advantages. Int J Hydrogen Energy 39:11175-11185 1616. Poh CK, Lim SH, Lin J, Feng YP (2014) Tungsten carbide support for single-atom platinum-based fuel cell catalysts: first principles study on the metal-support interactions and O2 dissociation on WxC low-index surfaces. J Phys Chem C 118:13525-13538 1617. Ren H, Chen Y, Huang Y, Deng W, Vlachos DG, Chen JG (2014) Tungsten carbides as selective deoxygenation catalysts: experimental and computational studies of converting C3 oxygenates to propene. Green Chem 16(2):761-769 1618. Shi M-Q, Kang L-Z, Jiang Y, Ma C-A (2014) Microwave-assisted synthesis of mesoporous tungsten carbide / carbon for fuel cell applications. Catal Lett 144:278-284 1619. Shi M-Q, Zhang W-T, Zhao D, Chu Y-Q, Ma C-A (2014) Reduced graphene oxide – supported tungsten carbide modified with ultra-low platinum- and ruthenium-loading for methanol oxidation. Electrochim Acta 143:222-231

664

2 Tungsten Carbides

1620. Shi M-Q, Zhao D, Liu W-M, Chu Y-Q, Ma C-A (2014) Investigation of platinum dispersed on reduced graphene oxide – supported tungsten carbide via sacrificial Cu adlayers for methanol oxidation. Chin J Chem 32:233-240 1621. Shi M-Q, Liu W-M, Zhao D, Chu Y-Q, Ma C-A (2014) Synthesis of palladium nanoparticles supported on reduced graphene oxide – tungsten carbide composite and the investigation of its performance for electrooxidation of formic acid. J Solid State Electrochem 18:1923-1932 1622. Tomas-Garcia AL, Li Q, Jensen JO, Bjerrum NJ (2014) High surface area tungsten carbides: synthesis, characterization and catalytic activity towards the hydrogen evolution reaction in phosphoric acid at elevated temperatures. Int J Electrochem Sci 9:1016-1032 1623. Wang K, Wang Y, Liang Z, Liang Y, Wu D, Song S, Tsiakaras P (2014) Ordered mesoporous tungsten carbide – carbon composites promoted Pt catalyst with high activity and stability for methanol electrooxidation. Appl Catal B 147:518-525 1624. Wang L, Li M, Huang Z, Li Y, Qi S, Yi C, Yang B (2014) Ni-WC/C nanocluster catalysts for urea electrooxidation. J Power Sources 264:282-289 1625. Xi Y, Huang L, Forrey RC, Cheng H (2014) Interactions between hydrogen and tungsten carbide: a first principles study. RSC Adv 4(75):39912-39919 1626. Xu YH, Zhou JJ, Zhou T, Chao YH, Yan S, Jiang XC, Chen XJ, Zhu WS, Li HM (2014) Extraction joined with adsorption and catalytic oxidation of dibenzothiophene with commercially available tungsten carbide. In: Proc. 2nd Int. congress on advanced materials (AM 2013), Zhenjiang, China, 16-19 May 2013. Key Eng Mater 575-576:539-542 1627. Bucharkina TV, Gavrilova NN, Kryzhanovskiy AS, Skudin VV, Shulmin DA (2015) Dry reforming of methane in contactor and distributor membrane reactors. Petrol Chem 55(10):932-939 1628. Chen Y-X, Zheng Y, Li M, Zhu X-F (2015) Arene production by W2C/MCM-41-catalyzed upgrading of vapours from fast pyrolysis of lignin. Fuel Process Technol 134:46-51 1629. Di Valentin C, Fittipaldi D, Pacchioni G (2015) Methanol oxidation reaction on α-tungsten carbide versus platinum (111) surfaces: a DFT electrochemical study. ChemCatChem 7(21):3533-3543 1630. Fan X, Zhou H, Guo X (2015) WC nanocrystals grown on vertically aligned carbon nanotubes: an efficient and stable electrocatalyst for hydrogen evolution reaction. ACS Nano 9(5):5125-5134 1631. Hassan A, Paganin VA, Ticianelli EA (2015) Pt modified tungsten carbide as anode electrocatalyst for hydrogen oxidation in proton exchange membrane fuel cell: CO tolerance and stability. Appl Catal B 165:611-619 1632. Han S, Youn DH, Lee MH, Lee JS (2015) Tungsten carbide and CNT-graphene-supported Pd electrocatalyst toward electrooxidation of hydrogen. ChemCatChem 7(9):1483-1489 1633. He C, Tao J, Ke Y, Qiu Y (2015) Graphene-supported small tungsten carbide nanocrystals promoting a Pd catalyst towards formic acid oxidation. RSC Adv 5(82):66695-66703 1634. Hsu IJ, Chen JG, Jiang X, Willis BG (2015) Atomic layer deposition synthesis and evaluation of core-shell Pt-WC electrocatalysts. J Vac Sci Technol A 33(1):01A129 (8 pp.) 1635. Huang K, Bi K, Xu JC, Liang C, Lin S, Wang WJ, Yang TZ, Du YX, Zhang R, Yang HJ, Fan DY, Wang YG, Lei M (2015) Novel graphite-carbon encased tungsten carbide nanocomposites by solid-state reaction and their ORR electrocatalytic performance in alkaline medium. Electrochim Acta 174:172-177 1636. Hunt ST, Kokumai TM, Zanchet D, Román-Leshkov Yu (2015) Alloying tungsten carbide nanoparticles with tantalum: impact on electrochemical oxidation resistance and hydrogen evolution activity. J Phys Chem C 119:13691-13699 1637. Kelly TG, Ren H, Chen JG (2015) Decomposition pathways of C2 oxygenates on Rhmodified tungsten carbide surfaces. Surf Sci 640:89-95 1638. Liu Y, Li G-D, Yuan L, Ge L, Ding H, Wang D, Zou X (2015) Carbon-protected bimetallic carbide nanoparticles for a highly efficient alkaline hydrogen evolution reaction. Nanoscale 7(7):3130-3136

References

665

1639. Liu Z, Li P, Zhai F, Wan Q, Volinsky AA, Qu X (2015) Amorphous carbon modified nano-sized tungsten carbide as a gas diffusion electrode catalyst for the oxygen reduction reaction. RSC Adv 5(87):70743-70748 1640. Li Z, Li B, Liu Zhi, Liu Zhe, Li D (2015) A tungsten carbide / iron sulphide / FePt nanocomposite supported on nitrogen-doped carbon as an efficient electrocatalyst for oxygen reduction reaction. RSC Adv 5(128):106245-106251 1641. Meng F, Hu E, Zhang L, Sasaki K, Muckerman JT, Fujita E (2015) Biomass-derived highperformance tungsten-based electrocatalysts on graphene for hydrogen evolution. J Mater Chem A 3(36):18572-18577 1642. Meyer S, Nikiforov AV, Petrushina IM, Köhler K, Christensen E, Jensen JO, Bjerrum NJ (2015) Transition metal carbides (WC, Mo2C, TaC, NbC) as potential electrocatalysts for the hydrogen evolution reaction (HER) at medium temperatures. Int J Hydrogen Energy 40:29052911 1643. Pan J-M, Yang W, Sun H-B, Zheng X, Li G-H (2015) Preparation and electrocatalytic activity of tungsten carbide – montmorillonite composite. Acta Phys Chim Sin 31(5):9981006 (in Chinese) 1644. Schaidle JA, Thompson LT (2015) Fischer-Tropsch synthesis over early transition metal carbides and nitrides: CO activation and chain growth. J Catal 329:325-334 1645. Sheng T, Lin X, Chen Z-Y, Hu P, Sun S-G, Chu Y-Q, Ma C-A, Lin W-F (2015) Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study. Phys Chem Chem Phys 17:25235-25243 1646. Stellwagen DR, Bitter JH (2015) Structure-performance relations of molybdenum and tungsten carbide catalysts for deoxygenation. Green Chem 17(1):582-593 1647. Tang C, Wang D, Wu Z, Duan B (2015) Tungsten carbide hollow microspheres as electrocatalyst and platinum support for hydrogen evolution reaction. Int J Hydrogen Energy 40:3229-3237 1648. Vijayakumar P, Senthil-Pandian M, Lim SP, Pandikumar A, Huang NM, Mukhopadhyay S, Ramasamy P (2015) Investigations of tungsten carbide nanostructures treated with different temperatures as counter electrodes for dye sensitized solar cells (DSSC) applications. J Mater Sci Mater Electron 26:7977-7986 1649. Wannakao S, Artrith N, Limtrakul J, Kolpak AM (2015) Engineering transition metal coated tungsten carbides for efficient and selective electrochemical reduction of CO2 to methane. ChemSusChem 8(16):2745-2751 1650. Wang K, Pan Z, Tzorbatzoglou F, Zhang Y, Wang Y, Tsiakaras P, Song S (2015) An investigation of WC stability during the preparation of Pt@WC/OMC via a pulse microwave assisted polyol method. Appl Catal B 166-167:224-230 1651. Wang L, Du T, Cheng J, Xie X, Yang B, Li M (2015) Enhanced activity of urea electrooxidation on nickel catalysts supported on tungsten carbides / carbon nanotubes. J Power Sources 280:550-554 1652. Xiong L, Zheng L, Liu C, Jin L, Liu Q, Xu J (2015) Tungsten carbide microspheres with high surface area as platinum catalyst supports for enhanced electrocatalytic activity. J Electrochem Soc 162(4):F468-F473 1653. Xue F, Zhu L, Wang J, Tu Z (2015) Catalytic role of surface pre-treatment of noble-metallike tungsten carbide powder on electroless deposition of nickel. Surf Coat Technol 265:3237 1654. Yan Z, Li F, Xie J, Miu X (2015) Hollow tungsten carbide / carbon sphere promoted Pt electrocatalyst for efficient methanol oxidation. RSC Adv 5(9):6790-6796 1655. Zhao Z, Yang H (2015) Ni-W2C/mpg-C3N4 as a promising catalyst for selective hydrogenation of nitroarenes to corresponding aryl amines in the presence of Lewis acid. J Mol Catal A 398:268-274 1656. Bukola S, Merzougui B, Akinpelu A, Zeama M (2016) Cobalt and nitrogen co-doped tungsten carbide catalyst for oxygen reduction and hydrogen evolution reactions. Electrochim Acta 190:1113-1123

666

2 Tungsten Carbides

1657. Chen Z, Qin M, Chen P, Jia B, He Q, Qu X (2016) Tungsten carbide / carbon composite synthesized by combustion-carbothermal reduction method as electrocatalyst for hydrogen evolution reaction. Int J Hydrogen Energy 41:13005-13013 1658. Di J, Li Y, Zhao Z, Zheng H (2016) A facile synthesis of tungsten carbide / carbon nanocomposite as a non-platinum electrocatalyst for methanol oxidation. J Nanosci Nanotechnol 16(7):7579-7583 1659. Gao J, Wu S, Chen J, Li Y, Li G (2016) Mesoporous tungsten carbide nanoslices with pure phase and superior electrocatalysis. Electrochim Acta 222:728-734 1660. Guo H, Zhang B, Li C, Peng C, Dai T, Xie H, Wang A, Zhang T (2016) Tungsten carbide: a remarkably efficient catalyst for the selective cleavage of lignin C-O bonds. ChemSusChem 9(22):3220-3229 1661. Guo S-D, Hu X-C, Yang J-G, Chen H, Zhou Y (2016) Palladium nanoparticles supported on hollow mesoporous tungsten carbide microsphere as electrocatalyst for formic acid oxidation. J Fuel Chem Technol 44(6):698-702 (in Chinese) 1662. Han BJ, Huang ZJ, Wu G, Zhou CY, Li YS, Wang QH, Zhang YL, Yin YH, Wu ZP (2016) Growth of carbon nanoshells on tungsten carbide for loading Pt with enhanced electrocatalytic activity and stable anti-poisoning performance. RSC Adv 6(79):75178-75185 1663. Han L, Xu M, Han Y, Yu Y, Dong S (2016) Core-shell-structured tungsten carbide encapsulated within nitrogen-doped carbon spheres for enhanced hydrogen evolution. ChemSusChem 9(19):2784-2787 1664. He S-W, Xu R-D, Hu G, Chen B (2016) Electrosynthesis and performance of WC and Co3O4 co-doped α-PbO2 electrodes. RSC Adv 6(4):3362-3371 1665. Hunt ST, Milina M, Alba-Rubio AC, Hendon CH, Dumesic JA, Román-Leshkov Y (2016) Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts. Science 352(6288):974-978 1666. Kang J, Kim H-M, Saito N, Lee M-H (2016) A simple synthesis method for nanostructured Co-WC / carbon composites with enhanced oxygen reduction reaction activity. Sci Technol Adv Mater 17(1):37-44 1667. Lang X, Shi M-Q, Jiang Y, Chen H, Ma C-A (2016) Tungsten carbide / porous carbon core-shell nanocomposites as a catalyst support for methanol oxidation. RSC Adv 6(17):13873-13880 1668. Leal GF, Moya SF, Meira DM, Barrett DH, Teixeira-Neto E, Curvelo AAS, TeixeiraDaSilva V, Rodella CB (2016) Promotion effects of Pd on tungsten carbide catalysts: physico-chemical properties and cellulose conversion performance. RSC Adv 6(90):8775687766 1669. Liu C, Zhou D, Zhou J, Xie Z, Xia Y (2016) Synthesis and characterization of tungsten carbide and application to electrocatalytic hydrogen evolution. RSC Adv 6(80):76307-76311 1670. Liu X, Nie M, Nie C, Cao Y, Zuo W, Li Q, Du S, Lu S (2016) The properties of hydrogen evolution of AuPdPt-WC/C nanocomposite catalyst in simulated sea water solution. J Funct Mater 47(2):02135-02138 (in Chinese) 1671. Li Z, Liu Zhi, Li B, Liu Zhe, Li D, Wang H, Li Q (2016) Hollow hemisphere-shaped macroporous graphene / tungsten carbide / platinum nanocomposite as an efficient electrocatalyst for the oxygen reduction reaction. Electrochim Acta 221:31-40 1672. Nie M, Liu X, He B, Li Q, Du S, Lu S, Jiang C, Lei D (2016) Investigation of the AuPdPtWC/C electrocatalyst for hydrogen evolution reaction. J Electrochem Soc 163(7):H485-H490 1673. Pan Y-X, Zhou T, Han J, Hong J, Wang Y, Zhang W, Xu R (2016) CdS quantum dots and tungsten carbide supported on anatase-rutile composite TiO2 for highly efficient visible-lightdriven photocatalytic H2 evolution from water. Catal Sci Technol 6(7):2206-2213 1674. Shi M-Q, Zhang W-T, Li Y-Y, Chu Y-Q, Ma C-A (2016) Tungsten carbide – reduced graphene oxide intercalation compound as co-catalyst for methanol oxidation. Chin J Catal 37:1851-1859

References

667

1675. Singla G, Singh K, Pandey OP (2016) Study on single step solid state synthesis of WC@C nanocomposite and electrochemical stability of synthesized WC@C & Pt/WC@C for alcohol oxidation (methanol/ethanol). J Alloys Compd 665:186-196 1676. Sullivan MM, Bhan A (2016) Acid site densities and reactivity of oxygen-modified transition metal carbide catalysts. J Catal 344:53-58 1677. Sullivan MM, Chen C-J, Bhan A (2016) Catalytic deoxygenation on transition metal carbide catalysts. Catal Sci Technol 6(3):602-616 1678. Sun J, Liang B, Huang Y, Wang X (2016) Synthesis of nanostructured tungsten carbonitride (WNxCy) by carbothermal ammonia reduction on activated carbon and its application in hydrazine decomposition. Catal Today 274:123-128 1679. Urzhuntsev GA, Kodenev EG, Echevskii GV (2016) Prospects for using Mo- and Wcontaining catalysts in hydroisomerization: a patent review. II. Catalysts based on molybdenum and tungsten carbides. Catal Indust 8(3):224-230 1680. Wang K, Wang Y, Tong Y, Pan Z, Song S (2016) A robust versatile hybrid electrocatalyst for the oxygen reduction reaction. ACS Appl Mater Interfaces 8:29356-29364 1681. Won BD, Ham H, Cho JM, Lee J-B, Kim C-U, Roh H-S, Moon DJ, Bae JW (2016) Effect of Mn promoter on Rh / tungsten carbide on product distributions of alcohols and hydrocarbons by CO hydrogenation. RSC Adv 6(103):101535-101543 1682. Xia X, Yates JLR, Jones G, Sarwar M, Harkness I, Thompsett D (2016) Theoretical exploration of novel catalyst support materials for fuel cell applications. J Mater Chem A 4(39):15181-15188 1683. Yan Z, Gao L, Zhao X, Wei W, Xie J, Shen PK, Zhu F (2016) Exterior and small carbide particle promoted platinum electrocatalyst for efficient methanol oxidation. RSC Adv 6(71):66665-66671 1684. Yao Z, Jiang J, Zhao Y, Luan F, Zhu J, Shi Y, Gao H, Wang H (2016) Insights into the deactivation mechanism of metal carbide catalysts for dry reforming of methane via comparison of nickel-modified molybdenum and tungsten carbides. RSC Adv 6(24):1994419951 1685. Zhang X, Lu Z, Yang Z (2016) A theoretical understanding on the CO-tolerance mechanism of the WC (0001) supported Pt monolayer: some improvement strategies. Appl Surf Sci 389:455-461 1686. Zhang X, Lu Z, Yang Z (2016) A comparison study of oxygen reduction on the supported Pt, Pd, Au monolayer on WC (0001). J Power Sources 321:163-173 1687. Zhang X, Zhong X, Yang Z, Song J, Lu H (2016) Carbon-covered tungsten carbide nanoparticles: solid-state synthesis and application as stable electrocatalysts for the hydrogen evolution reaction. Chem Res Chin Univ 32(6):1016-1018 1688. Zhuang H, Tkalych AJ, Carter EA (2016) Surface energy as a descriptor of catalytic activity. J Phys Chem C 120:23698-23706 1689. Zhuang H, Tkalych AJ, Carter EA (2016) Understanding and tuning the hydrogen evolution reaction on Pt-covered tungsten carbide cathodes. J Electrochem Soc 163(7):F629F636 1690. Bott-Neto JL, Beck W, Jr, Varanda LC, Ticianelli EA (2017) Electrocatalytic activity of platinum nanoparticles supported on different phases of tungsten carbides for the oxygen reduction reaction. Int J Hydrogen Energy 42:20677-20688 1691. Braun M, Esposito D (2017) Hydrogenation properties of nanostructured tungsten carbide catalysts in a continuous-flow reactor. ChemCatChem 9(3):393-397 1692. Chen Z-Y, Duan L-F, Chu Y-Q, Sheng J-F, Lin W-F, Ma C-A (2017) Fabricating coreshell WC@C/Pt structures and its enhanced performance for methanol electrooxidation. Chin J Chem Phys 30(4):450-456 1693. Chen Z-Y, Duan L-F, Sheng T, Lin X, Chen Y-F, Chu Y-Q, Sun S-G, Lin W-F (2017) Dodecahedral W@WC composite as efficient catalyst for hydrogen evolution and nitrobenzene reduction reactions. ACS Appl Mater Interfaces 9:20594-20602

668

2 Tungsten Carbides

1694. Gao R, Zhou Y, Liu X, Wang J (2017) N-doped defective carbon layer encapsulated W2C as a multifunctional cathode catalyst for high performance Li-O2 battery. Electrochim Acta 245:430-437 1695. Guo H, Zhang B, Qi Z, Li C, Ji J, Dai T, Wang A, Zhang T (2017) Valorization of lignin to simple phenolic compounds over tungsten carbide: impact of lignin structure. ChemSusChem 10(3):523-532 1696. He K, Xie J, Yang Z, Shen R, Fang Y, Ma S, Chen X, Li X (2017) Earth-abundant WC nanoparticles as an active noble-metal-free co-catalyst for the highly boosted photocatalytic H2 production over g-C3N4 nanosheets under visible light. Catal Sci Technol 7(5):1193-1202 1697. Huo L, Liu B, Gao Z, Zhang J (2017) 0D/2D heterojunctions of molybdenum carbide – tungsten carbide quantum dots / N-doped graphene nanosheets as superior and durable electrocatalysts for hydrogen evolution reaction. J Mater Chem A 5(35):18494-18501 1698. Kang JS, Kim J, Lee MJ, Son YJ, Jeong J, Chung DY, Lim A, Choe H, Park HS, Sung YE (2017) Electrochemical synthesis of nanoporous tungsten carbide and its application as electrocatalysts for photoelectrochemical cells. Nanoscale 9(17):5413-5424 1699. Kislov VR, Skudin VV, Adamu A (2017) New bimetallic Mo2C-WC/Al2O3 membrane catalysts in the dry reforming of methane. Kinet Catal 58(1):73-80 1700. Liang Y-Y, Chen L, Ma C-A (2017) Kinetics and thermodynamics of H2O dissociation and CO oxidation on the Pt / WC (0001) surface: a density functional theory study. Surf Sci 656:7-16 1701. Li H, Chen Z, Yu Q, Zhu W, Cui W (2017) Effects of tungsten carbide on the electrocatalytic activity of PbO2-WC composite inert anodes during zinc electrowinning. J Electrochem Soc 164(14):H1064-H1071 1702. Liu C, Zhou J, Xiao Y, Yang L, Yang D, Zhou D (2017) Structural and electrochemical studies of tungsten carbide / carbon composites for hydrogen evolution. Int J Hydrogen Energy 42:29781-29790 1703. Liu Y, Yun S, Zhou X, Hou Y, Zhang T, Li J, Hagfedt A (2017) Intrinsic origin of superior catalytic properties of tungsten-based catalysts in dye-sensitized solar cells. Electrochim Acta 242:390-399 1704. Li Y, Wu G, Liu T, Wu Z, Yin Y, Chen D (2017) WxC/GC synthesis by an ion-exchange carbonization method and its electrochemical performance. Rare Met Mater Eng 46(12):3947-3952 (in Chinese) 1705. Lu J, Zhang L, Jing S, Luo L, Yin S (2017) Remarkably efficient PtRh alloyed with nanoscale WC for hydrogen evolution in alkaline solution. Int J Hydrogen Energy 42:59935999 1706. Mehdad A. Jentoft RE, Jentoft FC (2017) Passivation agents and conditions for Mo2C and W2C: effect on catalytic activity for toluene hydrogenation. J Catal 347:89-101 1707. Morozov MA, Akimov AS, Zhuravkov SP, Zolotukhina NY, Sviridenko NN, Golovko AK, Vosmerikov AV, Fedushchak TA (2017) Kataliticheskie svoistva poroshkov karbida volframa pri krekinge tyazhelogo neftyanogo syrya (Catalytic properties of tungsten carbide powders in cracking heavy petroleum feedstock). Bull Tomsk Polytech Univ Geo Assets Eng 328(8):16-23 (in Russian) 1708. Shi M-Q, Yang P-P, Huang L-Z, Chen H, Mao X-B (2017) Heterostructures in carbondoped tungsten nitride and its effect on electrocatalytic properties for methanol oxidation. Electrochim Acta 238:210-219 1709. Singla G, Singh K, Pandey OP (2017) Catalytic activity of tungsten carbide – carbon (WC@C) core-shell structures for ethanol electro-oxidation. Mater Chem Phys 186:19-28 1710. Sohn Y, Jung JY, Kim P (2017) Facile synthesis of tungsten carbide – carbon composites for oxygen reduction reaction. Korean J Chem Eng 34(8):2162-2168 1711. Song L, Wang T, Wang Y, Xue H, Fan X, Guo H, Xia W, Gong H, He J (2017) Porous iron-tungsten carbide electrocatalyst with high activity and stability toward oxygen reduction reaction: from the self-assisted synthetic mechanism to its active-species probing. ACS Appl Mater Interfaces 9:3713-3722

References

669

1712. Song L, Wang T, Ma Y, Xue H, Guo H, Fan X, Xia W, Gong H, He J (2017) Functional species encapsulated in nitrogen-doped porous carbon as a highly efficient catalyst for the oxygen reduction reaction. Chem Eur J 23:3398-3405 1713. Terracciano AC, De Oliveira S, Siddhanti D, Blair R, Vasu SS, Orlovskaya N (2017) Pd enhanced WC catalyst to promote heterogeneous methane combustion. Appl Therm Eng 114:663-672 1714. Wang F-M, He P, Li Y, Shifa TA, Deng Y, Liu K, Wang Q, Wang F, Wen Y, Wang Z, Zhan X, Sun L, He J (2017) Interface engineered WxC@WS2 nanostructure for enhanced hydrogen evolution catalysis. Adv Funct Mater 27:1605802 (7 pp.) 1715. Wang J, Chen W, Wang X, Wang E (2017) N-doped graphene supported WxC composite material as an efficient non-noble metal electrocatalyst for hydrogen evolution reaction. Electrochim Acta 251:660-671 1716. Wang X-L, Tang Y-J, Huang W, Liu C-H, Dong L-Z, Li S-L, Lan Y-Q (2017) Efficient electrocatalyst for the hydrogen evolution reaction derived from polyoxotungstate / polypyrrole / graphene. ChemSusChem 10(11):2402-2407 1717. Wang Y, Su J, Dong L, Zhao P, Zhang Y, Wang W, Jia S, Zang J (2017) Platinum supported on a hybrid of nickel and tungsten carbide on new-diamond electrocatalyst for methanol oxidation and oxygen reduction reaction. ChemCatChem 9(20):3982-3988 1718. Zeng M, Chen Y, Li J, Xue H, Mendes RG, Liu J, Zhang T, Rümmeli MH. Fu L (2017) 2D WC single crystal embedded in graphene for enhancing hydrogen evolution reaction. Nano Energy 33:356-362 1719. Abbas SC, Wu J, Huang Y, Babu DD, Anandhababu G, Ghausi MA, Wu M, Wang Y (2018) Novel strongly coupled tungsten-carbon-nitrogen complex for efficient hydrogen evolution reaction. Int J Hydrogen Energy 43:16-23 1720. Chen Li, Chen W, Wang E (2018) Graphene with cobalt oxide and tungsten carbide as a low-cost counter electrode catalyst applied in Pt-free dye-sensitized solar cells. J Power Sources 380:18-25 1721. Choi J, Jeong T-G, Cho BW, Jung Y, Oh SH, Kim Y-T (2018) Tungsten carbide as a highly efficient catalyst for polysulphide fragmentations in Li-S batteries. J Phys Chem C 122(14):7664-7669 1722. Dai T, Li C, Li L, Zhao ZK, Zhang B, Cong Y, Wang A (2018) Selective production of renewable para-xylene by tungsten carbide catalyzed atom-economic cascade reactions. Angew Chem Int Ed 57(7):1808-1812 1723. Do Rêgo UA, Lopes T, Bott-Neto JL, Tanaka AA, Ticianelli EA (2018) Oxygen reduction electrocatalysis on transition metal – nitrogen modified tungsten carbide nanomaterials. J Electroanal Chem 810:222-231 1724. Hassan A, Ticianelli EA (2018) Activity and stability of dispersed multi-metallic Pt-based catalysts for CO tolerance in proton exchange membrane fuel cell anodes. An Acad Brasil Ciên 90(1/1):697-718 1725. He S, Boom J, Van Der Gaast R, Seshan K (2018) Hydro-pyrolysis of lignocellulosic biomass over alumina supported platinum, Mo2C and WC catalysts. Front Chem Sci Eng 12(1):155-161 1726. Jain A, Ramasubramaniam A (2018) Tuning core-shell interactions in tungsten carbide – Pt nanoparticles for the hydrogen evolution reaction. Phys Chem Chem Phys 20(36):2326223271 1727. Jin H, Chen J, Mao S, Wang Y (2018) Transition metal induced the contraction of tungsten carbide lattice as superior hydrogen evolution reaction catalyst. ACS Appl Mater Interfaces 10:22094-22101 1728. Karuppanan KK, Panthalingal MK, Biji P (2018) Nanoscale catalyst support materials for proton-exchange membrane fuel cells. In: Hussain CM (ed) Handbook of nanomaterials for industrial applications, 468-495. Elsevier, Amsterdam, Oxford

670

2 Tungsten Carbides

1729. Lei D, Nie M, Cao Y, Zuo W, Tian X, Zhao Z, Li Q (2018) Properties of AuPdPt-WC/C nanocomposite catalyst in simulated sea water solution for hydrogen evolution. Mater Res Innov 22(4):183-186 1730. Liu C, Wen Y, Lin L, Zhang H, Li X, Zhang S (2018) Facile in situ formation of high efficiency nanocarbon supported tungsten carbide nanocatalysts for hydrogen evolution reaction. Int J Hydrogen Energy 43:15650-15658 1731. Liu S, Wang C, Dong S, Hou H, Wang B, Wang X, Chen X, Cui G (2018) A mesoporous tungsten carbide nanostructure as a promising cathode catalyst decreases overpotential in LiO2 batteries. RSC Adv 8:27973-27978 1732. Liu Z, Huo X, Xi K, Li P, Yue L, Huang M, Suo G, Xu L, Wang W, Qu X (2018) Thickness controllable and mass produced WC@C@Pt hybrid for efficient hydrogen production. Energy Storage Mater 10:268-274 1733. Li X, Yun S, Zhang C, Fang W, Huang X, Du T (2018) Application of nanoscale transition metal carbides as accelerants in anaerobic digestion. Int J Hydrogen Energy 43:1926-1936 1734. Li Y-Y, Huang L-Z, Cai X-W, Chen Z-Y, Liu W-M, Shi M-Q (2018) In situ synthesis of sheet WC/C and its application in methanol oxidation. Chin J Inorg Chem 34(8):1437-1447 (in Chinese) 1735. Ma Y-Y, Lang Z-L, Yan L-K, Wang Y-H, Tan H-Q, Feng K, Xia Y-J, Zhong J, Liu Y, Kang Z-H, Li Y-G (2018) Highly efficient hydrogen evolution triggered by a multiinterfacial Ni/WC hybrid electrocatalyst. Energy Environ Sci 11(8):2114-2123 1736. Morozov MA, Fedushchak TA, Akimov AS, Mikubaeva EV, Zhuravkov SP, Vosmerikov AV (2018) Thermo-catalytic conversion of petroleum paraffin in the presence of tungsten carbide powders. In: Proc. Int. symp. on hierarchical materials “Development and applications for new technologies and reliable structures”, Tomsk, Russian Federation, 1-5 Oct 2018. AIP Conf Proc 2051:020203 (8 pp.) 1737. Towannang M, Thiangkaew A, Maiaugree W, Ratchaphonsaenwong K, Jarernboon W, Pimanpang S, Amornkitbamrung V (2018) Thermally deposited palladium – tungsten carbide and platinum – tungsten carbide counter electrodes for a high performance dye-sensitized solar cell based on organic T–/T2 electrolyte. J Nanosci Nanotechnol 18(2):1207-1214 1738. Tong Y-J, Wu S-Y, Chen H-T (2018) Adsorption and reaction of CO and H2O on WC (0001) surface: a first principles investigation. Appl Surf Sci 428:579-585 1739. Venkatesan K, He S, Seshan K, Selvam P, Vinu R (2018) Selective production of aromatic hydrocarbons from lignocellulosic biomass via catalytic fast hydropyrolysis using W2C/γ-Al2O3. Catal Commun 110:68-73 1740. Wang F, Jiang J, Wang K, Zhai Q, Sun H, Liu P, Feng J, Xia H, Ye J, Li Z, Li F, Xu J (2018) Activated carbon supported molybdenum and tungsten carbides for hydrotreatment of fatty acids into green diesel. Fuel 228:103-111 1741. Wang L, Zhu S, Marinkovic N, Kattel S, Shao M, Yang B, Chen JG (2018) Insight into the synergistic effect between nickel and tungsten carbide for catalysing urea electrooxidation in alkaline electrolyte. Appl Catal B 232:365-370 1742. Wang SL, Zhu Y, Luo X, Huang Y, Chai J, Wong TI, Xu GQ (2018) 2D WC/WO3 heterogeneous hybrid for photocatalytic decomposition of organic compounds with vis-NIR light. Adv Funct Mater 28:1705357 (8 pp.) 1743. Won BD, Jeong MH, Kim MH, Chung C-H, Moon DJ, Suh Y-W, Baik JH, Bae JW (2018) Rh-Mn / tungsten carbides for direct synthesis of mixed alcohols from syngas: effect of tungsten carbide phases. Micropor Mesopor Mater 255:44-52 1744. Wu K, Wang Y, Cui W, Ruan B, Wu M (2018) Synthesis of transition metal (VIB) compounds catalysts as counter electrodes in dye-sensitized solar cells. Ionics 24:883-890 1745. Zhong S-W, Hu X-C, Yu Y, Yu C-L, Zhou Y (2018) Core-shell hierarchical tungsten carbide composite microspheres towards methanol electrooxidation. J Fuel Chem Technol 46(5):585-591 (in Chinese)

References

671

1746. Do Rêgo UA, Lopes T, Bott-Neto JL, Gómez-Marin AM, Tanaka AA, Ticianelli EA (2019) Non-noble Fe-Nx/C electrocatalysts on tungsten carbides / N-doped carbons for the oxygen reduction reaction. Electrocatal 10:134-148 1747. Fang H, Roldan A, Tian C, Zheng Y, Duan X, Chen K, Ye L, Leoni S, Yuan Y (2019) Structural tuning and catalysis of tungsten carbide for the regioselective cleavage of C-O bonds. J Catal 369:283-295 1748. Göhl D, Garg A, Paciok P, Mayrhofer KJJ, Heggen M, Shao-Horn Y, Dunin-Borkowski RE, Román-Leshkov Yu, Ledendecker M (2020) Engineering stable electrocatalysts by synergistic stabilization between carbide cores and Pt shells. Nature Mater 19(3):287-291 1749. Gromov NV, Zhdanok AA, Medvedeva TB, Lukoyanov IA, Poluboyarinov VA, Taran OP, Parmon VN, Timofeeva MN (2019) Self-propagating high-temperature synthesis of materials based on tungsten carbide for one-pot hydrolysis-hydrogenolysis of cellulose into ethylene glycol and 1,2-propylene glycol. J Siberian Fed Univ Chem 2(12):269-281 1750. Huang L-Z, Luo X-G, Jiang Y-K, Mao X-B, Shi M-Q (2019) Oxygen deficiency assisted synthesis of network-like tungsten carbide – carbon nanotubes composites for methanol oxidation. Ceram Int 45:16976-16981 1751. Hussain S, Vikraman D, Feroze A, Song W, An K-S, Kim H-S, Chun S-H, Jung J (2019) Synthesis of Mo2C and W2C nanoparticle electrocatalysts for the efficient hydrogen evolution reaction in alkali and acid electrolytes. Front Chem 7:716 (11 pp.) 1752. Hu J, Li K, Mao X, Xu P, Liu D, Tan C, Chen Y, Liu X (2019) Preparation of spherical WC-W2C composite powder via noble metal – free catalytic electroless nickel plating for selective laser melting. Mater Res Express 6:125627 (12 pp.) 1753. Hu Y, Yu B, Li W, Ramadoss M, Chen Y (2019) W2C nanodot – decorated CNT networks as a highly efficient and stable electrocatalyst for hydrogen evolution in acidic and alkaline media. Nanoscale 11(11):4876-4884 1754. Li J, Huang H-C, Wang J, Zhao Y, Chen J, Bu Y-X, Chen S-B (2019) Polymeric tungsten carbide nanoclusters: structural evolution, ligand modulation and assembled nanomaterials. Nanoscale 11(42):19903-19911 1755. Ma Y, Lang Z, Du J, Yan L, Wang Y, Tan H, Khan SU, Liu Y, Kang Z, Li Y (2019) A switchable-selectivity multiple-interface Ni-WC hybrid catalyst for efficient nitroarene reduction. J Catal 311:174-182 1756. Mehdad A. Jentoft RE, Jentoft FC (2019) Single-phase mixed molybdenum-tungsten carbides: synthesis, characterization and catalytic activity for toluene conversion. Catal Today 323:112-122 1757. Shao M, Chen W, Ding S, Lo KH, Zhong X, Yao L, Ip WF, Xu B, Wang X, Pan H (2019) WXy/g-C3N4 (WXy = W2C, WS2, or W2N) composites for highly efficient photocatalytic water splitting. ChemSusChem 12(14):3355-3362 1758. Tong R, Sun Z, Wang X, Wang S, Pan H (2019) Ultra-fine WC1–x nanocrystals: an efficient co-catalyst for the significant enhancement of photocatalytic hydrogen evolution on g-C3N4. J Phys Chem C 123:26136-26144 1759. Wang T, Xu M, Chen W, Li X, Li F, Wang X, Li Y, Liu D, Wang E (2019) Polyoxometalate-derived multi-component X/W2C@X,N-C (X = Co, Si, Ge, B and P) nanoelectroncatalysts for efficient triiodide reduction in dye-sensitized solar cells. Chem Eur J 25:1-9 1760. Wei X, Li N (2019) Tungsten carbide / carbon composites coated with little platinum nanoparticles derived from the redox reaction between in situ synthesized WC1–x and chloroplatinic acid as the electrocatalyst for hydrogen evolution reaction. Appl Surf Sci 463:1154-1160 1761. Yang Z, Chen M, Xia M, Wang M, Wang X (2019) An effective and durable interface structure design for oxygen reduction and methanol oxidation electrocatalyst. Appl Surf Sci 487:655-663

672

2 Tungsten Carbides

1762. Zhang Q, Luo F, Hu H, Xu R, Qu K, Yang Z, Xu J, Cai W (2019) A robust electrocatalytic activity toward the hydrogen evolution reaction from W/W2C hetero-structured nanoparticles coated with a N, P dual-doped carbon layer. Chem Commun 55(65):9665-9668 1763. Zhang Y, Zhang M, Tang L, Wang J, Zhu Y, Feng C, Deng Y, He W, Hu Y (2020) Platinum like co-catalysts tungsten carbide loaded hollow tubular g-C3N4 achieving effective space separation of carriers to degrade antibiotics. Chem Eng J 391:123487 (12 pp.) 1764. Zhao T, Gao J, Wu J, He P, Li Y, Yao J (2019) Highly active cobalt / tungsten carbide @ N-doped porous carbon nanomaterials derived from metal-organic frameworks as bifunctional catalysts for overall water splitting. Energy Technol 7(4):1800969 (10 pp.) 1765. Zhao Y, Zhang X, Yang Z (2019) Activation mechanisms of silver toward CO oxidation by tungsten carbide substrate: a density functional theory study. Phys Lett A 383:2436-2442 1766. Zhou Y, Li X, Yu C, Hu XC, Yin Y, Guo S, Zhong S (2019) Synergistic and durable PtWC catalyst for methanol electrooxidation in ionic liquid aqueous solution. ACS Appl Energy Mater 2:8459-8463 1767. Brković SM, Marčeta-Kaninski MP, Lausević PZ, Saponjić AB, Radulović AM, Rakić AA, Pašti IA, Nikolić VM (2020) Non-stoichiometric tungsten carbide-oxide – supported PtRu anode catalysts for PEM fuel cells – from basic electrochemistry to fuel cell performance. Int J Hydrogen Energy 45(27):13929-13938 1768. Chen Z, Gong W, Cong S, Wang Z, Song G, Pan T, Tang X, Chen J, Lu W, Zhao Z (2020) Eutectoid-structured WC/W2C heterostructures: a new platform for long-term alkaline hydrogen evolution reaction at low overpotentials. Nano Energy 68:104335 (9 pp.) 1769. Fang Y, Zhang T, Wu Y, Liu Y, Guan J, Du X, Wang L, Zhang M (2020) Stacked Co6W6C nanocrystals anchored on N-doping carbon nanofibers with excellent electrocatalytic performance for HER in wide range pH. Int J Hydrogen Energy 45:1901-1910 1770. Gao Y, Cheng J, Chen P, Wei B, Gao D, Xu D (2020) Novel combustion-carbonization preparation of mesoporous tungsten carbide as a highly active catalyst for oxygen reduction. New J Chem 44(10):4004-4010 1771. Huang J, Hong W, Li J, Wang B, Liu W (2020) High-performance tungsten carbide electrocatalysts for the hydrogen evolution reaction. Sustain Energy Fuels 4(3):1078-1083 1772. Lewandowski M, Szymańska-Kolasa A, Sayag C, Djéga-Mariadassou G (2020) Activity of molybdenum and tungsten oxycarbides in hydrodenitrogenation of carbazole leading to isomerization secondary reaction of bicyclohexyl. Results using bicyclohexyl as feedstock. Appl Catal B 261:118239 (12 pp.) 1773. Li J, You S, Liu M, Zhang P, Dai Y, Yu Y, Ren N, Zou J (2020) ZIF-8-derived carbon thin layer protected WC/W24O68 micro-sized rods with enriched oxygen vacancies as efficient Pt co-catalysts for methanol oxidation and oxygen reduction. Appl Catal B 265:118574 (11 pp.) 1774. Meng C, Li R, Ning Y, Pavlovska A, Bauer E, Fu Q, Bao X (2020) Visualizing formation of tungsten carbide model catalyst and its interaction with oxygen. ChemCatChem 12:10361045 1775. Morse JR, Juneau M, Baldwin JW, Porosoff MD, Willauer HD (2020) Alkali promoted tungsten carbide as a selective catalyst for the reverse water gas shift reaction. J CO2 Utiliz 35:38-46 1776. Na H, Choi H, Oh J-W, Kim DB, Cho YS (2020) In situ processed tungsten carbide / carbon black – supported platinum electrocatalysts for enhanced electrochemical stability and activity. Green Chem 22(6):2028-2035 1777. Nia NS, Guillén-Villafuerte O, Griesser C, Manning G, Kunze-Liebhäuser J, Arévalo C, Pastor E, García G (2020) W2C-supported PtAuSn – a catalyst with the earliest ethanol oxidation onset potential and the highest ethanol conversion efficiency to CO2 known till date. ACS Catal 10:1113-1122 1778. Xia M, Guo H-Y, Wu J-L, Hussain MI, Zhang N (2020) A versatile route for the synthesis of Pt-loaded mesoporous CNT heterostructure. Fullerenes Nanotubes Carbon Nanostruct 28(5):377-380

References

673

1779. Zhang J, She Y (2020) Unveiling the decomposition mechanism of formic acid on Pd / WC (0001) surface by using density function theory. Chin J Catal 41(3):415-425 1780. Zhang J, She Y (2020) Decomposition mechanism of HCOOH on Pd / WC (0001) surfaces: a density functional theory study. Mol Simul 46(13):947-956 1781. Zhang J, She Y (2020) Mechanism of methanol decomposition on Pd / WC (0001) surface unveiled by first principles calculations. Front Chem Sci Eng 14(6):1052-1064 1782. Semenov-Kobzar AA, Obolonchik VA, Akinina ZS (1969) Stability of transition metal carbides under anodic polarization conditions. Powder Metall Met Ceram 8(5):399-402 1783. Mirumachi K, Hijikata K (1972) Corrosion of cemented carbides. J Jpn Soc Powder Powder Metall 19(1):18-22 (in Japanese) 1784. Palanker VSh, Baybatyrov EN, Sokolsky DV (1975) A thermodesorption method for the investigation of hydrogen adsorption on electrodes, its application to tungsten carbide along with electrochemical methods. Electrochim Acta 20(1):51-55 1785. Sokolsky DV, Palanker VSh, Baybatyrov EN (1975) Electrochemical hydrogen reaction on tungsten carbide. Electrochim Acta 20(1):71-77 1786. Kretzschmar C, Wiesner K (1978) Performance of tungsten carbide anodes and iron phthalocyanine cathodes in fuel cells with sulphuric acid electrolyte. Russ J Electrochem 14(9):1160-1163 1787. Cavalotti P, Colombo D, Ducati U, Jemmi G (1979) Elettrodi per pile a combustibile idrogeno-ossigeno (Hydrogen-oxygen electrodes for fuel cells). Rivista Combust 33(3-4):9397 (in Italian) 1788. Sedletskii RV, Sibirkova VT (1979) Chronovoltamperometry of powdered substances on a stationary inert electrode. Tungsten carbide and nickel. Russ J Electrochem 15(6):679-685 1789. Ghandehari MH (1980) Anodic behaviour of cemented WC – 6 % Co alloy in phosphoric acid solutions. J Electrochem Soc 127(10):2144-2147 1790. Zóltowski P (1980) Hydrogen evolution reaction on smooth tungsten carbide electrodes. Electrochim Acta 25(12):1547-1554 1791. Vijh AK, Bélanger G, Jacques R (1981) Electrochemical reactions on some cemented metal carbides. J Power Sources 6(3):229-243 1792. Merkulova ND, Boikova GV, Zhutaeva GV, Tarasevich MR, Shumilova NA (1984) Selectivity of tungsten carbide and platinum in the cathodic reactions of the sulphate cycle. Russ J Appl Chem 57(10/1):2087-2091 1793. Aleksandrova AN, Freid MKh, Zyatkova LA (1985) Electrochemical behaviour of tungsten carbide in acidic solutions. Russ J Appl Chem 58(5/1):945-949 1794. Tsirlina GA, Petrii OA (1985) Mechanism of hydrogen evolution of smooth stoichiometric tungsten carbide. Russ J Electrochem 21(5):653-660 1795. Tsirlina GA, Petrii OA (1985) Electrochemical behaviour of disperse tungsten semicarbide. Russ J Electrochem 21(6):761-765 1796. Zóltowski P (1986) The mechanism of the activation process of the tungsten carbide electrode. Electrochim Acta 31(1):103-111 1797. Tsirlina GA, Petrii OA (1987) Nature of the processes occurring at anodic potentials on tungsten carbides. Russ J Electrochem 23(1):35-43 1798. Tsirlina GA, Petrii OA (1987) Role of carbon deficiency and anodic activation in the electrochemistry of carbide materials. Electrochim Acta 32(4):637-647 1799. Hofman B, Scholl H (1988) Voltammetric characteristics of tungsten carbide based electrodes in some non-aqueous and mixed solvents. Russ J Electrochem 24(9):1113-1118 1800. Hofman B, Scholl H (1988) Voltammetry of mixed tungsten-titanium carbide in nonaqueous and mixed solvents. Russ J Electrochem 24(9):1175-1178 1801. Scholl H, Hofman B (1990) Anodic behaviour of carbide electrodes of the type (WC, M) (M = Fe, Co, Ni) in methanol. Russ J Electrochem 26(6):691-693 1802. Tomlinson WJ, Ayerst NJ (1989) Anodic polarization and corrosion of WC-Co hardmetals containing small amounts of Cr3C2 and/or VC. J Mater Sci 24:2348-2354

674

2 Tungsten Carbides

1803. Masuzawa T, Kimura M (1991) Electrochemical surface finishing of tungsten carbide. CIRP Ann Manuf Technol 40(1):199-202 1804. Streng B, Möbius A, Wiesner K, Nikolova V, Nikolov I, Vitanov T (1991) Electrolytic recovery of iron from pickling solutions by tungsten carbide gas-diffusion anodes J Appl Electrochem 21:317-320 1805. Korolev YuM, Polukarov YuM, Zanozin VM (1992) Decarburization of tungsten carbide during electrochemical application of cobalt coatings in aqueous solutions. Powder Metall Met Ceram 31(6):476-479 1806. Nikolov I, Papazov G, Naidenov V (1992) Activity and corrosion of tungsten carbide recombination electrodes during lead/acid battery operation. J Power Sources 40(3):333-340 1807. Nikolov I, Papazov G, Naidenov V (1992) Performance of tungsten carbide recombination electrodes under various operating conditions. J Power Sources 40(3):341-346 1808. . Scholl H, Hofman B, Rauscher A (1992) Anodic polarization of cemented carbides of the type [(WC, M): M = Fe, Ni or Co] in sulphuric acid solution. . Electrochim Acta 37(3):447452 1809. Takatani Y, Tomita T, Harada Y (1992) Corrosion behaviour of carbides in sodium chloride solution. J Soc Mater Sci Jpn 41(468):1348-1353 (in Japanese) 1810. Nikolova V, Nikolov I, Vitanov T, Wiesner K (1993) Behaviour of tungsten carbide hydrogen-diffusion electrodes in chloride etching solutions. J Appl Electrochem 23:12681272 1811. Scholl H, Hofman B, Kupis J, Polański K (1994) Anodic dissolution of cemented carbides of the type [(WC, M): M = Co, Ni or Fe] in sulphuric acid solution. Electrochemical impedance spectroscopy. Electrochim Acta 39(1):115-117 1812. Wentzel EJ (1995) Erosion-corrosion resistance of tungsten carbide hard metals with different binder compositions. MSc thesis, University of Cape Town, South Africa 1813. Human AM, Exner HE (1996) Electrochemical behaviour of tungsten carbide hardmetals. Mater Sci Eng A 209:180-191 1814. Wiçcek B (1996) Electrochemical hydrogen evolution reaction on tungsten carbide. Polish J Chem 70(3):343-353 1815. Wentzel EJ, Allen C (1997) The erosion-corrosion resistance of tungsten carbide hard metals. Int J Refract Met Hard Mater 15:81-87 1816. Guilemany JM, Fernández J, De Paco JM, Sánchez J (1998) Corrosion resistance of HVOF WC-Co and TiC-Ni-Ti coatings sprayed on commercial steel. Surf Eng 14(2):133-135 1817. Satyvaldiev A, Sagyndykov Zh, Abdukarimov AA, Osmonkanova GN (1999) Electrochemical dissolution of hard alloys based on tungsten carbide. Russ J Appl Chem 72(9):16431644 1818. Trueman AR, Schweinsberg DP, Hope GA (1999) A study of the effect of cobalt additions on the corrosion of tungsten carbide / carbon steel metal matrix composites. Corros Sci 41:1377-1389 1819. Imasato S, Sakaguchi S, Sugano K, Hayashi Y (2000) Research of corrosion properties by potentiostatic polarization of WC-Ni-Cr3C2 cemented carbide. J Jpn Soc Powder Powder Metall 47(5):541-546 (in Japanese) 1820. Imasato S, Sakaguchi S, Okada T, Hayashi Y (2001) Effect of WC grain size on corrosion resistance of WC-Co cemented carbide. J Jpn Soc Powder Powder Metall 48(7):609-615 (in Japanese) 1821. Lausecker U (2001) Tungsten carbide resists corrosion 80 times better. Adv Mater Processes 159(7):9 1822. Malyshev VV, Kushkhov HB, Shapoval VI (2002) High-temperature electrochemical synthesis of carbides, silicides and borides of VI group metals in ionic melts. J Appl Electrochem 32:573-579 1823. Bozzini B, De Gaudenzi GP, Fanigliulo A, Mele C (2003) Anodic behaviour of WC-Co type hardmetal. Mater Corros 54:295-303

References

675

1824. Bozzini B, De Gaudenzi GP, Fanigliulo A, Mele C (2004) Electrochemical oxidation of WC in acidic sulphate solution. Corros Sci 46:453-469 1825. Malyshev VV, Hab AI (2004) Separation of cobalt and tungsten carbide by anodic dissolution of solid alloys in phosphoric acid. Mater Sci 40(4):555-559 1826. Morishita T, Soneda Y, Hatori H, Inagaki M (2007) Carbon coated tungsten and molybdenum carbides for electrode of electrochemical capacitor. Electrochim Acta 52:24782484 1827. Guo Z, Zhu X, Huang H (2008) Electrochemical properties of Al/Pb-WC-ZrO2 composite coatings. In: Hu X, Fillery B, Qasim T, Duan K (eds) Structural integrity and failure. Proc. Int. conf. on structural integrity and failure (SIF 2008), Perth, Western Australia, 9-11 July 2008. Adv Mater Res 41-42:369-375 1828. Hosoda Y, Sunada S, Yamamoto T, Majima K (2008) Influence of Co content on corrosion characteristics of WC-Cr3C2-Co based alloys. J Jpn Soc Powder Powder Metall 55(12):836-841 (in Japanese) 1829. Malyshev VV, Gab AI, Gaune-Escard M (2008) Initial stages of nucleation of molybdenum and tungsten carbide phases in tungstate-molybdate-carbonate melts. J Appl Electrochem 38:315-320 1830. Boonyongmaneerat Y, Saengkiettiyut K, Saenapitak S, Sangsuk S (2009) Effects of WC addition on structure and hardness of electrodeposited Ni-W. Surf Coat Technol 203:35903594 1831. Ma L-L (2010) Corrosion behaviour of cemented carbide in water. Mater Sci Eng Powder Metall 15(6):635-639 (in Chinese) 1832. Patowari PK, Mishra UK, Saha P, Mishra PK (2010) Surface modification of C40 steel using WC-Cu P/M green compact electrodes in EDM. Int J Manuf Technol Manag 21(12):83-98 1833. Malyshev VV, Gab AI (2011) High-temperature galvanic coatings of molybdenum and tungsten and their carbides from ionic melts: electrodeposition from halide-oxide and oxide melts. Protect Met Phys Chem Surf 47(5):629-637 1834. Malyshev VV, Gab AI (2011) High-temperature electrometallurgical synthesis of tungsten and molybdenum carbides. Russ J Non-Ferr Met 52(3):262-265 1835. Potgieter JH, Thanjekwayo N, Olubambi P, Maledi N, Potgieter-Vermaak SS (2011) Influence of Ru additions on the corrosion behaviour of WC-Co cemented carbide alloys in sulphuric acid. Int J Refract Met Hard Mater 29:478-487 1836. Yeo S, Kim D-J, Park J-W (2011) Enhanced corrosion resistance of WC-Co with an ion beam mixed silicon carbide coating. Int J Refract Met Hard Mater 29:582-585 1837. Malyshev VV, Gab AI (2012) High-temperature galvanic coatings of molybdenum, tungsten and carbides thereof ionic solutions. II. Physico-chemical properties. Protect Met Phys Chem Surf 48(2):238-242 1838. Torabi A, Etsell TH, Semagina N, Sarkar P (2012) Electrochemical behaviour of tungsten carbide – based materials as candidate anodes for solid oxide fuel cells. Electrochim Acta 67:172-180 1839. Torabi A, Etsell TH (2012) Tungsten carbide based anodes for solid oxide fuel cells: preparation, performance and challenges. J Power Sources 212:47-56 1840. Xu RD, Huang LP, Zhou JF, Zhan P, Guan YY, Kong Y (2012) Effects of tungsten carbide on electrochemical properties and microstructural features of Al/Pb-PANI-WC composite inert anodes used in zinc electrowinning. Hydrometall 125-126:8-15 1841. Chen Z, Xie K, Hong X (2013) Anode behaviour of Sn/WC/graphene triple layered composite for lithium-ion batteries. Electrochim Acta 108:674-679 1842. Nikmanesh S, Doroodmand MM, Sheikhi MH, Zarifikar A, Zahabi A (2013) Specific CH4 gas sensor based on tungsten carbide / SnO2 core-shell modified interdigitated electrode. In: Proc. 21st Iranian conf. on electrical engineering (ICEE 2013), Mashhad, Iran, 14-16 May 2013, 6599583 (7 pp.). Institute of Electrical and Electronics Engineers, New York

676

2 Tungsten Carbides

1843. Azzura I (2014) Corrosion behaviour of WC-Co in high sulphate content. In: Proc. Int. conf. on key engineering materials (ICKEM 2014), Bali, Indonesia, 22-23 Mar 2014. Adv Mater Res 911:82-86 1844. Guan YY, Xu RD, Huang LP, Chen H, He S (2014) Effects of tungsten carbide on electrochemical properties of composite inert anodes. Mater Sci Technol 22(5):66-72 (in Chinese) 1845. Jiang Y, Yang JF, Xie ZM, Gao R, Fang QF (2014) Corrosion resistance of W-Cr-C coatings fabricated by spark-plasma sintering method. Surf Coat Technol 254:202-206 1846. Katiyar PK, Randhawa NS, Hait J, Jana RK, Singh KK, Mankhand TR (2014) Anodic dissolution behaviour of tungsten carbide scraps in ammoniacal media. In: Proc. 17th Int. conf. on non-ferrous minerals and metals (ICNFM 2013), Ranchi, India, 5-6 July 2013. Adv Mater Res 828:11-20 1847. Lin N, He Y, Wu C, Liu S, Xiao X, Jiang Y (2014) Influence of TiC additions on the corrosion behaviour of WC-Co hardmetals in alkaline solution. Int J Refract Met Hard Mater 46:52-57 1848. Malyshev VV, Gab AI, Pisanenko AD, Soloviev VV, Chernenko LA (2014) Electrodeposition of tungsten and molybdenum carbides onto the surface of disperse dielectric and semiconductor materials. Materialwiss Werkstofftech 45(1):51-56 1849. Malyshev VV, Shakhnin D, Gab AI, Gaune-Escard M, Astrelin IM (2014) Effect of electrolysis parameters on the coating composition and properties during electrodeposition of tungsten carbides and zirconium diborides. In: Gaune-Escard M, Haarberg GM (eds) Molten salts chemistry and technology, pp. 295-301. John Wiley, Chichester, UK 1850. Malyshev VV, Shakhnin D, Gab AI, Gaune-Escard M, Astrelin IM (2014) Galvanic coatings of molybdenum and tungsten carbides from oxide melts: electrodeposition and initial stages of nucleation. In: Gaune-Escard M, Haarberg GM (eds) Molten salts chemistry and technology, pp. 303-317. John Wiley, Chichester, UK 1851. Tomás-García AL, Jensen JO, Bjerrum NJ, Li Q (2014) Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid. Electrochim Acta 137:639-646 1852. Yang H-T, Chen B-M, Liu H-R, Guo Z-C, Zhang Y-C, Li X, Xu R-D (2014) Effects of manganese nitrate concentration on the performance of an aluminium substrate β-PbO2MnO2-WC-ZrO2 composite electrode material. Int J Hydrogen Energy 39:3087-3099 1853. Yang H-T, Chen B-M, Guo Z-C, Liu H-R, Zhang Y-C, Huang H, Xu R-D, Fu R-C (2014) Effects of current density on preparation and performance of Al / conductive coating / αPbO2-CeO2-TiO2 / β-PbO2-MnO2-WC-ZrO2 composite electrode materials. Trans Nonferr Met Soc China 24:3394-3404 1854. Brookes KJA (2015) Corrosion damage in WC/Co. Met Powder Rep 70(2):82-87 1855. Farahmand P, Kovacevic R (2015) Corrosion and wear behaviour of laser cladded Ni-WC coatings. Surf Coat Technol 276:121-135 1856. Kamdi Z, Phang CY, Ahmad H (2015) Corrosion behaviour of WC-Co cermet coatings. In: Yunos NFDM, Zakaria Z, Munusamy SRRA, Ying LB, Jamil NH, Halif NA (eds) Proc. Int. conf. on functional materials and metallurgy (ICoFM 2014), Pulau Pinang, Malaysia, 1718 Sep 2014. Mater Sci Forum 819:87-90 1857. Malyshev VV, Soloviev VV, Chernenko LA, Rozhko VN (2015) Management of composition cathodic products in the electrolysis of molybdenum-, tungsten- and carbonbearing halogenide-oxide and oxide melts. Materialwiss Werkstofftech 46(1):5-9 1858. Oliveira AB, Bastos AC, Fernandes CM, Pinho CMS, Senos AMR, Soares E, Sacramento J, Zheludkevich MI, Ferreira MGS (2015) Corrosion behaviour of WC 10 % AISI 304 cemented carbides. Corros Sci 100:322-331 1859. Xi XL, Si G, Nie ZR, Ma LW (2015) Electrochemical behaviour of tungsten ions from WC scrap dissolution in a chloride melt. Electrochim Acta 184:233-238 1860. Zhang L, Wan Q-L, Huang B-Y, Liu Z-M, Zhu J-F (2015) Effects of WC grain sizes and aggressive media on the electrochemical corrosion behaviours of WC-Co cemented carbides.

References

677

In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2015), Reims, France, 4-7 Oct 2015, 124663 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 1861. Bae KY, Lim CW, Cho SH, Kim BH, Yoon WY (2016) Tungsten carbide – coated LiV3O8 cathodes with enhanced electrochemical properties for lithium metal batteries. J Nanosci Nanotechnol 16(10):10613-10619 1862. Bozzini B, Busson B, De Gaudenzi GP, Humbert C, Mele C, Tedeschi S, Tadjeddine A (2016) Corrosion of cemented carbide grades in petrochemical slurries. Part I. Electrochemical adsorption of CN–, SCN– and MBT: a study based on in situ SFG. Int J Refract Met Hard Mater 60:37-51 1863. He S-W, Xu R-D, Wang J, Han S, Chen B (2016) Preparation and electrochemical properties of Pb – 0.3 wt% Ag / Pb-WC composite inert anodes. J Wuhan Univ Technol Mater Sci Ed 31(4):811-817 1864. Kamdi Z, Voisey KT (2016) Corrosion mechanism of tungsten carbide – based coatings in different aqueous media. In: Proc. 24th scientific conf. of the Microscopy Society of Malaysia (SCMSM 2015), Malacca, Malaysia, 2-4 Dec 2015. Key Eng Mater 694:167-171 1865. Li L, Sui H, Zhang W, Li X, Yang K, Hagfeldt A, Wu M (2016) Mesoporous carbonimbedded W2C composites as flexible counter electrodes for dye-sensitized solar cells. J Mater Chem C 4(28):6778-6783 1866. Li M, Xi XL, Nie ZR, Ma L, Liu QQ (2016) Electrochemical extraction of tungsten derived from WC scrap and electrochemical properties of tungsten ion in LiCl-KCl molten salt. J Electrochem Soc 163(13):D728-D733 1867. Zhang L, Chen Y, Wan Q-L, Liu T, Zhu J-F, Tian W (2016) Electrochemical corrosion behaviours of straight WC-Co alloys: exclusive variation in grain sizes and aggressive media. Int J Refract Met Hard Mater 57:70-77 1868. Li ZW, Lin CG, Xie XC, Cao RJ, Lin ZK (2017) Selective electrolytic corrosion behaviours of WC in WC-Co cemented carbide. In: Han Y, Fan R, Xiong B, Liu X, Nie Z, Zhu M, Zhao J, Zhang J, Liu X (eds) Proc. 17th IUMRS Int. conf. in Asia (IUMRS-ICA 2016), Qingdao, China, 20-24 Oct 2016. Mater Sci Forum 898:1478-1484 1869. Li M, Liu QQ, Xi XL, Nie ZR (2017) A new green approach for recovery of metallic tungsten through electrolysis of tungsten carbide scrap anode in molten salts. In: Han Y, Fan R, Xiong B, Liu X, Nie Z, Zhu M, Zhao J, Zhang J, Liu X (eds) Proc. 17th IUMRS Int. conf. in Asia (IUMRS-ICA 2016), Qingdao, China, 20-24 Oct 2016. Mater Sci Forum 898:18711879 1870. Oishi T, Yaguchi M (2017) Influence of partial pressure of water vapour on anodic dissolution of tungsten from superhard alloy tools in molten sodium hydroxide. Int J Refract Met Hard Mater 69:254-258 1871. Xi XL, Xiao XJ, Nie ZR, Zhang LW, Ma LW (2017) Electrolytic separation of cobalt and tungsten from cemented carbide scrap and the electrochemical behaviour of metal ions. J Electroanal Chem 794:254-263 1872. Zhang W-B, Ma X-J, Kong L-B (2017) Nanocrystalline intermetallic tungsten carbide: nanoscaled solidoid synthesis, non-faradaic pseudocapacitive property and electrode material application. Adv Mater Interfaces 4(13):1700099 (10 pp.) 1873. Zhang Y, Guo Z (2017) Anodic behaviour and microstructure of Pb – Ca – 0.6 % Sn, Pb – Co3O4 and Pb – WC composite anodes during Cu electrowinning. J Alloys Compd 724:103111 1874. Anijdan SHM, Sabzi M, Asadian M, Jafarian HR (2019) Effect of sub-layer temperature during HFCVD process on morphology and corrosion behaviour of tungsten carbide coating. Int J Appl Ceram Technol 16(1):243-253 1875. Göhl D, Mingers AM, Geiger S, Schalenbach M, Cherevko S, Knossalla J, Jalalpoor D, Schüth F, Mayrhofer KJJ, Ledendecker M (2018) Electrochemical stability of hexagonal tungsten carbide in the potential window of fuel cells and water electrolysers investigated in a half-cell configuration. Electrochim Acta 270:70-76

678

2 Tungsten Carbides

1876. Huntsman P, Skeaff J, Pawlak M, Beaudoin R (2018) Transformation/dissolution characterization of tungsten and tungsten compounds for aquatic hazard classification. Integr Environ Assess Manag 14(4):498-508 1877. Nelwalani NB, Van Der Merwe J (2018) The effect of pH on slurry erosion-corrosion of tungsten carbide overlays alloyed with Ru. J Therm Spray Technol 27:483-499 1878. Wood RJK, Herd S, Thakare MR (2018) A critical review of the tribocorrosion of cemented and thermal sprayed tungsten carbide. Tribol Int 119:491-509 1879. Zhang LW, Nie ZR, Xi XL, Ma LW (2018) Electrochemical separation and extraction of cobalt and tungsten from cemented scrap. Separ Purif Technol 195:244-252 1880. Zhang LW, Nie ZR, Xi XL (2018) Preparation of tungsten nanoparticles from spent tungsten carbide by molten salt electrolysis. In: Han YF (ed) Proc. Chinese Materials Research Society conf. (CMC 2017), Yinchuan City, Ningxia, China, 6-12 July 2018. Mater Sci Forum 913:961-968 1881. Zhang LW, Nie ZR, Xi XL, Ma LW, Xiao XJ, Li M (2018) Electrochemical dissolution of tungsten carbide in NaCl-KCl-Na2WO4 molten salt. Metall Mater Trans B 49(1):334-340 1882. Zonensain O, Fadida S, Fisher I, Gao J, Danek M, Eizenberg M (2018) Thermal stability of atomic layer deposited WCxNy electrodes for metal oxide semiconductor devices. J Appl Phys 123(3):035101 (6 pp.) 1883. Göhl D, Rueß H, Pander M, Zeradjanin AR, Mayrhofer KJJ, Schneider JM, Erbe A, Ledendecker M (2020) Transition metal – carbon bond enthalpies as descriptor for the electrochemical stability of transition metal carbides in electrocatalytic applications. J Electrochem Soc 167(2):021501 (8 pp.) 1884. Kamimoto Y, Kasuga R, Takeshita K, Hagio T, Kuroda K, Ichino R, Deevanhxay P (2020) Electrochemical behaviour of tungsten carbide – cobalt alloy using molten hydroxide as electrolyte under low temperature. In: Proc. 5th 3R (Reduce-Reuse-Recycling) Int. scientific conf. on materials cycles and waste management (5th 3RINCs 2019), Bangkok, Thailand, 27 Feb – 1 Mar 2019. J Mater Cycles Waste Manag 22(2):348-353 1885. Kozina GK (1970) Issledovanie kontaktnogo vzaimodeistviya tugoplavkikh karbidov i materialov na ikh osnove s zhidkimi metallami i splavami (A study of the contact interaction of refractory carbides and materials on their basis with liquid metals and alloys). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 1886. Samsonov GV, Panasyuk AD, Kozina GK (1971) Smachivanie tugoplavkikh karbidov rasplavlennymi metallami i splavami (Wetting of refractory carbides by molten metals and alloys). In: Eremenko VN (ed) Fizicheskaya khimiya poverkhnostnykh yavlenii v rasplavakh (Physical chemistry of the surface phenomena in melts), pp. 206-208. Naukova Dumka, Kyiv (in Russian) 1887. Korniyenko K (2008) Carbon – iron – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. D, Part 2, pp. 327-356. Springer, Berlin, Heidelberg 1888. Bergström M (1977) The eta-carbides in the ternary system Fe-W-C at 1250 °C. Mater Sci Eng 27(3):257-269 1889. Uhrenius B (1980) Calculation of phase equilibria in the Fe-W-C system. Calphad 4(3):173-191 1890. Gustafson P (1987) A thermodynamic evaluation of the C-Fe-W system. Metall Trans A 18(2):175-188 1891. Rivlin VG (1985) Phase equilibria in iron ternary alloys. 19. Critical review of constitution of carbon – iron – tungsten system. Int Met Rev 30(6):259-274 1892. English JJ (1961) Binary and ternary phase diagrams of columbium, molybdenum, tantalum and tungsten. Technical Report DMIC-152, Contract AF-33(616)-7747, pp. 1-226. Defence Metals Information Centre, Battelle Memorial Institute, Columbus, Ohio

References

679

1893. Gabriel A, Pastor H, Deo DM, Basu S, Allibert CH (1986) New experimental data in the C-Fe-W, C-Co-W, C-Ni-W, C-Fe-Ni-W and C-Co-Ni-W cemented carbides systems and their application to sintering conditions. Int J Refract Met Hard Mater 5(4):215-221 1894. Raghavan V (1994) The C-Fe-W (carbon-iron-tungsten) system. J Phase Equilib 15(4):429-430 1895. Pollock CB, Stadelmaier HH (1970) The η carbides in the Fe-W-C and Co-W-C systems. Metall Trans A 1(4):767-770 1896. Panov VS, Chuvilin AM (2001) Tekhnologiya i svoistva spechennykh tverdykh splavov i izdelii iz nikh (Technology and properties of sintered hard alloys and their components). MISIS, Moscow (in Russian) 1897. Johansson T, Uhrenius B (1978) Phase equilibria, isothermal reactions and a thermodynamic study in the Co-W-C system at 1150°C. Met Sci 12(2):83-94 1898. Guillermet AF (1989) Thermodynamic properties of the Co-W-C system. Metall Trans A 20(5):935-956 1899. Nowotny H, Rogl P, Schuster JC (1982) Structural chemistry of complex carbides and related compounds. J Solid State Chem 44:126-133 1900. Uhrenius B, Carlsson B, Franzen T (1976) A study of the Co-W-C system at liquidus temperatures. Scand J Met 5(2):49-56 1901. Kruse O, Jansson B, Frisk K (2001) Experimental study of invariant equilibria in the CoW-C and Co-W-C-Me (Me = Ti, Ta, Nb) systems. J Phase Equilib 22(5):552-555 1902. Markström A, Sundman B, Frisk K (2005) A revised thermodynamic description of the Co-W-C system. J Phase Equilib Diff 26(2):152-160 1903. Bondar A, Bochvar N, Dobatkina T, Krendelsberger N (2010) Carbon – cobalt – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 2, pp. 249-289. Springer, Berlin, Heidelberg 1904. Gustafson P, Gabriel A, Ansara I (1987) Thermodynamic evaluation of the C-Ni-W system. Z Metallkd 78(2):151-156 1905. Fiedler M-L, Stadelmaier HH (1975) The ternary system Ni-W-C. Z Metallkd 66(7):402404 1906. Bochvar N, Rokhlin L (2010) Carbon – nickel – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 2, pp. 579-594. Springer, Berlin, Heidelberg 1907. Gaziev GA, Krylov OV, Roginskii SZ, Samsonov GV, Fokina EA, Yanovskii MI (1961) Degidrirovanie tsiklogeksana na nekotorykh karbidakh, boridakh i silitsidakh (Dehydrogenation of cyclohexane on some carbides, borides and silicides). Doklady AN SSSR 140(4):863-866 (in Russian) 1908. Grosheva VM, Samsonov GV (1966) Kataliticheskie svoistva nekotorykh tugoplavkikh soedinenii v reaktsii termicheskogo razlozheniya metana (Catalytic properties of some refractory compounds in the thermal decomposition of methane). Kinet Catal 7(5):892-894 (in Russian) 1909. Samsonov GV, Bulankova TG, Dodak PA, Prshedromirskaya EM, Sinelnikova VS, Sleptsov VM (1969) Kataliticheskie svoistva karbidov I silitsidov perekhodnykh metallov v reaktsii degidrirovaniya etilbenzola v stirol (Catalytic properties of transition metal carbides and silicides in the dehydrogenation of ethylbenzene to styrene). Kinet Catal 10(5):10571061 (in Russian) 1910. Kharlamov AI (1980) Priroda kataliticheskogo deistviya metallopodobnykh soedinenii d-metallov (The nature of the catalytic action of metal-like compounds of d-metals). Kinet Catal 21(1):245-251 (in Russian) 1911. Ilchenko NI, Chebotareva NP, Shvidak NV (1976) Oxidation of ammonia on transition metal carbides. React Kinet Catal Lett 4(3):343-349 1912. Kharlamov AI, Kosolapova TYa, Rafal AN, Kirillova NV (1980) Kataliticheskaya aktivnost metallopodobnykh karbidov v reaktsii okisleniya okisi ugleroda (Catalytic activity

680

2 Tungsten Carbides

of metal-like carbides in the oxidation reaction of carbon monoxide). Kinet Catal 21(3):721727 (in Russian) 1913. Svintsova LG, Shimanovskaya VV, Ilchenko NI, Golodets GI (1982) Okislenie okisi ugleroda na karbidakh perekhodnykh metallov (Oxidation of carbon monoxide on transition metal carbides). Kinet Catal 23(2):398-401 (in Russian) 1914. Kharlamov AI, Kirillova NV, Yatsimirskii VK (1980) Kinetics of CO oxidation over metal-like carbides. React Kinet Catal Lett 13(2):105-110 1915. Kharlamov AI, Kirillova NV, Yatsimirskii VK (1981) The catalytic properties of transition element carbides and nitrides in the oxidation of carbon monoxide. Theor Exp Chem 17(2):168-179 1916. Samsonov GV, Boiko PA (1969) Issledovanie vliyaniya dobavok karbidov perekhodnykh metallov IV-VI grupp na protsess vosstanovleniya osnovnogo uglekislogo nikelya vodorodom (A study of the effect of additions of transition metal carbides of IV-VI groups on the process of nickel hydroxide carbonate reduction with hydrogen). Zh Prikl Khim 42(6):1220-1224 (in Russian) 1917. Klimak ZA, Samsonov GV (1970) Vosstanovlenie okisi zheleza vodorodom v prisutstvii dobavok nekotorykh karbidov (Reduction of iron oxide with hydrogen in the presence of additives of some carbides). Kinet Catal 11(6):1394-1401 (in Russian) 1918. Oyama ST (1996) Introduction to the chemistry of transition metal carbides and nitrides. In: Oyama ST (ed) The chemistry of transition metal carbides and nitrides, pp. 1-27. Chapman & Hall, London, Glasgow 1919. Santhanam AT (1996) Application of transition metal carbides and nitrides in industrial tools. In: Oyama ST (ed) The chemistry of transition metal carbides and nitrides, pp. 28-52. Chapman & Hall, London, Glasgow 1920. Kral C, Lengauer W, Rafaja D, Ettmayer P (1998) Critical review on the elastic properties of transition metal carbides, nitrides and carbonitrides. J Alloys Compd 265:215-233 1921. Paderno YuB, Samsonov GV, Khrenova LM (1959) Vysokotemperaturnye spai geksaborida lantana i okisi toriya s tugoplavkimi metallami (High-temperature junctions of lanthanum hexaboride and thorium oxide with refractory metals). Elektron Tekh Ser SVCh Tekh (4):165-172 (in Russian) 1922. Voitovich RF (1971) Tugoplavkie soedineniya. Termodinamicheskie kharakteristiki. (Refractory compounds. Thermodynamic characteristics.) Naukova Dumka, Kyiv (in Russian) 1923. Schwarzkopf P, Glaser FW (1953) Struktur und chemische Eigenschaften der Boriden der Übergangsmetallen der vierten, fünften und sechsten Gruppe (Structure and chemical properties of the borides of transition metals of the fourth, fifth and sixth groups). Z Metallkd 44(8):353-358 (in German) 1924. Samsonov GV, Strashinskaya LV, Shiller ÉA (1962) Vzaimodeistvie metallopodobnykh karbidov, nitridov i boridov s zhidkimi metallami (The interaction of metal-like carbides, nitrides and borides with liquid metals). In: Tumanov VI (ed) Metallovedenie i tekhnologiya proizvodstva metallokeramicheskikh tverdykh splavov, tugoplavkikh metallov i soedinenii na ikh osnove (Metallography and production technology of metal-ceramic hard alloys, refractory metals and compounds based on them), pp. 156-162. Metallurgizdat, Moscow (in Russian) 1925. Samsonov GV, Strashinskaya LV, Shiller ÉA (1962) Kontaktnoe vzaimodeistvie metallopodobnykh karbidov, nitridov i boridov s tugoplavkimi metallami pri vysokikh temperaturakh (The contact interaction of metal-like carbides, nitrides and borides with refractory metals at high temperatures). Izv AN SSSR OTN Metall Toplivo (5):167-180 (in Russian) 1926. Samsonov GV (1959) Kharakter vzaimodeistviya boridov titana, tsirkoniya i volframa s ikh karbidami (Character of the interaction of titanium, zirconium and tungsten borides with their carbides). In: Frantsevich IN (ed) Voprosy poroshkovoi metallurgii i prochnosti

References

681

materialov (Problems of powder metallurgy and strength of materials), Vol. 7, pp. 72-99. UkrSSR Academy of Sciences, Kyiv (in Russian) 1927. Glaser FW (1952) Contribution to the metal-carbon-boron systems. J Met 4(4):391-396 1928. Raine T, Edwards R (1952) Die Löslichkeit verschiedenen Karbide in den Bindemetallen Kobalt, Nickel und Eisen bei 1250 °C (The solid solubility of some stable carbides in the binding metal cobalt, nickel and iron at 1250 °C). Angew Chem 64(17):483 (in German) 1929. Edwards R, Raine T (1953) Die Löslichkeit verschiedenen Karbide in den Bindemetallen (The solid solubility of various carbides in the binding metals). In: Benesovsky F (ed) Pulvermetallurgie (Powder metallurgy). Proc. 1st Plansee seminar, Reutte, Tyrol, 22-26 June 1952, Vol. 1, pp. 232-243. Springer, Wien (in German) 1930. Rautala P, Norton JT (1952) Tungsten-cobalt-carbon system. J Met 4(10):1045-1050 1931. Chaporova IN, Chernyavskii KS (1975) Struktura spechennykh tverdykh splavov (Structure of sintered hard alloys). Metallurgiya, Moscow (in Russian) 1932. Mukha II (1981) Tverdye splavy v melkoseriinom proizvodstve (Hard alloys in smallscale production). Naukova Dumka, Kyiv (in Russian) 1933. Borisova AL, Evtushenko OV (1979) Diffusional processes in the welding of some refractory carbides to metals. Powder Metall Met Ceram 18(7):481-487 1934. Chaporova IN, Tretyakov VI, Shchetilina EA, Makarenko TG (1959) K voprosu tverdofaznoi rastvorimosti karbida volframa v kobalte i nikele (On the problem of solid solubility of tungsten carbide in cobalt and nickel). In: Tretyakov VI, Chaporova IN (eds) Tverdye splavy. Trudy Vsesoyuznogo nauchno-issledovatelskogo i proektnogo instituta tverdykh splavov i tugoplavkikh metallov (VNIITS). (Hard alloys. Proc. of All-Union Scientific Research and Design Institute of Hard Alloys and Refractory Metals (VNIITS)), Vol. 1, pp. 177-190. Metallurgizdat, Moscow (in Russian) 1935. Chaporova IN, Shchetilina EA (1961) Granitsy odnofaznoi i dvukhfaznoi oblastei v sistemakh W-C-Co i W-C-Ni (Boundaries of the single-phase and two-phase regions in the W-C-Co and W-C-Ni systems). Izv AN SSSR OTN Metall Toplivo (1):126-132 (in Russian) 1936. Schenk H, Frohberg MG, Steinmetz E (1963) Untersuchungen zur gegenseitigen Aktivität beeinflussen die Löslichkeit homogener metallischer Substanzen. Teil I. Experimentelle Untersuchungen von Mangan – Kohlenstoff – X –, Kobalt – Kohlenstoff – X –, Nickel – Kohlenstoff – X – Systemen in flüssigem Zustand (Investigations on the mutual activities influence in homogeneous metallic substances solubility. Part I. Experimental investigations of manganese – carbon – X, cobalt – carbon – X and nickel – carbon – X systems in liquid state). Arch Eisenhüttenwes 34(1):37-42 (in German) 1937. Gabriel A, Pastor H, Deo DM, Basu S, Allibert CH (1985) New experimental data in the C-Co-W, C-Fe-W, C-Fe/Ni-W and C-Co/Ni-W systems and their applications to sintering conditions. In: Bildstein H, Ortner HM (eds) New applications, recycling and technology of refractory metals and hard materials. Proc. 11th Int. Plansee seminar, Reutte, Tirol, Austria, 20-24 May 1985, Vol. 2, pp. 509-525. Plansee Holding AG, Reutte, Austria 1938. Kobakhidze SA, Chaporova IN, Kudryavtseva VI (1988) Thermodynamic calculation of phase boundaries in the regions of cobalt and nickel corners of the W-C-Co and W-C-Ni phase diagrams. Russ Metall (3):193-194 1939. Ettmayer P, Suchentrunk R (1970) Über die thermische Stabilität der Eta-Carbide (On the thermal stability of eta-carbides). Monatsh Chem 101(4):1098-1103 (in German) 1940. Brownlee LD, Edwards R, Raine T (1956) Effect of carbon content on the properties of tungsten carbide / cobalt hard metal. In: Proc. symp. on powder metallurgy, London, UK, 1-2 Dec 1954, pp. 302-304. Iron and Steel Institute, London 1941. Yasinskaya GA (1965) Reaction between refractory compounds and molten metals. Refract Indust Ceram 6(1-2):70-72 1942. Yasinskaya GA (1966) The wetting of refractory carbides, borides and nitrides by molten metals. Powder Metall Met Ceram 5(7):557-559

682

2 Tungsten Carbides

1943. Borisova AL (1985) Sovmestimost tugoplavkikh soedinenii s metallami i grafitom (The compatibility of refractory compounds with metals and graphite). Naukova Dumka, Kyiv (in Russian) 1944. Mukha IM, Globa LV, Shcherbakova LI, Mukha NI (1975) Diffusional reactions of the components of a VK hard alloy with tungsten. Powder Metall Met Ceram 14(4):325-327 1945. Mukha IM, Globa LV, Shcherbakova LI, Mukha NI (1975) Effects of cobalt content and welding conditions upon the diffusional reactions of VK hard alloys with tungsten. Powder Metall Met Ceram 14(11):910-915 1946. Kuzma YuB, Lakh VI, Stadnyk BI, Gladyshevskii EI (1964) Rentgenostrukturnoe issledovanie splavov sistemy W-Re-C (An X-ray structural study of alloys of the W-Re-C system). In: Sakharov BA (ed) Renii. Trudy II Vsesoyuznogo soveshchaniya po probleme reniya, Moskva, 17-18 noyab. 1964 (Rhenium. Proc. 2nd All-Union meeting on the problem of rhenium, Moscow, 17-18 Nov 1964), pp. 168-174. Nauka, Moscow (in Russian) 1947. Savitsky EM, Povarova KB, Makarov PV, Zavarzina EK (1977) Phase-Zusammensetzung, Struktur und Eigenschaften von vakuumgeschmolzenem W – C – (Zr, Hf, Nb, Ta, Re) Legierung (Phase composition, structure and properties of vacuum-melted W – C – (Zr, Hf, Nb, Ta, Re) alloys). Planseeber Pulvermetall 25(3):168-185 (in German) 1948. Savitsky EM, Povarova KB, Makarov PV (1982) Physikalische-chemische Grundlagen des Legierens von warmfesten Wolframlegierungen (Physical and chemical principles underlying alloying of heat-resistant tungsten alloys). Z Metallkd 73(2):92-97 (in German) 1949. Alekseeva ZM, Ivanov OS (1975) Nekotorye novye dannye eksperimentalnogo issledovaniya fazovogo stroeniya splavov i diagram sostoyaniya system U-C-Mo (-W, -Cr, Re) (Some new data of the experimental investigation of the phase structure of alloys and the phase diagrams of the U-C-Mo (-W, -Cr, -Re) systems). In: Thermodynamics of nuclear materials – 1974. Proc. symp. on the thermodynamics of nuclear materials, Vienna, Austria, 21-25 Oct 1974, Vol. 2, pp. 175-184. International Atomic Energy Agency, Vienna (in Russian) 1950. Ugajin M, Suzuki Y, Shimokawa J (1972) Contribution to the study of the system U-PuW-C. J Nucl Mater 43(3):277-292 1951. Chubb W, Keller DL (1964) Constitution of the systems of uranium and carbon with molybdenum, niobium, rhenium, tungsten and yttrium. In: Russell LE, Bradbury BT, Harrison JDL, Hedger HJ, Mardon PG (eds) Carbides in nuclear energy. Proc. Int. symp. on carbides in nuclear energy, Harwell, England, 5-7 Nov 1963, Vol. 1 – Physical and chemical properties, phase diagrams, pp. 208-230. Macmillan, London 1952. Jeitschko W, Behrens RK (1986) Ternary carbides with Ho2Cr2C3 and UMoC2 type structure. Z Metallkd 77(12):788-793 1953. Behrens RK, Jeitschko W (1990) UW4C4, a distorted structure derived from UCr4C4 and the ternary U-W-C system. J Less-Common Met 160(1):185-192 1954. Jones DW, McColm IJ, Yerkess J, Clark NJ (1988) Carbon species in the crystal structures of uranium – transition element carbides, UMC2. J Solid State Chem 74(2):304-313 1955. Nowotny H, Kieffer R, Benesovsky F, Laube E (1958) Zur Kenntnis der Doppelkarbide in den Systemen: U-Cr-C, U-Mo-C und U-W-C (To the knowledge of the double carbides in the systems: U-Cr-C, U-Mo-C and U-W-C). Monatsh Chem 89(6):692-700 (in German) 1956. Kotelnikov RB, Bashlykov SN, Kashtanov AI, Menshikova TS (1969) Vysokotemperaturnoe yadernoe toplivo (High-temperature nuclear fuels). Atomizdat, Moscow (in Russian) 1957. Kotelnikov RB, Bashlykov SN, Kashtanov AI, Menshikova TS (1978) Vysokotemperaturnoe yadernoe toplivo (High-temperature nuclear fuels), 2nd ed. Atomizdat, Moscow (in Russian) 1958. Ugajin M, Takahashi I, Suzuki Y, Abe J, Kurihara M (1973-1974) Thermodynamic estimations for the system U-Pu-W-C. J Nucl Mater 49:151-160 1959. Ugajin M, Abe J, Suzuki Y, Takahashi I, Kurihara M (1976) Phase equilibria in system UPu-W-C. J Nucl Sci Technol 13(1):36-39

References

683

1960. Alekseeva ZM (1987) Dvoinye tugoplavkie karbidy urana (Binary refractory uranium carbides). Nauka, Moscow (in Russian) 1961. Vomhof T, Pöttgen R, Jeitschko W (1993) Magnetic properties of the ternary uranium transition metal carbides UCrC2, UCr4C4, UW4C4, U5Re3C8 and U2NiC3. J Alloys Compd 196(1-2):173-176 1962. Shick AB, Ivanovskii AL, Shveikin GP (1996) Electronic structure and magnetic properties of titanium and tungsten carbides doped with actinides. Inorg Mater 32(7):725-728 1963. Ugajin M (1976) Phase equilibrium study on system uranium-plutonium-tungsten-carbon. Technical Report JAERI-M-6804, pp. 1-100. Japan Atomic Energy Research Institute, Tokyo 1964. Alekseeva ZM, Ivanov OS (1973) Inditsirovanie poroshkogramm soedinenii UMoC2–x, UWC2–x i Z-fazy sistemy U-W-C (The assignment of indices of the X-ray powder patterns of compounds UMoC2–x, UWC2–x and Z-phase of the U-W-C system). In: Ivanov OS (ed) Stroenie i svoistva splavov dlya atomnoi energetiki (The structure and properties of alloys for nuclear power engineering), pp.19-26. Nauka, Moscow (in Russian) 1965. Ugajin M, Abe J (1973) The ternary compound PuWC1.75. J Nucl Mater 47(1):117-120 1966. Shevchuk LA, Dudetskaya LR, Gurinovich VI, Tkacheva VA (1978) Fazovye ravnovesiya v splavakh zhelezo – uglerod – vofram (Phase equilibria in the iron – carbon – tungsten alloys). Vestsi Akad Navuk BSSR Ser Fiz Tekh Navuk (1):43-46 (in Russian) 1967. Shurin AK, Dmitrieva GP (1974) Fazovye ravnovesiya v splavakh perekhodnykh metallov s tugoplavkimi karbidami (Phase equilibria in the alloys of transition metals with refractory carbides). Metallofizika (Akad Nauk Ukr SSR Inst Metallofiz) (53):91-97 (in Russian) 1968. Greenbank JC (1971) Carbon solute interactions in Fe-Cr-C, Fe-Mo-C and Fe-W-C alloys. J Iron Steel Inst 209(12):986-990 1969. Jellinghaus W (1968) Pulvermetallurgische Beiträge zu den Dreistoffsystemen Eisen – Wolfram – Kohlenstoff und Eisen – Molybdan – Kohlenstoff (Powder metallurgical contributions to the three component systems of iron – tungsten – carbon and iron – molybdenum – carbon). Arch Eisenhüttenwes 39(9):705-718 (in German) 1970. Uhrenius B, Harvig H (1975) A thermodynamic evaluation of carbide solubilities in the Fe-Mo-C, Fe-W-C and Fe-Mo-W-C systems at 1000 °C. Metal Sci 9(2):67-82 1971. Yurchenko OS (1971) Stability of iron and nickel during heating in contact with refractory compounds. 10(1):35-38 1972. Yurchenko OS (1971) Issledovanie nekotorykh zakonomernostei tverdofaznogo vzaimodeistviya metallov semeistva zheleza s tugoplavkimi soedineniyami (A study of some regularities of the solid state interaction of iron family metals with refractory compounds). PhD thesis, Kyiv Engineering Institute, Kyiv, Ukraine (in Russian) 1973. Hoffmann A, Mohs R (1974) Gleichgewichtsuntersuchungen im kobaltreichen Teil des Systems Co-W-C bei 1250 °C (Equilibrium studies in the cobalt-rich part of the Co-W-C system at 1250 °C). Metall 28(7):661-666 (in German) 1974. Johansson T (1977) Solidification studies in the Co-W-C system. PhD thesis, Uppsala Universitet, Sweden 1975. Åkesson L (1983) An experimental and thermodynamic study of the Co-W-C system in the temperature range 1470-1700 K. In: Viswanadham RK, Rowcliffe DJ, Gurland J (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Jackson Hole, Wyoming, 23-28 Aug 1981, pp. 71-82. Plenum Press, New York, London 1976. Shchetilina EA, Tumanov VI, Serebrova OI (1964) O rastvorimosti karbidov tugoplavkikh metallov v kovalte (On the solubility of refractory metal carbides in cobalt). Izv AN SSSR OTN Metall Gornoe Delo (6):142-147 (in Russian) 1977. Voigt K, Voigt U (1974) Untersuchungen zu Bindemetallzusammensetzung der Wolframkarbid – Kobalt – Hartmetalle (Investigations on the binder metal composition of tungsten carbide – cobalt – hard metals). Neue Hütte 19(2):103-107 (in German) 1978. Evtushok TM, Burykina AL (1968) Issledovanie vzaimodeistviya grafita s tugoplavkimi soedineniyami i zhidkimi metallami (A study of the interaction of graphite with refractory compounds and liquid metals). In: Frantsevich IN, Samsonov GV (eds) Vzaimodeistvie

684

2 Tungsten Carbides

materialov vysokotemperaturnogo naznacheniya so sredoi (The interaction of materials for high-temperature application with the environment), pp. 221-228. Naukova Dumka, Kyiv (in Russian) 1979. Dergunova VS, Levinskii YuV, Shurshakov AN, Kravetskii GA (1974) Vzaimodeistvie ugleroda s tugoplavkimi metallami (The interaction of carbon with refractory metals). Metallurgiya, Moscow (in Russian) 1980. Mortensen A, Llorca J (2010) Metal matrix composites. Ann Rev Mater Res 40:243-270 1981. Vieira MT, Cavaleiro A, Trindade B (2002) The effects of a third element on structure and properties of W-C/N. Surf Coat Technol 151-152:495-504 1982. Fernandes CM, Popovich V, Matos M, Senos AMR, Viera MT (2009) Carbide phases formed in WC-M (M = Fe/Ni/Cr) systems. Ceram Int 35:369-372 1983. Suetin DV, Shein IR, Ivanovskii AL (2009) Electronic properties of hexagonal tungsten monocarbide (h-WC) with 3d impurities from first principles calculations. Phys B 404:18871891 1984. Suetin DV, Shein IR, Ivanovskii AL (2010) Effect of 4d metal impurities on the structure, electronic properties and stability of hexagonal WC from data of FLAPW-GGA calculations. Phys Solid State 52(12):2450-2457 1985. Fernandes CM, Senos AMR (2011) Cemented carbide phase diagrams: a review. Int J Refract Met Hard Mater 29:405-418 1986. Grüter H (1959) Untersuchungen in den Systemen Co-C, Co-W und Co-W-C (Studies in the Co-C, Co-W and Co-W-C systems). PhD thesis, Westfalischen Wilhelms-Universität zu Münster, Germany (in German) 1987. Holleck H (1983) Constitutional aspects in the development of new hard materials. In: Viswanadham RK, Rowcliffe DJ, Gurland J (eds) Science of hard materials. Proc. Int. conf. on science of hard materials, Jackson Hole, Wyoming, 23-28 Aug 1981, pp. 849-861. Plenum Press, New York, London 1988. Uhrenius B, Forsén K, Haglund B-O, Andersson I (1995) Phase equilibria and phase diagrams in carbide systems. J Phase Equilib 16(5):430-440 1989. Weidow J, Johansson S, Andrén H-O, Wahnström G (2011) Transition metal solubilities in WC in cemented carbide materials. J Am Ceram Soc 94(2):605-610 1990. Li X-Q, Lai Y-G, Chen J (2012) Microstructure and mechanical properties of WCp reinforced iron-based alloy by mechanical alloying and spark-plasma sintering. Mater Sci Eng Powder Metall 17(5):599-603 (in Chinese) 1991. Bondarenko VP, Andreyev IV, Savchuk IV, Matviichuk OO, Ievdokymova OV, Galkov AV (2013) Recent research on the metal-ceramic composites based on the decamicrongrained WC. Int J Refract Met Hard Mater 39:18-31 1992. Tillmann W. Elrefaey A, Wojarski L (2013) Brazing of cutting materials. In: Sekulić DP (ed) Advances in brazing: science, technology and applications, pp. 423-471. Woodhead Publishing, Oxford, Cambridge, UK 1993. Fang ZZ, Koopman MC, Wang H (2014) Cemented tungsten carbide hardmetal – an introduction. In: Sarin VK, Mari D, Llanes L (eds) Comprehensive hard materials, Vol. 1 – Hardmetals, pp. 123-137. Elsevier, Amsterdam, Heidelberg 1994. Liu C (2015) Alternative binder phases for WC cemented carbides. MSc thesis, KTH Royal Institute of Technology, Stockholm, Sweden 1995. Peng Y, Du Y, Zhou P, Zhang W, Chen W, Chen L, Wang S, Wen G, Xie W (2014) CSUTDCC1 – a thermodynamic database for multicomponent cemented carbides. Int J Refract Met Hard Mater 42:57-70 1996. Peng Y, Buchegger C, Lengauer W, Du Y, Zhou P (2016) Solubilities of grain-growth inhibitors in WC-Co-based cemented carbides: thermodynamic calculations compared to experimental data. Int J Refract Met Hard Mater 61:121-127 1997. Lauter L, Hochenauer R, Buchegger C, Bohn M, Lengauer W (2016) Solid-state solubilities of grain-growth inhibitors in WC-Co and WC-MC-Co hardmetals. J Alloys Compd 675:407-415

References

685

1998. Frisk K, Markström A (2008) Effect of Cr and V on phase equilibria in Co-WC based hardmetals. Int J Mater Res 99(3):287-293 1999. Suetin DV, Medvedeva NI (2016) Structural, electronic and magnetic properties of η-carbides M3W3C (M = Ti, V, Cr, Mn, Fe, Co, Ni). J Alloys Compd 681:508-515 2000. Garsía J, Ciprés VC, Blomqvist A, Kaplan B (2019) Cemented carbide microstructures: a review. Int J Refract Met Hard Mater 80:40-68 2001. Lindmayer M, Roth M (1979) Contact resistance and arc erosion of W/Ag and WC/Ag. IEEE Trans Compon Hybrid Manuf Technol 2(1):70-75 2002. Lindmayer M, Roth M, Clasing M (1979) Kontaktwiderstand und Abbrand von W/Ag und WC/Ag (Contact resistance and arc erosion of W/Ag and WC/Ag). Metall 33(7):740-743 (in German) 2003. Banker DC (1984) High current contact material design constraints for tokamak devices. J Nucl Mater 122-123:1352-1356 2004. Slade PG, Bindas JA (1990) Contact resistance variations of tungsten contacts operated in air and silver – tungsten carbide contacts operated in vacuum. In: Braunovic M (ed) Electrical contacts – 1990. Proc. 36th IEEE annual Holm conf. on electrical contacts and 15th Int. conf. on electrical contacts, Montreal, Quebec, Canada, 20-24 Aug 1990, pp. 530-537. Illinois Institute of Technology, Chicago, Illinois 2005. Slade PG, Bindas JA (1991) Contact resistance variations of tungsten contacts operated in air and silver – tungsten carbide contacts operated in vacuum. IEEE Trans Compon Hybrid Manuf Technol 14(1):2-7 2006. Behrens V, Honig T, Kraus A (1999) Tungsten and tungsten carbide based contact materials used in low voltage vacuum contactors. In: Electrical contacts – 1999. Proc. 45th IEEE annual Holm conf. on electrical contacts, Pittsburgh, Pennsylvania, 4-6 Oct 1999, pp. 105-110. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2007. Schulman MB, Slade PG, Loud LD, Li W (1999) Influence of contact geometry and current on effective erosion of Cu-Cr, Ag-WC and Ag-Cr vacuum contact materials. IEEE Trans Compon Pack Technol 22(3):405-413 2008. Temborius S, Lindmayer M, Gentsch D (2003) Properties of WC-Ag and WC-Cu for vacuum contactors. IEEE Trans Plasma Sci 31(5):945-952 2009. Ochi S, Miyamoto S, Koga H, Kan N, Harada T, Ito T, Koyama K, Yamade S (2006) The effect of contact material composition of Ag-WC and axial magnetic field intensity on interrupting capability and chopping current. In: Proc. 22nd Int. symp. on discharges and electrical insulation in vacuum, Matsue, Japan, 25-29 Sep 2006, Vol. 1, pp. 285-288. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2010. Mittelstadt CR (2012) Silver – tungsten vs silver – tungsten carbide contact performance in environmental testing. In: Electrical contacts – 2012. Proc. 58th IEEE annual Holm conf. on electrical contacts, Portland, Oregon, 23-26 Sep 2012, pp. 165-171. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2011. Mützel T, Niederreuther R (2011) Development of contact material solutions for lowvoltage circuit breaker applications (2). In: Electrical contacts – 2011. Proc. 57th IEEE annual Holm conf. on electrical contacts, Minneapolis, Minnesota, 11-14 Sep 2011, pp. 117-122. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2012. Mützel T, Kempf B (2013) Neue Erkenntnisse zum Schaltverhalten von Silber – Wolframkarbid Kontaktwerkstoffen (New findings on the switching behaviour of silver – tungsten carbide contact materials). In: Proc. 22. Fachtagung Albert-Keil-Kontaktseminar vom Kontaktverhalten und Schalten (Proc. 22nd symp. Albert Keil contact seminar on contact performance and switching), Karlsruhe, Germany, 9-11 Oct 2013. VDE Fachber (69):35-42 (in German) 2013. Jung H, Nestler D, Wielage B, Lampke T (2014) Reinforcement of conducting silverbased materials. Medžiagotyra 20(3):247-251 2014. Mützel T, Kempf B (2014) Silver – tungsten carbide contacts for circuit breaker applications. In: Electrical contacts – 2014. Proc. 60th IEEE annual Holm conf. on electrical

686

2 Tungsten Carbides

contacts, New Orleans, Louisiana, 12-15 Oct 2014, pp. 302-308. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2015. Ray N, Kempf B, Mützel T, Froyen L, Vanmeensel K, Vleugels J (2015) Effect of WC particle size and Ag volume fraction on electrical contact resistance and thermal conductivity of Ag-WC contact materials. Mater Design 85:412-422 2016. Ray N, Kempf B, Wiehl G, Mützel T, Heringhaus F, Froyen L, Vanmeensel K, Vleugels J (2017) Novel processing of Ag-WC electrical contact materials using spark-plasma sintering. Mater Design 121:262-271 2017. Leung C-H, Kim H (1984) A comparison of Ag/W, Ag/WC and Ag/Mo electrical contacts. IEEE Trans Compon Hybrid Manuf Technol 7(1):69-75 2018. Guan Z, Hwang I, Li X (2018) Highly concentrated WC reinforced Ag matrix nanocomposite manufactured by molten salt assisted stir casting. In: Wang L (ed) Proc. 46th SME North American manufacturing research conf. (NAMRC 46), College Station, Texas, 18-22 June 2018. Proc Manuf 26:146-151 2019. Ray N, Froyen L, Vanmeensel K, Vleugels J (2018) Wetting and solidification of silver alloys in the presence of tungsten carbide. Acta Mater 144:459-469 2020. Sugiura K, Iwashige T, Tsuruta K, Chen C, Nagao S, Sugahara T, Suganuma K (2019) In situ TEM observation of sintered Ag die-attach layer with added tungsten carbide particles while heating to high temperature. Jpn J Appl Phys 58:100910 (5 pp.) 2021. Allen SE, Streicher E (1998) Effect of microstructure on the electrical performance of AgWC-C contact materials. In: Electrical contacts – 1998. Proc. 44th IEEE annual Holm conf. on electrical contacts, Arlington, Virginia, 26-28 Oct 1998, pp. 276-285. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2022. Uysal M, Akbulat H, Tokur M, Algül H, Çetinkaya T (2016) Structural and sliding wear properties of Ag/graphene/WC hybrid nanocomposites produced by electroless co-deposition. J Alloys Compd 654:185-195 2023. Luo X (2019) The effect of different WC particle size on arc erosion of Ag-12WC-3C static contact material. In: Wang J, Zhao J (eds) Proc. 7th Int. conf. on reliability of electrical products and electrical contacts (ICREPEC 2019), Suzhou, China, 4-6 Nov 2019, pp. 328333. International Academic Publishers, Oxford, UK 2024. Hasanabadi M, Omidvar H, Shamsipur A (2017) Effect of BAg1 Ni-electroplating on microstructure and properties of WC-Co brazed joints. Mater Sci Technol 33(17):2110-2119 2025. Zhang XZ, Liu GW, Tao JN, Shao HC, Fu H, Pan TZ, Qiao GJ (2017) Vacuum brazing of WC-8Co cemented carbides to carbon steel using pure Cu and Ag-28Cu as filler metal. J Mater Eng Perform 26:488-494 2026. Li Y, Zhu Z, He Y, Chen H, Jiang C, Han D, Li J (2016) WC particulate reinforced joint by ultrasonic-associated brazing of WC-Co/35CrMo. J Mater Process Technol 238:15-21 2027. Li Y, Zhang X, Zhu Z, He Y, Han D, Chen H (2017) Effect of element Ni diffusion on microstructure and mechanical properties of brazed joints of cemented carbide and steel. Rare Met Mater Eng 46(6):1120-1125 (in Chinese) 2028. Hasanabadi M, Shamsipur A, Najafi-Sani H, Omidvar H, Sakhaei S (2017) Interfacial microstructure and mechanical properties of tungsten carbide brazed joints using Ag-Cu-Zn + Ni/Mn filler alloy. Trans Nonferr Met Soc China 27:2638-2646 2029. Jiang C, Chen H, Zhao X, Qiu S, Han D, Gou G (2018) Microstructure and mechanical properties of brazing bonded WC-15Co/35CrMo joint using AgNi/CuZn/AgNi composite interlayers. Int J Refract Met Hard Mater 70:1-8 2030. Sarhan AAD (2020) Dissimilar vacuum brazing of WC-Co and cold work steel utilizing a new near-eutectic silver-copper filler alloy. Proc Inst Mech Eng B 234(6-7):1019-1031 2031. Del Campo L, Pérez-Sáez RB, González-Fernández L, Tello MJ (2009) Kinetics inversion in isothermal oxidation of uncoated WC-based carbides between 450 and 800 °C. Corros Sci 51:707-712

References

687

2032. Żurek J, Wessel E, Niewolak L, Schmitz F, Kern T-U, Singheiser L, Quadakkers WJ (2004) Anomalous temperature dependence of oxidation kinetics during steam oxidation of ferritic steels in the temperature range 550-650 °C. Corros Sci 46:2301-2317 2033. Shabalin IL (2019) Prospects of nanotechnology and design of materials based on refractory compounds. Russ J Non-Ferr Met 60(5):583-589 2034. Guan Z, Hwang I, Pan S, Li X (2018) Scalable manufacturing of Ag 40 wt.% Cu – WC nanocomposite microwires. J Micro Nano Manuf 6(3):031008 (8 pp.) 2035. Pan S, Guan Z, Yao G, Cao C, Li X (2019) Study on electrical behaviour of copper and its alloys containing dispersed nanoparticles. Curr Appl Phys 19:452-457 2036. Voiculescu I, Geanta V, Binchiciu H, Iovanas D, Stefanoiu R (2017) Dissimilar brazed joints between steel and tungsten carbide. In: Sandu AV, Abdullah MMAB, Vizureanu P, Ghazali CMR, Sandu I (eds) Proc. Int. Conf. on innovative research (ICIR EuroInvent 2017), Iasi, Romania, 25-26 May 2017. IOP Conf Series Mater Sci Eng 209(1):012021 (8 pp.) 2037. Leung C-H, Wingert PC, Kim HJ (1986) Comparison of reignition properties of several Ag/W, Ag/WC and Ag/Mo electrical contact materials. IEEE Trans Compon Hybrid Manuf Technol 9(1):86-91 2038. Sakairi K, Tsuji H, Tsuchiya K, Harada T (1983) Effect of additive of tungsten carbide on performance of Ag-Ni contact materials and unsymmetrical combination of Ag/Ni/WC with Ag-SnO2. In: Electrical contacts – 1983. Proc. 29th IEEE annual Holm conf. on electrical contacts, Chicago, Illinois, 26-28 Sep 1983, pp. 199-210. Illinois Institute of Technology, Chicago, Illinois 2039. Satoh M, Yanagida T, Iwasaki T (1997) Dispersion and compounding process of particulate Ag-Ni alloy and fine WC powder using a high-speed elliptical rotor type powder mill. J Jpn Soc Powder Powder Metall 44(6):618-621 (in Japanese) 2040. Tamang S, Aravindan S (2019) Brazing of c-BN to WC-Co by Ag-Cu-In-Ti alloy through microwave hybrid heating for cutting tool application. Mater Lett 254:145-148 2041. Sechi Y, Tsumura T, Nakata K (2010) Dissimilar laser brazing of boron nitride and tungsten carbide. Mater Design 31:2071-2077 2042. Sechi Y, Nagatsuka K, Nakata K (2014) Effect of composition of titanium in silvercopper-titanium braze alloy on dissimilar laser brazing of binderless cubic boron nitride and tungsten carbide. In: Takahashi Y (ed) Proc. Int. symp. on interfacial joining and surface technology (IJST 2013), Icho Kaikan, Japan, 27-29 Nov 2013. IOP Conf Series Mater Sci Eng 61(1):012019 (8 pp.) 2043. Misra PS, Upadhyaya GS (1975) Properties of sintered aluminium dispersed with titanium and tungsten carbides. Int J Powder Metall Powder Technol 11(2):129-134 2044. Misra PS, Upadhyaya GS (1984) Bonding in sintered aluminium – refractory compounds composites: an electronic and microstructural evidence. In: Upadhyaya GS (ed) Sintered metal-ceramic composites, pp. 255-257. Elsevier Science, Amsterdam 2045. Ghaisas S (1991) Diffusion barrier performance of pulsed laser deposited amorphous tungsten carbide films. J Appl Phys 70(12):7626-7628 2046. Kobashi M, Harata M, Choh T (1993) Dispersion behaviour of several carbides into molten aluminium and mechanical properties of TiC/Al composite. J Jpn Inst Light Met 43(10):522-527 (in Japanese) 2047. Upadhyaya GS (1995) Particulate metal matrix composites through powder metallurgy: some specific systems. In: Newaz GM, Neber-Aeschbacher H, Wohlbier FH (eds) Metal matrix composites. Key Eng Mater 104-107(1):141-154 2048. Siegel DJ, Hector LG, Jr, Adams JB (2001) Stoichiometry and adhesion of Al/WC. In: Bulatov V, Colombo L, Cleri F, Lewis LJ, Mousseau N (eds) Proc. Int. symp. on advances in materials theory and modelling – bridging over multiple length and time scales – at the 2001 MRS spring meeting, San Francisco, California, 18-20 Apr 2001. Mater Res Soc Symp Proc 677:AA4.25 (6 pp.) 2049. Siegel DJ, Hector LG, Jr, Adams JB (2003) Ab initio study of Al-ceramic interfacial adhesion. Phys Rev B 67(9):092105 (4 pp.)

688

2 Tungsten Carbides

2050. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ (2004) Synthesis, crystal structure and density of (W1–xAlx)C. J Solid State Chem 177:2265-2270 2051. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2005) Crystal structure and carbon vacancy hardening of (W0.5Al0.5)C1–x prepared by a solid-state reaction. ChemPhysChem 6:2099-2103 2052. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2005) Synthesis and high-pressure sintering of (W0.5Al0.5)C. Mater Res Bull 40:701-707 2053. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2005) Synthesis and characterization of (W0.8Al0.2)C0.8 deduction solid solution. Mater Sci Eng B 117:321-324 2054. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2005) Synthesis and characterization of the off-stoichiometric compound (W0.8Al0.2)C0.7. Adv Eng Mater 7(3):130-133 2055. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2005) Preparation and characterization of a novel solid solution of aluminium in tungsten carbide by mechanically activated high-temperature reaction. J Mater Res 21(7):1700-1703 2056. Liang Q-S, Mao C-H, Yang J, Du J (2009) Analysis of the interfacial reaction in WCp / 2024 Al composites. Powder Metall Technol 27(5):327-330, 335 (in Chinese) 2057. Li F-Q, Wei L-F, Li L-Q, Chen Y-B (2009) Microstructures of WCp/Al metal matrix composites layer produced by hybrid laser-TIG melt injection. Chin J Nonferr Met 19(4):619-624 (in Chinese) 2058. He X, Bai Y, Zhu C, Sun Y, Li M, Barsoum MW (2010) General trends in the structural, electronic and elastic properties of the M3AlC2 phases (M = transition metal): a first principle study. Comput Mater Sci 49:691-698 2059. Liang Q-S, Mao C-H, Yang J (2011) Effects of powder hot-pressing process on mechanical properties of WCp / 2024 Al composites. J Mater Eng (12):63-67 (in Chinese) 2060. Lü L, Huang T, Zhong M (2011) WC nanoparticles implanting strengthening on aluminium alloy surface via laser shock peening. Chin J Lasers 38(12):1203006 (8 pp.) (in Chinese) 2061. Gnanasundarajayaraja B, Selvakumar N (2012) Effect of WC content in aluminium metal matrix sintered powder composites. Eur J Sci Res 82(1):9-16 2062. Herrmann M, Raethel J, Berger L-M (2013) On the possibility of the incorporation of Al into the WC lattice. Int J Refract Met Hard Mater 41:495-500 2063. Liu CY, Wang Q, Jia YZ, Zhang B, Jing R, Ma MZ, Jing Q, Liu RP (2013) Evaluation of mechanical properties of 1060 Al reinforced with WC particles via warm accumulative roll bonding process. Mater Design 43:367-372 2064. Mao C-H, Sun X-D, Liang Q-S, Yang J, Du J (2013) Interfacial reaction process of the hot-pressed WC / 2024 Al composite. Rare Met 32(4):397-401 2065. Selvakumar N, Gnanasundarajayaraja B, Rajeshkumar P (2013) Enhancing the properties of Al-WC nanocomposites using liquid metallurgy. Exp Tech 40(1):129-135 2066. Amirkhanlou S, Ketabchi M, Parvin N, Drummen GPC (2014) Structural evaluation and mechanical properties of aluminium / tungsten carbide composites fabricated by continual annealing and press bonding (CAPB) process. Metall Mater Trans B 45(6):1992-1999 2067. Amirkhanlou S, Ketabchi M, Parvin N, Khorsand S, Carreño F (2014) Manufacturing of nanostructured Al/WCp metal matrix composites by accumulative press bonding. In: Toth LS (ed) Proc. 6th Int. conf. on nanomaterials by severe plastic deformation (NanoSPD6), Metz, France, 30 June – 4 July 2014. IOP Conf Series Mater Sci Eng 63:012001 (5 pp.) 2068. Amirkhanlou S, Ketabchi M, Parvin N, Khorsand S, Carreño F (2014) Effect of processing cycles on aluminium / tungsten carbide composites prepared by continual annealing and press bonding process. In: Toth LS (ed) Proc. 6th Int. conf. on nanomaterials by severe plastic deformation (NanoSPD6), Metz, France, 30 June – 4 July 2014. IOP Conf Series Mater Sci Eng 63:012002 (4 pp.) 2069. Razavi M, Mobasherpour I (2014) Production of aluminium nanocomposite reinforced by tungsten carbide particles via mechanical milling and subsequent hot-pressing. Int J Mater Res 105(11):1103-1110

References

689

2070. Lekatou AG, Karantzalis AE, Evangelou A, Gousia V, Kaptay G, Gácsi Z, Baumli P, Simon A (2015) Aluminium reinforced by WC and TiC nanoparticles (ex situ) and aluminide particles (in situ): microstructure, wear and corrosion behavior. Mater Design 65:1121-1135 2071. Narayan S, Rajeshkannan A (2015) Workability behavior of powder metallurgy carbide reinforced aluminium composites during hot forging. Mater Manuf Process 30:1196-1201 2072. Simon A, Lipusz D, Baumli P, Balint P, Kaptay G, Gergely G, Sfikas A, Lekatou A, Karantzalis AE, Gácsi Z (2015) Microstructure and mechanical properties of Al-WC composites. Arch Metall Mater 60(2):1517-1521 2073. Borodianskiy K, Zinigrad M (2016) Modification performance of WC nanoparticles in aluminium and an Al-Si casting alloy. Metall Mater Trans B 47(2):1302-1308 2074. Liu CY, Jiang HJ, Wang CX, Li YP, Luo K (2016) Fabrication and strengthening mechanisms of Al/WC particles composite prepared by accumulative roll bonding. In: Han Y, Wu Y, Li G, Pan F, Fan R, Liu X (eds) Proc. Chinese materials conf. on special and high performance structural materials (CMC 2015), Guiyang, China, 10-14 July 2015. Mater Sci Forum 849:397-401 2075. Narayan S, Rajeshkannan A (2016) Workability studies of sintered aluminium composites during hot deformation. Proc Inst Mech Eng B 230(3):494-504 2076. Shon I-J (2016) Effect of Al on sintering and mechanical properties of WC-Al composites. Ceram Int 42:17884-17891 2077. Sivakumar M, Vignesh M, Sridhar R, Srihari K, Ramasubramanian R (2016) Heat treatment effect on mechanical properties and SEM analysis of Al 6061 / WC / B4C / Ti / Cr metal matrix composites. Int J Mech Eng Technol 7(2):232-243 2078. Lekatou AG, Gkikas N, Karantzalis AE, Kaptay G, Gácsi Z, Baumli P, Simon A (2017) Effect of wetting agent and carbide volume fraction on the wear response of aluminium matrix composites reinforced by WC nanoparticles and aluminide particles. Arch Metall Mater 62(2B):1235-1242 2079. Narayan S, Rajeshkannan A (2017) Studies on formability of sintered aluminium composites during hot deformation using strain hardening parameters. J Mater Res Technol 6(2):101-107 2080. Pakdel A, Witecka A, Rydzek G, Shri DNA (2017) A comprehensive microstructural analysis of Al-WC micro- and nano-composites prepared by spark-plasma sintering. Mater Design 119:225-234 2081. Ravikumar K, Kiran K, Sreebalaji VS (2017) Characterization of mechanical properties of aluminium / tungsten carbide composites. Measurement 102:142-149 2082. Sadeghpour A, Derakhshandeh-Haghighi R (2017) Fabrication of Al/WC micro-composite surface layer on 6061 Al substrate using gas tungsten arc welding (GTAW). Trans Indian Inst Met 70(1):59-67 2083. Arivukkarasan S, Dhanalakshmi V, Stalin B, Ravichandran M (2018) Mechanical and tribological behaviour of tungsten carbide reinforced aluminium LM4 matrix composites. Particul Sci Technol 36(8):967-973 2084. Chantziara E, Lentzaris K, Lekatou AG, Karantzalis AE (2018) Solid particle erosion response of aluminium reinforced with tungsten carbide nanoparticles and aluminide particles. In: Pantelakis S, Koubias S (eds) Proc. 5th Int. conf. of engineering against failure (ICEAF-V 2018), Chios Island, Greece, 20-22 June 2018. MATEC Web Conf 188:03002 (8 pp.) 2085. Emadinia O, Vieira MT, Vieira MF (2018) Effect of reinforcement type and dispersion on the hardening of sintered pure aluminium. Metals 8(10):786 (16 pp.); doi:10.3390/ met8100786 2086. Huang G, Hou W, Shen Y (2018) Evaluation of the microstructure and mechanical properties of WC particle reinforced aluminium matrix composites fabricated by friction stir processing. Mater Charact 138:26-37

690

2 Tungsten Carbides

2087. Kumar KR, Sreebalaji VS, Pridhar T (2018) Characterization and optimization of abrasive water jet machining parameters of aluminium / tungsten carbide composites. Measurement 117:57-66 2088. Narayanan MR, Nallusamy S (2018) Experimental analysis of aluminium alloy metal matrix composite with tungsten carbide by in situ method using SEM. Rasāyan J Chem 11(1):355-360 2089. Sivamurugan P, Gorabhai MM (2018) Investigation of mechanical properties for aluminium based metal matrix composites. Int J Mech Product Eng Res Devel (Special Issue):263-270 2090. Kumar KR, Nishasoms X (2019) Desirability based multi-objective optimization and analysis of WEDM characteristics of aluminium (6082) / tungsten carbide composites. Arab J Sci Eng 44:893-909 2091. Kumar KR, Radhika N, Sam M (2019) Synthesis of aluminium composites using squeeze casting and investigating the effect of reinforcements on their mechanical and wear properties. Trans Indian Inst Met 72(9):2299-2310 2092. Sachit TS, Mohan N (2019) Wear rate optimization of tungsten carbide (WC) nanoparticles reinforced aluminium LM4 alloy composites using Taguchi techniques. Mater Res Express 6:066564 (12 pp.) 2093. Mottaghi M, Ahmadian M (2017) Comparison of the wear behaviour of WC/(FeAl-B) and WC-Co composites at high temperatures. Int J Refract Met Hard Mater 67:105-114 2094. Zhou S, Wang L, Wang SC, Xue Q (2011) Comparative study of simplex doped nc-WC/aC and duplex doped nc-WC/a-C(Al) nanocomposite coatings. Appl Surf Sci 257:6971-6979 2095. Kumar GBV, Swamy ARK, Ramesha A (2012) Studies on properties of as-cast Al 6061WC-Gr hybrid MMCs. J Compos Mater 46(17):2111-2122 2096. Dhas DSEJ, Velmurugan C, Wins KLD, Boopathi-Raja KP (2019) Effect of tungsten carbide, silicon carbide and graphite particulates on the mechanical and microstructural characteristics of AA 5052 hybrid composites. Ceram Int 45:614-621 2097. Arenas FJ, Matos A, Cabezas M, Di Rauso C, Grigorescu C (2001) Densification, mechanical properties and wear behaviour of WC-VC-Co-Al hardmetals. Int J Refract Met Hard Mater 19:381-387 2098. Qiao Z, Ma X, Zhao W, Tang H, Cai S, Zhao B (2008) A novel (W-Al)-C-Co composite cemented carbide prepared by mechanical alloying and hot-pressing sintering. Int J Refract Met Hard Mater 26:251-255 2099. Li X, Xiao Z, Li Y, Yang C, Shao M (2010) WC-8Co-2Al (wt.%) cemented carbides prepared by mechanical milling and spark-plasma sintering. In: Chandra T, Wanderka N, Reimers W, Ionescu M (eds) Proc. 6th Int. conf. on processing and manufacturing of advanced materials (THERMEC’2009), Berlin, Germany, 25-29 Aug 2009. Mater Sci Forum 638-642:1817-1823 2100. Basak AK, Celis J-P, Ponthiaux P, Wenger F, Vardavoulias M, Matteazzi P (2012) Effect of nanostructuring and Al alloying on corrosion behaviour of thermal sprayed WC-Co coatings. Mater Sci Eng A 558:377-385 2101. Liu J, Ma X, Tang H, Zhao W (2012) Vacuum sintering of novel cemented carbide hard alloy (W0.4Al0.6)C0.5 – Co. Int J Refract Met Hard Mater 32:7-10 2102. Sireesha K, Siva-Ramakrishna C, Viswanath-Manta SR (2015) Processing and mechanical characterization of Al-WC-Co hybrid composite produced by powder metallurgy process. Int J Appl Eng Res 10(17): 37758-37762 2103. Zhang L, Zhang R, Yang J, Lei M (2016) Vacuum diffusion bonding of textured WC-Co cemented carbide and aluminium. Trans China Weld Inst 37(1):95-98 (in Chinese) 2104. Zhu H, Yang X, Tan D, Li Y, He W, Tang B (2016) Effect of aluminium element on tungsten products in the preparation of WC-Co cemented carbide. Mater Sci Eng Powder Metall 21(2):202-208 (in Chinese) 2105. Krishna GUB, Ranganatha P, Rajesh GL, Auradi V, Kumar MS, Vasudeva B (2019) Studies on dry sliding wear characteristics of cermet WC-Co particulate reinforced Al 7075

References

691

metal matrix composite. In: Proc. Int. conf. on advances in materials, manufacturing and applied sciences (ICAMMAS 17), Chennai, Tamil Nadu, India, 30-31 Mar 2017. Mater Today Proc 16:343-350 2106. Chen C-S, Yang C-C, Chai H-Y, Yeh J-W, Chau JLH (2014) Novel cermet material of WC / multi-element alloy. Int J Refract Met Hard Mater 43:200-204 2107. Luo W, Liu Y, Luo Y, Wu M (2018) Fabrication and characterization of WCAlCoCrCuFeNi high-entropy alloy composites by spark-plasma sintering. J Alloys Compd 754:163-170 2108. Luo W, Liu Y, Shen J (2019) Effects of binders on the microstructures and mechanical properties of ultra-fine WC – 10 % AlxCoCrCuFeNi composites by spark-plasma sintering. J Alloys Compd 791:540-549 2109. Mueller-Grunz A, Alveen P, Rassbach S, Useldinger R, Moseley S (2019) The manufacture and characterization of WC-(Al)CoCrCuFeNi cemented carbides with nominally high-entropy alloy binders. Int J Refract Met Hard Mater 84:105032 (13 pp.) 2110. Zhou P-L, Xiao D-H, Zhou P-F, Yuan T-C (2018) Microstructure and properties of ultrafine grained AlCrFeCoNi/WC cemented carbides. Ceram Int 44:17160-17166 2111. Zhou P-F, Xiao D-H, Yuan T-C (2017) Comparison between ultra-fine grained WC-Co and WC-HEA cemented carbides. Powder Metall 60(1):1-6 2112. Shivam V, Shadangi Y, Basu J, Mukhopadhyay NK (2019) Alloying behaviour and thermal stability of mechanically alloyed nano AlCoCrFeNiTi high-entropy alloy. J Mater Res 34(5):787-795 2113. Hua G-R, Gong X-Y, Ju Z-L, Tian Z-J, Zhao J-F, Huang Y-H (2010) Ceramic coating of WC – Co – NiCrAl / laser-remelting microstructure and corrosion characteristics. J Aeronaut Mater 30(6):39-42 (in Chinese) 2114. Nath S, Pityana S, Majumdar JD (2012) Laser surface alloying of aluminium with WC + Co + NiCr for improved wear resistance. Surf Coat Technol 206:3333-3341 2115. Ezquerra BL, Biurrun TS, Cabezas LL, Moreno JMS, Lopez FI, Pampliega RM (2018) Sintering of WC hardmetals with Ni-Co-Cr-Ti-Al multi-component alloys. Int J Refract Met Hard Mater 77:44-53 2116. Zhang X, Liu G, Tao J, Guo Y, Wang J, Qiao G (2018) Brazing of WC-8Co cemented carbide to steel using Cu-Ni-Al alloys as filler metal: microstructures and joint mechanical behaviour. J Mater Sci Technol 34:1180-1188 2117. Jiang C-P, Hao J-M, Zhu J-C (2010) Wear behaviour of plasma sprayed WC composite coating. Trans Mater Heat Treat 31(8):117-120 (in Chinese) 2118. Long J, Li K, Chen F, Yi M, Du Y, Lu B, Zhang Z, Wang Y, Cheng K, Zhang K (2017) Microstructure evolution of WC grains in WC-Co-Ni-Al alloys: effect of binder phase composition. J Alloys Compd 710:338-348 2119. Long J, Zhang W, Wang Y, Du Y, Zhang Z, Lu B, Cheng K, Peng Y (2017) A new type of WC-Co-Ni-Al cemented carbide: grain size and morphology of γ′-strengthened composite binder phase. Scripta Mater 126:33-36 2120. Nahvi SM, Jafari M (1999) Microstructural and mechanical properties of advanced HVOF-sprayed WC-based cermet coatings. Surf Coat Technol 286:95-102 2121. Hussong B, Pfeiffer J, Lehmert B, Wojarski L, Tillman W (2013) Comparative investigation of standard WC-Co and a new WC-FeCrAl feedstock powder. In: Innovative coating solutions for the global economy. Proc. Int. thermal spray conf. and exposition (ITSC 2013), Busan, South Korea, 13-15 May 2013, pp. 8-15. ASM International, Metals Park, Ohio 2122. Almond EA, Roebuck B (1988) Identification of optimum binder phase compositions for improved WC hard metals. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:237-248 2123. Jha AK, Ramchandran TR, Upadhyaya GS (1983) Transmission electron microscopy of Al-Cu based powder metallurgical composites. Pract Metallogr 20(11):562-569

692

2 Tungsten Carbides

2124. Evirgen A, Öveçoğlu ML (2010) Characterization investigations of a mechanically alloyed and sintered Al – 2 wt.% Cu alloy reinforced with WC particles. J Alloys Compd 496:212217 2125. Rodríguez-Cabriales G, Lometo-Sánchez AM, Guía-Tello JC, Medrano-Prieto HM, Gutiérrez-Castañeda EJ, Estrada-Guel I, Garay-Reyes CG, Hernández-Rivera JL, CruzRivera JJ, Maldonado-Orozco MC, Martínez-Sánchez R (2020) Synthesis and characterization of Al-Cu-Mg system reinforced with tungsten carbide through powder metallurgy. Mater Today Commun 22:100758 (7 pp.) 2126. Yang C, Wei T, Liu LH, Qu SG, Li XQ, Li YY (2012) Microstructure and mechanical properties of nanocrystalline WC particle reinforced Ti-based composites with nano/ultrafine grained intermetallic matrix from spark-plasma sintering and crystallization of amorphous phase. Int J Mater Res 103(5):613-619 2127. Choi-Yim H, Busch R, Köster U, Johnson WL (1999) Synthesis and characterization of particulate reinforced Zr57Nb5Al10Cu15.4Ni12.6 bulk metallic glass composites. Acta Metall 47(8):2455-2462 2128. Sólyom J, Roósz A, Teleszky I, Sólyom B (2003) Laser alloying of the surface layer of Al4.5Cu1Si alloy with TiC and WC particles. In: Gyulai J (ed) Proc. 3rd Hungarian conf. on materials science, testing and informatics, Balatonfured, Hungary, 14-17 Oct 2001, pp. 37-44. Bay Zoltan Institute for Materials Science and Technology, Budapest, Hungary 2129. Subramanian R, Schneibel JH (1998) FeAl-TiC and FeAl-WC composites – melt infiltration processing, microstructure and mechanical properties. Mater Sci Eng A 244:103112 2130. Zhu Z-X, Xu B-S, Ma S-N, Du Z-Y, Liu W-M (2003) Tribological properties of Fe-Al / WC composite coating prepared by high-velocity arc spraying. Tribol 23(3):174-178 (in Chinese) 2131. Liu N, Zhang G, Ren G (2013) Research on the sintering process of the Fe-Al-WC composite materials. In: Gao S, Hu T (eds) Proc. 2nd Int. conf. on mechanical engineering, materials and energy (ICMEME 2012), Dalian, China, 26-27 Oct 2012. Appl Mech Mater 281:400-413 2132. Liu J, Ma X, Tang H, Zhao W (2012) Preparation, mechanical properties of novel (W0.5Al0.5)C0.5 – Fe – Ni composite by mechanical alloying and sintering. Int J Refract Met Hard Mater 34:41-46 2133. Zuo M, Zhao DG, Wang ZQ, Geng HR (2015) Investigation on WC-Al composite coating of AZ 91 alloy by mechanical alloying. Mater Sci Technol 31(9):1051-1057 2134. Martin JH, Yahata BD, Clough EC, Mayer JA, Hundley JM, Schaedler TA (2018) Additive manufacturing of metal matrix composites via nanofunctionalization. MRS Commun 8(2):297-302 2135. Kulkov SN, Gnyusov SF, Gladkii SP (1989) Interaction in systems WC-Ni-Al and WCNiTi in sintering and impregnation. Powder Metall Met Ceram 28(5):403-405 2136. Zhou X, Chen C, Chang C, Yu J, Hu H (1997) Microstructure of laser cladding of intermetallic-ceramic composite coatings. J Univ Sci Technol Beijing Miner Metall Mater 4(3):8-10 2137. Erol A, Yönetken A (2008) Microwave sintering of electroless Ni plated WC and Al powders. In: Proc. European Int. powder metallurgy congress and exhibition (Euro PM 2008), Manheim, Germany, 29 Sep – 1 Oct 2008, Vol. 3, pp. 39-45. The European Powder Metallurgy Association, Shrewsbury, UK 2138. Correa EO, Santos JN, Klein AN (2011) Microstructure and mechanical properties of WCNi-Al based cemented carbides developed for engineering applications. Int J Mater Res 102(11):1369-1373 2139. Liu J, Ma X, Tang H, Zhao W (2011) Reactive sintering study of a novel cemented carbide hard alloy (W0.5Al0.5)C0.5-Ni. J Alloys Compd 509:33-37 2140. Wang Y, Chen C, Zhang Z, Long J, Xu T, Liu X, Zhang L, Peng Y, Zhou P, Du Y (2014) Phase equilibria in the Al-C-Ni-W quaternary system. Proc. 18th Int. Plansee seminar, Int.

References

693

conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 3-7 June 2013. Int J Refract Met Hard Mater 46:43-51 2141. Jeitschko W, Nowotny H, Benesovsky F (1964) Die Dreistoffe: Molybdän – und Wolfram – Aluminium – Kohlenstoff (The ternary systems: molybdenum – and tungsten – aluminium – carbon). Monatsh Chem 95(1):30-38 (in German) 2142. Xiong Y-J, Qiu Z-L, Li R-D, Yan T-C, Wu H, Liu J-H (2015) Preparation of ultra-fine grain Ni-Al-WC coating with interlocking bonding on austenitic stainless steel by laser clad and friction stir processing. Trans Nonferr Met Soc China 25:3685-3693 2143. Yuan J, Zhang X, Zhang C, Sun K, Liu C (2016) In situ synthesis of NiAl/WC composites by thermal explosion reaction. Ceram Int 42:10992-10996 2144. Liang GY, Wong TT (1997) Investigation of microstructure of laser cladding Ni-WC layer on Al-Si alloy. J Mater Eng Perform 6:41-45 2145. Li C, Li S, Liu C, Zhang Y, Deng P, Guo Y, Wang J, Wang Y (2019) Effect of WC addition on microstructure and tribological properties of bimodal aluminium composite coatings fabricated by laser surface alloying. Mater Chem Phys 234:9-15 2146. Sorokin LM, Efimenko LP, Kalmykov AE, Smolin YuI (2004) Electron-microscopic study of the surface layer of an aluminium-silicon alloy after laser alloying with tungsten carbide. Phys Solid State 46(5):983-988 2147. Li F, Gao Z, Zhang Y, Chen Y (2016) Alloying effect of titanium on WCp/Al composite fabricated by coincident wire-powder laser deposition. Mater Design 93:370-378 2148. Dorigoni C, Laidani N, Miotello A, Calliari L (1998) Ar+-implantation effects on the interfacial properties of the WC / Ti-6Al-4V system. Surf Coat Technol 100-101:358-361 2149. Laidani N, Dorigoni C, Miotello A, Calliari L, Scarel G, Sancrotti M (1998) Depthprofiling via X-ray photoemission and Auger spectroscopies of N+-implanted tungsten carbides grown on the Ti-6Al-4V alloy. Thin Solid Films 317:477-480 2150. Chen Y, Liu D, Li L, Li F, Chen S (2008) Formation mechanism of WCp / Ti-6Al-4V graded metal matrix composites layer produced by laser melt injection. Chin J Lasers 35(11):1718-1722 (in Chinese) 2151. Chen Y, Liu D, Li F, Li L (2008) WCp / Ti-6Al-4V graded metal matrix composites layer produced by laser melt injection. 202:4780-4787 2152. Liu D, Li F, Chen Y, Li L (2008) WCp / Ti-6Al-4V graded composite layers prepared by laser melt injection. Rare Met Mater Eng 37(10):1790-1794 (in Chinese) 2153. Chen Y, Liu D, Li L, Li F (2009) Microstructure evolution of single crystal WCp reinforced Ti-6Al-4V metal matrix composites produced at different cooling rates. J Alloys Compd 484:108-112 2154. Li L, Liu D, Chen Y, Wang C, Li F (2009) Electron microscopy study of reaction layers between single crystal WC particle and Ti-6Al-4V after laser melt injection. Acta Mater 57:3606-3614 2155. Liu D, Li L, Li F, Chen Y (2010) Microfracture behaviour of single crystal particle reinforced WCp / Ti-6Al-4V functionally graded materials layer. Rare Met Mater Eng 39(8):1431-1434 (in Chinese) 2156. Liu D, Hu P, Min G (2015) Interfacial reaction in cast WC particulate reinforced titanium metal matrix composites coating produced by laser processing. Optics Laser Technol 69:180186 2157. Li F, Gao Z, Li L, Chen Y (2016) Microstructural study of MMC layers produced by combining wire and coaxial WC powder feeding in laser direct metal deposition. Optics Laser Technol 77:134-143 2158. Farayibi PK, Folkes J, Clare AT, Oyelola O (2011) Cladding of pre-blended Ti-6Al-4V and WC powder for wear-resistant applications. Surf Coat Technol 206:372-377 2159. Farayibi PK, Murray JW, Huang L, Boud F, Kinnell PK, Clare AT (2014) Erosion resistance of laser clad Ti-6Al-4V / WC composite for water-jet tooling. J Mater Process Technol 214:710-721

694

2 Tungsten Carbides

2160. Çelik ON (2013) Microstructure and wear properties of WC particle reinforced composite coating on Ti-6Al-4V alloy produced by the plasma transferred arc method. Appl Surf Sci 274:334-340 2161. Yang G, Wang W, Qin L, Bian H (2013) Microstructure and property of laser metal deposition composite coating on Ti-6Al-4V alloy surface. High Power Laser Particle Beams 25(10):2723-2728 (in Chinese) 2162. Shamanian M, Mohammadnezhad M, Szpunar J (2014) Production of high-strength Al/Al2O3/WC composite by accumulative roll bonding. J Mater Eng Perform 23:3152-3158 2163. Moropene T, Sacks N, Lioma D, Botef I (2015) Low pressure cold gas dynamic spraying of a WC – 10 wt.% (Ni – Al – Al2O3 – Zn) coating. In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2015), Reims, France, 4-7 Oct 2015, 124663 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 2164. Li YZ, Wang QZ, Xiao BL, Ma ZY (2011) Fabrication and welding of aluminium matrix composite reinforced with WC and B4C particles. In: Proc. 18th Int. conf. on composite materials (ICCM 2011), Jeju, South Korea, 21-26 Aug 2011 (4 pp.) https://www.iccmcentral.org/Proceedings/ICCM18proceedings/papers/F12-6-AF1041.pdf Accessed 19 November 2020 2165. Kumar SSM, Kumar HS (2019) Tribological properties of aluminium (LM 25) reinforced with boron carbide and tungsten carbide. Int J Mech Product Eng Res Devel 9(5):1099-1110 2166. Qiao Z, Cheng J, Kong L, Bi Q, Yang J (2013) Investigation of (WAl)C-Co ceramic composites with the additions of fluoride solid lubricants: preparation, mechanical properties and tribological behaviors. Int J Refract Met Hard Mater 41:322-328 2167. Cheng J, Qiao Z, Yin B, Hao J, Yang J, Liu W (2015) High-temperature tribological behaviors of (WAl)C-Co ceramic composites with the additive of fluoride solid lubricants. Mater Chem Phys 163:262-271 2168. Hsiao WT, Su CY, Huang TS, Liao WH (2013) Wear resistance and microstructural properties of Ni-Al / h-BN / WC-Co coatings deposited using plasma spraying. Mater Charact 79:84-92 2169. Ding F, Li S, Zhang P, Wei D, Chen X, Wang S (2019) Wear-resisting properties of epoxy / WC-Co / Al coating on 300M steel. Mater Sci Forum 947:148-154 2170. Zhao Z, Liu J, Tang H, Ma X, Zhao W (2015) Cr3C2 doped W0.6Al0.4C0.8-Co hard alloys prepared by hot-pressing. Int J Refract Met Hard Mater 48:333-337 2171. Anish A, Kumar MA (2018) Characterization of aluminium matrix reinforced with tungsten carbide and molybdenum disulphide hybrid composite. In: Prabhu S, Senthil R, Stalin JMR, Ambigai R (eds) Proc. 2nd Int. conf. on advances in mechanical engineering (ICAME 2018), Kattankulathur, India, 22-24 Mar 2018. IOP Conf Series Mater Sci Eng 402:012006 (9 pp.) 2172. Stalin B, Arivukkarasan S, Prabhu GA (2015) Microstructure and mechanical properties evaluation of aluminium matrix reinforced with tungsten carbide and silicon carbide. Int J Appl Eng Res 10(55):3994-3999 2173. Cao F, Chen C, Wang Z, Muthuramalingam T, Anbuchezhiyan G (2019) Effects of silicon carbide and tungsten carbide in aluminium metal matrix composites. Silicon 11:2625-2632 2174. Karpinos DM, Zilberberg VG, Épik AP, Batalin GI, Beloborodova EA (1969) Use of diffusion and plasma coatings for increasing the durability of electrodes in molten aluminium. Powder Metall Met Ceram 8(11):907-910 2175. Chantziara E, Lentzaris K, Lekatou AG, Karantzalis AE (2019) Sliding wear and solid particle erosion response of aluminium reinforced with tungsten carbide nanoparticles. Fatigue Fract Eng Mater Struct 42:1548-1562 2176. Huang L, Lu D-P, Sun H-Y, Wang J, Xiang J-H (2012) Oxidation behaviour of Fe 40 Al – x WC – 1 Y2O3 composite coating prepared by HVOF thermal spray. J Northeast Univ 33(S1):92-96 (in Chinese) 2177. Yamaguchi T, Okada M (1978) Interaction between cemented tungsten carbide and molten copper base alloys. J Jpn Weld Soc 47(7):413-418 (in Japanese)

References

695

2178. Wang X, Tan D, Zhu H, He W, Ouyang C-X, Zou Z, Yi Z, Kuang H (2018) Effect mechanism of arsenic on the growth of ultra-fine tungsten carbide powder. Adv Powder Technol 29:1348-1356 2179. Nguyen H-V, Manh T, Eggen T, Aasmundtveit KE (2016) Au-Sn solid-liquid interdiffusion (SLID) bonding for mating surfaces with high roughness. In: Factor B (ed) Proc. 6th electronic system – integration technology conf. and exhibition (ESTC 2016), Grenoble, France, 13-16 Sep 2016, 776469 (6 pp.). The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 2180. Mustain HA, Brown WD, Ang SS (2009) Tungsten carbide as a diffusion barrier on silicon nitride active-metal-brazed substrates for silicon carbide power device. J Electron Packag 131(3):0345021-0345023 2181. Kolosvetov YuP, Navrotskii BS, Zhunkovskii GL (1972) Boronizing of the carbide constituents of hard alloy tools. Powder Metall Met Ceram 11(12):1015-1017 2182. Rogl P, Bittermann H (1999) Ternary metal boron carbides. Int J Refract Met Hard Mater 17:27-32 2183. Schuster JC (1990) The Al-C-W (aluminium-carbon-tungsten) system. In: Petzow G (ed) Ternary alloys: a comprehensive compendium of evaluated constitutional data and phase diagrams. Vol. 3, pp. 575-577. Wiley-VCH, Weinheim, New York 2184. Rogl P (2009) Boron – carbon – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 1, pp. 427-449. Springer, Berlin, Heidelberg 2185. Rudy E (1970) The phase diagram W-B-C. In: Experimental phase equilibria of selected binary, ternary and higher order systems. Technical Report AFML-TR-69-117, Contract USAF 33(615)-67-C-1513, Part 5, pp. 1-51. Air Force Materials Laboratory, WrightPatterson Air Force Base, Ohio 2186. Rogl P, Bittermann H (1999) Ternary metal boron carbides – constitution, thermodynamics, compound formation and structural chemistry. In: Gogotsi YG, Andrievskii RA (eds) Materials science of carbides, nitrides and borides, pp. 29-46. Kluwer Academic, Dordrecht 2187. Kumar AKN, Watabe M, Kurokawa K (2013) Effect of boron on the microstructure of spark-plasma sintered ultra-fine WC. Vacuum 88:88-92 2188. Debnárová S, Souček P, Vašina P, Zábranský L, Buršíková V, Mirzaei S, Pei YT (2019) The tribological properties of short range ordered W-B-C protective coatings prepared by pulsed magnetron sputtering. Surf Coat Technol 357:364-371 2189. Miranda JC, Ramalho A (2001) Abrasion resistance of thermal sprayed composite coatings with a nickel alloy matrix and a WC hard phase. Effect of deposition technique and remelting. Tribol Lett 11(1):37-48 2190. Škamat J, Černašėjus O, Čepukė Ž, Višniakov N (2019) Pulsed laser processed NiCrFeCSiB/WC coating versus coatings obtained upon applying the conventional remelting techniques: evaluation of the microstructure, hardness and wear properties. Surf Coat Technol 374:1091-1099 2191. Li Q, Lei TC, Chen WZ (1999) Microstructural characterization of WCp reinforced Ni-CrB-Si-C composite coatings. Surf Coat Technol 114:285-291 2192. Wu P, Chen XL, Jiang EY (2003) Morphology and gradient distribution of WC phase in laser clad NiCrBSiC-WC composite layers. Phys Stat Sol A 199(2):214-219 2193. Xiao H, Xiao B, Liu S, Wu H (2019) Interfacial analysis of vacuum brazing diamond/WC mixed abrasives with Ni-Cr-B-Si active filler. Vacuum 164:158-164 2194. Tehrani AM, Oliynyk AO, Parry M, Rizvi Z, Couper S, Lin F, Miyagi L, Sparks TD, Brgoch J (2018) Machine learning directed search for ultra-incompressible superhard materials. J Am Chem Soc 140:9844-9853 2195. Márquez-Herrera A, Bermúdez-Rodríguez G, Hernández-Rodríguez EN, Melendez-Lira M, Zapata-Torres M (2016) Boride coating on the surface of WC-Co-based cemented carbide. Int J Mater Res 107(7):676-679

696

2 Tungsten Carbides

2196. Glezer AM, Chicherin YuE, Shvarts VI, Shalin SV (1992) High-strength amorphous alloys with carbide strengthening. Met Sci Heat Treat 34(9):548-551 2197. Ramesh MR, Prakash S, Nath SK, Sapra PK, Venkataraman B (2010) Solid particle erosion of HVOF sprayed WC-Co / NiCrFeSiB coatings. Wear 269:197-205 2198. Amel-Farzad H, Taheri-Nassaj E, Meertens D, Dunin-Borkowski RE, Tavabi AH (2017) Low-temperature pressureless “immediate sintering” of a novel nanostructured WC / Co / NiCrSiB alloy cemented carbide. Scripta Mater 139:100-103 2199. Pascal D-T, Muntean R, Kazamer N, Marginean G, Brandl W, Serban V-A (2016) Characteristics of high-temperature vacuum brazed WC-Co-NiCrBSi functional composite coatings. In: Shrbená J (ed) Proc. 8th Int. conf. on nanomaterials – research and application (NANOCON 2016), Brno, Czech republic, 19-21 Oct 2016, pp. 775-780. Tanger Ltd., Ostrava, Czech Republic 2200. Farooq T, Davies TJ (1990) Preparation of some new tungsten carbide hardmetals. Powder Metall Int 22(4):12-16 2201. Farooq T, Davies TJ (1991) Tungsten carbide hard metals cemented with ferroalloys. Int J Powder Metall 27(4):347-355 2202. Kimura H, Masumoto T, Makino A, Sasaki T (1984) High-frequency properties in a particle-dispersed amorphous Co70.5Fe4.5Si10B15 composite with zero magnetostriction. In: Proc. 5th Int. conf. on liquid and amorphous metals, Los Angeles, California, 15-19 Aug 1983. J Non-Cryst Solids 61-62:1335-1340 2203. Korobov Yu, Khudorozhkova Yu, Hillig H, Vopneruk A, Kotelnikov A, Burov S, Balu P, Makarov A, Chernov A (2019) The effect of thicknesses of laser-deposited NiBSi-WC coating on a Cu-Cr-Zr substrate. In: Proc. Int. conf. on advanced materials with hierarchical structure for new technologies and reliable structures, Tomsk, Russian Federation, 9-13 Oct 2017. Photonics 6(4):127 (10 pp.); doi:10.3390/photonics6040127 2204. Sidhu TS, Malik A, Prakash S, Agrawal RD (2007) Oxidation and hot corrosion resistance of HVOF WC-NiCrFeSiB coating on Ni- and Fe-based superalloys at 800 °C. In: Marple BR, Hyland MM, Lau Y-C, Li C-J, Lima RS, Montavon G (eds) Proc. Int. thermal spray conference, Beijing, China, 14-16 May 2007. J Therm Spray Technol 16(5-6):844-849 2205. Smirnov AN, Kozlov EV, Radchenko MV, Knyazkov KV, Knyazkov VL (2016) State of Ni-Cr-B-Si-Fe / WC coatings after plasma powder surfacing with nanopowder modifier. Steel Transl 46(4):251-255 2206. Han CF, Zhang XD, Sun YF (2019) Microstructure and properties of NiFeCrBSi/WC composite coatings fabricated by vacuum cladding. Phys Met Metallogr 120(9):898-906 2207. Tobar MJ, Álvarez C, Amado JM, Rodríguez G, Yáñez A (2006) Morphology and characterization of laser clad composite NiCrBSi-WC coatings on stainless steel. Surf Coat Technol 200:6313-6317 2208. Han Y, Sun D, Gu X, Li H, Xuan Z (2010) Microstructures and erosion resistance of plasma-sprayed WCp/NiCrBSi composite coatings. China Weld Eng Ed 19(2):1-5 2209. Gao LX, Liu T, Zhang DQ (2013) Preparation of NiCrBSi-WC brazed coating and its microstructure characteristics. Surf Interface Analysis 45:767-772 2210. Hou S, Bao C, Zhai B (2013) Interfacial characteristics and elevated temperature wear behaviour of WCp-NiCrBSi / refractory steel composite. Acta Mater Compos Sin 30(5):125131 (in Chinese) 2211. Joo HG, Lee KY (2014) Effect of boron on wear and erosion of WC-Ni vacuum brazed coating. Int J Mater Res 105(8):802-809 2212. Sheppard P, Koiprasert H (2014) Effect of W dissolution in NiCrBSi-WC and NiBSi-WC arc sprayed coatings on wear behaviors. Wear 317:194-200 2213. Deschuyteneer D, Petit F, Gonon M, Cambier F (2015) Processing and characterization of laser clad NiCrBSi/WC composite coatings – influence of microstructure on hardness and wear. Surf Coat Technol 283:162-171

References

697

2214. Fernández MR, García A, Cuetos JM, González R, Noriega A, Cadenas M (2015) Effect of actual WC content on the reciprocating wear of a laser cladding NiCrBSi alloy reinforced with WC. Wear 324-325:80-89 2215. Huang S, Sun D, Xu D, Wang W, Xu H (2015) Microstructures and properties of NiCrBSi/WC biomimetic coatings prepared by plasma spray welding. J Bionic Eng 12(4):592-603 2216. Luo X, Li J, Li GJ (2015) Effect of NiCrBSi content on microstructural evolution, cracking susceptibility and wear behaviors of laser cladding WC / Ni-NiCrBSi composite coatings. J Alloys Compd 626:102-111 2217. Yang Z-J, Li Y-X, Yan W, Zhou W-X, Yu W (2015) Wear resistances of Ni-base Cr3C2 and WC reinforced coating deposited by plasma transferred arc welding. Mater Sci Eng Powder Metall 20(6):922-927 (in Chinese) 2218. Zhang ZQ, Wang HD, Xu BS, Zhang GS (2015) Characterization of microstructure and rolling contact fatigue performance of NiCrBSi / WC-Ni composite coatings prepared by plasma spraying. Surf Coat Technol 261:60-68 2219. Chen C-J, Zhang M, Liu X, Wang X-N, Li Y (2016) Microstructure characteristics of NiCrBSi/WC coatings on medium Ni-Cr infinite chilled cast iron by laser cladding. Int J Surf Sci Eng 10(2):162-178 2220. McIntosh L, Falsafi J, Fitzpatrick S, Blackwell PL (2016) Wear behaviour of laser cladded Ni-based WC composite coating for Inconel hot extrusion: practical challenges and effectiveness. In: Goh YM, Case K (eds) Advances in manufacturing technology – XXX. Proc. 14th Int. conf. on manufacturing research (ICMR 2016), incorporating 31st Nat. conf. on manufacturing research, Loughborough, UK, 6-8 Sep 2016, Vol. 3, pp. 149-154. IOS Press, Amsterdam 2221. Pascal D-T, Serban V-A, Marginean G (2016) Optimization of process parameters for the manufacturing of high-temperature vacuum brazed WC-NiCrBSi coatings. In: Nicoarǎ M, Uţu I-D, Opriṣ C (eds) Proc. 6th Int. conf. on advanced materials and structures (AMS 2015), Timişoara, Romania, 16-17 Oct 2015. Solid State Phenom 254:164-169 2222. Zhou S, Lei J, Dai X, Guo J, Gu Z, Pan H (2016) A comparative study of the structure and wear resistance of NiCrBSi / 50 wt.% WC composite coatings by laser cladding and laser induction hybrid cladding. Int J Refract Met Hard Mater 60:17-27 2223. Deschuyteneer D, Petit F, Gonon M, Cambier F (2017) Influence of large particle size – up to 1.2 mm – and morphology on wear resistance in NiCrBSi/WC laser cladded composite coatings. Surf Coat Technol 311:365-373 2224. Ortiz A, García A, Cadenas M, Fernández MR, Cuetos JM (2017) WC particles distribution model in the cross-section of laser cladded NiCrBSi + WC coatings, for different wt.% WC. Surf Coat Technol 324:298-306 2225. Vostřák M, Houdková Š, Bystrianský M, Česánek Z (2018) The influence of process parameters on structure and abrasive wear resistance of laser clad WC-NiCrBSi coatings. Mater Res Express 5:096522 (15 pp.) 2226. Shishkovsky I, Kakovkina N, Sherbakov V (2019) Layerwise fabrication of refractory NiCrSiB composite with gradient grow of tungsten carbide additives by selective laser melting. Optics Laser Technol 120:105723 (7 pp.) 2227. Usana-Ampaipong T, Dumkum C, Tuchinda K, Tangwarodomnukun V, Teerapra-watekul B, Qi H (2019) Surface and subsurface characteristics of NiCrBSi coating with different WC amount prepared by flame spray method. J Therm Spray Technol 28:580-590 2228. Vernhes L, Azzi M, Bousser E, Klemberg-Sapieha JE (2015) Hybrid Co-Cr / W-WC and Ni-W-Cr-B / W-WC coating systems. In: Agarwal A, Lau Y-C, Widener CA, Turunen E, Bolelli G, Concustell A, McDonald A, Toma F-L (eds) Proc. Int. thermal spray conf. and exposition (ITSC 2015), Long Beach, California, 11-14 May 2015, Vol. 2, pp. 1031-1038. ASM International, Metals Park, Ohio

698

2 Tungsten Carbides

2229. Takahashi S, Maruyama K (1996) Effect of Si on mechanical properties and microstructures of Ni-B-Si-WC-Mo alloys. J Jpn Soc Powder Powder Metall 43(4):504-509 (in Japanese) 2230. Vélez M, Quiñones H, Di Giampaolo AR, Lira J, Grigorescu IC (1999) Electroless Ni-B coated WC and VC powders as precursors for liquid phase sintering. Int J Refract Met Hard Mater 17:99-102 2231. Zielinski PG, Ast DG (1983) Preparation of rapidly solidified ribbons with second phase particles. J Mater Sci Lett 2:495-498 2232. Myung W-N, Yang S-J, Kim H-G, Lee J-B (1991) Crystallization characteristics and viscous flow behaviour of WC / amorphous Ni73Si10B17 metal matrix composites. Mater Sci Eng A 133:513-517 2233. Grigorescu IC, Di Rauso C, Drira-Halouani R, Lavelle B, Di Giampaolo R, Lira J (1995) Phase characterization in Ni alloy – hard carbide composites for fused coatings. Surf Coat Technol 76-77:494-498 2234. Gassmann RC (1996) Laser cladding with (WC+W2C) Co-Cr-C and (WC+W2C) Ni-B-Si composites for enhanced abrasive wear resistance. Mater Sci Technol 12(8):691-696 2235. Jang K-H, Seo S-P, Kim C-Y, Kim K-Y, Lee G-G (2010) Effect of Si on the mechanical properties of WC-Ni hard metal. In: Lee J-H (ed) Proc. 3rd Int. conf. on multi-functional materials and structures (MFMS 2010), Jeonju, South Korea, 14-18 Sep 2010. Adv Mater Res 123-125:1211-1214 2236. Kim Y-W, Lee J-G (1995) Strengthening of silicon carbide by surface compressive layer. J Mater Sci 30:1005-1008 2237. Ybarra LAC, Chimanski A, Pereira GJ, Machado IF, Yoshimura HN (2017) Effect of milling time on microstructure and mechanical properties of composite WC – (Fe3Al – B) consolidated by spark-plasma sintering. In: Klein AN, Gomes UU, Junior NV, Zoz H (eds) Proc. 10th Int. Latin American conf. on powder technology (PTECH 2015), Rio de Janeiro, Brazil, 8-11 Nov 2015. Mater Sci Forum 899:487-492 2238. Matsumoto A, Kobayashi K, Nishio T, Ozaki K (2002) Effect of boron addition on structure and mechanical properties of FeAl-WC composites. J Jpn Soc Powder Powder Metall 49(12):1089-1093 (in Japanese) 2239. Ahmadian M, Wexler D, Chandra T, Calka A (2005) Abrasive wear of WC-FeAl-B and WC-Ni3Al-B composites. Int J Refract Met Hard Mater 23:155-159 2240. Ahmadian M, Wexler D, Calka A, Chandra T (2007) The effect of boron on the hardness and fracture toughness of WC-FeAl-B and WC-Ni3Al-B composites. In: Chandra T, Tsuzaki K, Militzer M, Ravindran C (eds) Proc. 5th Int. conf. on processing and manufacturing of advanced materials (THERMEC’2006), Vancouver, Canada, 4-8 July 2006, Part 1. Mater Sci Forum 539-543:962-967 2241. Ahmadian M, Reid M, Dippenaar R, Chandra T, Wexler D, Calka A (2010) In situ observations of the densification behaviour of WC-FeAl-B composites during liquid phase sintering. In: Chandra T (ed) Proc. 6th Int. conf. on processing and manufacturing of advanced materials (THERMEC’2009), Berlin, Germany, 25-29 Aug 2009. Mater Sci Forum 638642:921-926 2242. Rad MH, Ahmadian M, Golozar MA (2012) Investigation of the corrosion behaviour of WC-FeAl-B composites in aqueous media. Int J Refract Met Hard Mater 35:62-69 2243. Ahmadian M, Chandra T, Wexler D, Calka A (2007) Effect of boron on the WC morphology in submicron tungsten carbide – aluminide composites. In: Chang YW, Kim NJ, Lee CS (eds) Proc. 6th Pacific Rim Int. conf. on advanced materials and processing (PRICM6), Jeju Island, South Korea, 5-9 Nov 2007, Part 1. Mater Sci Forum 561-565:675-678 2244. Ahmadian M, Wexler D, Chandra T, Calka A (2008) Liquid phase sintering of submicron WC composites containing new binder based on boron doped aluminides. Int J Modern Phys B 22(18-19):3296-3303

References

699

2245. Long J-Z, Zhang Z-J, Xu T, Peng W, Wei X-Y, Lu B-Z, Li R-Q (2012) WC-Ni3Al-B composites prepared through Ni + Al elemental powder route. Trans Nonferr Met Soc China 22(4):847-852 2246. Kaptay G, Lovas A, Szigeti F, Bárczy P, Bolyán L (1997) Correlation between the abrasive ability of ceramic reinforced amorphous metal matrix composites and the adhesion energy between the amorphous matrix and the ceramic particles. Mater Sci Eng A 226228:1083-1088 2247. Just Ch, Ilo S, Badisch E (2010) Influence of processing conditions on the carbide/matrix interface in sintered composite layers. Surf Coat Technol 205:35-42 2248. Hou S, Bao C, Fu G (2019) Interface characteristics and high-temperature wear properties of refractory steel matrix composite reinforced by zoning CTCp/NiCrBSi. Rare Met Mater Eng 48(7):2364-2370 (in Chinese) 2249. Niranatlumpong P, Koiprasert H (2011) Phase transformation of NiCrBSi-WC and NiBSiWC arc sprayed coatings. Surf Coat Technol 206:440-445 2250. Hou S, Bao C, Li Y (2015) Dissolving mechanism of the WC/W 2Cp in NiCrBSi alloy and surface modification for the WC/W2Cp by carburizing. Rare Met Mater Eng 44(7):1772-1776 (in Chinese) 2251. Hou S, Bao C, Li Y (2015) Effect of surface-modified WC/W2Cp on wear behaviour of WC/W2Cp – NiCrBSi / refractory steel composite. Rare Met Mater Eng 44(9):2270-2274 (in Chinese) 2252. Sundaramoorthy R, Tong SX, Parekh D, Subramanian C (2017) Effect of matrix chemistry and WC types on the performance of Ni-WC based MMC overlays deposited by plasma transferred arc (PTA) welding. Wear 376-377:1720-1727 2253. Grabis J, Šteins I, Sīpola I, Rašmane D (2015) Formation of high-temperature compounds in W-C-B system by reactive spark-plasma sintering. Medžiagotyra 21(3):369-371 2254. Ji H, Li M, Lu Y, Wang C (2012) Mechanical properties and microstructure of hybrid ultrasonic resistance brazing of WC-Co / BeCu. J Mater Process Technol 212:1885-1891 2255. Hough RL (1965) Continuous pyrolytic graphite composite filaments. AIAA J 3(2):291296 2256. Buhsmer CP, Crayton PH (1969) Carbon self-diffusion in tungsten carbide. J Met 21(3):A51-A55 2257. Buhsmer CP, Crayton PH (1971) Carbon self-diffusion in tungsten carbide. J Mater Sci 6:981-988 2258. Takatsu S, Saijo K, Yagi M, Shibuki K, Echigoya J (1991) Microstructure of diamond films near the interface with WC substrate. Mater Sci Eng A 140:747-752 2259. Gonzalez-Hernandez J, Chao BS, Ovchinsky SR, Allred DD (1996) The structure of W/C (0.15 < γ < 0.8) multilayers annealed in argon or air. J X-Ray Sci Technol 6:1-31 2260. Kim G-H (1997) Transmission electron microscope observation of diamond/WC interface. J Cryst Growth 178:634-638 2261. Enachescu M, Van Der Oetelaar Carpick RW, Ogletree DF, Flipse CFJ, Salmeron M (1998) Atomic force microscopy study of an ideally hard contact: the diamond (111) / tungsten carbide interface. Phys Rev Lett 81(9):1877-1879 2262. Voevodin AA, O’Neill JP, Zabinski JS (1999) Tribological performance and tribochemistry of nanocrystalline WC / amorphous diamond-like carbon composites. Thin Solid Films 342:194-200 2263. Wänstrand O, Larsson M, Hedenqvist P (1999) Mechanical and tribological evaluation of PVD WC/C coatings. Surf Coat Technol 111:247-254 2264. Balden M, García-Rosales C, Behrisch R, Roth J, Paz P, Etxeberria J (2001) Chemical erosion of carbon doped with different fine-grain carbides. J Nucl Mater 290-293:52-56 2265. Carvalho NJM, De Hosson JTM (2001) Nanoindentation study of PVD WC/C coatings supported by cross-sectional electron microscopy observations: cross-sectional electron microscopy and nanoindentation observations. Surf Eng 17(2):105-111

700

2 Tungsten Carbides

2266. Carvalho NJM, De Hosson JTM (2001) Characterization of mechanical properties of tungsten carbide / carbon multilayers: cross-sectional electron microscopy and nanoindentation observations. J Mater Res 16(8):2213-2222 2267. Carvalho NJM, De Hosson JTM (2001) Microstructure investigation of magnetron sputtered WC/C coatings deposited on steel substrates. Thin Solid Films 388:150-159 2268. Rincón C, Zambrano G, Carvajal A, Prieto P, Galindo H, Martínez E, Lousa A, Esteve J (2001) Tungsten carbide / diamond-like carbon multilayer coatings on steel for tribological applications. Surf Coat Technol 148:277-283 2269. Carvalho NJM, De Hosson JTM (2002) Nanoindentations studies of WC/C and TiN/(Ti,Al)N multilayer PVD coatings combined with cross-sectional electron microscopy observations. In: Meng WJ, Kumar A, Doll GL, Doll YT, Veprek S, Chung YW (eds) Proc. MRS Int. symp. “Surface engineering 2001 – fundamentals and applications, Boston, Massachusetts, 26-29 Nov 2001. Mater Res Soc Symp Proc 697:15-20 2270. Carvalho NJM, Kooi BJ, De Hosson JTM (2002) Studies of WC/C and TiN/(Ti,Al)N multilayer PVD coatings combined with cross-sectional electron microscopy. In: Proc. SAE Int. off-highway congress – co-located with CONEXPO-CON/AGG, Las Vegas, Nevada, 1921 Mar 2002. SAE Tech Papers 2002, pp. 325-328. The Society of Automotive Engineers International, Warrendale, Pennsylvania 2271. Park SJ, Lee K-R, Ko D-H, Eun KY (2002) Microstructure and mechanical properties of WC-C nanocomposite films. Diam Relat Mater 11:1747-1752 2272. Cha SI, Hong SH (2003) Microstructures of binderless tungsten carbides sintered by spark-plasma sintering process. Mater Sci Eng A 356:381-389 2273. Swab JJ (2003) Tungsten carbides for armour applications. In: Kriven WM, Lin H-T (eds) Proc. 27th Int. conf. on advanced ceramics and composites, Cocoa Beach, Florida, 26-31 Jan 2003. Ceram Eng Sci Proc A 24(3):447-453 2274. Zambrano G, Riascos H, Prieto P, Restrepo E, Devia A, Rincón C (2003) Optical emission spectroscopy study of r.f. magnetron sputtering discharge used for multilayers thin film deposition. Surf Coat Technol 172:144-149 2275. Ordás N, Echeberria J, Balden M, Lindig S, Garsía-Rosales C (2004) Mejora de las propiedades termomecánicas de grafio isótropo, elaborado a partir de mesofase carbonosa, mediante la adición de carburos (Improvement of the thermo-mechanical properties of isotropic graphite, produced from carbonaceous mesophase, by the addition of different carbides). Bol Soc Españ Ceram Vid 43(2):544-546 (in Spanish) 2276. Huang Y-S, Qiu W-Q, Luo C-P, Huang C-E (2006) Morphology, structure and adhesion of modified diamond films. Mater Sci Technol 14(1):109-112 (in Chinese) 2277. Samra HA, Hong R, Jiang X (2007) The preparation of diamond / tungsten carbide composite films by microwave plasma-assisted CVD. Chem Vap Deposition 13:17-20 2278. Shi X, Yang H, Sun P, Shao G, Duan X, Zhen X (2007) Synthesis of multi-walled carbon nanotube – tungsten carbide composites by the reduction and carbonization process. Carbon 45:1735-1742 2279. Fu B-Y, He D-Y, Jiang J-M, Li X-Y (2008) Microstructure and wear behaviour of arc sprayed WC-Co / FeCrB and WC-Ni / FeCrB composite coatings. In: Lei MK, Zhu XP, Xu KW, Xu BS (eds) Proc. 5th Int. conf. on surface engineering (ICSE 2007), Dalian, China, 710 July 2007. Key Eng Mater 373-374:468-471 2280. Pujada BR, Tichelaar FD, Janssen GCAM (2008) Hardness of and stress in tungsten carbide – diamond-like-carbon multilayer coatings. Surf Coat Technol 203:562-565 2281. Scharf TW, Romanes MC, Mahdak KC, Hwang JY, Banerjee R, Evans RD, Doll GL (2008) Atomic-scale structure and composition of tungsten carbide reinforced diamond-likecarbon films. Appl Phys Lett 93(15):151909 (3 pp.) 2282. Abad MD, Sánchez-López JC, Cusnir N, Sanjines R (2009) WC/a-C nanocomposite thin films: optical and electrical properties. J Appl Phys 105(3):033510 (6 pp.)

References

701

2283. Bobzin K, Bagcivan N, Goebbels N, Yilmaz K, Hoehn B-R, Michaelis K, Hochmann M (2009) Lubricated PVD CrAlN and WC/C coatings for automotive applications. Surf Coat Technol 204:1097-1101 2284. Pujada BR, Tichelaar FD, Arnoldbik WM, Sloof WG, Janssen GCAM (2009) Growth stress in tungsten carbide – diamond-like-carbon coatings. J Appl Phys 105(3):033502 (4 pp.) 2285. Wu Z, Yang Y, Gu D, Li Q, Feng D, Chen Z, Tu B, Webley PA, Zhao D (2009) Silicatemplated synthesis of ordered mesoporous tungsten carbide / graphitic carbon composites with nanocrystalline walls and high surface areas via a temperature-programmed carburization route. Small 5(23):2738-2749 2286. Yin J, Zhang H-B, Xiong X, Huang B, Zuo J-L (2009) Ablation properties of carbon/carbon composites with tungsten carbide. Appl Surf Sci 255:5036-5040 2287. Kalin M, Roman E, Ožbolt L, Vižintin J (2010) Metal-doped (Ti, WC) diamond-likecarbon coatings: reactions with extreme-pressure oil additives under tribological and static conditions. Thin Solid Films 518:4336-4344 2288. Porrati F, Sacher R, Strauss M, Andrusenko I, Gorelik T, Kolb U, Bayarjargal L, Winkler B, Huth M (2010) Artificial granularity in two-dimensional arrays of nanodots fabricated by focused-electron-beam-induced deposition. Nanotechnol 21:375302 (7 pp.) 2289. Wang B, Tian C, Wang L, Wang R, Fu H (2010) Chitosan: a green carbon source for the synthesis of graphitic nanocarbon, tungsten carbide and graphitic nanocarbon / tungsten carbide composites. Nanotechnol 21:025606 (9 pp.) 2290. Wang M-S, Golberg D, Bando Y (2010) Superstrong low-resistant carbon nanotube – carbide – metal nanocontacts. Adv Mater 22:5350-5355 2291. Grasso S, Hu C, Maizza G, Sakka Y (2011) Spark-plasma sintering of diamond binderless WC composites. J Am Ceram Soc 95(8):2423-2428 2292. Lin ZJ, Zhang JZ, Li BS, Wang LP, Mao H-K, Hemley RJ, Zhao Y (2011) Superhard diamond / tungsten carbide nanocomposites. Appl Phys Lett 98(12):121914 (3 pp.) 2293. Mo JL, Zhu MH (2011) Tribological investigation of WC/C coating under dry sliding conditions. Wear 271:1998-2005 2294. Nazarchuk SN, Bochechka AA, Gavrilova VS, Romanko LA, Belyavina NN, Aleksandrova LI, Tkach VN, Kuzmenko EF, Zabolotnyi SD (2011) The diamond – tungsten carbide polycrystalline composite material. J Superhard Mater 33(1):1-12 2295. Nakagawa I, Hirata A (2011) Fabrication of self-lubricative sintered tungsten carbide body by the addition of carbon onion. J Jpn Soc Precision Eng 77(1):111-115 (in Japanese) 2296. Neto MA, Silva EL, Fernandes AJS, Oliveira FJ, Silva RF (2011) Deposition of alpha-WC / a-C nanocomposite thin films by hot-filament CVD. Surf Coat Technol 206:103-106 2297. Yin J, Zhang H-B, Zuo J-L (2011) Structural and ablative properties of C/C composites perform added WC powder. J Solid Rocket Technol 34(3):360-363 (in Chinese) 2298. Chen Y, Nie X (2012) Study of the fatigue wear behaviors of a tungsten carbide – diamond-like-carbon coating on 316L stainless steel. J Vac Sci Technol A 30(5):051506 (5 pp.) 2299. Hirata A, Nakagawa I (2011) Improvement in mechanical properties of self-lubricating tungsten carbide sintered body including carbon onion. J Jpn Soc Precision Eng 78(3):226230 (in Japanese) 2300. Singla G, Singh K, Pandey OP (2014) Structural and thermal analysis of in situ synthesized C-WC nanocomposites. Ceram Int 40:5157-5164 2301. Li M, Sun YH, Dong B, Wu HD, Gao K (2015) Study on effects of CNTs on the properties of WC-based impregnated diamond matrix composites. Mater Res Innov 19:S559S563 2302. Pu J, He D, Wang L (2015) Effects of WC phase contents on the microstructure, mechanical properties and tribological behaviors of WC/a-C superlattice coatings. Appl Surf Sci 357:2039-2047

702

2 Tungsten Carbides

2303. Singla G, Singh K, Pandey OP (2015) Synthesis of carbon coated tungsten carbide nanopowder using hexane as carbon source and its structural, thermal and electrocatalytic properties. Int J Hydrogen Energy 40:5628-5637 2304. Kornaus K, Gubernat A, Zientara D, Rutkowski P, Stobierski L (2016) Mechanical and thermal properties of tungsten carbide – graphite nanoparticles nanocomposites. Polish J Chem Technol 18(2):84-88 2305. Benedetti M, Fontanari V, Torresani E, Girardi C, Giordanino L (2017) Investigation of lubricated rolling behaviour of WC/C, WC/C-CrN, DLC based coatings and plasma nitriding of steel for possible use in worm gearing. Wear 378-379:106-113 2306. He D, Pu J, Lu Z, Wang L, Zhang G, Xue Q (2017) Simultaneously achieving superior mechanical and tribological properties in WC/a-C nanomultilayers via structural design and interfacial optimization. J Alloys Compd 698:420-432 2307. Nemati N, Bozorg M, Penkov OV, Shin D-G, Sadighzadeh A, Kim D-E (2017) Functional multi-nanolayer coatings of amorphous carbon / tungsten carbide with exceptional mechanical durability and corrosion resistance. ACS Appl Mater Interfaces 9:30149-30160 2308. Cao T, Li X, Li J, Zhang M, Qiu H (2018) Effect of sintering temperature on phase constitution and mechanical properties of WC – 1.0 wt.% carbon nanotube composites. Ceram Int 44:164-169 2309. Stakhniv NE, Devin LN, Bochechka AA, Osadchii AA, Nazarchuk SN, Rychev SV (2018) A study of the influence of phase composition of cutting inserts made of diamond – tungsten carbide nanocomposite on the process of finish turning of aluminium alloys and brass. J Superhard Mater 40(3):197-205 2310. Sun S, Wang Y, Lu Xiao, Lu Xia, Mao C, Zeng Z, Xue Q (2018) Achieving excellent tribological performance of a-C:WC film by controlling sub-nanostructure. Tribol Int 128:6574 2311. Wang L, Li L, Kuang X (2018) Effect of substrate bias on microstructure and mechanical properties of WC-DLC coatings deposited by HiPIMS. Surf Coat Technol 352:33-41 2312. Tong Z, Wen M, Lv C, Zhang Q, Yin Y, Liu X, Li Y, Liao C, Wu Z, Dionysiou DD (2020) Ultra-thin and coiled carbon nanosheets as Pt carriers for high and stable electrocatalytic performance. Appl Catal B 269:118764 (9 pp.) 2313. Zhang K, Shi Z, Zhang X, Zhang Z, Ge B, Xia H, Guo Y, Qiao G (2017) Molten salt synthesis of continuous tungsten carbide coatings on graphite flakes. Ceram Int 43(11):80898097 2314. Zhang X, Xie W, Ge B, Wang K, Shi Z, Yang W, Xia H, Wang J (2020) Enhancing the mechanical and thermophysical properties of highly oriented graphite flake composites by formation of a uniform three-dimensional tungsten carbide skeleton reinforcement. Compos A 131:105800 (10 pp.) 2315. Zhang Yo, Yun S, Wang Z, Zhang Ya, Wang C, Arshad A, Han F, Si Y, Fang W (2020) Highly efficient bio-based porous carbon hybridized with tungsten carbide as counter electrode for dye-sensitized solar cell. Ceram Int 46(10):15812-15821 2316. Meng H, Shen PK (2005) Tungsten carbide nanocrystal promoted Pt/C electrocatalysts for oxygen reduction. J Phys Chem B 109:22705-22709 2317. Le Roux H (1976) Microstructure of reversibly crystallizing turbostratic graphite in heattreated WC-Co hard metals. Acta Metall 24:299-305 2318. Bronshtein DKh (1982) Effect of the combined carbon of tungsten monocarbide on the reaction of diamond with a hard metal. Powder Metall Met Ceram 21(8):650-654 2319. Bronshtein DKh, Maistrenko AL, Simkin ÉS, Tsypin NV (1990) Strength of diamondcontaining composite material based on tungsten carbide hard alloy. Powder Metall Met Ceram 29(9):720-724 2320. Itoh H, Nakamura T, Iwahara H, Sakamoto H (1994) Microstructural control of boundary region between CVD diamond film and cemented carbide substrate. J Mater Sci 29:14041410

References

703

2321. Voloshin MN, Kolomiets VP (1996) Struktura kompozitsii WC-Co-almaz poluchennoi elektroimpulsnym spekaniem (Structure of the WC-Co-diamond composite produced by electropulse sintering). Sverkhtv Mater (2):3-8 (in Russian) 2322. Kear BH, Sadangi R (1997) Synthesis of WC/Co/diamond nanocomposites. Particul Sci Technol 15(2):176 2323. Fang ZZ, Griffo A, White B, Lockwood G, Belnap D, Hilmas G, Bitler J (2001) Fracture resistant super hard materials and hardmetals composite with functionally designed microstructure. Int J Refract Met Hard Mater 19:453-459 2324. Tan GL, Wu XJ, Li ZQ (2003) Preparation and mechanical properties of nanostructured tungsten carbide alloys strengthened by carbon nanotubes. In: Komarneni S, Parker JC, Watkins JJ (eds) Proc. MRS symp. on continuous nanophase and nanostructured materials, Boston, Massachusetts, 1-5 Dec 2003. Mater Res Soc Symp Proc 788:449-452 2325. Cabral G, Ali N, Titus E, Gracio J (2005) Cobalt diffusion in different microstructured WC-Co substrates during diamond chemical vapour deposition. J Phase Equilib Diff 26(5):411-416 2326. Schwarz J, Meteva K, Grigat A, Schubnov A, Metev S, Vollertsen F (2005) Synthesis of diamond coatings on tungsten carbide with photon plasmatron. Diam Relat Mater 14:302-307 2327. Zhang F, Sun J, Shen J (2005) Effects of carbon nanotubes incorporation on the grain growth and properties of WC/Co nanocomposites. In: Zhong Z, Saka H, Kim TH, Holm EA, Han Y, Xie X (eds) Proc. 5th Pacific Rim Int. conf. on advanced materials and processing (PRICM-5), Beijing, China, 2-5 Nov 2004. Mater Sci Forum 475-479(2):989-992 2328. Griboval-Constant A, Giraudon J-M, Twagishema I, Leclercq G, Rivas ME, Alvarez J, Pérez-Zurita MJ, Goldwasser MR (2006) Characterization of new Co and Ru on α-WC catalysts for Fischer-Tropsch reaction. Influence of the carbide surface state. J Mol Catal A 259:187-196 2329. Michalski A, Rosiński M (2008) Sintering diamond / cemented carbides by the pulse plasma sintering method. J Am Ceram Soc 91(11):3560-3565 2330. Shi XL, Yang H, Wang S, Shao G, Duan X (2008) Fabrication and properties of WC – 10Co cemented carbide reinforced by multi-walled carbon nanotubes. Mater Sci Eng A 486:489-495 2331. Bobrovnitchii G, Skury ALD, Filgueira M, Monteiro SN, Tardim RC (2010) Study on WC-Co-diamond based composites used in cutters of drill bits. In: Salgado L, Filho FA (eds) Proc. 7th Int. Latin-American conf. on powder technology, Atibaia – São Paulo, Brazil, 10 Nov 2009. Mater Sci Forum 660-661:489-494 2332. Grigoryev EG, Roslyakov AV (2010) The electro-discharge compaction of powder tungsten carbide – cobalt – diamond composite material. In: Olevsky EA, Bordia R (eds) Advances in sintering science and technology. Proc. Int. conf. on sintering, La Jolla, California, 16-20 Nov 2008. Ceram Trans 209:205-209 2333. Lay S, Donnadieu P, Loubradou M (2010) Polarity of prismatic facets delimiting WC grains in WC-Co alloys. Micron 41:472-477 2334. Sun L, Yang T, Jia C, Xiong J (2011) Effects of graphite on the microstructure and properties of ultra-fine WC – 11 Co composites by spark-plasma sintering. Rare Met 30(1):63-67 2335. Hao SZ, Zhang Y, Xu Y, Gey N, Grosdidier T, Dong C (2013) WC/Co composite surface structure and nanographite precipitate induced by high current pulsed electron beam irradiation. Appl Surf Sci 285P:552-556 2336. Sidorenko DA, Zaitsev AA, Kirichenko AN, Levashov EA, Kurbatkina VV, Loginov PA, Rupasov SI, Andreev VA (2013) Interaction of diamond grains with nanosized alloying agents in metal-matrix composites as studied by Raman spectroscopy. Diam Relat Mater 38:59-62 2337. Lisovskii AF, Bondarenko NA (2014) The role of interphase and contact surface in the formations of structures and properties of diamond – (WC-Co) composites. A review. J Superhard Mater 36(3):145-155

704

2 Tungsten Carbides

2338. Bondarenko NA, Zhukovskii AN, Mechnik VA (2008) Osnovy sozdaniya almazosoderzhashchikh kompozitsionnykh materialov dlya porodorazrushayushchikh instrumentov (Fundamentals of the development of diamond-containing composite materials for rock destruction tools). Bakul Institute for Superhard Materials, National Academy of Sciences of Ukraine, Kyiv (in Russian) 2339. Tsypin NV (1983) Iznosostoikost kompozitsionnykh almazosoderzhashchikh materialov dlya burovogo instrumenta (Wear resistance of composite diamond-containing materials for drilling tools). Naukova Dumka, Kyiv (in Russian) 2340. Novikov NV, Bondarenko NA, Zhukovskii AN, Mechnik VA (2005) Struktura ta vlastyvosti vkladyshiv sverdla, spechenykh garyachym presuvannyam (Structure and properties of drill bit inserts sintered by hot-pressing). Dopov NAN Ukrainy (3):93-97 (in Ukrainian) 2341. Novikov NV, Tsypin NV, Maistrenko AL, Vovchanovskii IF (1983) Almazosoderzhashchie kompozitsionnye materialy na osnove tverdykh splavov (Diamond-containing composite materials based on hard alloys). Sverkhtv Mater (2):1-5 (in Russian) 2342. Bondarenko NA, Novikov NV, Mechnik VA, Oleinik GS, Vereshchaka VM (2004) Strukturni osoblyvosti nadtverdykh kompozytiv almaz-WC-6Co, shcho vidrizbyayutsya znosostiykistyu (Structural features of diamond-WC-6Co superhard composites that differ in wear resistance). Sverkhtv Mater (6):1-13 (in Ukrainian) 2343. Novikov NV, Maistrenko AL, Trefilov VI, Kovtun VI (1993) Properties of VK6-diamond composites sintered in shock waves. Powder Metall Met Ceram 32(4):377-379 2344. Lisovskii AF, Bondarenko NA (2012) Thermodynamic study of the doping of the diamond-WC-Co composition with silicides of transition metals. J Superhard Mater 34(4):239-242 2345. Maistrenko AL, Polushin NI (2014) Instrumenty dlya stroitelnoi industrii, gornye i burovye porodorazrushayushchie instrumenty (Tools for the building construction industry, mining and drilling rock destruction tools). In: Novikov NV, Klimenko SA (eds) Instrumenty iz sverkhtverdykh materialov (Tools from superhard materials), 2nd ed., pp. 579-604. Mashinostroenie, Moscow (in Russian) 2346. Rodríguez MA, Gil L, Camero S, Fréty N, Santana Y, Caro J (2014) Effects of the dispersion time on the microstructure and wear resistance of WC/Co-CNTs HVOF sprayed coatings. Surf Coat Technol 258:38-48 2347. Nasser A, Shinagawa K, El-Hofy H, Moneim AA (2016) Enhancing stability of Co gradient in nanostructured WC-Co functionally graded composites using graphene additives. J Ceram Soc Jpn 124(12):1191-1198 2348. Sidorenko DA, Levashov E, Loginov P, Shvyndina N, Skryleva E, Yerokhin A (2016) Self-assembling WC interfacial layer on diamond grains via gas-phase transport mechanism during sintering of metal matrix composite. Mater Design 106:6-13 2349. Li J, Yue W, Qin W, Mao Q, Gao B, Li Y (2017) Effect of quenching processes on microstructures and tribological behaviours of polycrystalline diamond compact (PCD/WCCo) in annealing treatment. Diam Relat Mater 79:79-87 2350. Nieto A, Jiang L, Kim J, Kim D-E, Schoenung JM (2017) Synthesis and multi-scale tribological behaviour of WC-Co / nanodiamond nanocomposites. Sci Rep 7(1):1-11 2351. Nieto A, Kim J, Penkov OV, Kim D-E, Schoenung JM (2017) Elevated temperature wear behaviour of thermally sprayed WC-Co / nanodiamond composite coatings. Surf Coat Technol 315:283-293 2352. Tian H, Guo M, Wang C, Tang Z, Wei S, Xu B (2017) Microstructure and wear behaviour of graphene oxide modified self-lubricated wear-resistant coating. Rare Met Mater Eng 46(7):1881-1886 (in Chinese) 2353. Mohanty D, Kar S, Paul S, Bandyopadhyay PP (2018) Carbon nanotube reinforced HVOF sprayed WC-Co coating. Mater Design 156:340-350

References

705

2354. Sun J, Zhao J, Gong F, Li Z, Ni X (2018) Design, fabrication and characterization of multi-layer graphene reinforced nanostructured functionally graded cemented carbides. J Alloys Compd 750:972-979 2355. Sun J, Zhao J (2018) Multi-layer graphene reinforced nano-laminated WC-Co composites. Mater Sci Eng A 723:1-7 2356. Annalakshmi M, Balasubramanian P, Chen S-M, Chen T-W (2019) Enzyme-free electrocatalytic sensing of hydrogen peroxide using a glassy carbon electrode modified with cobalt nanoparticle – decorated tungsten carbide. Microchim Acta 186:265 (9 pp.) 2357. Champagne B (1987) Properties of WC-Co / steel composites. Int J Refract Met Hard Mater 6(3):155-160 2358. Zhang J, Chen J, Jiang Y, Zhou F, Wang G, Wang R (2016) Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction. Appl Surf Sci 389:157-164 2359. Sakaguchi S, Oho K, Ito H, Nakamura R (1987) Some properties of infiltrated WC-Ni / Fe-Cr-C alloys. Int J Refract Met Hard Mater 6(1):48-52 2360. Sidorenko DA, Levashov EA, Kuptsov KA, Loginov PA, Shvyndina NV, Skryleva EA (2017) Conditions for the in situ formation of carbide coatings on diamond grains during their sintering with Cu-WC binders. Int J Refract Met Hard Mater 69:273-282 2361. Yin S, Cai M, Wang C, Shen PK (2011) Tungsten carbide promoted Pd-Fe as alcoholtolerant electrocatalysts for oxygen reduction reactions. Energy Environ Sci 4(2):558-563 2362. Jiang X, Fassbender J, Hillebrands B (1994) Elastic constants of WC – a-C:H composite films studied by Brillouin spectroscopy. Phys Rev B 49(19):13815-13819 2363. Evans RD, Shiller PJ, Howe JY (2011) Adhesion of tungsten carbide reinforced amorphous hydrocarbon thin films (WC/a-C:H) to steel substrates for tribological applications. J Appl Phys 109(2):023518 (6 pp.) 2364. Mahmoudi B, Hager CH, Jr, Doll GL (2015) Effects of normal and shear stresses in rolling and mixed mode contact on the micropitting wear of WC/a-C:H tribological coating. Surf Coat Technol 283:96-100 2365. Mahmoudi B, Tury B, Hager CH, Jr, Doll GL (2015) Effects of black oxide and a WC/aC:H coating on the micropitting of SAE 52100 bearing steel. Tribol Lett 58:20 (9 pp.) 2366. Mahmoudi B, Doll GL, Hager CH, Jr, Evans RD (2015) Influence of a WC/a-C:H tribological coating on micropitting wear of bearing steel. Wear 350-351:107-115 2367. Makówka M, Pawlak W, Konarski P, Wendler B (2016) Hydrogen content influence on tribological properties of nc-WC/a-C:H coatings. Diam Relat Mater 67:16-25 2368. Moskalewicz T, Wendler B, Makówka M, Czyrska-Filemonowicz A (2011) Microstructural characterization of low-friction carbon-based nanocomposite coatings. In: Falcieri E (ed) Proc. 10th Multinat. congress on microscopy (MCM 2011), Urbino, Italy, 4-9 Sep 2011, pp. 579-580. Società Italiana di Scienze Microscopiche, Urbino, Italy 2369. Wang W, Pelenovich VO, Yousaf MI, Yan S, Bin H, Wang Z, Tolstogouzov AB, Kumar P, Yang B, Fu DJ (2016) Microstructure, mechanical and tribological properties of WC/aC:H coatings deposited by cathodic arc ion-plating. Vacuum 132:31-39 2370. Fouts JA, Shiller PJ, Mistry KK, Evans RD, Doll GL (2017) Additive effects on the tribological performance of WC/a-C:H and TiC/a-C:H coatings in boundary lubrication. Wear 372-373:104-115 2371. Málek V, Makówka M, Kormunda M, Ryšánek P (2017) Tribological properties and abrasion resistance of thin films of tungsten carbide. In: Shrbená J (ed) Proc. 26th Int. conf. on metallurgy and materials (METAL 2017), Brno, Czech republic, 24-26 May 2017, pp. 13721376. Tanger Ltd., Ostrava, Czech Republic 2372. Nouvellon C, Belchi R, Libralesso L, Douhéret O, Lazzaroni R, Snyders R, Thiry D (2017) WC/C:H films synthesized by an hybrid reactive magnetron sputtering / plasma enhanced chemical vapour deposition process: an alternative to Cr (VI) based hard chromium plating. Thin Solid Films 630:79-85

706

2 Tungsten Carbides

2373. Chang C-L, Yang F-C (2018) Synthesis and characteristics of nc-WC/a-C:H thin films deposited via a reactive HIPIMS process using optical emission spectrometry feedback control. Surf Coat Technol 350:1120-1127 2374. Soltanahmadi S, Charpentier T, Nedelcu I, Khetan V, Morina A, Freeman HM, Brown AP, Brydson R, Van Eijk MCP, Neville A (2019) Surface fatigue behaviour of a WC/a-C:H thin film and the tribochemical impact of zinc dialkyldithiophosphate. ACS Appl Mater Interfaces 11:41676-41687 2375. Lofaj F, Kabátová M, Dobrovodský J, Cempura G (2020) Hydrogenation and hybridization in hard W-C:H coatings prepared by hybrid PVD-PECVD method with methane and acetylene. Int J Refract Met Hard Mater 88:105211 (12 pp.) 2376. Banerjee S, Sutradhar G (2018) Study on wear behaviour of Mg-Gr-WC nanocomposite using response surface methodology. In: Singh SK, Purohit R, Parveen A (eds) Proc. 8th Int. conf. on materials processing and characterization (ICMPC-2018), Madhapur, India, 16-18 Mar 2018. Mater Today Proc 5(9/3):17664-17673 2377. Kim D-W, Li OL, Pootawang P, Saito N (2014) Solution plasma synthesis process of tungsten carbide on N-doped carbon nanocomposite with enhanced catalytic ORR activity and durability. RSC Adv 4(32):16813-16819 2378. Zhu H, Sun Z, Chen M, Cao H, Li K, Cai Y, Wang F (2017) Highly porous composite based on tungsten carbide and N-doped carbon aerogels for electrocatalyzing oxygen reduction reaction in acidic and alkaline media. Electrochim Acta 236:154-160 2379. Feng Q, Xiong Y, Xie L, Zhang Z, Lu X, Wang Y, Yuan X-Z, Fan J, Li H, Wang H (2019) Tungsten carbide encapsulated in grape-like N-doped carbon nanospheres: one-step facile synthesis for low-cost and highly active electrocatalysts in proton exchange membrane water electrolyzers. ACS Appl Mater Interfaces 11:25123-25132 2380. Hirschhorn JS, Andersen PJ (1969) Effects of processing and powder characteristics on the wear and friction properties of some nickel-base materials. Powder Metall 12(24):344-355 2381. Hirschhorn JS, Daver EM (1969) Wear and friction studies of nickel – tungsten carbide – graphite composites. Powder Metall 12(24):519-537 2382. Xiao Y, Shi W, Luo J, Liao Y (2014) The tribological performance of TiN, WC/C and DLC coatings measured by the four-ball test. Ceram Int 40:6919-6925 2383. Chen Z, Li H, Ren L, Li Y, Liu C (2020) Effect of tungsten carbide addition on the wear resistance of flame-sprayed self-lubricating Ni-graphite coatings. J Mater Eng Perform 29:1156-1164 2384. Ma B, Zhang Z, Liu B (2000) Research on hot-pressing method for fabrication of diamond and tungsten carbide composite button. Powder Metall Technol 18(1):28-30 (in Chinese) 2385. Shi X, Shao G, Duan L, Tang F, Yuan R (2005) Effect of activated sintering on diamond enhanced tungsten carbide composite bits. Powder Metall Technol 23(2):100-103 (in Chinese) 2386. Wang Y, Wang Z, Zhang H, Zhu Y (2010) Analysis of microstructure and properties of Ti-C-WC reinforced Ni-based composite coating by argon arc cladding. Trans China Weld Inst 31(10):47-49 (in Chinese) 2387. Gladyshevskii EI, Telegus VS, Fedorov TF, Kuzma YuB (1967) Ternary system of W-CrC. Russ Metall (1):97-100 2388. Eremenko VN, Velikanova TYa, Bondar AA (1986) Diagramma sostoyaniya sistemy CrW-C pri vysokikh temperaturakh (The constitution diagram of the Cr-W-C system at high temperatures). Dopov Akad Nauk Ukr RSR Ser A Fiz Mat Tekh Nauki 48(11):74-78 (in Russian) 2389. Bondar AA, Velikanova TYa (1996) Aspects of construction diagrams of ternary systems formed by chromium with carbon and d-transition metals. Powder Metall Met Ceram 35(78):484-496 2390. Velikanova TYa, Bondar AA, Grystiv AV, Dovbenko OI (2001) Metallochemistry of chromium with d-metals and carbon. J Alloys Compd 320:341-352

References

707

2391. Velikanova TYa, Eremenko VN (1988) Relationships governing phase equilibria in refractory carbide – bearing systems of transition metals. Powder Metall Met Ceram 27(2):145-149 2392. Eremenko VN, Velikanova TYa (1983) Use of the phase diagrams of ternary transition metal systems containing carbides in the development of heat-resisting hard alloys. Powder Metall Met Ceram 22(12):1010-1021 2393. Watson A, Kroupa A (2010) Carbon – chromium – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 2, pp. 379-396. Springer, Berlin, Heidelberg 2394. Sun W, Hu R, Liu H, Zhang H, Liu J, Yang L, Wang H, Zhu M (2016) Silicon / wolfram carbide @ graphene composite: enhancing conductivity and structure stability in amorphous silicon for high lithium storage performance. Electrochim Acta 191:462-472 2395. Brukl CE (1965) The Ti-Si-C, Nb-Si-C and W-Si-C systems. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFML-TR-65-2, Contract USAF 33(615)-1249, Part 2, Vol. 7, pp. 1-57. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 2396. Yan G, Wu C, Tan H, Feng X, Yan L, Zang H, Li Y (2017) N-carbon coated P-W2C composite as efficient electrocatalyst for hydrogen evolution reactions over the whole pH range. J Mater Chem A 5(2):765-772 2397. Meng H, Shen PK (2005) The beneficial effect of the addition of tungsten carbides to Pt catalysts on the oxygen electroreduction. Chem Commun 41(35):4408-4410 2398. Bai T (2013) Fabrication and properties of WC-Al2O3 cemented carbide reinforced by single-walled carbon nanotubes. In: Jun Z (ed) Proc. 2nd Int. symp. on manufacturing systems engineering (ISMSE 2013), Singapore, 27-29 July 2013. Appl Mech Mater 404:91-94 2399. Bai T, Xie T (2017) Fabrication and mechanical properties of WC-Al2O3 cemented carbide reinforced by CNTs. Mater Chem Phys 201:113-119 2400. Yin J, Huang Z, Liu X, Zhang Z, Jiang D (2013) Microstructure, mechanical and thermal properties of in situ toughened boron carbide – based ceramic composites co-doped with tungsten carbide and pyrolytic carbon. J Eur Ceram Soc 33:1647-1654 2401. Yin J, Huang Z, Liu X, Zhang Z, Jiang D (2016) Corrigendum to “Microstructure, mechanical and thermal properties of in situ toughened boron carbide – based ceramic composites co-doped with tungsten carbide and pyrolytic carbon”. J Eur Ceram Soc 36:949 2402. Remanan M, Bhowmik S, Varshney L, Jayanarayanan K (2019) Tungsten carbide, boron carbide and MWCNT reinforced poly(aryl ether ketone) nanocomposites: morphology and thermomechanical behaviour. J Appl Polym Sci 136(5):47032 (13 pp.) 2403. Medjahed A, Derradji M, Zegaoui A, Wu R, Li B, Wang Y, Hou L, Zhang J, Zhang M (2019) Fabrication process, tensile and gamma rays shielding properties of newly developed fiber metal laminates based on an Al-Li alloy and carbon fiber – tungsten carbide nanoparticles reinforced phthalonitrile resin composite. Adv Eng Mater 21(2):1800779 (9 pp.) 2404. Szaniawska E, Rutkowska IA, Seta E, Tallo I, Lust E, Kulesza PJ (2020) Photoelectrochemical reduction of CO2: stabilization and enhancement of activity of copper (I) oxide semiconductor by over-coating with tungsten carbide and carbide-derived carbons. Electrochim Acta 341:136054 (14 pp.) 2405. Laptev AV, Myslyvchenko OM, Tolochyn OI, Karpets MV, Kuzmenko LM, Silinska TA (2018) Features of the interaction and phase formation in the WC-Fe2O3-C system when heated in vacuum and in argon. J Superhard Mater 40(4):243-253 2406. Laptev AV, Myslyvchenko OM, Tolochyn OI, Karpets MV, Silinska TA, Kuzmenko LM (2018) Interaction and phase formation in the WC-Fe2O3-NiO-C system heated in vacuum and argon. Powder Metall Met Ceram 57(1-2):49-56 2407. Ma M, You S, Wang W, Liu G, Qi D, Chen X, Qu J, Ren N (2016) Biomass-derived porous Fe3C / tungsten carbide / graphitic carbon nanocomposite for efficient electrocatalysis of oxygen reduction. ACS Appl Mater Interfaces 8:32307-32316

708

2 Tungsten Carbides

2408. Liu XY, Shi XL, Duan LC, Tang FL (2004) Research on diamond enhanced rare-earth and iron-rich carbide tungsten composite button and its bit. In: Xu X (ed) Advances in grinding and abrasive processes. Selected papers from the 12th grinding and machining conf., Kunming, China, 28-30 Nov 2003. Key Eng Mater 258-259:97-100 2409. Zhu W, McCune RC, DeVries JE, Tamor MA, Simon-Ng KY (1994) Characterization of diamond films on binderless W-Mo composite carbide. Diam Relat Mater 3(10):1270-1276 2410. Liu C, Komatsu M, Nino A, Sugiyama S, Taimatsu H (2012) Preparation of WC-MoC ceramics and their mechanical properties. J Jpn Soc Powder Powder Metall 59(8):479-483 2411. Baghirov OÉ (2017) Kompozitsionnye materialy almaz – (WC-Co-NbN) dlya burovykh dolot (Diamond – (WC-Co-NbN) composite materials for drilling bits). SOCAR Proc (2):013-022 (in Russian) 2412. Zeng T (2005) Wear performance of WC-NiP composites under corrosion condition. Corros Protect 26(12):510-511, 533 (in Chinese) 2413. Kitiwan M, Goto T (2019) Fabrication of tungsten carbide – diamond composites using SiC-coated diamond. Int J Refract Met Hard Mater 85:105053 (7 pp.) 2414. Gong Z-Q, Wang C-M, Cui H-Z, Zhang W-Y (2019) Effect of graphene on the microstructure and properties of nickel-based tungsten carbide coatings by laser cladding. Powder Metall Technol 37(5):323-331 (in Chinese) 2415. Zhang L-N, Ma Y-Y, Lang Z-L, Wang Y-H, Khan SU, Yan G, Tan H-Q, Zang H-Y, Li YG (2018) Ultra-fine cable-like WC/W2C heterojunction nanowires covered by graphitic carbon towards highly efficient electrocatalytic hydrogen evolution. J Mater Chem A 6(31):15395-15403 2416. Kurlov AS, Rempel AA (2007) Effect of sintering temperature on the phase composition and microhardness of WC – 8 wt.% Co cemented carbide. Inorg Mater 43(6):602-607 2417. Voevodin AA, O’Neill JP, Zabinski JS (1999) Nanocomposite tribological coatings for aerospace applications. Surf Coat Technol 116-119:36-45 2418. Voevodin AA, O’Neill JP, Zabinski JS (1999) WC/DLC/WS2 nanocomposite coatings for aerospace tribology. Tribol Lett 6(2):75-78 2419. Sundberg J, Nyberg H, Särhammar E, Gustavsson F, Kubart T, Nyberg T, Jacobson S, Jansson U (2013) Influence of Ti addition on the structure and properties of low-friction WS-C coatings. Surf Coat Technol 232:340-348 2420. Lin J-F, Pitkänen O, Mäklin J, Puskas R, Kukovecz A, Dombovari A, Toth G, Kordas K (2015) Synthesis of tungsten carbide and tungsten disulphide on vertically aligned multiwalled carbon nanotube forests and their applications as non-Pt electrocatalysts for the hydrogen evolution reaction. J Mater Chem A 3(28):14609-14616 2421. Shi M, Li W, Fang J, Jiang Z, Gao J, Chen Z, Sun F, Xu Y (2018) Electronic structure tuning during facile construction of two-phase tungsten based electrocatalyst for hydrogen evolution reaction. Electrochim Acta 283:834-841 2422. Nagatsuka K, Sechi Y, Miyamoto Y, Nakata K (2012) Characteristics of dissimilar laserbrazed joints of isotropic graphite to WC-Co alloy. Mater Sci Eng B 177:520-523 2423. Nagatsuka K, Sechi Y, Nakata K (2012) Dissimilar joint characteristics of SiC and WC-Co alloy by laser brazing. In: Takahashi Y (ed) Eco-materials and eco-innovation for global sustainability. Proc. Int. symp. on materials science and innovation for sustainable society, (ECO-MATES 2011), Osaka, Japan, 28-30 Nov 2011. J Phys Conf Series 379(1):012047 (9 pp.) 2424. Ghasali E, Pakseresht AH, Agneli M, Marzbanpour AH, Ebadzadeh T (2015) WC-Co particles reinforced aluminium matrix by conventional and microwave sintering. Mater Res 18(6):1197-1202 2425. Johnston JM, Catledge SA (2016) Metal boride phase formation on tungsten carbide (WCCo) during microwave plasma chemical vapour deposition. Appl Surf Sci 364:315-321 2426. Wang X, Song X, Zhang Z, Liu Xu, Liu Xi, Yang C, Li Y (2016) Preparation and mechanical properties of hard metals using graphene as carbon source. Rare Met Mater Eng 45(12):3262-3266 (in Chinese)

References

709

2427. Kang N, Ma W, Heraud L, El-Mansori M, Li F, Liu M, Liao H (2018) Selective laser melting of tungsten carbide reinforced maraging steel composite. Addit Manuf 22:104-110 2428. Kang N, Ma W, Li F, Liao H, Liu M, Coddet C (2018) Microstructure and wear properties of selective laser melted WC reinforced 18Ni-300 steel matrix composite. Vacuum 154:69-74 2429. Linder D (2015) High-entropy alloys – alternative binders in cemented carbides. MSc thesis, Linköping University, Sweden 2430. Linder D, Holmström E, Norgren S (2018) High-entropy alloy binders in gradient sintered hardmetal. Int J Refract Met Hard Mater 71:217-220 2431. Humenik M, Jr, Parikh NM (1956) Cermets. 1. Fundamental concepts related to microstructure and physical properties of cermet systems. J Am Ceram Soc 39(2):60-63 2432. Fukatsu T (1961) Structure and property of binder phase of WC-Co composition. J Jpn Soc Powder Powder Metall 8(5):183-194 (in Japanese) 2433. Kingery WD, Niki E, Narasimhan MD (1961) Sintering of oxide and carbide-metal compositions in presence of a liquid phase. J Am Ceram Soc 44(1):29-35 2434. Tumanov VI, Funke VF, Trukhanova ZS, Novikova TA, Kuznetsova KF (1964) The heat treatment of tungsten carbide – cobalt alloys. Powder Metall Met Ceram 3(2):131-133 2435. Kreimer GS, Vakhovskaya MR (1965) The effect of carbon content on the mechanical properties of tungsten carbide – cobalt hard alloys. Powder Metall Met Ceram 4(6):454-459 2436. Krushinskii AN (1966) Investigation of the conditions of the formation of hard alloys with an uneven distribution of the carbide phase. Communication 1. Powder Metall Met Ceram 5(3):220-223 2437. Krushinskii AN (1966) Investigation of the effect of the temperature at which tungsten carbide is produced on the formation of solid solutions with a non-uniform distribution of the carbide phase. Communication 2. Powder Metall Met Ceram 5(4):273-276 2438. Li CJ, Ohmori A, Harada Y (1966) Formation of an amorphous phase in thermally sprayed WC-Co. J Therm Spray Technol 5(1):69-73 2439. Tumanov VI, Shchetilina EA, Elmanova SM, Cheredinov AA (1969) Plastic deformation and magnetic properties of solid solutions of tungsten carbide in cobalt. Powder Metall Met Ceram 8(2):142-145 2440. Tumanov VI (1969) Study of the structure of hard cermet WC-Co and WC-TiC-Co alloys by magnetic methods. Powder Metall Met Ceram 8(3):231-234 2441. Coster M, Chermant JL, Deschanvres A (1972) Cinetique de croissance des cristaux de WC dans le cobalt (Kinetics of growth of WC crystals in cobalt). Mem Sci Rev Metall 69(9):465-478 (in French) 2442. Chermant JL, Coster M, Deschanvres A (1975) Utilisation de la métallographie quantitative et de la stéréologie à l’etude des matériaux composites. 1. Etude critique des méthodes. Application à la fractographie quantitative. (Use of quantitative metallography and stereology in the study of composite materials. I. Critical study of the methods. Application to quantitative fractography.) Metallogr 8:271-291 (in French) 2443. Chermant JL, Coster M, Osterstock F (1976) Utilisation de la métallographie quantitative et de la stéréologie à l’etude des matériaux composites. II. Application à l’etude de la rupture d’eprouvettes de flexion en WC-Co. (Use of quantitative metallography and stereology in the study of composite materials. II. Application to the study of the fracture of bending test specimens of WC-Co.) Metallogr 9:503-523 (in French) 2444. Chermant JL, Osterstock F (1976) Fracture toughness and fracture of WC-Co composites. J Mater Sci 11:1939-1951 2445. Nelson RJ, Milner DR (1972) Densification processes in the tungsten carbide – cobalt system. Powder Metall 15(30):346-363 2446. Petrova EM, Shcherban NI (1972) Solid-phase reactions in cobalt – carbide systems. Powder Metall Met Ceram 11(1):28-32 2447. Samsonov GV, Panasyuk AD, Kozina GK, Dyakonova LV (1972) Contact reaction of refractory compounds with liquid metals. II. Reaction of carbides of subgroups Va and VIa metals with liquid transition metals. Powder Metall Met Ceram 11(8):629-631

710

2 Tungsten Carbides

2448. Samsonov GV, Panasyuk AD, Kozina GK (1972) O vzaimodeistvii metallopodobnykh karbidov s zhidkimi perekhodnymi metallami (On the interaction of metal-like carbides with liquid transition metals). In: Eremenko VN (ed) Smachivaemost i poverkhnostnye svoistva rasplavov i tverdykh tel (Wettability and surface properties of melts and solids), pp. 85-102. Naukova Dumka, Kyiv (in Russian) 2449. Jonsson H (1973) Composition and microstructure of binder phases of slowly cooled WCCo cemented carbides. Planseeber Pulvermetall 21(3):187-208 2450. Day JP, Ruoff AL (1973) Pressure dependence of elastic moduli of tungsten carbide cermet. J Appl Phys 44(6):2447-2448 2451. Suzuki H, Hayashi K, Tanase T (1973) Calorimetric studies on WC-Co cemented carbide. J Jpn Inst Met 37(1):9-13 (in Japanese) 2452. Suzuki H, Tanase T, Hayashi K (1973) Microscopic examination on ε′-phase in cemented carbide. J Jpn Soc Powder Powder Metall 20(2):55-61 (in Japanese) 2453. Suzuki H, Hayashi K, Fuke Y (1973) The grain size of binder phase in WC-Co alloy. J Jpn Soc Powder Powder Metall 19(8):346-353 (in Japanese) 2454. Suzuki H (1966) Variations in some properties of sintered tungsten carbide – cobalt alloys with particle size and binder composition. Trans Jpn Inst Met 7(2):112-116 2455. Suzuki H, Hayashi K, Yamamoto T, Miyake K (1974) Strengthening phenomena of WCCo cemented carbide prepared by hot isostatic pressing. J Jpn Soc Powder Powder Metall 21(4):108-111 (in Japanese) 2456. Suzuki H, Tanase T, Nakayama F (1975) The mechanism of pore formation in WC-Co cemented carbide. J Jpn Soc Powder Powder Metall 22(6):192-197 (in Japanese) 2457. Suzuki H, Hayashi K, Fukuda M, Tanase T, Nakayama F (1975) Relations between transverse rupture strength of WC-Co cemented carbides and cooling rate after sintering. J Jpn Soc Powder Powder Metall 22(7):226-231 (in Japanese) 2458. Suzuki H, Hayashi K, Yamamoto T (1975) Relations between impact strength and structural defects in WC-Co cemented carbide. J Jpn Soc Powder Powder Metall 22(5):160166 (in Japanese) 2459. Suzuki H, Tanase T, Nakayama F (1976) Strength decrease in WC-Co low carbon cemented carbide due to precipitation treatment. J Jpn Soc Powder Powder Metall 23(5):163166 (in Japanese) 2460. Fukuda M, Tsuchiya N, Suzuki H (1987) The interfacial reaction between WC-Co cemented carbide and glasses. J Jpn Soc Powder Powder Metall 34(8):344-348 (in Japanese) 2461. Lisovskii AF, Bondarenko VP, Vishnevskii AS, Nikityuk AF (1974) Kinetics of penetration of molten cobalt into hard alloys. Powder Metall Met Ceram 13(6):496-498 2462. Nissenholts Z, Barta J (1974) Sintering of WC-Co alloy in hydrocarbon-hydrogen mixtures. Planseeber Pulvermetall 22(2):81-90 2463. Chaporova IN (1975) Rol tverdofaznogo spekaniya v formirovanii struktury splavov WCCo (Role of solid-phase sintering in the formation of the structure of WC-Co alloys). Tsvet Met (12):60-61 (in Russian) 2464. Ivensen VA (1975) Effect of tungsten carbide grain size on the strength of WC-Co alloys. Powder Metall Met Ceram 14(1):60-64 2465. Sarin VK, Johannesson T (1975) On the deformation of WC-Co cemented carbides. Met Sci 9(1):472-476 2466. Tkachenko YuG, Sychev VV, Apininskaya LM, Kanecskaya TsA, Sharivker SYu, Astakhov EA, Garda AP (1975) Wear-resistant hard alloy coatings. Powder Metall Met Ceram 14(7):552-554 2467. Venter R, Critchley S, De Malherbe MC (1975) The evaluation of tungsten carbide properties as applied to high pressure equipment. Mater Sci Eng 19:201-210 2468. Almond EA, May AT, Roebuck B (1976) Stress corrosion cracking of a 6 % cobalt / tungsten carbide hard metal. J Mater Sci 11:565-568 2469. Froschauer L, Fulrath RM (1976) Direct observation of liquid-phase sintering in the system tungsten carbide – cobalt. J Mater Sci 11:142-149

References

711

2470. Meredith B, Milner DR (1976) Densification mechanisms in the tungsten carbide – cobalt system. Powder Metall 19(1):38-45 2471. Warren R (1976) Determination of the interfacial energy ratio in two-phase systems by measurement of interphase contact. Metallogr 9:183-191 2472. Chermant JL, Coster M, Deschanvres A, Iost A (1977) Étude de la cinétique de croissance de systems carbure-métal (A study of the grain growth kinetics of carbide-metal systems). J Less-Common Met 52:177-196 (in French) 2473. Eschnauer HR, Knotek O (1977) Complex carbide powders for plasma spraying. In: Bunshah RF (ed) Proc. 2nd Int. conf. on metallurgical coatings, San Francisco, California, 28 Mar – 1 Apr 1977. Thin Solid Films 45:287-294 2474. Lisovskii AF (1977) Mechanism of penetration of liquid metals into sintered WC-Co hard alloys. Powder Metall Met Ceram 16(8):612-615 2475. Pikunov DV, Tretyakov VI (1977) Ob anizotropii mezhfaznoi energii v kristallakh WC splavov WC-Co (On the anisotropy of interphase energy in the WC crystals of WC-Co alloys). Tsvet Met (3):64-65 (in Russian) 2476. Kovalchenko MS, Bronshtein DKh, Ochkas LF, Tsypin NV (1978) Densification kinetics in the hot-pressing of VK6 hard alloy. Powder Metall Met Ceram 17(7):517-519 2477. Gerlich D, Kennedy GC (1979) The elastic moduli and their pressure derivatives for tungsten carbide with different amounts of cobalt binder. J Appl Phys 50(5):3331-3333 2478. Roebuck B (1979) The tensile strength of hardmetals. J Mater Sci 14:2837-2844 2479. Westin L, Franzen T (1979) Eutectic reactions during solidification of Co-W-C alloys containing 10-17 at.% W and 8-14 at.% C. Scand J Metall 8(5):205-215 2480. Hagege S, Vicens J, Nouet G, Delavignette P (1980) Analysis of structure defects in tungsten carbide. Phys Stat Sol A 61(2):675-687 2481. Sharma NK, Ward ID, Fraser HL, Williams WS (1980) STEM analysis of grain boundaries in cemented carbides. J Am Ceram Soc 63(3-4):194-196 2482. Bronshtein DKh, Simkin ÉS, Panich AN, Tsypin NV (1981) Optimization of the hotpressing of VK6 hard metal. Powder Metall Met Ceram 20(5):334-337 2483. LeRoux H (1981) The martensitic transformation in and the transverse rupture strength of certain heat-treated WC – 25 wt.% Co hardmetals. In: Ortner HM (ed) Trends in refractory metals, hard metals and special materials and their technology. Proc. 10th Int. Plansee seminar, Reutte, Tirol, Austria, 1-5 June 1981. High Temp High Press 13(5):503-506 2484. Luyckx SB (1981) Some features of the eta-phase in substoichiometric WC – 6 % Co alloys. In: Ortner HM (ed) Trends in refractory metals, hard metals and special materials and their technology. Proc. 10th Int. Plansee seminar, Reutte, Tirol, Austria, 1-5 June 1981. High Temp High Press 13(5):507-510 2485. Tuma H, Ciznerova M (1981) Termodynamicka studie a rovnovazny diagram systemu CoW-C v oblasti bohate na kobalt v teplotnim rozsahu 1000-1200 °C ( Thermodynamic study and the equilibrium diagram of the system Co-W-C in cobalt-rich region in the temperature range of 1000-1200 °C). Kovove Mater 19(4):389-403 (in Czech) 2486. Tumanov VI, Romanova NI, Elmanova SM, Cheredinov AA (1981) Regulation and determination of the phase composition of tungsten hard metals. Powder Metall Met Ceram 20(4):275-278 2487. Alfintseva RA, Kadyrov VKh, Fedorenko VK, Sharypov AZ (1982) Structural investigations of detonation-deposited tungsten carbide – cobalt coatings. Powder Metall Met Ceram 21(10):772-776 2488. Deshmukh R, Gurland J (1982) Orientation of contiguous tungsten carbide crystals in sintered WC-Co as determined from slip line traces. Metallogr 15:383-390 2489. Kang SG, Fromm E (1982) Reaction of oxygen with WC powder compacts and WC-Co hardmetals at high temperatures and low pressures. Powder Metall Int 14(4):201-204 2490. Kolchin OP (1982) Control over the structure of hard metals and other hetero-phase materials produced by liquid-phase sintering. I. Liquid-phase migration and general principles of sintering of “skeletonless” alloys. Powder Metall Met Ceram 21(9):694-697

712

2 Tungsten Carbides

2491. Kolchin OP (1982) Control over the structure of hard metals and other hetero-phase materials produced by liquid-phase sintering. II. Principles of optimum design of hard metals. Powder Metall Met Ceram 21(10):768-771 2492. LeRoux H (1982) Spatial relationship between WC and Co in cemented carbides. Int J Refract Met Hard Mater 1(4):166-167 2493. Dusza J, Parilák Ĺ, Diblk J, Šlesar M (1983) Elastic and plastic behaviour of WC-Co composites. Ceram Int 9(4):144-146 2494. Friederich KM (1983) Cobalt enrichment at tungsten carbide grain boundaries in hardmetals. Met Sci 17(9):456-458 2495. Lee JW, Browne JD, Jaffrey D (1983) Some stereological properties of hexagonal prisms. Metallogr 16:255-264 2496. Bronshtein DKh, Simkin ÉS, Sklyar SI, Cherepenina ES (1984) Distribution of the cementing phase in hot-pressed hard metals. Powder Metall Met Ceram 23(3):208-210 2497. Larson FG, Hong J, Goodson R, Voytek M (1984) Hot isostatic pressing of cemented carbides. Int J Refract Met Hard Mater 3(1):30-34 2498. Novikov NV, Devin LN, Mitlikin MD, Ulyanenko AP (1984) Influence of the matrix structure and properties on the crack resistance of sintered carbides. Powder Metall Met Ceram 23(12):968-971 2499. Pastor H (1984) Fabrication et proprietes d’utilisation des cermets carbure de tungsten – cobalt. Prospective dans le domaine de la coupe. (Fabrication and service properties of tungsten carbide – cobalt cermets. Outlook for their use in metal cutting.) Mater Techn 72(12):433-450 (in French) 2500. Sale FR (1984) Thermochemistry and phase equilibria in the W-O, W-C and related WCo-containing ternary systems. J Less-Common Met 100:277-297 2501. Chernyavskii KS (1985) Stereological characteristics of hetero-phase materials. Powder Metall Met Ceram 24(1):73-77 2502. Holleck H (1985) Ternäre Carbidsysteme mit Mangan, Eisen, Kobalt und Nickel und deren Bedeutung für verschleißfeste Werkstoffe (Ternary carbide systems with manganese, iron, cobalt and nickel and their significance for wear-resistant materials). Metall 39(7):634645 (in German) 2503. Kharlamov YuA, Ryaboshapko BL, Pisklov YuI, Shmyreva TP (1985) Change in phase composition of VK8 powder in detonation-gas spraying. Powder Metall Met Ceram 24(11):855-859 2504. Krawitz AD (1985) The use of X-ray stress analysis for WC-base cermets. Mater Sci Eng 75:29-36 2505. Laugier MT (1985) A microstructural model for hardness in WC-Co composites. Acta Metall 33(11):2093-2099 2506. Maritzen W, Ettmayer P, Kny E (1985) Lattice parameters and saturation magnetization of Co-W-C alloys. Powder Metall Int 17(2):68-71 2507. Tu D, Chang S, Chao C, Lin C (1985) Tungsten carbide phase transformation during the plasma spray process. J Vac Sci Technol A 3(6):2479-2482 2508. Aleksandrova LI, Loshak MG, Gorbacheva TB, Varaksina AV (1986) An X-ray diffraction investigation of heat-treated WC-Co sintered carbides. Powder Metall Met Ceram 25(5):437-441 2509. Chernyavskii KS (1986) A stereological analysis of the formation of the structure of WCCo alloys during consolidation of the carbide powder. Powder Metall Met Ceram 25(3):225229 2510. Luyckx SB (1986) An empirical correlation between bulk toughness and Palmqvist crack length in WC-Co. J Mater Sci Lett 5:357-358 2511. Roebuck B, Bennet EG (1986) Phase size distribution in WC/Co hardmetal. Metallogr 19:27-47

References

713

2512. Zur Megede D, Heitz E (1986) Das Korrosionsverhalten von Hartmetall-Verbundwerkstoffen in chloridhaltigen wäßrigen Lösungen (Corrosion behaviour of hardmetal composites in chloride containing aqueous solutions). Werkst Korros 37(5):207-214 (in German) 2513. Kudryavtseva VI, Chaporova IN, Varaksina AV (1987) Heat treatment of WC-Co sintered carbides and parts of them. Powder Metall Met Ceram 26(5):396-400 2514. Laugier MT (1987) Palmqvist toughness in WC-Co composites viewed as a ductile / brittle transition. J Mater Sci Lett 6:768-770 2515. Laugier MT (1987) Comparison of toughness in WC-Co determined by a compact tensile technique with model predictions. J Mater Sci Lett 6:779-780 2516. Laugier MT (1987) Hertzian indentation of ultra-fine grain size WC-Co composites. J Mater Sci Lett 6:841-843 2517. Laugier MT (1987) Palmqvist indentation toughness in WC-Co composites. J Mater Sci Lett 6:897-900 2518. Li J, Wu T, Ren S, Shi H (1987) Martensitic transformation in the binder of a WC-Co cemented carbide. J Central South Inst Min Metall 18(6):649-652 (in Chinese) 2519. Schultrich B, Wetzig K (1987) Investigation of laser irradiation of WC-Co cemented carbides inside a scanning electron microscope (LASEM) J Mater Sci 22:3361-3367 2520. Tronche A, Fauchais P (1987) Hard coatings (Cr2O3, WC-Co) properties on aluminium or steel substrates. Mater Sci Eng 92:133-144 2521. Alekseev NV, Bronshtein DKh, Grechikov MI, Simkin ÉS, Tsypin NV (1988) Hot-pressed hard alloy matrix materials with finely disperse cobalt powders. Powder Metall Met Ceram 27(9):730-733 2522. Hellsing M (1988) High resolution microanalysis of binder phase in as sintered WC-Co cemented carbides. Mater Sci Technol 4(9):824-829 2523. Park J-K, Eun KY, Yoon DN (1988) Anomalous growth of the complex carbide phase in carbon-deficient WC-Co hard metal during the infiltration of eutectic liquid. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:233-236 2524. Tomlinson WJ, Linzell CR (1988) Anodic polarization and corrosion of cemented carbides with cobalt and nickel binders. J Mater Sci 23:914-918 2525. Blinkov IV, Vishnevetskaya IA, Kostyukovich TG, Ostapovich AO (1989) Plasma metal coating of finely divided carbides for spray deposition and weld facing. Powder Metall Met Ceram 28(1):17-21 2526. Gumnitskii YaM, Pelekh MP, Givlyud NN (1989) Special features of kinetics of hightemperature oxidation of VK8VK alloy. Mater Sci 24(5):458-463 2527. Luyckx SB (1989) WC-Co components with textured surfaces. In: Bildstein H. Ortner HM (ed) High-temperature and wear-resistant materials in a world of changing technology. Proc. 12th Int. Plansee seminar, Reutte, Tirol, Austria, 8-12 May 1989, Vol. 2 – Wear-resistant mate-rials, pp. 215-221. Plansee Holding AG, Reutte, Austria 2528. Nishimura T, Ishibashi O, Imasato S, Takechi K, Tokumoto K (1989) Presintering of WCNi cemented carbides in H2-CH4 atmosphere. J Jpn Soc Powder Powder Metall 36(2):110114 (in Japanese) 2529. Raichenko AI, Chernikova ES (1989) Theoretical analysis of the heating of pseudoalloys by the passage of an electric current. Powder Metall Met Ceram 28(7):517-519 2530. Antonopoulos JG, Delavignette P, Karakostas Th, Komninou Ph, Laurent-Pinson E, Lay S, Nouet G, Vicens J (1990) Coincidence in hexagonal materials. In: Proc. Int. congress on intergranular and interphase boundaries in materials, Paris, France, 4-8 Sep 1989. J Phys Colloq C1(1):61-69 2531. Kumazawa M (1990) Mechanism of crystal growth and coalescence of tungsten carbide in the presence of cobalt liquid phase. Mater Trans Jpn Inst Met 31(8):685-688 2532. Larikov LN, Tishkova TT, Tyshkevich VM, Shmatko OA (1990) Study of the kinetics of oxidation of W-Co and WC-Co alloys. Protect Met 25(4):524-526

714

2 Tungsten Carbides

2533. Marshall DB, Morris WL, Cox BN, Dadkhah S (1990) Toughening mechanisms in cemented carbides. J Am Ceram Soc 73(10):2938-2943 2534. Spiegler R, Schmauder S, Sigl LS (1990) Fracture toughness evaluation of WC-Co alloys by indentation testing. J Hard Mater 1(3):147-158 2535. Vicens J, Lay S, Benjdir M, Nouet G (1990) Nature of the boundary planes in tungsten carbide – cobalt composites. In: Proc. Int. congress on intergranular and interphase boundaries in materials, Paris, France, 4-8 Sep 1989. J Phys Colloq C1(1):353-358 2536. Kaliya MA, Loshak MG (1991) Problem of the mechanism of hardening hard alloys by heat treatment. Powder Metall Met Ceram 30(7):84-86 2537. Luyckx SB, Katzourakis J (1991) Preparation and properties of WC-Co textured components. Mater Sci Technol 7(5):472-474 2538. Nordgren A (1991) Microstructural characterization of cemented carbides using SEM based automatic image analysis. Int J Refract Met Hard Mater 10:61-81 2539. Tsuchiya N, Fukuda M, Nakai T, Suzuki H (1991) Strength decrease of WC-Co alloy due to surface oxidation. J Jpn Soc Powder Powder Metall 38(4):505-509 (in Japanese) 2540. Bhaumik SK, Upadhyaya GS, Vaidya ML (1992) Alloy design of WC – 10 Co hard metals with modifications in carbide and binder phases. Int J Refract Met Hard Mater 11:9-22 2541. Bhaumik SK, Upadhyaya GS, Vaidya ML (1992) A transmission electron microscopy study of WC – 10 Co cemented carbides with modified hard and binder phases. Mater Charact 28:241-249 2542. Nerz J, Kushner B, Rotolico A (1992) Microstructural evaluation of tungsten carbide – cobalt coatings. J Therm Spray Technol 1(2):147-152 2543. Ulyanov VL, Chernov IP, Botaki AA, Chakhlov BV (1992) Acoustic emission investigations of structural changes in tungsten carbide metal-ceramics during thermal and radiation treatment and hydrogenation. Glass Ceram 49(10):473-477 2544. Andrén H-O, Rolander U, Lindahl P (1993-1994) Phase composition in cemented carbides and cermets. Int J Refract Met Hard Mater 12:107-113 2545. Colin C, Durant L, Favrot N, Besson J, Barbier G, Delannay F (1993-1994) Processing of functional gradient WC-Co cermets by powder metallurgy. Int J Refract Met Hard Mater 12:145-152 2546. Guilemany JM, Sanchiz I, Mellor BG, Llorca N, Miguel JR (1993-1994) Mechanical property relationships of Co/WC and Co-Ni-Fe/WC hard metal alloys. Int J Refract Met Hard Mater 12:199-206 2547. Luyckx SB, Barlow-Jones W, Koursaris A, Mastrantonis N (1993-1994) Healing of cracks in WC-Co in the temperature range 600-800 °C. Int J Refract Met Hard Mater 12:89-93 2548. Uhrenius B (1993-1994) Evaluation of molar volumes in the Co-W-C system and calculation of volume fractions of phases in cemented carbides. Int J Refract Met Hard Mater 12:121-127 2549. Boo M-H, Oh S-W, Takano N, Kishi Y, Hirose Y (1993) X-ray stress measurement of WC-Co alloy: X-ray study of plastic deformation of WC-Co alloy. In: Puthli RS, Dos Santos JF, Berg S, Ellinas CP, Ueda Y (eds) Proc. 3rd Int. offshore and polar engineering conf., Singapore, 6-11 June 1993, Vol. 4, pp. 458-461. International Society of Offshore and Polar Engineers, Golden, Colorado 2550. Cavaleiro A, Trindade B, Vieira MT (1993) Structural analysis of sputtered (W-C)1–xMx (M ≡ Fe, Co) films with 0 ≤ x ≤ 0.20. Surf Coat Technol 60:411-415 2551. Kobayashi K, Takayanagi T, Miwa K (1993) Preparation of the hard metals containing small amounts of cobalt by mechanical alloying treatment. J Jpn Soc Powder Powder Metall 40(1):62-65 (in Japanese) 2552. Lee IC, Hondo H, Sakuma T (1993) Non-uniform carbide grain growth during hightemperature compressive deformation in WC – 13 wt.% Co. Scripta Metall Mater 28:97-102 2553. Shinohara K, Ueda F, Tanase T (1993) Thermal expansion coefficient and thermal conductivity of WC based cemented carbides. J Jpn Soc Powder Powder Metall 40(1):29-32 (in Japanese)

References

715

2554. Tomita T, Takatani Y, Kobayashi Y, Harada Y, Nakahira H (1993) Durability of WC/Co sprayed coatings in molten pure zinc. ISIJ Int 33(9):982-988 2555. Ammann JJ, Schaller R (1994) Influence of a changing microstructure on high temperature relaxation peaks, an example: WC – 11 wt.% Co. J Alloys Compd 211-212:397-401 2556. Bouaouadja N, Hamidouche M, Osmani H (1994) Fracture toughness of WC-Co cemented carbides at room temperature. J Mater Sci Lett 13:17-19 2557. Konyashin IYu (1994) The mechanism of interaction between Cl-containing gaseous phase and cemented carbides in the chemical vapour deposition process. Thin Solid Films 249:174-182 2558. Tani K, Tomita T, Kobayashi Y, Takatani Y, Harada Y (1994) Durability of sprayed WC/Co coatings in Al-added zinc bath. ISIJ Int 34(10):822-828 2559. Vicens J, Benjdir M, Nouet G, Dubon A, Laval JY (1994) Cobalt intergranular segregation in WC-Co composites. J Mater Sci 29:987-994 2560. Kwon P, Dharan CKH (1995) Effective moduli of high volume fraction particulate composites. Acta Metall Mater 43(3):1141-1147 2561. Spriggs GE (1995) A history of fine grained hardmetal. Int J Refract Met Hard Mater 13(5):241-255 2562. Suzuki H, Terada O, Ike H (1995) Pore formation in micro-grained WC-Ni alloy. J Jpn Soc Powder Powder Metall 42(11):1341-1344 (in Japanese) 2563. Basu SN, Sarin VK (1996) Oxidation behaviour of WC-Co. Mater Sci Eng A 209:206-212 2564. Cho KH, Lee JW, Chung IS (1996) A study on the formation of anomalous large WC grain and the eta phase. Mater Sci Eng A 209:298-301 2565. Kuwano S, Itoh Y, Ohtomo H, Hirozumi S, Murata S (1996) Condition of spraying WCCo hard layer by low pressure plasma spray. J Surf Finish Soc Jpn 47(3):235-239 (in Japanese) 2566. O’Quigley DGF, Luyckx S, James MN (1996) New results on the relationship between hardness and fracture toughness of WC-Co hardmetal. Mater Sci Eng A 209:228-230 2567. Voitovich VB, Sverdel VV, Voitovich RF, Golovko EI (1996) Oxidation of WC-Co, WCNi and WC-Co-Ni hard metals in the temperature range 500-800 °C. Int J Refract Met Hard Mater 14:289-295 2568. Xueming MA, Gang JI (1996) Nanostructured WC-Co alloy prepared by mechanical alloying. J Alloys Compd 245:L30-L32 2569. Grimberg I, Soifer K, Bouaifi B, Draugelates U, Weiss BZ (1997) Tungsten carbide coatings deposited by high-velocity oxy-fuel spraying on a metallized polymeric substrate. In: Proc. Int. conf. on metallurgical coatings and thin films, San Diego, California, 22-26 Apr 1996 (ICMCTF’96). Surf Coat Technol 90:82-90 2570. Human AM, Exner HE (1997) The relationship between electrochemical behaviour and inservice corrosion of WC based cemented carbides. Int J Refract Met Hard Mater 15:65-71 2571. Kim BK, Ha GH, Lee DW (1997) Sintering and microstructure of nanophase WC/Co hardmetals. J Mater Process Technol 63:317-321 2572. Leitner G, Jaenicke-Roessler K, Gestrich T, Breuning T (1997) Shrinkage, liquid phase formation and gas reactions during the sintering of WC-Co hard metals. In: McKotch RA, Webb R (eds) Advances in powder metallurgy and particulate materials. Proc. Int. conf. on powder metallurgy and particulate materials, Chicago, Illinois, 29 June – 2 July 1997, Part 1, Vol. 2, pp. 12-75. Metal Powder Industries Federation, Princeton, New Jersey 2573. Milman YuV, Chugunova S, Goncharuck V, Luyckx S, Northrop IT (1997) Low and high temperature hardness of WC – 6 % Co alloys. Int J Refract Met Hard Mater 15:97-101 2574. Penrice TW (1997) Some characteristics of the binder phase in cemented carbides. Int J Refract Met Hard Mater 15:113-121 2575. Suda Y, Nakazono T, Ebihara K, Baba K (1997) Pulsed laser deposition of tungsten carbide thin films on silicon (100) substrate. Nucl Instrum Meth B 121:396-399

716

2 Tungsten Carbides

2576. De Villiers-Lovelock HL (1998) Powder / processing / structure relationships in WC-Co thermal spray coatings: a review of the published literature. J Therm Spray Technol 7:357373 2577. Barbezat G, Müller E, Walser B (1988) Applying tungsten carbide cobalt coatings by high-velocity combustion spraying. Sulzer Tech Rev 70(4):4-10 2578. Karimi A, Verdon Ch, Barbezat G (1993) Microstructure and hydroabrasive wear behaviour of high-velocity oxy-fuel thermally sprayed WC – Co(Cr) coatings. Surf Coat Technol 57(1):81-89 2579. Sarin VK (1977) Morphology of eta phase in cemented WC-Co alloys. In: Hausner HH (ed) Modern developments in powder metallurgy, Vol. 10, pp. 553-565. Metal Powder Industries Federation, Princeton, New Jersey 2580. Rangaswamy S, Herman H (1986) Metallurgical characterization of plasma sprayed WCCo coatings. In: Eaton NF (ed) Advances in thermal spraying. Proc. 11th Int. thermal spraying conf. (ITSC’86), Welding Institute of Canada, Montréal, Québec, 8-12 Sep 1986, pp. 101110. Pergamon Press, New York, Oxford 2581. Ramnath V, Jayaraman N (1989) Characterization and wear performance of plasma sprayed WC-Co coatings. Mater Sci Technol 5(4):382-388 2582. Kim HJ, Kweon YG, Chang RW (1994) Wear and erosion behaviour of plasma sprayed WC-Co coatings. J Therm Spray Technol 3(2):169-178 2583. Varacalle DJ, Jr, Acosta E, Figert J, Syma M, Worthington J, Carrillo D (1996) Experimental / analytical investigations of air plasma spray tungsten carbide – cobalt coatings at Kelly Air Force Base. In: Berndt CC (ed) Thermal spray: practical solutions for engineering problems, pp. 699-707. ASM International, Metals Park, Ohio 2584. Mazars P, Manesse D, Lopvet C (1986) Structures de revetements de carbure de tungstene obtenus par differents procedes de projection (Structures of tungsten carbide coatings obtained by different spray processes). In: Eaton NF (ed) Advances in thermal spraying. Proc. 11th Int. thermal spraying conf. (ITSC’86), Welding Institute of Canada, Montréal, Québec, 8-12 Sep 1986, pp. 111-120. Pergamon Press, New York, Oxford (in French) 2585. Mäntylä TA, Niemi KJ, Vuoristo PMJ, Barbezat G, Nicoll AR (1991) Abrasion wear resistance of tungsten carbide coatings prepared by various thermal spraying techniques. In: Blum-Sandmeier S, Eschnauer H, Huber P, Nicoll AR (eds) Proc. 2nd Plasma-Technik symp., Lucerne, Switzerland, 5-7 June 1991, Vol. 1, pp. 287-297. Sulzer Metco AG, Wohlen, Switzerland 2586. Nerz JE, Kushner BA, Rotolico AJ (1990) Effects of deposition methods on the physical properties of tungsten carbide – 12 wt.% cobalt thermal spray coatings. In: Yazici RM (ed) Protective coatings: processing and characterization. Proc. TMS Northeast regional meeting, Hoboken, New Jersey, 3-5 May 1989, pp. 133-143. The Minerals, Metals and Materials Society, Pittsburgh, Pennsylvania 2587. Nerz JE, Kushner BA, Rotolico AJ (1990) Zusammenhang zwischen Pulververarbeitungs und Abscheidungmethoden für Woltramcarbid – Kobalt – Beschichtungen in Flugzeugqualität (Relationship between powder processing and deposition methods for aircraft grade tungsten carbide – cobalt coatings). In: Thermische Spritz-konferenz (TS 90). Proc. thermal spray conf., Essen, Germany, 29-31 Aug 1990, pp. 47-51. Deutsche Verband für Schweisstechnik, Düsseldorf, Germany (in German) 2588. Dorfman MR, Kushner BA, Nerz JE, Rotolico AJ (1989) A technical assessment of highvelocity oxygen-fuel versus high-energy plasma tungsten carbide – cobalt coatings for wear resistance. In: Bucklow IA (ed) Proc. 12th Int. thermal spray conf., London, 4-9 June 1989, pp. 108.1-108.12. The Welding Institute, Cambridge, UK 2589. Nerz JE, Kushner BA, Rotolico AJ (1991) Characterization of tungsten carbide coatings as a function of powder manufacturing and deposition technologies. In: Vincenzini P (ed) High performance ceramic films and coatings. Proc. satellite symp. 1 on high performance ceramic films and coatings of 7th Int. meeting on modern ceramics technologies (7th CIMTEC – World

References

717

ceramics congress), Montecatini Terme, Italy, 27-30 June 1990, pp. 27-36. Elsevier Science, Amsterdam, London 2590. Gille G, Leitner G, Hermel W (1998) Shrinkage behaviour of WC-Co hard metals (Schwindungsverhalten von WC-Co hartmetallen). Z Metallkd 89(2):73-76 (in German) 2591. Haglund S, Ågren J, Uhrenius B (1998) Solid state sintering of cemented carbides – an experimental study. Z Metallkd 89(5):316-322 2592. Haglund S, Ågren J, Lindskog P (1998) Sintering of WC-Co under axial load. Z Metallkd 89(5):323-326 2593. Jacobs L, Hyland MM, De Bonte M (1998) Comparative study of WC-cermet coatings sprayed via the HVOF and the HVAF process. J Therm Spray Technol 7:213-218 2594. Jia K, Fischer TE, Gallois B (1998) Microstructure, hardness and toughness of nanostructured and conventional WC-Co composites. Nanostruct Mater 10(5):875-891 2595. Kim S, Park J-K, Lee D (1998) Effect of grain motion on the coarsening of WC grains in the carbon saturated liquid phase sintering of WC-Co alloys. Scripta Mater 38(10):1563-1569 2596. Nolan D, Mercer P, Samandi M (1998) Microstructural stability of thermal sprayed WCCo composite coatings in oxidising atmospheres at 450 °C. Surf Eng 14(2):124-128 2597. Shatov AV, Firstov SA, Shatova IV (1998) The shape of WC crystals in cemented carbides. Mater Sci Eng A 242:7-14 2598. Yao Z, Stiglich JJ, Sudarshan TS (1998) Nanosized WC-Co holds promise for the future. Met Powder Rep 53(3):26-33 2599. Gardon M, Etienne S, Fantozzi G (1989) High-temperature mechanical spectrometry on WC-Co (25 %) cermets. In: De With G, Terpstra RA, Metselaar R (eds) Euro-Ceramics. Proc. 1st European Ceramic Society conf. (ECerS ’89), Maastricht, The Netherlands, 18-23 June 1989, Vol. 3 – Engineering ceramics: including bioceramics, pp. 3.356-3.360. Elsevier Applied Science, New York 2600. Lai H-Y, Yang J (1985) Effect of heat treatment on structure and properties of WC-Co hardmetals. In: Bildstein H, Ortner HM (eds) New applications, recycling and technology of refractory metals and hard materials. Proc. 11th Int. Plansee seminar, Reutte, Tirol, Austria, 20-24 May 1985, Vol. 2, pp. 679-685. Plansee Holding AG, Reutte, Austria 2601. Lai H-Y, Yang J (1988) Investigation of heat treatment of WC-Co hardmetals and transformation temperature of cobalt binder phase. In: Gummeson PU, Gustafson DA (eds) Modern developments in powder metallurgy, Vol. 19, pp. 23-29. Metal Powder Industries Federation, Princeton, New Jersey 2602. Verdon C, Karimi A, Martin J-L (1998) A study of high-velocity oxy-fuel thermally sprayed tungsten carbide based coatings. Part. 1. Microstructures. Mater Sci Eng A 246:11-24 2603. Xueming MA, Gang JI, Ling Z, Yuanda D (1998) Structure and properties of bulk nanostructured WC-Co alloy by mechanical alloying. J Alloys Compd 264:267-270 2604. Cho KH, Chung IS, Lee JW (1999) Influence of carbon content on the properties of binder and carbide phase of cemented carbide. Int Ceram Rev 48(1):30-35 2605. Fang Z, Lockwood G, Griffo A (1999) A dual composite of WC-Co. Metall Mater Trans A 30:3231-3238 2606. Kato M, Zhang D, Nakasa K (1999) Analysis of cracking and delamination processes of WC-Co coating under bending load. J Soc Mater Sci Jpn 48(6):629-635 (in Japanese) 2607. Lavergne O, Allibert CH (1999) Dissolution mechanism of tungsten carbide in cobaltbased liquids. High Temp High Press 31(3):347-355 2608. Milman YuV, Luyckx S, Northrop IT (1999) Influence of temperature, grain size and cobalt content on the hardness of WC-Co alloys. Int J Refract Met Hard Mater 17:39-44 2609. Nicolae P (1999) Applications of WC-Co gradient materials. In: Kaisser W (ed) Proc. 5th Int. symp. on functionally graded materials (FGM ’98), Dresden, Germany, 26-29 Oct 1998. Mater Sci Forum 308-311:482-486 2610. Sadangi RK, McCandlish LE, Kear BH, Seegopaul P (1999) Grain growth inhibition in liquid phase sintered nanophase WC/Co alloys. Int J Powder Metall 35(1):27-33

718

2 Tungsten Carbides

2611. Saito M, Ito H, Suzuki H (1999) Some properties of WC – 10 mass% Co cemented carbide affected by carbonizing temperature of tungsten carbide powders. J Jpn Soc Powder Powder Metall 46(4):390-395 (in Japanese) 2612. Schwetzke R, Kreye H (1999) Microstructure and properties of tungsten carbide coatings sprayed with various high-velocity oxygen-fuel spray systems. In: Coddet C (ed) Proc. 15th Int. thermal spray conf., Nice, France, 25-29 May 1998. J Therm Spray Technol 8(3):433-439 2613. Stewart DA, Shipway PH, McCartney DG (1999) Abrasive wear behaviour of conventional and nanocomposite HVOF-sprayed WC-Co coatings. Wear 225-229:789-798 2614. Szutkowska M (1999) Fracture toughness measurement of WC-Co hardmetals by indentation method. J Adv Mater 31(3):3-7 2615. Takatani Y, Tomita T, Tani K, Harada Y (1999) Corrosion rate of thermal spray WC cermet coating. J Soc Mater Sci Jpn 48(11):1249-1254 (in Japanese) 2616. Zhang D, Kato M, Nakasa K, Tasaka K (1999) Effect of heating in air or vacuum on the delamination strength of WC-Co coating deposited by high-velocity flame spraying. J Soc Mater Sci Jpn 48(9):1065-1071 (in Japanese) 2617. Allibert C, Marty Ph, Gagnoud A, Fautrelle Y (2000) Estimate of the diffusion coefficient in Co based liquids. Int J Heat Mass Transfer 43:437-445 2618. Bartha L, Atató P, Tóth AL, Porat R, Berger S, Rosen A (2000) Investigation of HIPsintering of nanocrystalline WC/Co powder. J Adv Mater 32(3):23-26 2619. Du Randt D, Luyckx S, Markoulides D, Northrop IT, Whitefield DJ (2000) Comparison between ultra-fine WC-Co and fine WC-VC-Co alloys. Int J Mater Product Technol 15(3):270-274 2620. Factor M, Roman I (2000) Vickers microindentation of WC – 12 % Co thermal spray coating. Part 1. Statistical analysis of microhardness data. Surf Coat Technol 132(2-3):181193 2621. Factor M, Roman I (2000) Vickers microindentation of WC – 12 % Co thermal spray coating. Part 2. The between-operator reproducibility limits of microhardness measurement and alternative approaches to quantifying hardness of cemented carbide thermal spray coatings. Surf Coat Technol 132(1):65-75 2622. Gillia O, Bouvard D (2000) Phenomenological analysis of densification kinetics during sintering: application to WC-Co mixture. Mater Sci Eng A 279:185-191 2623. He J, Ice M, Dallek S, Lavernia EJ (2000) Synthesis of nanostructured WC – 12 % Co coating using mechanical milling and high-velocity oxygen-fuel thermal spraying. Metall Mater Trans A 31(2):541-553 2624. Kinoshita S, Saito T, Kobayashi M, Hayashi K (2000) Microstructure and mechanical properties of new WC-Co base cemented carbide having highly oriented plate-like triangular prismatic WC grains. J Jpn Soc Powder Powder Metall 47(5):526-533 2625. Laptev AV, Ponomarev SS, Ochkas LF (2000) Structural features and properties of alloy 84 % WC – 16 % Co, obtained by hot-pressing in the solid and liquid phases. I. Effect of the temperature at which the specimens are prepared on their density and structure. Powder Metall Met Ceram 39(11-12):607-617 2626. Laptev AV, Ponomarev SS, Ochkas LF (2000) Structural features and properties of alloy 84 % WC – 16 % Co, obtained by hot-pressing in the solid and liquid phases. II. Influence of the temperature at which the specimens are made on their physico-mechanical properties. Powder Metall Met Ceram 40(1-2):77-83 2627. Laptev AV, Ponomarev SS, Ochkas LF (2000) Solid-phase consolidation of fine-grained WC – 16 % Co hardmetal. J Adv Mater 33(3):42-51 2628. Liu B, Zhang Y, Ouyang S-X (2000) Study on the relation between structural parameters and fracture strength of WC-Co cemented carbides. Mater Chem Phys 62:35-43 2629. Sobolev VV, Guilemany JM, Calero JA (2000) Development of coating structure and adhesion during high-velocity oxygen-fuel spraying of WC-Co powder on a copper substrate. J Therm Spray Technol 9:100-106

References

719

2630. Zhitomirsky VN, Wald S, Factor M, Rabani L, Zoler D, Cuperman S, Bruma C, Roman I (2000) WC-Co coatings deposited by the electro-thermal chemical spray method. Surf Coat Technol 132:80-88 2631. Allibert CH (2001) Sintering features of cemented carbides WC-Co processed from fine powders. Int J Refract Met Hard Mater 19:53-61 2632. Casas B, Ramis X, Anglada M, Salla JM, Llanes L (2001) Oxidation-induced strength degradation of WC-Co hardmetals. Int J Refract Met Hard Mater 19:303-309 2633. Cha SI, Hong SH, Ha GH, Kim BK (2001) Mechanical properties of WC – 10 Co cemented carbides sintered from nanocrystalline spray conversion processed powders. Int J Refract Met Hard Mater 19:397-403 2634. Cha SI, Hong SH, Ha GH, Kim BK (2001) Microstructure and mechanical properties of nanocrystalline WC – 10 Co cemented carbides. Scripta Mater 44:1535-1539 2635. Christensen M, Wahnström G, Allibert C, Lay S (2005) Quantitative analysis of WC grain shape in sintered WC-Co cemented carbides. Phys Rev Lett 94(6):066105 (4 pp.) 2636. Cwajna J, Roskosz S (2001) Effect of microstructure on properties of sintered carbides. Mater Charact 46:197-201 2637. Frisk K, Dumitrescu L, Ekroth M, Jansson B, Kruse O, Sundman B (2001) Development of a database for cemented carbides: thermodynamic modelling and experiments. J Phase Equilib 22(6):645-655 2638. Gillia O, Josserond C, Bouvard D (2001) Viscosity of WC-Co compacts during sintering. Acta Mater 49:1413-1420 2639. He J, Ajdelsztajn L, Lavernia EJ (2001) Thermal stability of nanocrystalline WC-Co powder synthesized by using mechanical milling at low temperature. J Mater Res 16(2):478488 2640. Kear BH, Skandan G, Sadangi RK (2001) Factors controlling decarburization in HVOF sprayed nano-WC/Co hard coatings. Scripta Mater 44:1703-1707 2641. Kim BH, Suhr DS (2001) Characteristics of HVOF-sprayed WC-Co cermet coatings affected by WC particle size and fuel/oxygen ratio. Mater Trans Jpn Inst Met 42(5):833-837 2642. Kinoshita S, Saito T, Kobayashi M, Hayashi K (2001) Mechanisms for formation of highly oriented plate-like triangular prismatic WC grains in WC-Co base cemented carbides prepared from W and C instead of WC. J Jpn Soc Powder Powder Metall 48(1):51-60 2643. Kitamura K, Kobayashi M, Hayashi K (2001) Microstructural development and properties of new WC-Co base hardmetal prepared from CoxWyCz + C instead of WC. J Jpn Soc Powder Powder Metall 48(7):621-628 2644. Lee G-H, Kang S (2001) Synthesis of nano-sized WC-Co powders by reductioncarburization process. Mater Trans Jpn Inst Met 42(8):1575-1581 2645. Li T, Lou Q, Dong J, Wei Y, Liu J (2001) Phase transformation during surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser. Appl Phys A 73:391-397 2646. Li T, Lou Q, Dong J, Wei Y, Liu J (2001) Selective removal of cobalt binder in surface ablation of tungsten carbide hardmetal with pulsed UV laser. Surf Coat Technol 145:16-23 2647. Li T, Lou Q, Dong J, Wei Y, Liu J (2001) Modified surface morphology in surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser radiation. Appl Surf Sci 172:331-344 2648. Pogrebnyak AD, Ilyashenko MV, Kshnyakin VS, Tyurin YuN, Ivanov YuF (2001) The structure and properties of a hard alloy coating deposited by high-velocity pulsed plasma jet onto a copper substrate. Tech Phys Lett 27(9):749-751 2649. Przybyłowicz J, Kusiński J (2001) Structure of laser cladded tungsten carbide composite coatings. J Mater Process Technol 109:154-160 2650. Yang Z-M, Mao C-H, Du J, Daniel M, Yannick C, Serge H, Martin H (2001) Structure of nanocrystalline WC – 10 % Co powder. Trans Nonferr Met Soc China 11(4):529-534 2651. Zhu YC, Ding CX, Yukimura K, Xiao TD, Strutt PR (2001) Deposition and characterization of nanostructured WC-Co coating. Ceram Int 27:669-674

720

2 Tungsten Carbides

2652. Lavergne O, Robaut F, Hodaj F, Allibert CH (2002) Mechanism of solid-state dissolution of WC in Co-based solutions. Acta Mater 50:1683-1692 2653. Park C-D, Kim H-C, Shon I-J, Munir ZA (2002) One-step synthesis of dense tungsten carbide – cobalt hard materials. J Am Ceram Soc 85(11):2670-2677 2654. Pelekh T, Matsushita J-I (2002) Vickers hardness of WC-Co after high-temperature oxidation. J Ceram Soc Jpn 110(4):228-231 2655. Sommer M, Schubert W-D, Zobetz E, Warbichler P (2002) On the formation of very large WC crystals during sintering of ultra-fine WC-Co alloys. Int J Refract Met Hard Mater 20:41-50 2656. Takeda M, Morihiro N, Ebara R, Harada Y, Wang R, Kido M (2002) Corrosion behaviour of thermally sprayed WC coating in Na2SO4 aqueous solution. Mater Trans Jpn Inst Met 43(11):2860-2865 2657. De Macedo HR, Da Silva AGP, De Melo DMA (2003) The spreading of cobalt, nickel and iron on tungsten carbide and the first stage of hard metal sintering. Mater Lett 57:3924-3932 2658. Laczko L, Kotsis I, Harmat P, Bartha L (2003) Chemical transformations of hardmetal (WC-Co) nanopowders. Powder Metall 46(3):205-208 2659. Malyshev VV, Butov SA (2003) Separation of cobalt and tungsten carbide by anodic dissolution of hard alloys in phosphoric acid solutions. Russ J Appl Chem 76(3):383-386 2660. Bovkun GA, Laptev AV (2004) Relationship between erosion and mechanical characteristics of fine-grained hard alloy WC – 16 % Co obtained by solid-phase and liquidphase consolidation. I. Erosion resistance. Powder Metall Met Ceram 43(5-6):265-272 2661. Bovkun GA, Laptev AV (2004) Relationship between erosion and mechanical characteristics of fine-grained hard alloy WC – 16 % Co obtained by solid-phase and liquidphase consolidation. II. Mass transfer (cathode mass gain and transfer coefficient). Powder Metall Met Ceram 43(7-8):383-390 2662. Kim C-S, Rohrer GS (2004) Geometric and crystallographic characterization of WC surfaces and grain boundaries in WC-Co composites. Interface Sci 12(1):19-27 2663. Kim H-C, Oh D-Y, Shon I-J (2004) Synthesis of WC and dense WC – x vol.% Co hard materials by high-frequency induction heated combustion method. Int J Refract Met Hard Mater 22:41-49 2664. Kim H-C, Oh D-Y, Jiang G, Shon I-J (2004) Synthesis of WC and dense WC – 5 vol.% Co hard materials by high-frequency induction heated combustion. Mater Sci Eng A 368:10-17 2665. Zhang L, Chen S, Schubert WD, Huang B-Y, Wu E-X (2004) Thermostability of cemented carbides and its raw materials in oxygen. J Central South Univ Sci Technol 35(6):931-934 (in Chinese) 2666. Sofyan BT, Stefano M, Pardede HJ, Sofyan E (2005) Characteristics of HVOF WC-Co coating used for rocket nozzle application. Mater Forum 29:147-151 2667. Kumar V, Maheshwari P, Fang ZZ, Wright SI, Nowell MM (2005) A grain boundary analysis of cemented tungsten carbides using OIM. In: Proc. materials science and technology conf., Pittsburgh, Pennsylvania, 25-28 Sep 2005, Vol. 3, pp. 47-66. ASM International, Metals Park, Ohio 2668. Li T, Li Q, Fuh JYH, Yu PC, Wu CC (2006) Effects of lower cobalt binder concentrations in sintering of tungsten carbide. Mater Sci Eng A 430:113-119 2669. Mari D, Buss K, Benoit W (2006) Phase transitions at grain boundaries in WC-Co and internal friction peak analysis. Mater Sci Eng A 442:179-183 2670. Guerra-Rosa L, Lamon J, Figueiredo I, Costa-Oliveira FA (2006) A method to distinguish extrinsic and intrinsic fracture-origin populations in monolithic ceramics. J Eur Ceram Soc 26:3887-3895 2671. Sasaki A, Takeuchi F, Kawakami M, Ito H, Terada O, Hayashi K (2006) Generation of Co-rich layer on surface of sintered compact of submicro-grained WC-Co hardmetal. J Jpn Soc Powder Powder Metall 53(2):172-176 (in Japanese) 2672. Bonny K, De Baets P, Van Der Biest O, Vleugels J, Lauwers B (2007) Edge effects in sliding wear behaviour of ZrO2-WC composites and WC-Co cemented carbides. In: Chang

References

721

YW, Kim NJ, Lee CS (eds) Proc. 6th Pacific Rim Int. conf. on advanced materials and processing (PRICM-6), Jeju Island, South Korea, 5-9 Nov 2007. Mater Sci Forum 561565(1):503-506 2673. Laptev AV (2007) Densification of WC-Co alloys in solid-phase sintering (review). Powder Metall Met Ceram 46(7-8):317-324 2674. Laptev AV (2007) Structure and properties of WC-Co alloys in solid-phase sintering. I. Geometrical evolution. Powder Metall Met Ceram 46(9-10):415-422 2675. Laptev AV (2007) Structure and properties of WC-Co alloys in solid-phase sintering. II. Mechanical properties of samples. Powder Metall Met Ceram 46(11-12):517-524 2676. Schubert WD, Bock A, Lux B (1993) General aspects and limits of conventional ultra-fine WC powder manufacture and hard metal production. In: Bildstein H, Eck R (eds) Proc. 13th Int. Plansee seminar, Reutte, Tirol, Austria, 24-28 May 1993, Vol. 4, pp. 283-305. Plansee Holding AG, Reutte, Austria 2677. Schubert WD, Bock A, Lux B (1995) General aspects and limits of conventional ultra-fine WC powder manufacture and hard metal production. Int J Refract Met Hard Mater 13(5):281296 2678. Babich MM (1975) Neodnorodnost tverdykh splavov po soderzhaniyu i ee ustranenie (Inhomogeneity of hard alloys in content and its elimination). Naukova Dumka, Kyiv (in Russian) 2679. Snowball RF, Milner DR (1968) Densification processes in the tungsten carbide – cobalt system. Powder Metall 11(21):23-40 2680. Leitner G, Gestrich T, Gille G (1997) Shrinkage, liquid phase formation and gaseous reactions during sintering of WC-Co hardmetals and correlation to the WC grain size. In: Kneringer G, Rödhammer P, Wilhartitz P (eds) Proc. 14th Int. Plansee seminar, Reutte, Tirol, Austria, 12-16 May 1997, Vol. 2, pp. 86-99. Plansee Holding AG, Reutte, Austria 2681. Li T, Li Q, Lu L, Fuh JYH, Yu PC (2007) Abnormal growth of WC with small amount of cobalt. Philos Mag 87(36):5657-5671 2682. Maheshwari P, Fang ZZ, Sohn NY (2007) Early stage sintering densification and grain growth of nanosized WC-Co powders. Int J Powder Metall 43(2):41-47 2683. Rabouhi H, Boudrahem S, Grosbras M (2007) Etude comparee des proprietes de carbures cementes elabores par frittage et compression isostatique a chaud (A comparative study of the properties of cemented carbides produced by sintering and hot isostatic pressing). Ann Chim Sci Mater 32(1):11-18 (in French) 2684. Shao GQ, Guo JK, Duan XL, Sun P, Xiong Z, Shi XL (2007) The core/rim structure in cobalt / tungsten carbide nanocomposite powder. In: Bai C (ed) Proc. Int. China conf. on nanoscience and technology (ChinaNANO 2005), Beijing, China, 9-11 June 2005, Part 1. Solid State Phenom 121-123:227-230 2685. Carpinteri A, Pugno N (2008) Bio-inspired hierarchical nanomaterials for space applications. J Brit Interplanet Soc 61(8):290-294 2686. Choi J-C, Chang S-H, Cha Y-H, Oh I-H (2008) Fabrication and evaluation of WC – 3 wt.% Co compacts fabricated by spark-plasma sintering. Korean J Mater Res 18(7):357-361 (in Korean) 2687. Felten F, Schneider GA, Sadowski T (2008) Estimation of R-curve in WC/Co cermet by CT test. Int J Refract Met Hard Mater 26:55-60 2688. Guillermet AF (2008) Using calculated phase diagrams in the selection of the composition of cemented WC tools with a Co-Fe-Ni binder phase. In: The SGTE casebook: thermodynamics at work, 2nd ed., pp. 98-105. Woodhead Publishing, Cambridge, UK 2689. Kumar V, Fang ZZ, Wright SI, Nowell MM (2008) A grain boundary analysis of cemented tungsten carbides using OIM. In: Rollett AD (ed) Applications of texture analysis. Proc. 15th Int. conf. on textures of materials (ICOTOM 15), Pittsburgh, Pennsylvania, 1-6 June 2008. Ceram Trans 201:291-304

722

2 Tungsten Carbides

2690. Shi XL, Yang H, Shao GQ, Duan XL, Wang S (2008) Oxidation of ultra-fine cemented carbide prepared from nanocrystalline WC – 10 Co composite powder. Ceram Int 34:20432049 2691. Tolochin AI, Laptev AV, Golovkova ME, Kovalchenko MS (2008) Ultra-fine high-cobalt VK40 hard alloy. I. Structure and properties. Powder Metall Met Ceram 47(3-4):176-182 2692. Tolochin AI, Laptev AV, Golovkova ME, Kovalchenko MS (2008) Ultra-fine high-cobalt hard alloys. II. Connection between mechanical properties and structure. Powder Metall Met Ceram 47(5-6):316-323 2693. Zhang FL, Zhu M, Wang CY (2008) Parameters optimization in the planetary ball milling of nanostructured tungsten carbide / cobalt powder. Int J Refract Met Hard Mater 26:329-333 2694. Fang ZZ, Wang X, Ryu T, Hwang KS, Sohn HY (2009) Synthesis, sintering and mechanical properties of nanocrystalline cemented tungsten carbide – a review. Int J Refract Met Hard Mater 27(2):288-299 2695. Hewitt SA, Kibble KA (2009) Effects of ball milling time on the synthesis and consolidation of nanostructured WC-Co composites. Int J Refract Met Hard Mater 27:937948 2696. Shin S-G (2009) Computational and experimental study of grain growth in WC-Co and WC-VC-Co cemented carbides. Korean J Mater Res 19(11):588-595 2697. Shon I-J, Jeong I-K, Ko I-Y, Doh J-M, Woo K-D (2009) Sintering behaviour and mechanical properties of WC – 10 Co, WC – 10 Ni and WC – 10 Fe hard materials produced by high-frequency induction heated sintering. Ceram Int 35:339-344 2698. Suetin DV, Shein IR, Ivanovskii AL (2009) Structural, electronic and magnetic properties of η-carbides (Fe3W3C, Fe6W6C, Co3W3C and Co6W6C) from first principles calculations. Phys B 404:3544-3549 2699. Zhao S, Song X, Wei C, Zhang L, Liu X, Zhang J (2009) Effects of WC particle size on densification and properties of spark-plasma sintered WC-Co cermet. Int J Refract Met Hard Mater 27:1014-1018 2700. Balla VK, Bose S, Bandyopadhyay A (2010) Microstructure and wear properties of laser deposited WC – 12 % Co composites. Mater Sci Eng A 527:6677-6682 2701. Deorsola FA, Vallauri D, Ortigoza-Villalba GA, De Benedetti B (2010) Densification of ultra-fine WC – 12 Co cermets by pressure assisted fast electric sintering. Int J Refract Met Hard Mater 28:254-259 2702. Dobrzański LA, Dołżańska B (2010) Hardness to toughness relationship on WC-Co tool gradient materials evaluated by Palmqvist method. Arch Mater Sci Eng 43(2):87-93 2703. Hazell PJ, Appleby-Thomas GJ, Herlaar K, Painter J (2010) Inelastic deformation and failure of tungsten carbide under ballistic-loading conditions. Mater Sci Eng A 527:76387645 2704. Hayakawa K, Nakamura T, Tanaka S (2010) Elastic-plastic behaviour of WC-Co cemented carbide used for forging tool considering anisotropic damage and stress unilaterality. Int J Damage Mech 19(4):421-439 2705. Konyashin I, Hlawatschek S, Ries B, Lachmann F, Sologubenko A, Weirich T (2010) A new approach to fabrication of gradient WC-Co hardmetals. Int J Refract Met Hard Mater 28:228-237 2706. Lim NS, Das S, Park SY, Kim MC, Park CG (2010) Fabrication and microstructural characterization of nanostructured WC/Co coatings. Surf Coat Technol 205:430-435 2707. Liu A, Guo M, Hu HL (2010) Distribution and dissolution of WC particles in surface metal matrix composites produced by plasma melt injection. Surf Eng 26(8):623-628 2708. Liu X, Song X, Zhao S, Zhang J (2010) Spark-plasma sintering densification mechanism for cemented carbides with different WC particle sizes. J Am Ceram Soc 93(10):3153-3158 2709. Reichel B, Wagner K, Janisch DS, Lengauer W (2010) Alloyed W – (Co, Ni, Fe) – C phases for reaction sintering of hardmetals. Int J Refract Met Hard Mater 28:638-645

References

723

2710. Sahraoui T, Guessasma S, Ali-Jeridane M, Hadji M (2010) HVOF-sprayed WC-Co coatings: microstructure, mechanical properties and friction moment prediction. Mater Design 31:1431-1437 2711. Sofyan BT, Berndt CC, Stefano M, Pardede HJ (2010) WC-Co coatings for hightemperature rocket nozzle applications: an applications note. Int J Technol 1(1):48-56 2712. Wei C, Song X, Zhao S, Zhang L, Liu W (2010) In situ synthesis of WC-Co composite powder and densification by sinter-HIP. Int J Refract Met Hard Mater 28:567-571 2713. Weidow J, Andrén H-O (2010) Binder phase grain size in WC-Co-based cemented carbides. Scripta Mater 63:1165-1168 2714. Aristizabal M, Sánchez JM, Rodriguez N, Ibarreta F, Martinez R (2011) Comparison of the oxidation behaviour of WC-Co and WC-Ni-Co-Cr cemented carbides. Corros Sci 53:2754-2760 2715. Bonache V, Salvador MD, Busquets D, Burguete P, Martínez E, Sapiña F, Sánchez E (2011) Synthesis and processing of nanocrystalline tungsten carbide: towards cemented carbides with optimal mechanical properties. Int J Refract Met Hard Mater 29:78-84 2716. Bose A (2011) A perspective on the earliest commercial PM metal-ceramic composite: cemented tungsten carbide. Int J Powder Metall 47(2):31-50 2717. Chanthapan S, Kulkarni A, Singh J, Mehrotra P (2011) Sintering of tungsten carbide with/without cobalt and nano tungsten carbide powder in FAST. In: Proc. 8th Int. conf. on tungsten, refractory and hard materials, San Francisco, California, 18-21 May 2011, pp. 1016-1027. Metal Powder Industries Federation, Princeton, New Jersey 2718. Perez-Delgado Y, Bonny K, De Baets P, Neis PD, Malek O, Vleugels J, Lauwers B (2011) Impact of wire-EDM on dry sliding friction and wear of WC-based and ZrO2-based composites. Wear 271:1951-1961 2719. Ding ZX, Chen W, Wang Q (2011) Resistance of cavitation erosion of multimodal WC – 12 Co coatings sprayed by HVOF. Trans Nonferr Met Soc China 21(10):2231-2236 2720. Guo J, Fang ZZ, Fan P, Wang X (2011) Kinetics of the formation of metal binder gradient in WC-Co by carbon diffusion induced liquid migration. Acta Mater 59:4719-4731 2721. Jiang Y, Chen D (2011) Effect of cryogenic treatment on WC-Co cemented carbides. Mater Sci Eng A 528:1735-1739 2722. Klünsner T, Wurster S, Supancic P, Ebner R, Jenko M, Glätzle J, Püschel A, Pippan R (2011) Effect of specimen size on the tensile strength of WC-Co hardmetal. Acta Mater 59:4244-4252 2723. Konyashin IYu, Ries B, Lachmann F, Mazilkin AA, Straumal BB (2011) Novel hardmetal with nano-strengthened binder. Inorg Mater Appl Res 2(1):19-21 2724. Kumar A, Singh K, Pandey OP (2011) Sintering behaviour of nanostructured WC-Co composite. Ceram Int 37:1415-1422 2725. Kumi DO (2011) A study of WC – X systems for potential binders for WC. MSc thesis, University of Witwatersrand, Johannesburg, South Africa 2726. Kushkhov KB, Adamokova MN, Kvashin VA, Kardanov AL (2010) Electrochemical synthesis of hard alloy compositions based on tungsten carbide and an iron triad metal. Russ Metall (8):751-758 2727. Kushkhov KB, Adamokova MN, Kvashin VA, Kardanov AL (2011) Synthesis of functional and constructional nanomaterials on a basis tungsten, molybdenum carbides and metals of a triad of iron in ionic melts. In: Obraztsova E, Gallamov M (eds) Proc. 3rd nanotechnology Int. forum of RUSNANO, Moscow, Russia, 1-3 Nov 2010. J Phys Conf Series 291(1):012045 (16 pp.) 2728. Kurlov AS, Gusev AI, Rempel AA (2011) Vacuum sintering of WC – 8 wt.% Co hardmetals from WC powders with different dispersity. Int J Refract Met Hard Mater 29:221-231 2729. Lee J-C, Kim E-Y, Kim J-H, Kim W, Kim B-S, Pandey BD (2011) Recycling of WC-Co hardmetal sludge by a new hydrometallurgical route. Int J Refract Met Hard Mater 29:365371

724

2 Tungsten Carbides

2730. Li C, Peng W (2011) Effect of collocation ratio of coarse and fine WC on dual grain structure cemented carbide. In: Jiang Z, Liu X, Bu J (eds) Proc. Int. conf. on advances in materials and manufacturing processes (ICAMMP 2010), Shenzhen, China, 6-8 Nov 2010. Adv Mater Res 154-155:1040-1052 2731. Mannesson K, Jeppsson J, Borgenstam A, Ågren J (2011) Carbide grain growth in cemented carbides. Acta Mater 59:1912-1923 2732. Mannesson K, Borgh I, Borgenstam A, Ågren J (2011) Abnormal grain growth in cemented carbides – experiments and simulations. Int J Refract Met Hard Mater 29:488-494 2733. Mingard KP, Roebuck B, Marshall J, Sweetman G (2011) Some aspects of the structure of cobalt and nickel binder phases in hardmetals. Acta Mater 59:2277-2290 2734. Mukhopadhyay A, Basu B (2011) Recent developments in WC-based bulk composites. J Mater Sci 46:571-589 2735. Shi XL, Shao GQ, Duan XL, Yuan RZ, Lin HH (2005) Mechanical properties, phases and microstructure of ultra-fine hardmetals prepared by WC – 6.29 Co nanocrystalline composite powder. Mater Sci Eng A 392:335-339 2736. Cha SI, Hong SH, Kim BK (2003) Spark-plasma sintering behaviour of nanocrystalline WC – 10 Co cemented carbide powders. Mater Sci Eng A 351:31-38 2737. Kim H-C, Oh D-Y, Shon I-J (2004) Sintering of nanophase WC – 15 vol.% Co hard metals by rapid sintering process. Int J Refract Met Hard Mater 22:197-203 2738. Pirso J, Letunovitš S, Viljus M (2004) Friction and wear behaviour of cemented carbides. Wear 257:257-265 2739. Michalski A, Siemiaszko D (2007) Nanocrystalline cemented carbides sintered by the pulse plasma method. Int J Refract Met Hard Mater 25:153-158 2740. Sivaprahasam D, Chandrasekar SB, Sundaresan R (2007) Microstructure and mechanical properties of nanocrystalline WC – 12 Co consolidated by spark-plasma sintering. Int J Refract Met Hard Mater 25:144-152 2741. Kim H-C, Jeong I-K, Shon I-J, Ko I-Y, Doh J-M (2007) Fabrication of WC – 8 wt.% Co hard materials by two rapid sintering process. Int J Refract Met Hard Mater 25:336-340 2742. Niu QL, An QL, Chen M, Liu G, Wang CY (2011) Analysis on the microstructure of carbide reamers after the cryogenic treatment. In: Wang CY (ed) Proc. 4th Int. conf. on highspeed machining (ICHSM 2010), Guangzhou, China, 9-10 Oct 2010. Adv Mater Res 188:2631 2743. Putintseva MN, Bashurov YuP (2011) Phase transformations during annealing of WC-Co powders. Russ J Non-Ferr Met 52(3):280-284 2744. Weidow J, Andrén H-O (2011) APT analysis of WC-Co based cemented carbides. Ultramicroscopy 111:595-599 2745. Zavodinsky VG (2011) Ab initio study of the fcc-WC (100) surface and its interaction with cobalt monolayers. Appl Surf Sci 257:3581-3585 2746. Zavodinsky VG (2011) Cobalt layers crystallised on the WC (100) surface: spin-polarized ab initio study. Int J Refract Met Hard Mater 29:184-187 2747. Zhao S, Song X, Liu X, Wei C, Wang H, Gao Y (2011) Quantitative relationships between microstructure parameters and mechanical properties of ultra-fine cemented carbides. Acta Metall Sin 47(9):1188-1194 (in Chinese) 2748. Zhong Y, Shaw LL (2011) Growth mechanisms of WC in WC – 5.75 wt.% Co. Ceram Int 37:3591-3597 2749. Zhong Y, Zhu H, Shaw LL, Ramprasad R (2011) The equilibrium morphology of WC particles – a combined ab initio and experimental study. Acta Mater 59:3748-3757 2750. Aristizabal M, Ardila LC, Veiga F, Arizmendi M, Fernandez J, Sánchez JM (2012) Comparison of the friction and wear behaviour of WC-Ni-Co-Cr and WC-Co hardmetals in contact with steel at high temperatures. Wear 280-281:15-21 2751. Bao R, Yi J-H, Peng Y-D, Zhang H-Z, Li A-K (2012) Decarburization and improvement of ultra-fine straight WC – 8 Co sintered via microwave sintering. Trans Nonferr Met Soc China 22(4):853-857

References

725

2752. Brookes KJA (2012) Grain size distribution in WC and WC/Co. Met Powder Rep 67(2):30-32 2753. Gill SS, Singh J, Singh H, Singh R (2012) Metallurgical and mechanical characteristics of cryogenically treated tungsten carbide (WC-Co). Int J Adv Manuf Technol 58(1-4):119-131 2754. Gnidenko AA (2012) First principle simulation of the Co layers behaviour on a surface of hexagonal tungsten carbide. In: Galkin N (ed) Proc. Asian school-conf. on physics and technology of nanostructured materials (ASCO-NANOMAT 2011), Vladivostok, Russian Federation, 21-28 Aug 2011. Phys Proc 23:132-135 2755. Gonda H, Shirai Y, Ohashi O, Yasui T, Fukumoto M (2012) Diffusion bonding between cemented carbides using interlayer. Quart J Jpn Weld Soc 30(1):35-41 (in Japanese) 2756. Gu W-H, Jeong YS, Kim K, Kim J-C, Son S-H, Kim S (2012) Thermal oxidation behaviour of WC-Co hardmetal machining tool tip scraps. J Mater Process Technol 212:1250-1256 2757. Lin H, Tao B, Li Q, Li Y (2012) In situ synthesis of WC-Co nanocomposite powder via core-shell structure formation. Mater Res Bull 47:3283-3286 2758. Liu XM, Song XY, Wei CB, Gao Y, Wang HB (2012) Quantitative characterization of the microstructure and properties of nanocrystalline WC-Co bulk. Scripta Mater 66(10):825-828 2759. Ou XQ, Xiao DH, Shen TT, Song M, He YH (2012) Characterization and preparation of ultra-fine grained WC-Co alloys with minor La-additions. Int J Refract Met Hard Mater 31:266-273 2760. Salama AD, Sabuga W, Ulbig P (2012) Measurement of the elastic constants of pressure balance materials using resonance ultrasound spectroscopy. Measurement 45(10):2472-2475 2761. Shaw LL, Luo H, Zhong Y (2012) WC – 18 wt.% Co with simultaneous improvements in hardness and toughness derived from nanocrystalline powder. Mater Sci Eng A 537:39-48 2762. Vesel A, Mozetic M, Balat-Pichelin M (2012) Phase transformation in tungsten carbide – cobalt composite during high-temperature treatment in microwave hydrogen plasma. Ceram Int 38:6107-6113 2763. Wang Q, Li L, Yang G, Zhao X, Ding Z (2012) Influence of heat treatment on the microstructure and performance of high-velocity oxy-fuel sprayed WC - !2 Co coatings. Surf Coat Technol 206:4000-4010 2764. Wei CB, Song XY, Fu J, Liu XM, Gao Y, Wang HB, Zhao SX (2012) Microstructure and properties of ultra-fine cemented carbides – differences in spark-plasma sintering and sinterHIP. Mater Sci Eng A 552:427-433 2765. Zhang X, Liao L, Wang Y, Ye J, Xie K (2012) Synthesis of ultra-fine WC-Co core-shell composite powders by chemical reduction method. Asian J Chem 24(1):327-329 2766. Zhan Q, Yu L, Ye F, Xue Q, Li H (2012) Quantitative evaluation of the decarburization and microstructure evolution of WC-Co during plasma spraying. Surf Coat Technol 206:4068-4074 2767. Borgh I, Hedström P, Odqvist J, Borgenstam A, Ågren J, Gholinia A, Winiarski B, Withers PJ, Thompson GE, Mingard K, Gee MG (2013) On the three-dimensional structure of WC grains in cemented carbides. Acta Mater 61:4726-4733 2768. Chen L, Wang B, Yi D, Liu H (2013) Non-isothermal oxidation kinetics of WC – 6 Co cemented carbides in air. Int J Refract Met Hard Mater 40:19-23 2769. Fan P, Fang ZZ, Guo J (2013) A review of liquid phase migration and methods for fabrication of functionally graded cemented tungsten carbide. Int J Refract Met Hard Mater 36:2-9 2770. Konyashin I, Ries B, Lachmann F, Fry AT (2013) Gradient WC-Co hardmetals: theory and practice. Int J Refract Met Hard Mater 36:10-21 2771. Kurlov AS, Rempel AA (2013) Effect of cobalt powder morphology on the properties of WC-Co hard alloys. Inorg Mater 49(9):889-893 2772. Mingard KP, Jones HG, Gee MG, Roebuck, Nunn JW (2013) In situ observation of crack growth in a WC-Co hardmetal and characterization of crack growth morphologies by EBSD. Int J Refract Met Hard Mater 36:136-142

726

2 Tungsten Carbides

2773. Song X, Gao Y, Liu X, Wei C, Wang H, Xu W (2013) Effect of interfacial characteristics on toughness of nanocrystalline cemented carbides. Acta Mater 61:2154-2162 2774. Bounhoure V, Lay S, Loubradou M, Missiaen JM (2008) Special WC/Co orientation relationships at basal facets of WC grains in WC-Co alloys. J Mater Sci 43(3):892-899 2775. Wang H, Song X, Liu X, Gao Y, Wei C, Wang Y, Guo G (2013) Effect of carbon content of WC-Co composite powder on properties of cermet coating. Powder Technol 246:492-498 2776. Yuan J, Zhan Q, Huang J, Ding S, Li H (2013) Decarburization mechanisms of WC-Co during thermal spraying: insights from controlled carbon loss and microstructure characterization. Mater Chem Phys 142:165-171 2777. Yuan YG, Wang YK, Ding JJ, Sun WQ, Zhang XX, Bai JS (2013) Measurement of cobalt gradient in functionally graded WC-Co composites. In: Kim Y-H, Yarlagadda P (eds) Proc. Int. forum on mechanical and material engineering (IFMME 2013), Guangzhou, China, 13-14 June 2013. Adv Mater Res 774-776:1609-1612 2778. Yuan YG, Ding JJ, Wang YK, Sun WQ (2013) Fabrication of functionally gradient ultrafine grained WC-Co composites. In: Zheng L, Kuroda S-I, Liu H, Du B, Wei J, Zhao Y (eds) Proc. 3rd Int. conf. on applied mechanics, materials and manufacturing (ICAMMM 2013), Dalian, China, 24-25 Aug 2013. Appl Mech Mater 423-426:885-889 2779. Żórawski W (2013) The microstructure and tribological properties of liquid-fuel HVOF sprayed nanostructured WC – 12 Co coatings. Surf Coat Technol 220:276-281 2780. Aly ST, Amin ShK, El-Sherbiny SA, Abadir MF (2014) Kinetics of isothermal oxidation of WC – 20 Co hot-pressed compacts in air. J Therm Anal Calorim 118:1543-1549 2781. Bounhoure V, Lay S, Charlot F, Antoni-Zdziobek A, Pauty E, Missiaen JM (2014) Effect of C content on the microstructure evolution during early solid state sintering of WC-Co alloys. Int J Refract Met Hard Mater 44:27-34 2782. Konyashin I, Hlawatschek S, Ries B, Lachmann F, Dorn F, Sologubenko A, Weirich T (2009) On the mechanism of WC coarsening in WC-Co hardmetals with various carbon content. Int J Refract Met Hard Mater 27(2):234-243 2783. Borgh I, Hedström P, Borgenstam A, Ågren J, Odqvist J (2014) Effect of carbon activity and powder particle size on WC grain coarsening during sintering of cemented carbides. Int J Refract Met Hard Mater 42:30-35 2784. Chang S-H, Chen S-L (2014) Characterization and properties of sintered WC-Co and WCNi-Fe hard alloys. J Alloys Compd 585:407-413 2785. Gu L, Huang J, Xie C (2014) Effects of carbon contents on microstructure and properties of WC – 20 Co cemented carbides. Int J Refract Met Hard Mater 42:228-232 2786. Konyashin I (2014) Cemented carbides for mining, construction and wear parts. In: Sarin VK, Mari D, Llanes L (eds) Comprehensive hard materials. Vol. 1 – Hardmetals, pp.425-451. Elsevier, Amsterdam, Oxford 2787. Konyashin I, Lachmann F, Ries B, Mazilkin AA, Straumal BB, Kübel Chr, Llanes L, Baretzky B (2014) Strengthening zones in the Co matrix of WC-Co cemented carbides. Scripta Mater 83:17-20 2788. Konyashin I, Hlawatschek S, Ries B, Lachmann F, Vukovic M (2014) Cobalt capping on WC-Co hardmetals. Part I. A mechanism explaining the presence or absence of cobalt layers on hardmetal articles during sintering. Int J Refract Met Hard Mater 42:142-150 2789. Konyashin I, Hlawatschek S, Ries B, Lachmann F, Vukovic M (2014) Cobalt capping on WC-Co hardmetals. Part II. A technology for fabrication of Co coated articles during sintering. Int J Refract Met Hard Mater 42:136-141 2790. Konyashin I, Schäfer F, Cooper R, Ries B, Mayer J, Weirich T (2005) Novel ultra-coarse hardmetal grades with reinforced binder for mining and construction. Int J Refract Met Hard Mater 23:225-232 2791. Konyashin I, Senchihin V, Anikeev A, Glushkov V (1996) Development, production and application of novel grades of coated hardmetals in Russia. Int J Refract Met Hard Mater 14(1-3):41-48

References

727

2792. Konyashin I, Ries B, Lachmann F (2010) Near-nano WC-Co hardmetals: will they substitute conventional coarse-grain mining grades. Int J Refract Met Hard Mater 28:489-497 2793. Konyashin I, Eschner T, Aldinger F, Senchihin V (1999) Cemented carbides with uniform microstructure. Z Metallkd 90(6):403-406 2794. Konyashin I, Ries B, Lachmann F, Cooper R, Mazilkin A, Straumal B, Aretz A, Babaev V (2008) Hardmetals with nano-grain reinforced binder: binder fine structure and hardness. Int J Refract Met Hard Mater 26(6):583-588 2795. Konyashin I, Ries B, Lachmann F, Fry AT (2012) A novel sintering technique for fabrication of functionally gradient WC-Co cemented carbides. J Mater Sci 47(20):70727084 2796. Freemantle CS, Sacks N, Topic M, Pineda-Vargas CA (2014) Impurity characterization of zinc-recycled WC – 6 wt.% Co cemented carbides. Int J Refract Met Hard Mater 44:94-102 2797. Liu C, Lin N, He Y, Wu C, Jiang Y (2014) The effects of micron WC contents on the microstructure and mechanical properties of ultra-fine WC – (micron WC – Co) cemented carbides. J Alloys Compd 594:76-81 2798. Mandel K, Krüger L, Schimpf C (2014) Particle properties of submicron-sized WC – 12 Co processed by planetary ball milling. Int J Refract Met Hard Mater 42:200-204 2799. Ma N, Guo L, Cheng Z, Wu H, Ye F, Zhang K (2014) Improvement on mechanical properties and wear resistance of HVOF sprayed WC – 12 Co coatings by optimizing feedstock structure. Appl Surf Sci 320:364-371 2800. Ortner HM, Ettmayer P, Kolaska H (2014) The history of the technological progress of hardmetals. Int J Refract Met Hard Mater 44:148-159 2801. Rumman MR, Xie Z, Hong SJ, Ghomashchi R (2014) Powder refinement, consolidation and mechanical properties of cemented carbides – an overview. Powder Technol 261:1-13 2802. Sathish S, Geetha M, Asokamani R (2014) Comparative studies on the corrosion and scratch behaviours of plasma-sprayed ZrO2 and WC-Co coatings. In: Singh SK (ed) Proc. 3rd Int. conf. on materials processing and characterization (ICMPC-2014), Part 3, Hyderabad, India, 8-9 Mar 2014. Proc Mater Sci 6:1489-1494 2803. Su W, Sun Y, Wang H, Zhang X, Ruan J (2014) Preparation and sintering of WC – Co composite powders for coarse grained WC – 8 Co hardmetals. Int J Refract Met Hard Mater 45:80-85 2804. Torres Y, Bermejo R, Gotor FJ, Chicardi E, Llanes L (2014) Analysis on the mechanical strength of WC-Co cemented carbides under uniaxial and biaxial bending. Mater Design 55:851-856 2805. Trueba M, Aramburu A, Rodríguez N, Iparraguirre I, Elizalde MR, Ocaña I, Sánchez JM, Martínez-Esnaola JM (2014) In situ mechanical characterization of WC-Co hardmetals using microbeam testing. Int J Refract Met Hard Mater 43:236-240 2806. Yaman B, Mandal H (2014) Wear performance of spark-plasma sintered Co/WC and cBN/Co/WC composites. Int J Refract Met Hard Mater 42:9-16 2807. Yuan X, Rohrer GS, Song X, Chien H, Li J (2014) Modelling the interface area aspect ratio of carbide grains in WC-Co composites. Int J Refract Met Hard Mater 44:7-11 2808. Yuan Y, Ding J, Wang Y, Wang Q, Sun W, Bai J (2014) Optimization of process parameters for fabricating functionally gradient WC-Co composites. Int J Refract Met Hard Mater 43:109-114 2809. Álvarez EA, González-Oliver CJR, Soldera F, García JL (2015) Densification and FIB, SEM, TEM microstructures of WC composites with Fe or Co matrices. In: Schvezov CE (ed) Proc. Int. congress of science and technology of metallurgy and materials (SAM-CONAMET 2013), Puerto Iquazu, Argentina, 20-23 Aug 2013. Proc Mater Sci 8:406-413 2810. Chen L, Yi D, Wang B, Liu H, Wu C, Huang X, Li H, Gao Y (2015) The selective oxidation behaviour of WC-Co cemented carbides during the early oxidation stage. Corros Sci 94:1-5

728

2 Tungsten Carbides

2811. Chang S-H, Chang M-H, Huang K-T (2015) Study on the sintered characteristics and properties of nanostructured WC – 15 wt.% (Fe – Ni – Co) and WC – 15 wt.% Co hard metal alloys. J Alloys Compd 649:89-95 2812. Emani SV, Wang C, Shaw LL, Chen Z (2015) On the hardness of submicrometer-sized WC-Co materials. Mater Sci Eng A 628:98-103 2813. Fabijanić TA, Alar Ž, Pötschke J (2015) Potentials of nanostructured WC-Co hardmetal as reference material for Vickers hardness. Int J Refract Met Hard Mater 50:126-132 2814. Gu L, Huang J, Tang Y, Xie C, Gao S (2015) Influence of different post treatments on microstructure and properties of WC-Co cemented carbides. J Alloys Compd 620:116-119 2815. Johansson SAE, Petisme MVG, Wahnström G (2015) A computational study of special grain boundaries in WC-Co cemented carbides. Comput Mater Sci 98:345-353 2816. Krawitz A, Drake E (2015) Residual stresses in cemented carbides – an overview. Int J Refract Met Hard Mater 49:27-35 2817. Kumar TS, Prabu SB, Vasu K, Krishna MG (2015) Metallurgical characteristics and machining performance of nanostructured TNN-coated tungsten carbide tool. Int J Mater Res 106(4):378-390 2818. Lee S, Hong HS, Kim H-S, Hong S-J, Yoon J-H (2015) Spark-plasma sintering of WC-Co tool materials prepared with emphasis on WC core – Co shell structure development. Int J Refract Met Hard Mater 53:41-45 2819. Lekatou A, Sioulas D, Karantzalis AE, Grimanelis D (2015) A comparative study on the microstructure and surface property evaluation of coatings produced from nanostructured and conventional WC-Co powders HVOF-sprayed on Al 7075. Surf Coat Technol 276:539-556 2820. Marshall JM, Giraudel M (2015) The role of tungsten in the Co binder: effects on WC grain size and hcp-fcc Co in the binder phase. In: Llanes L (ed) Proc. 10th Int. conf. on the science of hard materials (ICSHM 10), Cancun, Mexico, 10-14 Mar 2014. Int J Refract Met Hard Mater 49:57-66 2821. Norgren S, García J, Blomqvist A, Yin L (2015) Trends in the P/M hard metal industry. In: Sigl L, Kestler H, Wagner J (eds) Proc. 18th Int. Plansee seminar, Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 3-7 June 2013. Int J Refract Met Hard Mater 48:31-45 2822. Ortner HM, Ettmayer P, Kolaska H, Smid I (2015) The history of the technological progress of hardmetals. Int J Refract Met Hard Mater 49:3-8 2823. Brookes KJA (1998) Hard metals and other hard materials, 3rd ed. International Carbide Data, East Barnet, Hertfordshire, UK 2824. Ortner HM (1999) Influence of trace elements on the properties of hard metals. In: Ortner HM (ed) Proc. Eur. conf. on advances in hard materials production (Euro PM 99), Turin, Italy, 8-10 Nov 1999, pp. 215-220. The European Powder Metallurgy Association, Shrewsbury, UK 2825. Panov VS (2015) Nanostructured sintered WC-Co hard metals (review). Powder Metall Met Ceram 53(11-12):643-654 2826. Falkovskii VA, Klyachko LI (2005) Tverdye splavy (Hard metals). Ruda I Metally, Moscow (in Russian) 2827. Andrievskii RA, Ragulya AV (2005) Nanostrukturnye materialy (Nanostructured materials). Akadema, Moscow (in Russian) 2828. Fang ZZ, Eason JW (1995) Study of nanostructured WC-Co composites. Int J Refract Met Hard Mater 13(5):297-303 2829. McCandlish LE, Kear BH, Kim BK (1992) Processing and properties of nanostructured WC-Co. Nanostruct Mater 1(2):119-121 2830. Wang X, Fang ZZ, Sohn HY (2008) Grain growth during the early stage of sintering of nanosized WC-Co powder. Int J Refract Met Hard Mater 26(3):232-241 2831 Sun L, Ha CC, Xian M (2007) A research on the grain growth of WC-Co cemented carbide. Int J Refract Met Hard Mater 25(2):121-124

References

729

2832. Azcona I, Ordonez A, Sanchez JM, Castro F (2002) Hot isostatic pressing of ultra-fine tungsten carbide – cobalt hardmetals. J Mater Sci 37(19):4189-4195 2833. Pellan M, Lay S, Missiaen J-M, Norgren S, Angseryd J, Coronel E, Persson T (2015) Effect of binder composition on WC grain growth in cemented carbides. J Am Ceram Soc 98(11):3596-3601 2834. Pellan M (2015) Development of grain boundaries and phase boundaries in WC-Co cemented carbides. PhD thesis, The Université Grenoble Alpes, France 2835. Petisme MVG, Johansson SAE, Wahnström G (2015) A computational study of interfaces in WC-Co cemented carbides. Model Simul Mater Sci Eng 23:045001 (29 pp.) 2836. Ponomarev SS, Shatov AV, Mikhailov AA, Firstov SA (2015) Carbon distribution in WC based cemented carbides. Int J Refract Met Hard Mater 49:42-56 2837. Rumman MR, Han S-T, Ghomashchi R, Kim H-S, Hong S-J (2015) Conventional sintering of WC with nano-sized Co binder: characterization and mechanical behaviour. Int J Refract Met Hard Mater 53:2-6 2838. Rumman MR, Xie Z, Hong S-J, Ghomashchi R (2015) Effect of spark-plasma sintering pressure on mechanical properties of WC – 7.5 wt.% nano Co. Mater Design 68:221-227 2839. Straumal BB, Konyashin I, Ries B, Straumal AB, Mazilkin AA, Kolesnikova KI, Gusak AM, Baretzky B (2015) Pseudopartial wetting of WC/WC grain boundaries in cemented carbides. Mater Lett 147:105-108 2840. Sun Y, Su W, Yang H, Ruan J (2015) Effects of WC particle size on sintering behaviour and mechanical properties of coarse-grained WC – 8 Co cemented carbides fabricated by unmilled composite powders. Ceram Int 41:14482-14491 2841. Su W, Sun Y, Feng J, Liu J, Ruan J (2015) Influences of the preparation methods of WCCo powders on the sintering and microstructure of coarse-grained WC – 8 Co hardmetals. Int J Refract Met Hard Mater 48:369-375 2842. Wang H, Song X, Wang Xu, Liu Xu, Wang Xi (2015) Fabrication of nanostructured WCCo coating with low decarburization. Int J Refract Met Hard Mater 53:92-97 2843. Wang Xi, Song X, Liu Xu, Liu Xi, Wang H, Zhou C (2015) Orientation relationship in WC-Co composite nanoparticles synthesized by in situ reactions. Nanotechnol 26:145705 (8 pp.) 2844. Xie C-H, Huang J-W, Tang Y-F, Gu L-N (2015) Effects of deep cryogenic treatment on microstructure and properties of WC – 11 Co cemented carbides with various carbon contents. Trans Nonferr Met Soc China 25:3023-3028 2845. Yousfi MA, Weidow J, Nordgren A, Falk LKL, Andrén H-O (2015) Deformation mechanisms in a WC-Co based cemented carbide during creep. Int J Refract Met Hard Mater 49:81-87 2846. Zaitsev AA, Borovinskaya IP, Vershinnikov VI, Konyashin I, Patsera EI, Levashov EA, Ries B (2015) Near-nano and coarse-grain WC powders obtained by the self-propagating high-temperature synthesis and cemented carbides on their basis. Part I. Structure, composition and properties of WC powders. Int J Refract Met Hard Mater 50:146-151 2847. Zaitsev AA, Vershinnikov VI, Konyashin I, Levashov EA, Borovinskaya IP, Ries B (2015) High-quality cemented carbides on the basis of near-nano and coarse-grain WC powders obtained by self-propagating high-temperature synthesis (SHS). Int J Self-Propag High-Temp Synth 24(3):152-160 2848. Zaitsev AA, Vershinnikov VI, Konyashin I, Levashov EA, Borovinskaya IP, Ries B (2015) Cemented carbides from WC powders obtained by the SHS method. Mater Lett 158:329-332 2849. Zhang H, Chen L, Sun J, Wang W, Wang Q (2015) An investigation of cobalt phase structure in WC-Co cemented carbides before and after deep cryogenic treatment. Int J Refract Met Hard Mater 51:201-206 2850. Zhang H, Wang Q, Sun J, Wang W, Chen L (2015) Deep cryogenic treatment technique for tungsten carbides and its development. Rare Met Mater Eng 44(6):1550-1554 (in Chinese)

730

2 Tungsten Carbides

2851. Zhang W, Liu X, Chen Z, Chen D, Peng C (2015) Latest development of WC-Co cemented carbide. Chin J Rare Met 39(2):178-186 (in Chinese) 2852. Chen L, Yi D, Wang B, Liu H, Wu C (2016) Mechanism of the early stages of oxidation of WC-Co cemented carbides. Corros Sci 103:75-87 2853. Emani SV, Dos Santos AFCR, Shaw LL, Chen Z (2016) Investigation of microstructure and mechanical properties at low and high temperatures of WC – 6 wt.% Co. Int J Refract Met Hard Mater 58:172-181 2854. Emanuelli L, Pellizzari M, Molinari A, Castellani F, Zinutti E (2016) Thermal fatigue behaviour of WC – 20 Co and WC – 30 (CoNiCrFe) cemented carbide. Int J Refract Met Hard Mater 60:118-124 2855. Fabijanić TA, Alar Ž, Ćorić D (2016) Influence of consolidation process and sintering temperature on microstructure and mechanical properties of near nano- and nano-structured WC-Co cemented carbides. Int J Refract Met Hard Mater 54:82-89 2856. Fabijanić TA, Jakovljević S, Franz M, Jeren I (2016) Influence of grain growth inhibitors and powder size on the properties of ultra-fine and nanostructured cemented carbides sintered in hydrogen. Metals 6(9):198 (12 pp.); doi:10.3390/met6090198 2857. Fan X, He D, Wang P, Li D, Liu Y, Ma D, Du Y, Gao S, Kou Z (2016) High pressure infiltration sintering behaviour of WC-Co alloys. High Press Res 36(4):585-594 2858. Huang Z, He Y (2016) Constitutive equation for WC-Co functionally graded cemented carbides and application. Rare Met Mater Eng 45(7):1705-1708 2859. Jiang C, Chen H, Wang Q, Li Y (2016) Effect of brazing temperature and holding time on joint properties of induction brazed WC-Co / carbon steel using Ag-based alloy. J Mater Process Technol 229:562-569 2860. Johansson SAE, Wahnström G (2016) First principles derived complexion diagrams for phase boundaries in doped cemented carbides. Curr Opin Solid State Mater Sci 20:299-307 2861. Kazamer N, Pascal D-T, Marginean G, Serban V-A, Codrean C, Uţu I-D (2016) A comparison between hardness, corrosion and wear performance of APS sprayed WC-CoMo, WC-Co coatings. In: Nicoarǎ M, Uţu I-D, Opriṣ C (eds) Proc. 6th Int. conf. on advanced materials and structures (AMS 2015), Timişoara, Romania, 16-17 Oct 2015. Solid State Phenom 254:71-76 2862. Konyashin I, Ries B, Hlawatschek S, Mazilkin A (2016) High-temperature capillarity in hardmetal surface layers. Mater Lett 167:254-257 2863. Konyashin I, Hlawatschek S, Ries B, Mazilkin A (2016) Co drifts between cemented carbides having various WC grain sizes. Mater Lett 167:270-273 2864. Konyashin I, Lengauer W (2016) Sintering mechanisms of functionally graded cemented carbides. Mater Sci Forum 835:116-198 2865. Laukkanen A, Pinomaa T, Holmberg K, Andersson T (2016) Effective interface model for design and tailoring of WC-Co microstructures. Powder Metall 59(1):20-30 2866. Li X, Liu Y, Liu B, Zhou J (2016) Effects of submicron WC addition on structures, kinetics and mechanical properties of functionally graded cemented carbides with coarse grains. Int J Refract Met Hard Mater 56:132-138 2867. González-Oliver CJR, Álvarez EA, García JL (2016) Kinetics of densification and grain growth in ultra-fine WC-Co composites. Int J Refract Met Hard Mater 59:121-131 2868. Åkesson L (1979) Thermodynamics and sintering studies in the Co-W-C system. Thermochim Acta 29:327-332 2869. Rumman MR, Rosinski M, Xie Z, Ghomashchi R (2016) Microstructure and mechanical properties of pulse plasma compacted WC-Co. Int J Refract Met Hard Mater 60:58-67 2870. Roa JJ, Jiménez-Piqué E, Tarragó JM, Sandoval DA, Mateo A, Fair J, Llanes L (2016) Hall-Petch strengthening of the constrained metallic binder in WC-Co cemented carbides: experimental assessment by means of massive nanoindentation and statistical analysis. Mater Sci Eng A 676:487-491

References

731

2871. Siwak P, Garbiec D (2016) Microstructure and mechanical properties of WC-Co, WC-CoCr3C2 and WC-Co-TaC cermets fabricated by spark-plasma sintering. Trans Nonferr Met Soc China 26:2641-2646 2872. Straumal BB, Mazilkin AA, Baretzky B (2016) Grain boundary complexions and pseudopartial wetting. Curr Opin Solid State Mater Sci 20:247-256 2873. Su W, Huang Z, Ren X, Chen H, Ruan J (2016) Investigation on morphology evolution of coarse-grained WC – 6 Co cemented carbides fabricated by ball-milling route and hydrogen reduction route. Int J Refract Met Hard Mater 56:110-117 2874. Tarragó JM, Roa JJ, Jiménez-Piqué E, Keown E, Fair J, Llanes L (2016) Mechanical deformation of WC-Co composite micropillars under uniaxial compression. Int J Refract Met Hard Mater 54:70-74 2875. Teppernegg T, Klünsner T, Kremsner C, Tritremmel C, Czettl C, Puchegger S, Marsoner S, Pippan R, Ebner R (2016) High-temperature mechanical properties of WC-Co hard metals. Int J Refract Met Hard Mater 56:139-144 2876. Wang X, Song X, Gao Y, Liu X, Wang H, Liu X (2016) Orientation distribution of characteristic planes in WC-Co cemented carbides. Rare Met Mater Eng 45(3):629-634 (in Chinese) 2877. Wang X, Wang H, Moscatelli R, Liu X, Song X (2016) Cemented carbides with highly oriented WC grains and formation mechanisms. Mater Sci Eng A 659:76-83 2878. Yang Q, Yang J, Yang H, Ruan J (2016) The effects of fine WC contents and temperature on the microstructure and mechanical properties of inhomogeneous WC – (fine WC-Co) cemented carbides. Ceram Int 42:18100-18107 2879. Yuan Y, Fu L, Li J (2016) Effects of WC particle size and Co content on the graded structure in functionally gradient WC-Co composites. In: Jawaid M, Kenawy E-R (eds) Proc. Int. symp. on materials application and engineering (SMAE 2016), Chiang Mai, Thailand, 20-21 Aug 2016. MATEC Web Conf 67:06012 (8 pp.) 2880. Żórawski W, Makrenek M, Góral A (2016) Mechanical properties and corrosion resistance of HVOF sprayed coatings using nanostructured carbide powders. Arch Metall Mater 61(4):1839-1846 2881. Budin S, Jaafar TR, Selamat MA (2017) Effect of sintering atmosphere on the mechanical properties of sintered tungsten carbide. In: Kida K (ed) Proc. Int. conf. on composite material, polymer science and engineering, Toyama City, Japan, 24-25 June 2017. MATEC Web Conf 130:03006 (8 pp.) 2882. Cao RJ, Lin CG, Xie XC, Lin ZK (2017) Determination of the average WC grain size of cemented carbides for hardness and coercivity. Int J Refract Met Hard Mater 64:160-167 2883. Feng Q, Song X, Xie H, Wang H, Liu X, Yin F (2017) Deformation and plastic coordination in WC-Co composite – molecular dynamics simulation of nanoindentation. Mater Design 120:193-203 2884. Guo Y, Li Z-Y, Li Y (2017) Preparation of η-phase powder and the effect of sintering process on the plate-like WC grains. Powder Metall Technol 35(1):39-45 (in Chinese) 2885. Jewell P, Shannahan L, Pagano S, DeMott R, Taheri M, Lamberson L (2017) Rate and microstructure influence on the fracture behaviour of cemented carbides WC-Co and WC-Ni. In: Ghosh S (ed) Proc. IUTAM symp. on integrated computational structure-material modelling of deformation and failure under extreme conditions, Baltimore, Maryland, 19-22 June 2016. Int J Fract 208:203-219 2886. Jonke M, Klünsner T, Supancic P, Harrer W, Glätzle J, Barbist R, Ebner R (2017) Strength of WC-Co hardmetals as a function of the effectively loaded volume. Int J Refract Met Hard Mater 64:219-224 2887. Khmyrov RS, Safronov VA, Gusarov AV (2017) Synthesis of nanostructured WC-Co hardmetal by selective laser melting. In: Manzhirov AV, Altenbach H, Gupta N (eds) Proc. IUTAM symp. on growing solids, Moscow, Russian Federation, 23-27 June 2015. Proc IUTAM 23:114-119

732

2 Tungsten Carbides

2888. Konyashin I, Sologubenko A, Weirich T, Ries B (2017) Complexion at WC-Co grain boundaries of cemented carbides. Mater Lett 187:7-10 2889. Konyashin I, Straumal BB, Ries B, Bulatov MF, Kolesnikova KI (2017) Contact angles of WC/WC grain boundaries with binder in cemented carbides with various carbon content. Mater Lett 196:1-3 2890. Konyashin I, Zaitsev AA, Sidorenko D, Levashov EA, Ries B, Konischev SN, Sorokin M, Mazilkin AA, Herrmann M, Kaiser A (2017) Wettability of tungsten carbide by liquid binders in WC-Co cemented carbides: is it complete for all carbon contents? Int J Refract Met Hard Mater 62:134-148 2891. Konyashin I, Zaitsev AA, Sidorenko D, Levashov EA, Konischev SN, Sorokin M, Hlawatschek S, Ries B, Mazilkin AA, Lauterbach S, Kleebe H-J (2017) On the mechanism of obtaining functionally graded hardmetals. Mater Lett 186:142-145 2892. Liu Y, Cheng J, Yin B, Zhu S, Qiao Z, Yang J (2017) Study of the tribological behaviours and wear mechanisms of WC-Co and WC-Fe3Al hard materials under dry sliding condition. Tribol Int 109:19-25 2893. Li W, Lin T, Song C, He P, Wang Q (2017) Properties of supersonic plasma sprayed WC – 17 Co nanocoating. Rare Met Mater Eng 46(3):807-811 (in Chinese) 2894. Mashhadikarimi M, Gomes UU, Oliveira MP, Guimarães RDS, Filgueira M (2017) Study HTHP sintered WC/Co hardmetal. Mater Res 20(1):138-143 2895. Mi P, Wang T, Ye F (2017) Influences of the compositions and mechanical properties of HVOF sprayed bimodal WC-Co coating on its high-temperature wear performance. Int J Refract Met Hard Mater 69:158-163 2896. Oskolkova TN, Glezer AM (2017) Surface hardening of hard tungsten carbide alloys: a review. Steel Transl 47(12):788-796 2897. Padmakumar M, Dinakaran D, Guruprasath J (2017) Characterization of cryogenically treated cemented carbide. Integr Ferroelectr 185(1):65-72 2898. Parker SR, Whiting MJ, Yeomans JA (2017) Control of carbon content in WC-Co hardmetal by heat treatment in reducing atmospheres containing methane. Int J Refract Met Hard Mater 66:204-210 2899. Pellan M, Lay S, Missiaen J-M, Norgren S, Angseryd J, Coronel E, Persson T (2017) EBSD study to analyse mechanisms of phase boundary and grain boundary development in WC-Co cemented carbides. Powder Metall 60(3):208-215 2900. Pristinskiy Yu, Peretyagin N, Solis-Pinargote NW (2017) Comparative studies on mechanical properties of WC-Co composites sintered by SPS and conventional techniques. In: Bratan S, Leonov S, Borbatyuk S, Roshchupkin S (eds) Proc. Int. conf. on modern trends in manufacturing technologies and equipment (ICMTMTE 2017), Sevastopol (occupied by Russia), Ukraine, 11-15 Sep 2017. MATEC Web Conf 129:02028 (8 pp.) 2901. Sidhu VPS, Goyal K, Goyal R (2019) Hot corrosion behaviour of HVOF-sprayed 93 (WCCr3C2) – 7 Ni and 83 WC – 17 Co coatings on boiler tube steel in coal fired boiler. Austral J Mech Eng 17(2):127-132 2902. Useldinger R, Schleinkofer U (2017) Creep behaviour of cemented carbides – influence of binder content, binder composition and WC grain size. Int J Refract Met Hard Mater 62:170175 2903. Walbrühl M, Linder D, Ågren J, Borgenstam A (2017) Diffusion modelling in cemented carbides: solubility assessment for Co, Fe and Ni binder systems. Int J Refract Met Hard Mater 68:41-48 2904. Wang H, Yang T, Song X, Liu X, Wang X, Wu X (2017) Wear resistance enhancement of bimodal-grained cemented carbide coating. Surf Coat Technol 309:759-766 2905. Wang Z, Gao P, Shang G, Wu J, Yang J, Lv J (2017) Effect of carbon source on the preparation of WC-Co composite powders by spray conversion process. J Funct Mater 48(11):11210-11215 (in Chinese)

References

733

2906. Yang J, Roa JJ, Schwind M, Odén M, Johansson-Jõesaar MP, Llanes L (2017) Grindinginduced metallurgical alterations in the binder phase of WC-Co cemented carbides. Mater Charact 134:302-310 2907. Yang T-E, Wang H-B, Song X-Y, Liu X-M, Hou C, Wang X-Z (2017) Corrosion resistance of HVOF-sprayed nano- and micro-structured WC-η coatings against molten zinc. J Inorg Mater 32(8):806-812 (in Chinese) 2908. Chicardi E, Bermejo R, Gotor FJ, Llanes L, Torres Y (2018) Influence of temperature on the biaxial strength of cemented carbides with different microstructures. Int J Refract Met Hard Mater 71:82-91 2909. Dhande ST, Kane VA, Dhobe MM, Gogte CL (2018) Influence of soaking periods in cryogenic treatment of tungsten carbide. In: Patil NG, Pawade RS, Lahane SV, Zine PU (eds) Proc. 2nd Int. conf. on materials, manufacturing and design engineering (iCMMD 2017), Maharashtra, India, 11-12 Dec 2017. Proc Manuf 20:318-328 2910. Yong AYL, Seah KHW, Rahman M (2006) Performance evaluation of cryogenically treated tungsten carbide tools in turning. Int J Mach Tools Manuf 46(15):2051-2056 2911. Gill SS, Singh R, Singh H, Singh J (2009) Wear behaviour of cryogenically treated tungsten carbide inserts under dry and wet turning conditions. Int J Mach Tools Manuf 49(34):256-260 2912. Murthy NH, Krishna M (2010) Performance analysis of cryogenically treated carbide drills in drilling white cast iron. Int J Appl Eng Res 1(3):553 2913. Gill SS, Singh R, Singh H, Singh J (2012) Metallurgical and mechanical characteristics of cryogenically treated tungsten carbide (WC-Co). Int J Adv Manuf Technol 58(1-4):119-131 2914. Ramji BR, Murthy NH, Krishna M (2010) Analysis of forces, roughness, wear and temperature in turning cast iron using cryotreated carbide inserts. Int J Eng Sci Technol 2(7):2521-2529 2915. Dvornik MI, Mikhailenko EA (2018) Issledovanie sostava, struktury i svoistv gradientnogo tverdogo splava, poluchennogo v rezultate sovmestnogo spekaniya ultramelkozernistogo i srednezernistogo sloev (A study of the composition, structure and properties of a graded hard alloy as a result of sintering of ultra-fine grained and medium grained layers). Tsvet Met (4):67-72 (in Russian) 2916. Elizalde MR, Ocaña I, Alkorta J, Sánchez-Moreno JM (2018) Mechanical strength assessment of single WC-WC interfaces present in WC-Co hardmetals through micro-beam bending experiments. Int J Refract Met Hard Mater 72:39-44 2917. Emanuelli L, Molinari A, Arrighetti G, Garoli G (2018) Effects of the sintering parameters on the liquid Co migration in WC-Co. Int J Refract Met Hard Mater 70:202-209 2918. Ezquerra BL, Lozada L, Van Den Berg H, Wolf M, Sánchez-Moreno JM (2018) Comparison of the thermal shock resistance of WC based cemented carbides with Co and CoNi-Cr based binder. Int J Refract Met Hard Mater 72:89-96 2919. Farag S, Konyashin I, Ries B (2018) The influence of grain growth inhibitors on the microstructure and properties of sub-micron, ultra-fine and nano-structured hardmetals – a review. Int J Refract Met Hard Mater 77:12-30 2920. Gant AJ, Morrell R, Wronski AS, Jones HG (2018) Edge toughness of tungsten carbide based hardmetals. Int J Refract Met Hard Mater 75:262-278 2921. Hanner LA, Pittari JJ, III, Swab JJ (2018) Dynamic hardness of cemented tungsten carbides. Int J Refract Met Hard Mater 75:294-298 2922. Han JS, Ha S, Johnson JL, German RM, Park SJ (2018) Grain size optimization for nanoscale tungsten carbide cobalt using master sintering curve model. Int J Refract Met Hard Mater 72:306-314 2923. Herd S, Wood RJK, Wharton JA, Higgs CF, III (2018) Explicit fracture modelling of cemented tungsten carbide (WC-Co) at the mesoscale. Mater Sci Eng A 712:521-530 2924. Kayser W, Bezold A, Broekmann C (2018) EBCD-based FEM simulation of residual stresses in a WC – 6 wt.% Co hardmetal. Int J Refract Met Hard Mater 73:139-145

734

2 Tungsten Carbides

2925. Kang S-Y, Baik K-H, Yoon S-H, Kim H-J (2018) Effects of feedstock powder characteristics on the microstructural features and erosion resistance of WC – 12 Co coatings. J Korean Inst Met Mater 56(2):113-120 2926. Karhu M, Lagerbom J, Kaunisto K, Suhonen T, Metsäjoki J, Turunen E (2018) Nanocrystalline WC-Co HVAF coatings by utilizing novel powder manufacturing route using water-soluble raw materials. J Therm Spray Technol 27:196-206 2927. Konyashin I, Ries B, Hlawatschek S, Mazilkin A (2018) Novel industrial hardmetals for mining, construction and wear applications. Int J Refract Met Hard Mater 71:357-365 2928. Konyashin I, Zaitsev A, Meledin A, Mayer J, Loginov P, Levashov E, Ries B (2018) Interfaces between model Co-W-C alloys with various carbon contents and tungsten carbide. Materials 11(3):404 (11 pp.); doi:10.3390/ma11030404 2929. Kovalchenko MS, Tolochyn OI, Litvin RV (2018) Densification dynamics of fine-grained WC + 25 wt.% Co cermet during low-temperature impact sintering in vacuum. Powder Metall Met Ceram 57(1-2):38-48 2930. Kresse T, Meinhard D, Bernthaler T, Schneider G (2018) Hardness of WC-Co hard metals: preparation, quantitative microstructure analysis, structure-property relationship and modelling. Int J Refract Met Hard Mater 75:287-293 2931. Kücher G, Luidold S, Czettl C, Storf C (2018) Lixiviation kinetics of cobalt from cemented carbides. Int J Refract Met Hard Mater 70:239-245 2932. Lamana MS, Pukasiewicz AGM, Sampath S (2018) Influence of cobalt content and HVOF deposition process on the cavitation erosion resistance of WC-Co coatings. Wear 398399:209-219 2933. Lee S-H, Kim D-H, Kim T-Y, Choi J-S, Choi J-W (2018) Investigation on failure analysis and optimization of WC-Co hardmetals after long-term use in a bottle cap forming machine. Int J Refract Met Hard Mater 74:99-106 2934. Li J, Cheng J, Chen P, Chen W, Wei C (2018) Fabrication of WC-Co cemented carbides with gradient distribution of WC grain size and Co composition by lamination pressing and microwave sintering. Ceram Int 44:11225-11232 2935. Liu C, Lin N, He YH, Liu WS, Ma YZ (2018) Influence of micron WC addition on the microstructure and mechanical properties of ultra-fine WC-Co cemented carbides at the elevated temperature. J Superhard Mater 40(1):40-46 2936. Liu K, Wang Z, Yin Z, Cao L, Yuan J (2018) Effect of Co content on microstructure and mechanical properties of ultra-fine grained WC-Co cemented carbide sintered by sparkplasma sintering. Ceram Int 44:18711-18718 2937. Liu X-M, Wang H-B, Song X-Y, Moscatelli R (2018) Elastic modulus of nanocrystalline cemented carbide. Trans Nonferr Met Soc China 28:966-973 2938. Li W, Xu P, Wang Y, Zou Y, Gong H, Lu F (2018) Laser synthesis and microstructure of micro- and nano-structured WC reinforced Co-based cladding layers on titanium alloy. J Alloys Compd 749:10-22 2939. Matveichuk AA, Davidenko SA (2018) On the interaction of the cobalt melt with polycrystalline tungsten monocarbide. J Superhard Mater 40(3):184-188 2940. Mi P, Ye F (2018) Structure and wear performance of the atmospheric heat-treated HVOF sprayed bimodal WC-Co coating. Int J Refract Met Hard Mater 76:185-191 2941. Mi P, Zhao H, Wang T, Ye F (2018) Sliding wear behaviour of HVOF sprayed WC – (nano-WC-Co) coating at elevated temperatures. Mater Chem Phys 206:1-6 2942. Mishra TK, Kumar A, Sinha SK, Sharma S (2018) Investigation of sliding wear behaviour of HVOF carbide coating. In: Singh SK, Purohit R, Parveen A (eds) Proc. 8th Int. conf. on materials processing and characterization (ICMPC-2018), Madhapur, India, 16-18 Mar 2018. Mater Today Proc 5(9/3):19539-19546 2943. Murdoch HA, Darling KA (2018) Metric mapping: a colour coded atlas for guiding rapid development of novel cermets and its application to “green” WC binder. Mater Design 150:64-74

References

735

2944. Padmakumar M, Guruprasath J, Achuthan P, Dinakaran D (2018) Investigation of phase structure of cobalt and its effect in WC-Co cemented carbides before and after deep cryogenic treatment. Int J Refract Met Hard Mater 74:87-92 2945. Padmakumar M, Dinakaran D, Guruprasath J (2018) Tribological behaviour of cryogenically treated WC – 9 Co cemented carbide. In: Sivaprasad K (ed) Proc. Int. conf. on emerging trends in materials and manufacturing engineering (IMME17), Tiruchirappalli, India, 10-12 Mar 2017. Mater Today Proc 5:7797-7807 2946. Parihar RS, Setti SG, Sahu RK (2018) Preliminary investigation on development of functionally graded cemented tungsten carbide with solid lubricant via ball milling and sparkplasma sintering. J Compos Mater 52(10):1363-1377 2947. Park C, Kim J, Kang S (2018) Effect of cobalt on the synthesis and sintering of WC-Co composite powders. J Alloys Compd 766:564-571 2948. Richter J, Chrapoński J (2018) Application of FIB in the preparation of TEM specimens of experimental supercoarse WC-Co(Ni) composites. Int J Refract Met Hard Mater 75:163-169 2949. Sandoval DA, Rinaldi A, Tarragó JM, Roa JJ, Fair J, Llanes L (2018) Scale effect in mechanical characterization of WC-Co composites. Int J Refract Met Hard Mater 72:157-162 2950. Sun F, Chen X, Zhao Z (2018) Synthesis of monocrystalline tungsten carbide powder in carbon saturated cobalt melt. Ceram Int 44:8716-8719 2951. Tarragó JM, Coureaux D, Torres Y, Jiménez-Piqué E, Schneider L, Fair J, Llanes L (2018) Strength and reliability of WC-Co cemented carbides: understanding micro-structural effects on the basis of R-curve behaviour and fractography. Int J Refract Met Hard Mater 71:221226 2952. Wada K (2018) Tungsten carbide based hardmetals used for high pressure experiment. Rev High Press Sci Technol 28(1):9-16 (in Japanese) 2953. Walbrühl M, Linder D, Ågren J, Borgenstam A (2018) A new hardness model for materials design in cemented carbides. Int J Refract Met Hard Mater 75:94-100 2954. Wang H, Hou C, Liu Xu, Liu Xi, Song X (2018) Phase evolution in synthesis of nanocrystalline WC-η composite powder by solid-state in situ reactions. Int J Refract Met Hard Mater 71:21-27 2955. Wang H, Hou C, Liu Xu, Liu Xi, Song X (2018) Wear resistance mechanisms of nearnanostructured WC-Co coatings. Int J Refract Met Hard Mater 71:122-128 2956. Wang T, Ye F (2018) The elevated-temperature wear behaviour evolution of HVOF sprayed tungsten carbide coatings: respond to heat treatment. Int J Refract Met Hard Mater 71:92-100 2957. Wang W, Lu Z, Zeng M, Zhu M (2018) Achieving combination of high hardness and toughness for WC – 8 Co hardmetals by creating dual scale structured plate-like WC. Ceram Int 44:2668-2675 2958. Weidow J, Ekström E, Kritikos M, Norgren S (2018) Impact of crystal defects on the grain growth of cemented carbides. Int J Refract Met Hard Mater 72:199-202 2959. Xi X, Liu Q, Nie Z, Li M, Ma L (2018) Electrochemical preparation of tungsten and cobalt from cemented carbide scrap in NaF-KF molten salts. Int J Refract Met Hard Mater 70:77-83 2960. Yang Q, Yang J, Wen Y, Zhang Q, Chen L, Chen H (2018) A novel route for the synthesis of ultra-fine WC – 15 wt.% Co cemented carbides. J Alloys Compd 748:577-582 2961. Yin G, Wang Y, Cui H, Lu F, Xu P (2018) Effect of holding time and interlayer’s thickness on the crack initiation and propagation and the dissolving behaviour of the heattreated facet WC grains. Int J Refract Met Hard Mater 71:45-60 2962. Zhang X, Guo Z, Chen C, Yang W (2018) Additive manufacturing of WC – 20 Co components by 3D gel-printing. Int J Refract Met Hard Mater 70:215-223 2963. Avdeenko EN, Zamulaeva EI, Zaitsev AA, Konyashin IYu, Levashov EA (2019) Structure and properties of coarse-grained WC-Co alloys with an especially homogeneous microstructure. Russ J Non-Ferr Met 60(5):542-548

736

2 Tungsten Carbides

2964. Chen J, Huang M, Fang ZZ, Koopman M, Liu W, Deng X, Zhao Z, Chen S, Wu S, Liu J, Qi W, Wang Z (2019) Microstructure analysis of high-density WC-Co composite prepared by one step selective laser melting. Int J Refract Met Hard Mater 84:104980 (6 pp.) 2965. Garbiec D, Siwak P (2019) Microstructural evolution and development of mechanical properties of spark-plasma sintered WC-Co cemented carbides for machine parts and engineering tools. Arch Civil Mech Eng 19:215-223 2966. Gao P-H, Chen B-Y, Wang W, Jia H, Li J-P, Yang Z, Guo Y-C (2019) Simultaneous increase of friction coefficient and wear resistance through HVOF sprayed WC – (nano WCCo). Surf Coat Technol 363:379-389 2967. Jiang Q, Tian Y, Shu F, Zhao H, Sun Y, He W, Xu B (2019) Strengthening mechanism and properties of Co-WC composite coatings deposited by plasma transferred arc welding. Micro Nano Lett 14(7):717-720 2968. Ke Z, Zheng Y, Zhang G, Ding Q, Zhang J, Wu H, Xu X, Lu X, Zhu X (2019) Microstructure and mechanical properties of dual-grain structured WC-Co cemented carbides. Ceram Int 45:21528-21533 2969. Konyashin I, Hinners H, Ries B, Kirchner A, Klöden B, Kieback B, Nilen RWN, Sidorenko DA (2019) Additive manufacturing of WC – 13 % Co by selective electron beam melting: achievements and challenges. Int J Refract Met Hard Mater 84:105028 (7 pp.) 2970. Laptev AV (2019) Some trends in improving WC-Co hardmetals. I. Hybrid and coarsegrained hardmetals. Powder Metall Met Ceram 58(1-2):42-57 2971. Laptev AV (2019) Some trends in improving WC-Co hardmetals. II. Functionally graded hardmetals. Powder Metall Met Ceram 58(3-4):170-183 2972. Loginov PA, Zaitsev AA, Konyashin I, Sidorenko DA, Avdeenko EN, Levashov EA (2019) In situ observation of hardmetal deformation processes by transmission electron microscopy. Part I. Deformation caused by bending loads. Int J Refract Met Hard Mater 84:104997 (7 pp.) 2973. Loginov PA, Zaitsev AA, Konyashin I, Sidorenko DA, Orekhov AS, Avdeenko EN, Levashov EA (2019) In situ observation of hardmetal deformation processes by transmission electron microscopy. Part II. Deformation caused by tensile loads. Int J Refract Met Hard Mater 84:105017 (8 pp.) 2974. Padmakumar M, Guruprasath J, Dinakaran D (2019) Influence of cryo-processing on properties of tungsten carbide with low, medium and high cobalt content. Mater Res Express 6:106597 (12 pp.) 2975. Padmakumar M, Guruprasath J, Dinakaran D (2019) Erratum: “Influence of cryoprocessing on properties of tungsten carbide with low, medium and high cobalt content” (2019 Mater. Res. Express 6 106597). Mater Res Express 6:119601 (2 pp.) 2976. Richter J, Harabas K (2019) Micro-abrasion investigations of conventional and experimental supercoarse WC – (Ni, Co, Mo) composites. Int J Refract Met Hard Mater 83:104986 (10 pp.) 2977. Sandoval DA, Rinaldi A, Notargiacomo A, Ther O, Roa JJ, Llanes L (2019) WC-base cemented carbides with partial and total substitution of Co as binder: evaluation of mechanical response by means of uniaxial compression of micropillars. Int J Refract Met Hard Mater 84:105027 (8 pp.) 2978. Su Q, Zhu S, Ding H, Bai Y, Di P (2019) Comparison of the wear behaviours of advanced and conventional cemented tungsten carbides. Int J Refract Met Hard Mater 79:18-22 2979. Yang Q, Deng D, Li J, Chen L, Guo S, Liu J, Chen H (2019) Fabrication and mechanical properties of WC – 10 Co cemented carbides with plate-like WC grains. J Alloys Compd 803:860-865 2980. Yuan X, Zhang X, Deng S (2019) Grain boundary character distributions of coincidence site lattice boundaries in WC-Co composites under plastic deformation. Rare Met Mater Eng 48(8):2454-2459

References

737

2981. Csanádi T, Vojtko M, Dusza J (2020) Deformation and fracture of WC grains and grain boundaries in a WC-Co hardmetal during microcantilever bending tests. Int J Refract Met Hard Mater 87:105163 (9 pp.) 2982. Ding Q, Zheng Y, Ke Z, Zhang GT, Wu H, Xu XY, Lu X, Zhu X (2020) Effects of fine WC particle size on the microstructure and mechanical properties of WC – 8 Co cemented carbides with dual-scale and dual-morphology WC grains. Int J Refract Met Hard Mater 87:105166 (7 pp.) 2983. Fan P, Zhang G (2020) Study on process optimization of WC – Co50 cermet composite coating by laser cladding. Int J Refract Met Hard Mater 87:105133 (11 pp.) 2984. Fries S, Genilke S, Wilms MB, Seimann M, Weisheit A, Kaletsch A, Bergs T, Schleifenbaum JH, Broeckmann C (2020) Laser-based additive manufacturing of WC-Co with high-temperature powder bed preheating. Steel Res Int 91:1900511 (7 pp.) 2985. Jablon BM, Mingard K, Winkelmann A, Naresh-Kumar G, Hourahine B, Trager-Cowan C (2020) Subgrain structure and dislocations in WC-Co hard metals revealed by electron channelling contrast imaging. Int J Refract Met Hard Mater 87:105159 (7 pp.) 2986. Lantsev EA, Malekhonova NV, Nokhrin AV, Chuvildeev VN, Boldin MS, Andreev PV, Smetanina KE, Blagoveshchenskii YuV, Isaeva NV, Murashov AA (2020) Spark-plasma sintering of fine-grained WC hard alloys with ultra-low cobalt content. J Alloys Compd 857:157535 (21 pp.) 2987. Parihar RS, Setti SG, Sahu RK (2020) Solid lubricant effect on the microstructure and hardness of the functionally graded cemented tungsten carbide. In: Voruganti HK, Kumar KK, Krishna PV, Jin X (eds) Advances in applied mechanical engineering. Select proc. 1st Int. conf. on applied mechanical engineering research (ICAMER 2019), Warangal, India, 2-4 May 2019, pp. 745-751. Springer Nature, Singapore 2988. Peng Y, Wang H, Zhao C, Hu H, Liu X, Song X (2020) Nanocrystalline WC-Co composite with ultra-high hardness and toughness. Compos B 197:108161 (11 pp.) 2989. Randhawa NS, Katiyar PK (2020) Potentiodynamic polarization behaviour and microscopic examination of tungsten carbide hard metal materials in supported ammoniacal medium. Portug Electrochim Acta 38(3):185-200 2990. Venter AM, Luzin V, Marais D, Saks N, Ogunmuyiwa EN, Shipway PH (2020) Independence of slurry erosion wear performance and residual stress in WC – 12 wt.% Co and WC – 10 wt.% VC – 12 wt.% Co HVOF coatings. Int J Refract Met Hard Mater 87:105101 (9 pp.) 2991. Wang K-F, Chou K-C, Zhang G-H (2020) Preparation of high-purity and ultra-fine WCCo composite powder by a simple two-step process. Adv Powder Technol 31(5):1940-1945 2992. Lantsev EA, Nokhrin AV, Boldin MS, Malekhonova NV, Andreev PV, Smetanina KE, Popov AA (2020) Experimental study of the influence of different carbon content on the shrinkage kinetics and structure evolution of ultra-low cobalt hard alloys during spark-plasma sintering. In: Mulyukov RR, Nazarov AA, Imayev RM (eds) Proc. open school – conf. of NIS countries “Ultra-fine grained and nanostructured materials – 2020” (UFGNM – 2020), Ufa, Russian Federation, 5-9 Oct 2020. IOP Conf Series Mater Sci Eng 1008(1):012049 (6 pp.) 2993. Lantsev EA, Chuvildeev VN, Nokhrin AV, Boldin MS, Tsvetkov YuV, Blagoveshchenskii YuV, Isaeva NV, Andreev PV, Smetanina KE (2020) Kinetics of spark-plasma sintering of WC – 10 % Co ultra-fine grained hard alloy. Inorg Mater Appl Res 11(3):586-597 2994. Lantsev EA, Chuvildeev VN, Nokhrin AV, Boldin MS, Malekhonova NV, Blagoveshchenskii YuV, Isaeva NV, Tsvetkov YuV, Andreev PV, Smetanina KE (2020) Study of the kinetics of spark-plasma sintering of ultra-fine grained hard alloys WC – 10 % Co. In: Proc. 8th Int. conf. on deformation and fracture of materials and nanomaterials (DFMN 2019), Moscow, Russian Federation, 19-22 Nov 2019. J Phys Conf Series 1431:012030 (9 pp.) 2995. Smetanina KE, Andreev PV, Lantsev EA, Vostokov MM, Malekhonova NV (2020) Studying the homogeneity of the phase composition of hard alloys based on WC-Co. In: Gorkunov ÉS, Irschik H (eds) Proc. 14th Int. conf. on mechanics, resource and diagnostics of

738

2 Tungsten Carbides

materials and structures (MRDMS 2020), Yekaterinburg, Russian Federation, 9-13 Nov 2020. AIP Conf Proc 2315:040035 (7 pp.) 2996. Smetanina KE, Andreev PV, Malekhonova NV, Lantsev EA (2019) Optimization of the phase composition of hard alloys obtained by spark-plasma sintering of powders WC – 10% Co. In: Proc. 15th Int. Russian-Chinese symp. “New materials and technologies”, Sochi, Russian Federation, 16-19 Oct 2019. J Phys Conf Series 1347(1):012064 (5 pp.) 2997. Eser E, Ogilvie RE, Taylor KA (1978) Friction and wear results from WC + Co coatings by d.c.-biased r.f. sputtering in a helium atmosphere. J Vac Sci Technol 15(2):401-405 2998. Ramalho A, Vieira MT, Miranda AS (1992) Tribological behaviour of W-C-Co coatings. J Mater Process Technol 31(1-2):225-234 2999. Eser E, Ogilvie RE, Taylor KA (1980) The effect of bias on d.c. and r.f. sputtered WC-Co coatings. Thin Solid Films 67(2):265-277 3000. Klimpel A, Dobrzański LA, Lisiecki A, Janicki D (2005) The study of properties of NiW2C and Co-W2C powders thermal sprayed deposits. J Mater Process Technol 164165:1068-1073 3001. Lou D, Hellman J, Luhulima D, Liimatainen J, Lindroos VK (2003) Interactions between tungsten carbide (WC) particulates and metal matrix in WC-reinforced composites. Mater Sci Eng A 340:155-162 3002. Machado IF, Girardini L, Lonardelli I, Molinari A (2009) The study of ternary carbides formation during SPS consolidation process in the WC-Co-steel system. Int J Refract Met Hard Mater 27:883-891 3003. Chen G, Zhang B, Wu Z, Shu X, Feng J (2017) Microstructure transformation and crack sensitivity of WC-Co/steel joint welded by electron beam. Vacuum 139:26-32 3004. Chen G, Shu X, Liu J, Zhang Bo, Zhang Bi, Feng J (2018) Investigation on microstructure of electron beam welded WC-Co/40Cr joints. Vacuum 149:96-100 3005. Ojo-Kupoluyi OJ, Tahir SM, Ariff AHM, Baharudin BTHT, Matori KA, Anuar MS (2017) Densification rate and interfacial adhesion of bilayer cemented tungsten carbide and steel. Int J Mater Res 108(12):1090-1098 3006. Zhao X, Yang DX, Takazawa K, Kamota S, Miyakoshi Y, Yamamori H, Tagashira K (2004) Formation of complex carbide in TIG welded joints of WC-Co hard metal and carbon steel. J Jpn Inst Met 68(2):98-101 (in Japanese) 3007. Knotek O, Lugscheider E, Tschech F (1975) Beitrag zur Stabilität von M6C-Carbiden in Co-Cr-W-C-Legierungen (Concerning the stability of M6C carbides in Co-Cr-W-C alloys). Härterei-Tech Mitt 20(6):335-337 (in German) 3008. Knotek O, Lugscheider E, Tschech F (1976) The formation of tungsten carbide in cobaltbase wear-resistant coating alloys. In: Proc. Int. conf. on metallurgical coatings, San Francisco, California, 5-8 Apr 1976. Thin Solid Films 39:263-268 3009. Knotek O, Seifahrt H, Kieffer R (1968) Beitrag zur untersuchung der kobaltreichen ecke im system Kobalt – Chrom – Wolfram – Kohlenstoff (Contribution to the investigation of the cobalt-rich corner in the cobalt – chromium – tungsten – carbon system). Arch Eisenhüttenwes 39(11):869-875 (in German) 3010. Inoue K, Yoshikiyo M, Yoshii S (1987) Co-Cr-W-C alloy thin films for perpendicular recording media. IEEE Trans Magnet 23(5):3651-3653 3011. Lisovskii AF, Tkachenko NV (1997) On the use of the MMI-phenomenon for the formation of nanostructures in WC-Co cemented carbides. Int J Refract Met Hard Mater 15:227-235 3012. López-Cantera E, Mellor BG (1998) Fracture toughness and crack morphologies in eroded WC-Co-Cr thermally sprayed coatings. Mater Lett 37:201-210 3013. Guilemany JM, Cabot PL, Fernández J, Paco JM, Sánchez J (1998) Improving the marine water corrosion resistance of HVOF steels coated with WC + 12 % Co + 4 % Cr. Sci Eng Compos Mater 7(3):205-208 3014. Wesmann JAR, Espallargas N (2016) Effect of atmosphere, temperature and carbide size on the sliding friction of self-mated HVOF WC-CoCr contacts. Tribol Int 101:301-313

References

739

3015. Sundin S, Haglund S (2000) A comparison between magnetic properties and grain size for WC/Co hard materials containing additives of Cr and V. Int J Refract Met Hard Mater 18:297-300 3016. Delanoë A, Bacia M, Pauty E, Lay S, Allibert CH (2004) Cr-rich layer at the WC/Co interface in Cr-doped WC-Co cermets: segregation or metastable carbide? J Cryst Growth 270:219-227 3017. Hashiya M, Kubo Y, Gierl Ch, Schubert WD (2009) The influence of carbon content and additions of growth inhibitors (V, Cr) on the formation of melt in WC-Co and WC-Ni alloys. In: Sigl LS, Rödhammer P, Wildner H (eds) Proc. 17th Int. Plansee seminar, Int. conf. on high-performance P/M materials, Reutte, Tyrol, Austria, 25-29 May 2009, Vol. 2 – P/M hard materials, pp. HM55/1-HM55/17. Plansee Metal AG, Reutte, Austria 3018. Murugan K, Ragupathy A, Balasubramanian V, Sridhar K (2014) Optimizing HVOF spray process parameters to attain minimum porosity and maximum hardness in WC – 10 Co – 4 Cr coatings. Surf Coat Technol 247:90-102 3019. Weidow J, Norgren S, Andrén H-O (2009) Effect of V, Cr, Mn additions on the microstructure of WC-Co. Int J Refract Met Hard Mater 27:817-822 3020. Chikarakara E, Aqida S, Brabazon D, Haher S, Picas JA, Punset M, Forn A (2010) Surface modification of HVOF thermal sprayed WC-CoCr coatings by laser treatment. Int J Mater Form 3(S1):801-804 3021. Lee CW, Han JH, Yoon J, Shin MC, Kwun SI (2010) A study on powder mixing for highfracture toughness and wear resistance of WC-Co-Cr coatings sprayed by HVOF. Surf Coat Technol 204:2223-2229 3022. Marginean G, Utu D (2010) Microstructure refinement and alloying of WC-CoCr coatings by electron beam treatment. Surf Coat Technol 205:1985-1989 3023. Weidow J, Andrén H-O (2010) Grain and phase boundary segregation in WC-Co with small V, Cr or Mn additions. Acta Mater 58:3888-3894 3024. Thakur L, Arora N, Jayaganthan R, Sood R (2011) An investigation on erosion behaviour of HVOF sprayed WC-CoCr coatings. Appl Surf Sci 258:1225-1234 3025. Bolelli G, Börner T, Bozza F, Cannillo V, Cirillo G, Lusvarghi L (2012) Cermet coatings with Fe-based matrix as alternative to WC-CoCr: mechanical and tribological behaviours. Surf Coat Technol 206:4079-4094 3026. Khoddamzadeh A, Liu R, Liang M, Yang Q (2012) Novel wear-resistant materials – carbon fiber reinforced low-carbon stellite alloy composites. Compos A 43:344-352 3027. Zavodinsky VG (2012) Ab initio study of inhibitors influence on growth of WC crystallites in WC/Co hard alloys. Int J Refract Met Hard Mater 31:263-265 3028. Hong S, Wu Y, Zheng Y, Wang B, Gao W, Lin J (2013) Microstructure and electrochemical properties of nanostructured WC – 10 Co – 4 Cr coating prepared by HVOF spraying. Surf Coat Technol 235:582-588 3029. Norgren S, Kusoffsky A (2013) On the solubility of chromium in the cubic carbide and M7C3 carbide in the WC-Co-Cr-Me systems (Me = Ti, Nb, Ta and Zr). Int J Refract Met Hard Mater 40:24-26 3030. Wang Q, Zhang S, Cheng Y, Xiang J, Zhao X, Yang G (2013) Wear and corrosion performance of WC – 10 Co – 4 Cr coatings deposited by different HVOF and HVAF spraying processes. Surf Coat Technol 218:127-136 3031. Weidow J, Olsson E, Andrén H-O (2013) Chemistry of binder phase grain boundary in WC-Co based cemented carbide. Int J Refract Met Hard Mater 41:366-369 3032. Zhang L, Xie M-W, Cheng X, Nan Q, Wang Z, Feng Y-P (2013) Microcharacteristics of binder phases in WC-Co cemented carbides with Cr-V and Cr-V-RE additives. Int J Refract Met Hard Mater 36:211-219 3033. Bolelli G, Berger L-M, Bonetti M, Lusvarghi L (2014) Comparative study of the dry sliding wear behaviour of HVOF-sprayed WC-(W,Cr)2C-Ni and WC-Co-Cr hardmetal coatings. Wear 309:96-111

740

2 Tungsten Carbides

3034. Chen W, Long A, Xiang J, Li S, Zhou W, Li Y (2014) Corrosion resistance of WC – 10 Co – 4 Cr HVOF coating in NaCl solution. J Central South Univ Sci Technol 45(10):33733378 (in Chinese) 3035. Bolelli G, Berger L-M, Börner T, Koivuluoto H, Lusvarghi L, Lyphout C, Marcocsan N, Matikainen V, Nylén P, Sassatelli P, Trache R, Vuoristo P (2015) Tribology of HVOF- and HVAF-sprayed WC – 10 Co – 4 Cr hardmetal coatings: a comparative assessment. Surf Coat Technol 265:125-144 3036. Bounhoure V, Lay S, Coindeau S, Norgren S, Pauty E, Missiaen JM (2015) Effect of Cr addition on solid state sintering of WC-Co alloys. Int J Refract Met Hard Mater 52:21-28 3037. Hong S, Wu Y, Zhang J, Zheng Y, Qin Y, Lin J (2015) Ultrasonic cavitation erosion of high-velocity oxygen-fuel (HVOF) sprayed near-nanostructured WC – 10 Co – 4 Cr coating in NaCl solution. Ultrason Sonochem 26:87-92 3038. Kaplan B, Blomqvist A, Selleby M, Norgren S (2015) Thermodynamic analysis of the WCo-Cr system supported by ab initio calculations and verified with quaternary data. Calphad 50:59-67 3039. Kaplan B, Norgren S, Schwind M, Selleby M (2015) Thermodynamic calculations and experimental verification in the WC-Co-Cr cemented carbide system. Int J Refract Met Hard Mater 48:257-262 3040. Kovaleva M, Tyurin Yu, Vasilik N, Kolesnichenko O, Prozorova M, Arseenko M, Yaprintsev M, Sirota V, Pavlenko I (2015) Effect of processing parameters on the microstructure and properties of WC – 10 Co – 4 Cr coatings formed by a new multi-chamber gas-dynamic accelerator. Ceram Int 41:15067-15074 3041. Wang H, Wang X, Song X, Liu Xu, Liu Xi (2015) Sliding wear behaviour of nanostructured WC-Co-Cr coatings. Appl Surf Sci 355:453-460 3042. Zhang W-C, Liu L-B, Zhang M-T, Huang G-X, Liang J-S, Li X, Zhang L-G (2015) Comparison between WC – 10 Co – 4 Cr and Cr3C2 – 25 NiCr coatings sprayed on H13 steel by HVOF. Trans Nonferr Met Soc China 25:3700-3707 3043. Berger L-M (2016) Binary WC- and Cr3C2-containing hardmetal compositions for thermally sprayed coatings. In: Proc. 18th Chemnitz seminar on materials engineering – 18. Werkstofftechnisches Kolloquium, Chemnitz, Germany, 10-11 Mar 2016. IOP Conf Series Mater Sci Eng 118:012010 (8 pp.) 3044. Gong T, Yao P, Zuo X, Zhang Z, Xiao Y, Zhao L, Zhou H, Deng M, Wang Q, Zhang A (2016) Influence of WC carbide particle size on the microstructure and abrasive wear behaviour of WC – 10 Cr – 4 Cr coatings for aircraft landing gear. Wear 362-363:135-145 3045. Hong S, Wu Y, Zhang J, Zheng Yug, Zheng Yua, Lin J (2016) Synergistic effect of ultrasonic cavitation erosion and corrosion of WC-Co-Cr and Fe-Cr-Si-B-Mn coatings prepared by HVOF spraying. Ultrason Sonochem 31:563-569 3046. Kumar RK, Kamaraj M, Seetharamu S, Pramod T, Sampathkumaran P (2016) Effect of spray particle velocity on cavitation erosion resistance characteristics of HVOF and HVAF processed 86 WC – 10 Cr – 4 Cr hydro turbine coatings. J Therm Spray Technol 25:12171230 3047. Myalska H, Szymański K, Moskal G (2016) Microstructure and selected properties of WC-Co-Cr coatings deposited by high-velocity thermal spray processes. In: Szczotok A, Szkliniarz A, Mendala J (eds) Selected proc. 23rd conf. on technologies and properties of modern utility materials (TPMUM 2015), Katowice, Poland, 15 May 2015. Solid State Phenom 246:117-122 3048. Wang H, Wang X, Song X, Liu X, Yang T (2016) Corrosion resistance of nanostructured WC-Co-Cr coating with Co-Cr alloy binder. In: Thermal spray – 2016. Proc. Int. thermal spray conf. and exposition (ITSC 2016), Shanghai, China, 10-12 May 2016, Vol. 2, pp.922926. DVS Media, Düsseldorf, Germany 3049. Zoei MS, Sadeghi MH, Salehi M (2016) Effect of grinding parameters on wear resistance and residual stress of HVOF-deposited WC – 10 Co – 4 Cr coating. Surf Coat Technol 307:886-891

References

741

3050. Cui X-Y, Wang C-B, Kang J-J, Yue W, Fu Z-Q, Zhu L-N (2017) Influence of the corrosion of saturated saltwater drilling fluid on the tribological behaviour of HVOF WC – 10 Co – 4 Cr coatings. Eng Fail Anal 71:195-203 3051. Ding X, Cheng X-D, Ding Z-X, Li C (2017) Properties and cavitation erosion behaviour of micro-nano WC – 10 Co – 4 Cr coatings sprayed by HVOF. Chin J Nonferr Met 27(8):16791686 (in Chinese) 3052. Hamilton A, Sharma A, Pandel U (2017) Solid particle erosion resistance of HVAFsprayed WC – 10 Co – 4 Cr coating on CA6NM steel. Surf Rev Lett 24:1850011 (5 pp.) 3053. Hong S, Wu Y, Wang B, Zhang J, Zheng Y, Qiao L (2017) The effect of temperature on the dry sliding wear behaviour of HVOF sprayed nanostructured WC-Co-Cr coatings. Ceram Int 43:458-462 3054. Vackel A, Sampath S (2017) Fatigue behaviour of thermal sprayed WC-Co-Cr – steel systems: role of process and deposition parameters. Surf Coat Technol 315:408-416 3055. Vashishtha N, Khatirkar RK, Sapate SG (2017) Tribological behaviour of HVOF sprayed WC – 12 Co, WC – 10 Co – 4 Cr and Cr3C2 – 25 NiCr coatings. Tribol Int 105:55-68 3056. Wang D, Zhang B, Jia C, Gao F, Yu Y, Chu K, Zhang M, Zhao X (2017) Influence of carbide grain size and crystal characteristics on the microstructure and mechanical properties of HVOF-sprayed WC-Co-Cr coatings. Int J Refract Met Hard Mater 69:138-152 3057. Garg D, Dyer PN, Dimos DB, Sunder S, Hintermann HE, Maillat M (1992) Lowtemperature chemical vapour deposition tungsten carbide coatings for wear/erosion resistance. J Am Ceram Soc 75(4):1008-1011 3058. Kelly CM, Garg D, Dyer PN (1992) Kinetics of chemical vapour deposition of tungsten carbide. Thin Solid Films 219:103-108 3059. Skaf DW, Warner AW, Dollahon NR, Fargo GH (1994) Microstructure and properties of CVD tungsten carbide from tungsten hexafluoride and dimethyl ether. Mater Charact 33:393402 3060. Oberste-Berghaus J, Marple B, Moreau C (2006) Suspension plasma spraying of nanostructured WC – 12 Co coatings. J Therm Spray Technol 15:676-681 3061. Moghaddam EG, Karimzadeh N, Varahram N, Davami P (2013) Investigation of the effect of tungsten substitution on microstructure and abrasive wear performance of in situ VCreinforced high-manganese austenitic steel matrix composite. Metall Mater Trans A 44:38263835 3062. Gill AS, Kumar S (2015) Surface alloying of H11 die steel by tungsten using EDM process. Int J Adv Manuf Technol 78:1585-1593 3063. Zhang H, Yu X, Nie Z, Tan C, Wang Fu, Cai Hu, Li Y, Wang Fa, Cai Ho (2018) Microstructure and growth mechanism of tungsten carbide coatings by atmospheric CVD. Surf Coat Technol 344:85-92 3064. Lakhotkin YuV, Kuzmin VP, Goncharov VL, Dushik VV, Rozhanskii NV, Rybkina TV (2010) Wear-, erosion- and corrosion-resistant coatings for extreme applications of oil-gas industry. In: Proc. Eur. corrosion congress (EUROCORR 2010), Moscow, Russian Federation, 13-17 Sep 2010, Vol. 2, pp. 1343-1349. Gubkin Russian State University of Oil and Gas, Moscow 3065. Krasovskii AI, Chuzhko RK, Tregulov VP, Balakhovskii OA (1981) Ftoridnyi protsess polucheniya volframa (Fluoride process of the preparation of tungsten). Nauka, Moscow (in Russian) 3066. Chuzhko RK (2002) The role of heterogeneous gas reactions in the synthesis of novel compounds and unusual structures by crystallization of refractory metals and interstitial phases. Russ J Inorg Chem 47(12):1809-1814 3067. Ding X, Cheng X-D, Shi J, Li C, Yuan C-Q, Ding Z-X (2018) Influence of WC size and HVOF process on erosion performance of WC – 10 Co – 4 Cr coatings. Int J Adv Manuf Technol 96:1615-1624

742

2 Tungsten Carbides

3068. Ding X, Cheng X-D, Li C, Yu X, Ding Z-X, Yuan C-Q (2018) Microstructure and performance of multi-dimensional WC-Co-Cr coating sprayed by HVOF. Int J Adv Manuf Technol 96:1625-1633 3069. Ding X, Cheng X-D, Yu X, Li C, Yuan C-Q, Ding Z-X (2018) Structure and cavitation erosion behaviour of HVOF sprayed multi-dimensional WC – 10 Co – 4 Cr coating. Trans Nonferr Met Soc China 28:487-494 3070. Han T, Deng C, Zhang X, Liu Q (2018) A model of splats deposition state and wear resistance of WC – 10 Co – 4 Cr coating. Ceram Int 44:4230-4236 3071. Hong S, Wu Y, Gao W, Zhang J, Zheng Yug, Zheng Yua (2018) Slurry erosion-corrosion resistance and microbial corrosion electrochemical characteristics of HVOF sprayed WC – 10 Co – 4 Cr coating for offshore hydraulic machinery. Int J Refract Met Hard Mater 74:7-13 3072. Meingast A, Coronel E, Blomqvist A, Norgren S, Wahnström G, Lattemann M (2018) High resolution STEM investigation of interface layers in cemented carbides. Int J Refract Met Hard Mater 72:135-140 3073. Pulsford J, Kamnis S, Murray J, Bai M, Hussain T (2018) Effect of particle and carbide grain sizes on a HVOAF WC-Co-Cr coating for the future application on internal surfaces: microstructure and wear. J Therm Spray Technol 27:207-219 3074. Qiao J, Zhu L-N, Yue W, Fu Z-Q, Kang J-J, Wang C-B (2018) The effect of attributes of micro-shapes of laser surface texture on the wettability of WC-Cr-Co metal ceramic coating. Surf Coat Technol 334:429-437 3075. Rovatti L, Lecis N, Dellasega D, Russo V, Gariboldi E (2018) Influence of aging in the temperature range 250-350 °C on the tribological performance of a WC-Co-Cr coating produced by HVOF. Int J Refract Met Hard Mater 75:218-224 3076. Shang Z, Xu C, Xie G, Yi J, Huang H (2018) High-speed grinding characteristics and machinability of WC – 10 Co – 4 Cr coatings deposited via high velocity oxygen fuel spraying. J Mech Sci Technol 32(7):3283-3290 3077. Upadhyaya R, Tailor S, Shrivastava S, Modi SC (2018) High performance thermalsprayed WC – 10 Co – 4 Cr coatings in narrow and complex areas. Surf Eng 34(5):412-421 3078. Vashishtha N, Sapate SG, Gahlot JS, Bagde P (2018) Effect of tribo-oxidation on friction and wear behaviour of HVOF sprayed WC – 10 Co – 4 Cr coating. Tribol Lett 66:56 (19 pp.) 3079. Campanelli SL, Contuzzi N, Posa P, Agelastro A (2019) Printability and microstructure of selective laser melting of WC/Co/Cr powder. Materials 12(15):2397 (12 pp.); doi:10.3390/ma12152397 3080. De Oro Calderon R, Edtmaier C, Schubert W-D (2019) Novel binders for WC-based cemented carbides with high Cr contents. Int J Refract Met Hard Mater 85:105063 (18 pp.) 3081. Farokhzadeh K, Fillion RM, Edrisy A (2019) The effect of deposition rate on microstructural evolution in WC-Co-Cr coatings deposited by high-velocity oxy-fuel thermal spray process. J Mater Eng Perform 28:7419-7430 3082. Matikainen V, Rubio-Peregrina S, Ojala N, Koivuluoto H, Schubert J, Houdková Š (2019) Erosion wear performance of WC – 10 Co – 4 Cr and Cr3C2 – 25 NiCr coatings sprayed with high-velocity thermal spray processes. Surf Coat Technol 370:196-212 3083. Panziera RC, De Oliveira ACC, Pereira M, Ratszunei F (2020) Study of the effects of the laser remelting process on the microstructure and properties of the WC – 10 Co – 4 Cr coating sprayed by HVOF. J Brazil Soc Mech Sci Eng 42:119 (8 pp.) 3084. Ji X, Zhao J, Wang H, Luo C (2018) Sliding wear of spark-plasma sintered CrFeCoNiCu high-entropy alloy coating with MoS2 and WC additions. Int J Adv Manuf Technol 96:16851691 3085. Velo IL, Gotor FJ, Alcalá MD, Real C, Córdoba JM (2018) Fabrication and characterization of WC-HEA cemented carbide based on the CoCrFeNiMn high-entropy alloy. J Alloys Compd 746:1-8 3086. Nugroho JA, Jodi DE, Park N, Kim S, Lee U, Baek ER (2019) Effects of tungsten carbide particle addition on friction stir processed Fe50(CoCrMnNi)50 medium-entropy alloy. JOM (J Miner Met Mater Soc) 71(10):3452-3459

References

743

3087. Holmström E, Lizárraga R, Linder D, Salmasi A, Wang W, Kaplan B, Mao H, Larsson H, Vitos L (2018) High-entropy alloys: substituting for cobalt in cutting edge technology. Appl Mater Today 12:322-329 3088. Zhou R, Chen G, Liu B, Wang J, Han L, Liu Y (2018) Microstructures and wear behaviour of (FeCoCrNi)1–x(WC)x high-entropy alloy composites. Int J Refract Met Hard Mater 75:5662 3089. An X, Liu Q (2016) Effect of WC particles on microstructure and properties of highentropy alloy SiFeCoCrTi coating synthesized by laser cladding. Rare Met Mater Eng 45(9):2424-2428 (in Chinese) 3090. Petrdlik M, Kulčickyj I (1972) Einfluss von Chrom und Nickel auf die Gefügeausbildung von WC-Co-Hartmetallen (Effect of chromium and nickel on the structure of sintered WC-Co alloys). Planseeber Pulvermetall 20(1):20-29 (in German) 3091. Wentzel EJ, Allen C (1995) Erosion-corrosion resistance of tungsten carbide hardmetals with different binder compositions. Wear 181-183(1):63-69 3092. Aristizabal M, Rodriguez N, Ibaretta F, Martinez R, Sánchez JM (2010) Liquid-phase sintering and oxidation resistance of WC-Ni-Co-Cr cemented carbides. Int J Refract Met Hard Mater 28:516-522 3093. Angelastro A, Campanelli SL, Casalino G, Ludovico AD (2013) Optimization of Ni-based WC/Co/Cr composite coatings produced by multilayer laser cladding. Adv Mater Sci Eng 2013:615464 (7 pp.) 3094. Li N, Zhang W, Peng Y, Du Y (2016) Effect of the cubic phase distribution on ultra-fine WC – 10 Co – 0.5 Cr – x Ta cemented carbide. J Am Ceram Soc 99(3):1047-1054 3095. Yamaguchi T, Okada M (1977) High-temperature reaction between cemented tungsten carbide and copper. J Am Ceram Soc 60(7-8):289-293 3096. Moon IH, Lee SL, Lee JS (1981) Effect of cobalt addition on the sinterability of the WCcopper electrical contact material. In: Hausner HH, Antes HW, Smith GD (eds) Modern developments in powder metallurgy. Proc. Int. powder metallurgy conf., Washington, DC, 22-27 June 1980, Vol. 13 – Ferrous and nonferrous materials, pp. 385-394. Metal Powder Industries Federation, Princeton, New Jersey 3097. Tsuchiya N, Suzuki H, Terada O (1988) Interfacial reaction between WC-Co cemented carbide and pure copper. J Jpn Soc Powder Powder Metall 35(2):72-77 (in Japanese) 3098. Wu T-F, Lee S-L, Chen M-H, Li Z-G, Lin J-C (2005) Effects of tungsten carbide and cobalt particles on corrosion and wear behaviour of copper matrix composites. Mater Sci Technol 21(3):295-304 3099. Gu D-D, Shen Y-F (2006) Processing and microstructure of submicron WC-Co particulate reinforced Cu matrix composites prepared by direct laser sintering. Mater Sci Eng A 435436:54-61 3100. Gu D-D, Shen Y-F, Dai P, Yang M-C (2006) Microstructure and property of sub-micro WC – 10 % Co particulate reinforced Cu matrix composites prepared by selective laser sintering. Trans Nonferr Met Soc China 16(2):357-362 3101. Gu D-D, Shen Y-F (2007) Fabrication of particle reinforced copper matrix composites by selective laser sintering. Acta Mater Compos Sin 24(1):53-59 (in Chinese) 3102. Lin N, Jiang Y, Zhang DF, Wu CH, He YH, Xiao DH (2011) Effect of Cu, Ni on the property and microstructure of ultra-fine WC – 10 Co alloys by sinter-HIPping. Int J Refract Met Hard Mater 29:509-515 3103. Lin N, Wu CH, Zhang DF, Jiang Y, He YH (2011) Effect of the partial substitution of Co by Cu on the properties of ultra-fine cemented carbide. Chin J Mater Res 25(6):667-672 (in Chinese) 3104. Mirski Z, Piwowarczyk T (2011) Wettability of hardmetal surfaces prepared for brazing with various methods. Arch Civil Mech Eng 11(2):411-419 3105. Lin N, He Y, Wu C, Jiang Y (2013) Influence of copper content on the microstructure and hardness of copper-doped tungsten carbide – cobalt bulk at the elevated temperature. Int J Refract Met Hard Mater 38:140-143

744

2 Tungsten Carbides

3106. Silva VL, Fernandes CM, Senos AMR (2016) Copper wettability on tungsten carbide surfaces. Ceram Int 42:1191-1196 3107. Huang Z, Ren X, Liu M, Xu C, Zhang X, Guo S, Chen H (2017) Effect of Cu on the microstructures and properties of WC – 6 Co cemented carbides fabricated by SPS. Int J Refract Met Hard Mater 62:155-160 3108. Li J, Cheng J, Chen P, Chen W, Wei B, Liu J (2018) Effects of partial substitution of copper for cobalt on the microstructure and properties of ultra-fine grained WC-Co cemented carbides. J Alloys Compd 735:43-50 3109. Su W, Wen Y, Zhang Q (2018) Effects of Ni and Cu additions on microstructures, mechanical properties and wear resistances of ultra-coarse grained WC – 6 Co cemented carbides. Int J Refract Met Hard Mater 70:176-183 3110. Ohmura H, Kawashiri K, Yoshida T (1988) Cemented tungsten carbide / carbon steel joint brazed with copper. Quart J Jpn Weld Soc 6(4):47-52 3111. Tokova LV, Zaitsev AA, Kurbatkina VV, Levashov EA, Sidorenko DA, Andreev VA (2014) The features of influences of ZrO2 and WC nanodispersed additives on the properties of metal matrix composite. Russ J Non-Ferr Met 55(2):186-190 3112. Huang S, Yang J, Lai W (1995) Influence of Cu addition on properties and structure of WC – 13 % Fe/Co/Ni cemented carbide. Powder Metall Technol 13(3):174-180 (in Chinese) 3113. Saito S, Okada M, Yamaguchi T (1979) Reaction between cemented tungsten carbide and molten Cu-Mn alloys. J Jpn Soc Powder Powder Metall 26(2):66-71 (in Japanese) 3114. Roberts PM (2014) Brazing tungsten carbide. Part 1. Setting the scene. Weld Cutting 13(4):216-219 3115. Roberts PM (2014) Brazing tungsten carbide. Part 2. Brazing filler materials and fluxes for use with tungsten carbide. Weld Cutting 13(5):294-297 3116. Lemus-Ruiz J, Ceja-Cárdenas L, Verduzco JA, Flores O (2008) Joining of tungsten carbide to nickel by direct diffusion bonding and using a Cu-Zn alloy. J Mater Sci 43:62966300 3117. Amirnasiri A, Parvin N, Haghshenas MS (2017) Dissimilar diffusion brazing of WC-Co to AISI 4145 steel using RBCuZn-D interlayer. J Manuf Process 28:82-93 3118. Burkov AA (2018) Electro-spark WC-Co coatings with different iron concentration. Weld Int 32(1):72-75 3119. Guillermet AF (1989) The Co-Fe-Ni-W-C phase diagram: a thermodynamic description and calculated sections for (Co-Fe-Ni) bonded cemented WC tools. Z Metallkd 80(2):83-94 3120. Krawitz A, Drake EF, Peck J (1979) Metallography of tungsten carbide – iron-nickel base cemented carbides. Int J Powder Metall Powder Technol 15(1):67-71, 73-77 3121. Prakash L, Holleck H, Thümmler F, Walter P (1981) Influence of the binder composition on the properties of WC-Fe/Co/Ni cemented carbides. In: Hausner HH, Antes HW, Smith GD (eds) Modern developments in powder metallurgy. Proc. Int. powder metallurgy conf., Washington, DC, 22-27 June 1980, Vol. 14 – Special materials, pp. 255-268. Metal Powder Industries Federation, Princeton, New Jersey 3122. Upadhyaya GS, Bhaumik SK (1988) Sintering of submicron WC – 10 wt.% Co hard metals containing nickel and iron. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:249-256 3123. Uhrenius B, Pastor H, Pauty E (1997) On the composition of Fe-Ni-Co-WC-based cemented carbides. Int J Refract Met Hard Mater 15:139-149 3124. Chen H, Feng K, Wei S, Xiong J, Guo Z, Wang H (2012) Microstructure and properties of WC-Co/3Cr13 joints brazed using Ni electroplated interlayer. Int J Refract Met Hard Mater 33:70-74 3125. Chang S-H, Chang P-Y (2014) Study on the mechanical properties, microstructure and corrosion behaviours of nano-WC-Co-Ni-Fe hard materials through HIP and hot-press sintering process. Mater Sci Eng A 618:56-62 3126. Chang S-H, Chang P-Y (2014) Investigation into the sintered behaviour and properties of nanostructured WC-Co-Ni-Fe hard metal alloys. Mater Sci Eng A 606:150-156

References

745

3127. Kim D, Choi Y, Kim Y, Jung S (2015) Characteristics of nanophase WC and WC – 3 wt.% (Ni, Co and Fe) alloys using a rapid sintering process for the application of friction stir processing tools. Adv Mater Sci Eng 2015:343619 (9 pp.) 3128. Guo Y, Wang Y, Gao B, Shi Z, Yuan Z (2016) Rapid diffusion bonding of WC-Co cemented carbide to 40Cr steel with Ni interlayer: effect of surface roughness and interlayer thickness. Ceram Int 42:16729-16737 3129. Gao Y, Luo B-H, He K-J, Jing H-B, Bai Z-H, Chen W, Zhang W-W (2017) Mechanical properties and microstructure of WC-Fe-Ni-Co cemented carbides prepared by vacuum sintering. Vacuum 143:271-282 3130. Gao Y, Luo B-H, He K-J, Zhang W-W, Bai Z-H (2018) Effect of Fe/Ni ratio on the microstructure and properties of WC-Fe-Ni-Co cemented carbides. Ceram Int 44:2030-2041 3131. Linder D, Hou Z, Xie R, Hedström P, Ström V, Holmström E, Borgenstam A (2019) A comparative study of microstructure and magnetic properties of a Ni-Fe cemented carbide: influence of carbon content. Int J Refract Met Hard Mater 80:181-187 3132. Wang X, Zhou D, Xu P (2019) WC-Co/Fe-Ni interface: effect of holding time on the microstructure, grain size and grain growth mechanism. Ceram Int 45:23320-23327 3133. Sun J, Wang B, Li B, Yang J (1998) Research of WC – 20 (Fe/Co/Ni) cemented carbide with rare-earth additives. Powder Metall Technol 16(4):265-267 (in Chinese) 3134. Nilsén F, Aaltio I, Ge Y, Söderberg O, Glavatskyy I, Lahelin M, Maki R, Hannula S-P (2016) Properties of the pulsed electric current sintered Ni-Mn-Ga-Co-WC composites. J Alloys Compd 656:408-415 3135. Panteleev IB, Lukashova TV, Ordanyan SS (2006) Oxidation resistance and hightemperature strength of WC-Co-Ni-Re(Mn) hard alloys. Powder Metall Met Ceram 45(78):342-345 3136. Panteleev IB, Lukashova TV, Ordanyan SS (2011) High-temperature strength and refractoriness of doped WC-Co-Ni-Re(Mn) hard alloys. Russ J Non-Ferr Met 52(3):295-297 3137. Han D, Mecholsky JJ, Jr (1991) Fracture behaviour of metal particulate – reinforced WCCo composites. Mater Sci Eng A 144:293-302 3138. Andersson G, Jansson B (2001) The solubility of cubic carbide formers in liquid cobalt. In: Kneringer G, Rödhammer P, Wildner H (eds) Powder metallurgical high-performance materials. Proc. 15th Int. Plansee seminar, Reutte, Tyrol, Austria, 28 May – 1 June 2001, Vol. 2 – P/M hard materials, pp. 662-676. Plansee Metal AG, Reutte, Austria 3139. Majagi SI, Upadhyaya GS (1989) Sintering of WC – 10 Co hardmetal containing superalloy. Int J Refract Met Hard Mater 8(4):232-235 3140. Forsén K (1983) An experimental and thermodynamic study on the Co-Ti-W-C system. Internal Technical Report LR-2244, pp. 1-37. Sandvik Coromant Research Centre, Stockholm, Sweden 3141. He P (1996) Microstructure and rupture strength of WC-Co-Ni cemented carbide. Powder Metall Technol 14(4):287-290 3142. Wang CB, Wang DL, Chen WX, Wang YY (2002) Tribological properties of nanostructured WC/CoNi and WC/CoNiP coatings produced by electro-deposition. Wear 253:563-571 3143. Sheng J-F, Ma C-A, Zhang C (2008) Preparation and electro-catalytic property of nanocrystalline tungsten carbide – cobalt – nickel composite. Acta Chim Sin 66(18):2087-2091 (in Chinese) 3144. Kim D-G, Lee J-H (2010) Kinetic study of WC particles incorporation in nickel composite plating. Surf Rev Lett 17(3):359-362 3145. Chen H, Feng K, Xiong J, Luo J, Guo Z, Wang H (2012) Characterization and forming process of a functionally graded WC-Co/Ni composite. Int J Refract Met Hard Mater 35:306310 3146. Su W, Sun Y, Liu J, Feng J, Ruan J (2015) Effects of Ni on the microstructure and properties of WC – 6 Co cemented carbides fabricated from WC – 6 (Co,Ni) composite powders. Ceram Int 41:3169-3177

746

2 Tungsten Carbides

3147. Jafari M, Enayati MH, Salehi M, Nahvi SM, Han JC, Park CG (2016) High-temperature oxidation behaviour of micro/nanostructured WC-Co coatings deposited from Ni-coated powders using high-velocity oxygen-fuel spraying. Surf Coat Technol 302:426-437 3148. Zhang X, Zhou J, Lin N, Li K, Fu K, Huang B, He Y (2016) Effects of Ni addition and cyclic sintering on microstructure and mechanical properties of coarse grained WC – 10 Co cemented carbides. Int J Refract Met Hard Mater 57:64-69 3149. Elkhoshkhany N, Hafnway A, Khaled A (2017) Electrodeposition and corrosion behaviour of nanostructured Ni-WC and Ni-Co-WC composite coating. J Alloys Compd 695:1505-1514 3150. Jafari M, Han J-C, Seol J-B, Park C-G (2017) Tribological properties of HVOF-sprayed WC-Co coatings deposited from Ni-plated powders at elevated temperature. Surf Coat Technol 327:48-58 3151. Jiménez H, Olaya JJ, Alfonso JE, Mtshali CB, Pineda-Vargas CA (2017) Corrosion resistance of Ni-based WC/Co coatings deposited by spray and fuse process varying the oxygen flow. J Therm Spray Technol 26:1708-1719 3152. Lu X, Tu Y, Zheng Y, Dong Z (2017) Microstructure and properties of WC-(Co-Ni) cemented carbides with plate-like WC grains. Mater Rev 31(10):73-76, 91 (in Chinese) 3153. Fang S, Hsu C-J, Klein S, Llanes L, Bähre D, Mücklich F (2018) Influence of laser pulse number on the ablation of cemented carbides (WC – CoNi) with different grain size. Lubricants 6(1):11 (10 pp.); doi:10.3390/lubricants6010011 3154. Fang S, Soldera F, Rosenkranz A, Herrmann T, Bähre D, Llanes L, Mücklich F (2018) Microstructural and metallurgical assessment of the laser-patterned cemented tungsten carbide (WC–CoNi). In: Wang L (ed) Proc. 46th Annual SME North American manufacturing research conf. (NAMRC 46), College Station, Texas, 18-22 June 2018. Proc Manuf 26:198204 3155. Fang S, Llanes L, Bähre D (2018) Laser surface texturing of a WC – CoNi cemented carbide grade: surface topography design for honing application. Tribol Int 122:236-245 3156. Sabzi M, Mersagh-Dezfuli S, Mirsaeedghazi SM (2018) The effect of pulse-reverse electroplating bath temperature on the wear/corrosion response of Ni-Co / tungsten carbide nanocomposite coating during layer deposition. Ceram Int 44:19492-19504 3157. Singh S, Gupta D, Jain V (2018) Processing of Ni – WC – 8 Co MMC casting through microwave melting. Mater Manuf Process 33(1):26-34 3158. Ferro-Rocha AM, Bastos AC, Cardoso JP, Rodrigues F, Fernandes CM, Soares E, Sacramento J, Senos AMR, Ferreira MGS (2019) Corrosion behaviour of WC hardmetals with nickel-based binders. Corros Sci 147:384-393 3159. Wang SQ, Xue YP, Ban CL, Xue YY, Taleb A, Jin Y (2020) Fabrication of robust tungsten carbide particles reinforced Co-Ni super-hydrophobic composite coating by electrochemical deposition. Surf Coat Technol 385:125390 (10 pp.) 3160. Jafari M, Enayati MH, Salehi M, Nahvi SM, Park CG (2013) Microstructural and mechanical characterizations of a novel HVOF-sprayed WC-Co coating deposited from electroless Ni-P coated WC – 12 Co powders. Mater Sci Eng A 578:46-53 3161. Guo Y, Gao B, Liu G, Zhou T, Qiao G (2015) Effect of temperature on the microstructure and bonding strength of partial transient liquid phase bonded WC-Co/40Cr joints using Ti/Ni/Ti interlayers. Int J Refract Met Hard Mater 51:250-257 3162. Lisovskii AF (2000) Cemented carbides alloyed with ruthenium, osmium and rhenium. Powder Metall Met Ceram 39(9-10):428-433 3163. Dotsenko VM, Simkin ÉS, Tsypin NV (1977) Effect of phosphorus additions on the hotpressing temperature and some properties of WC-Co hard alloys. Powder Metall Met Ceram 16(3):191-193 3164. Bronshtein DKh, Simkin ÉS, Mikhnovskaya AN (1983) Wear resistance of hard metal matrix materials alloyed with phosphorus. Powder Metall Met Ceram 22(9):770-773 3165. Zhang F, Shen J, Sun J (2004) The effect of phosphorus additions on densification, grain growth and properties of nanocrystalline WC-Co composites. J Alloys Compd 385(1-2):96103

References

747

3166. Konyashin I, Farag S, Ries B, Roebuck B (2019) WC-Co-Re cemented carbides: structure, properties and potential applications. Int J Refract Met Hard Mater 78:247-253 3167. Konyashin I, Schwedt A (2019) The influence of various Re:Co ratios on microstructures and properties of WC-Co-Re cemented carbides. Mater Lett 249:57-61 3168. Li G, Yan L, Li Z (1986) Application of rare earths in hard metals. Powder Metall Technol 4(1):25-30 (in Chinese) 3169. Lin C (1992) Composition, morphology and distribution of RE element containing phases in cemented carbide. Int J Refract Met Hard Mater 11:295-302 3170. Lin C (1993) Action of new rare earth additions in cemented carbide. J Mater Sci Technol 9(3):177-184 3171. Yang J, Xiong J (1994) Effects of rare earth additions on controlling martensitic phase change of cobalt phase in cemented carbide. Powder Metall Technol 12(1):12-14 (in Chinese) 3172. Xiong J, Yang J, Liu W, Xia X (1994) Investigation on addition of rare earth elements in YGR8 cemented carbide drawing die. Powder Metall Technol 12(2):118-121 (in Chinese) 3173. Sun L, He C, Lin C, Wang Y, Shi Y, Zhang S (1996) Effect of adding rare earth elements on cemented carbide YT14 by digital image. J Rare Earths 14(4):303-304 3174. He W, Tan D-Q, Lu L, Lu D-P, Zhu H-B, Kuang H (2015) Effect of Ce and Y on the microstructure and properties of YG6 cemented carbide. Chin Rare Earths 36(6):51-56 (in Chinese) 3175. Hayashi K, Suzuki H (1981) Some properties of ruthenium contained WC-Co and WC-βCo cemented carbides. J Jpn Soc Powder Powder Metall 28(3):108-109 (in Japanese) 3176. Tracey VA, Mynard BA (1981) Development of tungsten carbide – cobalt – ruthenium cutting tools for machining steels. In: Hausner HH, Antes HW, Smith GD (eds) Modern developments in powder metallurgy. Proc. Int. powder metallurgy conf., Washington, DC, 22-27 June 1980, Vol. 14 – Special materials, pp. 281-292. Metal Powder Industries Federation, Princeton, New Jersey 3177. Shing TL, Luyckx S, Northrop IT, Wolff I (2001) The effect of ruthenium additions on the hardness, toughness and grain size of WC-Co. Int J Refract Met Hard Mater 19:41-44 3178. Luyckx S (2002) High-temperature hardness of WC-Co-Ru. J Mater Sci Lett 21:16811682 3179. Li N, Zhang W, Du Y, Xie W, Wen G, Wang S (2015) A new approach to control the segregation of (Ta,W)C cubic phase in ultra-fine WC – 10 Co – 0.5 Ta cemented carbides. Scripta Mater 100:48-50 3180. Zaitsev AA, Konyashin IYu, Avdeenko EN, Svyndina NV, Levashov EA (2018) Structure and magnetic properties of WC – 50 % Co model alloys containing TaC additives. Russ J Non-Ferr Met 59(4):403-411 3181. Kudryavtsev VA, Savicheva EP (1989) Hardening of die sintered carbide parts by thermal diffusion impregnation of their surface with titanium from a coating. Powder Metall Met Ceram 28(4):327-329 3182. Lamim JD, De Oliveira HCP, Batista AC, Guimarães RS, Filgueira M (2010) Use of Ti in hard metal alloys. Part I. Structural and microstructural analysis. Materialwiss Werkstofftech 41(4):198-201 3183. Lamim JD, De Oliveira HCP, Batista AC, Guimarães RS, Filgueira M (2010) Use of Ti in hard metal alloys. Part II. Mechanical properties. Materialwiss Werkstofftech 41(8):666-669 3184. Lamim JD, De Oliveira HCP, Batista AC, Guimarães RS, Filgueira M (2010) Structural and microstructural characterization of nanostructured hardmetals of WC-Co/Ti/Ti+Co. In: Proc. World powder metallurgy congress and exhibition (World PM 2010), Florence, Italy, 10-14 Oct 2010, Vol. 1 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 3185. Lamim JD, De Oliveira HCP, Batista AC, Guimarães RS, Filgueira M (2010) Analysis of mechanical properties of nanostructured hardmetals of WC-Co/Ti/Ti-Co. In: Proc. World powder metallurgy congress and exhibition (World PM 2010), Florence, Italy, 10-14 Oct 2010, Vol. 3 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK

748

2 Tungsten Carbides

3186. Blagoveshchenskii YuV, Isaeva NV, Melnik YuI, Samokhin AV, Falkovskii VA (2010) Consolidation of nanopowders WC-Co with different inhibitors. In: Proc. World powder metallurgy congress and exhibition (World PM 2010), Florence, Italy, 10-14 Oct 2010, Vol. 1 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 3187. Brieseck M, Hünsche I, Caspers B, Gille G, Bohn M, Lengauer W (2012) Diffusion behaviour of the grain growth inhibitor VC in hardmetals. In: Bezverkhyy I, Chevalier S, Politano O (eds) Selected proc. 8th Int. conf. on diffusion in materials (DIMAT 2011), Dijon, France, 3-8 July 2011. Defect Diff Forum 323-325:509-514 3188. Suzuki H, Hayashi K, Tanase T, Tsuchiya S, Fuke Y (1974) The strengthening phenomena of Zn-added WC – 10 % Co cemented carbide. J Jpn Soc Powder Powder Metall 21(5):140143 (in Japanese) 3189. Yamaguchi T, Okada M (1978) Formation of lamellar structures in the reaction between cemented tungsten carbide and molten zinc. J Am Ceram Soc 61(11-12):529 3190. Yajima K, Yamaguchi T (1980) Reaction between cemented tungsten carbide and molten zinc. J Jpn Soc Powder Powder Metall 27(4):112-118 (in Japanese) 3191. Yajima K, Yamaguchi T (1982) Mechanism of lamellar structure formation in the reaction between cemented carbides and molten zinc. Powder Metall Int 14(2):90-94 3192. Kasparova TV, Zelikman AN, Bondarenko VP (1987) Failure of hard alloys in contact with molten zinc. Powder Metall Met Ceram 26(2):173-176 3193. Seong BG, Hwang SY, Kim MC, Kim KY (2001) Reaction of WC-Co coating with molten zinc in a zinc pot of a continuous galvanizing line. Surf Coat Technol 138:101-110 3194. Eso OO (2014) A microstructural study of zinc-treated WC-Co. In: Advances in tungsten, refractory and hard materials – IX. Proc. 9th Int. conf. on tungsten, refractory and hard materials, Orlando, Florida, 18-22 May 2014, pp. 65-75. Metal Powder Industries Federation, Princeton, New Jersey 3195. Tanihata K, Qin J, Lin J, Miyamoto Y, Yamamoto M, Yarii T, Tanaka R (1997) Mechanical properties of Al2O3/TiC/Ni FGMs doped with WC/Co. J Soc Mater Sci Jpn 46(7):775-780 (in Japanese) 3196. Tai W-P, Watanabe T (1998) Elevated-temperature toughness and hardness of a hotpressed Al2O3-WC-Co composite. J Am Ceram Soc 81(1):257-259 3197. Tai W-P, Watanabe T (1998) Fabrication and mechanical properties of Al2O3-WC-Co composites by vacuum hot-pressing. J Am Ceram Soc 81(6):1673-1676 3198. Shen J, Zhang F-M, Sun J-F (2005) Fabrication and mechanical properties of WC-CoAl2O3 nanocomposites by spark-plasma sintering. Trans Nonferr Met Soc China 15(2):233237 3199. Xiong Z, Shao G, Duan X, Shi X (2006) Preparation and properties of Al2O3/WC-Co cermet. Rare Met Mater Eng 35(S2):79-82 (in Chinese) 3200. Yang M, Liu Q-C, Huang Z-Q, Liu Q-Y (2010) Mechanical properties and micro-structure of Al2O3 / WC – 8 Co nanometer/micron composites. J China Coal Soc 35(3):494-497 (in Chinese) 3201. Chaiyacote V, Buggakupta W, Chuankrekkul N (2012) Effects of Co content on hardness and fracture toughness of Al2O3/WC-Co composites. J Austral Ceram Soc 48(2):253-256 3202. Boonpo J, . Chaiyacote V, Chuankrekkul N, Buggakupta W (2013) Influences of cobalt and zirconia on microstructural features and mechanical properties of the Al2O3/WC composites. In: Pearce JTH, Benyajati C-N, Otarawanna S, Yoriya S, Wansom S, Sooksimuang T, Sirikittikul D, Monmaturapoj N, Tongroon M, Mungkalasiri J (eds) Proc. 7th Int. conf. on materials science and technology (MSAT 2012), Bangkok, Thailand, 7-8 June 2012. Key Eng Mater 545:14-18 3203. Duan X, Zhang X, Ke C, Jiang S, Wang X, Li S, Guo W, Cheng X (2017) Microstructure and optical properties of Co-WC-Al2O3 duplex ceramic metal-dielectric solar selective absorbing coating prepared by high-velocity oxy-fuel spraying and sol-gel method. Vacuum 145:209-216

References

749

3204. Fazili A, Nikzad L, Rahimi-Pour MR, Razavi M, Salahi E (2017) Effect of Al2O3 ceramic binder on mechanical and microstructure properties of spark-plasma sintered WC-Co cermets. Int J Refract Met Hard Mater 69:189-195 3205. Chakradhar RPS, Prasad G, Venkateswarlu K, Srivastava M (2018) An investigation on the wear and corrosion behaviour of HVOF-sprayed WC – 12 Co – Al2O3 cermet coating. J Mater Eng Perform 27:1241-1248 3206. Fazili A, Derakhshandeh MR, Nejadshamsi S, Nikzad L, Razavi M, Ghasali E (2020) Improved electrochemical and mechanical performance of WC-Co cemented carbide by replacing a part of Co with Al2O3. J Alloys Compd 823:153857 (11 pp.) 3207. Yang T, Xiong J, Sun L, Guo Z, Qin K (2011) Effects of nano-Al2O3 and nano-ZrO2 on the microstructure, behaviour and abrasive wear resistance of WC – 8 Co cemented carbide. Rare Met 30(5):533-538 3208. Raman R, Varma PK (2004) Wear behaviour of detonation gun and plasma sprayed alumina and tungsten carbide coatings for mechanical seal applications – a comparative study. In: Sudarshan TS (ed) Proc. Int. Conf. on advances in surface treatment: research and applications (ASTRA), Hyderabad, India, 3-6 Nov 2003, pp. 584-590. International Advanced Research Centre for Powder Metallurgy & New Materials, Balapur, Telangana, India 3209. Shi X-L, Yang H, Shao G-Q, Duan X-L, Xiong Z (2007) Microwave sintering of Al2O3 / WC – 10 Co / ZrO2 / Ni cermets. J Central South Univ Sci Technol 38(4):623-628 (in Chinese) 3210. Lin N, He Y, Zou J (2017) Enhanced mechanical properties and oxidation resistance of tungsten carbide – cobalt cemented carbides with aluminium nitride additions. Ceram Int 43:6603-6606 3211. Arthur G, Johnson MP (1975) Dispersion of boron carbide in a tungsten carbide / cobalt matrix. In: Blocher JM, Jr, Hintermann HE, Hall LH (eds) Proc. 5th Int. conf. on chemical vapour deposition, Fulmer, Slough, Buckinghamshire, UK, 21-26 Sep 1975, pp. 509-522. The Electrochemical Society, Princeton, New Jersey 3212. Cura ME, Şahin FC, Addemir O, Radev DD (2004) Microstructural and mechanical investigation of hot-pressed WC-Co/B4C composites. In: Mandal H, Öveçoğlu L (eds) Euro Ceramics VIII. Proc. 8th conf. and exhibition of the European Ceramic Society, Istanbul, Turkey, 29 June – 3 July 2003. Key Eng Mater 264-268(2):1017-1020 3213. Chang L, Jiang Y, Wang W, Yue X, Ru H (2020) WC – 0.5 Co – x B4C materials prepared by spark-plasma sintering: formation of WC platelet grains. Int J Refract Met Hard Mater 86:105097 (6 pp.) 3214. Wang B, Wang W, Liao K, Xiao J, Zheng K, Zhang S (1999) Analysis of the properties of various hard alloy coatings on carbon steel surface by laser ablation. In: Gan F (ed) Proc. Int. conf. on industrial lasers (IL ’99), Wuhan, China, 22-27 Oct 1999. Proc SPIE Int Soc Optic Eng 3862:368-371 3215. Chkhartishvili L, Mikeladze A, Chedia R, Tsagareishvili O, Barbakadze N, Sarajishvili K, Darchiashvili M, Ugrekhelidze V, Korkia T (2020) Synthesizing fine-grained powders of complex compositions B4C-TiB2-WC-Co. Solid State Sci 108:106439 (8 pp.) 3216. Liu S, Hao J, Chu L, Song J (2020) Phase analysis of cemented carbide WC-Co boronized with yttrium. J Rare Earths 20(4):287-290 3217. Yuan J, Zhu Y, Ji H, Zheng X, Ruan Q, Niu Y, Liu Z, Zeng Y (2010) Microstructures and tribological properties of plasma sprayed WC-Co-Cu-BaF2/CaF2 self-lubricating wearresistant coatings. Appl Surf Sci 256:4938-4944 3218. Echeberria J, Martínez V, Sánchez JM, Bourgeois L, Barbier G, Hennicke J (2005) Sintering behaviour of low Co content cBN-WC/Co composites by either GE-HIP or FAST. In: Kneringer G, Rödhammer P, Wildner H (eds) Powder metallurgical high-performance materials. Proc. 16th Int. Plansee seminar, Reutte, Tyrol, Austria, 30 May – 3 June 2005, Vol. 2 – Plenary lectures & P/M hard materials, pp. 434-448. Plansee Metal AG, Reutte, Austria

750

2 Tungsten Carbides

3219. Bourgeois L, Barbier G, Hennicke J, Kessel H-U, Martínez V, Echeberria J, Sánchez JM, Harden P (2005) Development of CDCC composites by either HIP or FAST. In: Kneringer G, Rödhammer P, Wildner H (eds) Powder metallurgical high-performance materials. Proc. 16th Int. Plansee seminar, Reutte, Tyrol, Austria, 30 May – 3 June 2005, Vol. 2 – Plenary lectures & P/M hard materials, pp. 684-698. Plansee Metal AG, Reutte, Austria 3220. Martínez V, Echeberria J (2007) Hot isostatic pressing of cubic boron nitride – tungsten carbide / cobalt (cBN-WC/Co) composites: effect of cBN particle size and some processing parameters on their microstructure and properties. J Am Ceram Soc 90(2):415-424 3221. Yaman B, Mandal H (2009) Spark-plasma sintering of Co-WC cubic boron nitride composites. Mater Lett 63:1041-1043 3222. Michalski A, Rosiński M, Płocińska M, Szawłowski J (2011) Synthesis and characterization of cBN/WC-Co composites obtained by the pulse plasma sintering (PPS) method. In: Niihara K, Ohji T, Sakka Y, Goto T, Cheng Y-B, Akatsu T (eds) Proc. 3rd Int. congress on ceramics (ICC3), Symp. 14 – Advanced engineering ceramics and composites, Osaka, Japan, 14-18 Nov 2010. IOP Conf Series Mater Sci Eng 18(20):202016 (4 pp.) 3223. Rosiński M, Michalski A (2012) WC-Co/cBN composites produced by pulse plasma sintering method. J Mater Sci 47:7064-7071 3224. Bobrovnitchii GS, Diegues-Skury AL, Monteiro SN, De Azevedo MG (2012) Hard metal matrix composites reinforced with cubic boron nitride. In: Salgado L, Filho FA (eds) Selected proc. 8th Int. Latin-American conf. on powder technology, Florianópolis, Santa Catarina, Brazil, 6-9 Nov 2011. Mater Sci Forum 727-728:310-313 3225. Wang B, Matsumaru K, Yang J-F, Fu Z, Ishizaki K (2012) The effect of cBN additions on densification, microstructure and properties of WC-Co composites by pulse electric current sintering. J Am Ceram Soc 95(8):2499-2503 3226. Wang B, Qin Y, Jin F, Yang J-F, Ishizaki K (2014) Pulse electric current sintering of cubic boron nitride / tungsten carbide – cobalt (cBN/WC-Co) composites: effect of cBN particle size and volume fraction on their microstructure and properties. Mater Sci Eng A 607:490497 3227. Zhang J-F, Tu R, Goto T (2014) Spark-plasma sintering and characterization of WC-CocBN composites. In: Goto T, Fu Z, Zhang L (eds) Proc. 5th Int. symp. on advanced ceramics (ISAC 2013) and 3rd Int. symp. on advanced synthesis and processing technology for materials (ASPT 2013), Wuhan, China, 9-12 Dec 2013. Key Eng Mater 616:194-198 3228. He Q, Chen H, Li K, Dong L (2015) Effect of Co content on the densification, microstructure mechanical properties of cBN-WC/Co composites. In: Lin H, Gong J (eds) Proc. 5th Int. congress on ceramics (ICC 2014), Beijing, China, 17-21 Aug 2014. Key Eng Mater 655:41-44 3229. Li K, Chen H, He Q, Dong L (2015) Microstructure and properties of hot-pressing sintered tungsten carbide composites by adding cubic boron nitride. In: Lin H, Gong J (eds) Proc. 5th Int. congress on ceramics (ICC 2014), Beijing, China, 17-21 Aug 2014. Key Eng Mater 655:45-48 3230. Michalski A, Cymerman K, Rasiński M (2015) Microstructure of the cBN / WC – 6 Co composite produced by the pulse plasma sintering (PPS) method. Int J Refract Met Hard Mater 50:197-203 3231. Mao C, Ren Y, Gan H, Zhang M, Zhang J, Tang K (2015) Microstructure and mechanical properties of cBN-WC-Co composites used for cutting tools. Int J Adv Manuf Technol 76:2043-2049 3232. Mao C, Zhang M, Zhang J, Tang K, Gan H, Zhang G (2015) The effect of processing parameters on the performance of spark-plasma sintered cBN-WC-Co composites. J Mater Eng Perform 24:4612-4619 3233. Mao C, Sun X, Huang H, Kang C, Zhang M, Wu Y (2016) Characteristics and removal mechanism in laser cutting of cBN – WC – 10 Co composites. J Mater Process Technol 230:42-49

References

751

3234. Mao C, Liang C, Zhang Y, Zhang M, Hu Y, Bi Z (2017) Grinding characteristics of cBN – WC – 10 Co composites. Ceram Int 43:16539-16547 3235. Mao C, Zhang Y, Peng X, Zhang B, Hu Y, Bi Z (2018) Wear mechanism of single cBN – WC – 10 Co fiber cutter in machining Ti-6Al-4V alloy. J Mater Process Technol 259:45-57 3236. Mao C, Lu J, Zhao Z, Yin L, Hu Y, Bi Z (2018) Simulation and experiment of cutting characteristics for single cBN – WC – 10 Co fiber. Precis Eng 52:170-182 3237. Wang Z-N (2016) cBN-TiC and WC-Co composites: optimization of co-extruding conditions. Int J Appl Ceram Technol 13(2):412-420 3238. Zhang G, Chen H, Dong L, Yin Y, Li K (2016) Microstructure and mechanical properties of ultra-fine WC/Co cemented carbides with cubic boron nitride and Cr3C2 additions. Ceram Silikáty 60(2):85-90 3239. Langa T, Olubambi P, Shabalala T, Shongwe MB (2018) Densification and structural transformation during spark-plasma sintering of WC-Co-YSZ-cBN systems. Int J Refract Met Hard Mater 72:341-348 3240. Shin K-H, Kim Y, Lim S-H (2005) AC permeability of Fe-Co-Ge/WC/Phenol magnetostrictive composites. IEEE Trans Magnet 41(10):2784-2786 3241. Ivocevic M, Knight R, Kalidindi SR, Palmese GR, Sutter JK (2005) Adhesive/cohesive properties of thermally sprayed functionally graded coatings for polymer matrix composites. J Therm Spray Technol 14:45-51 3242. Muthuraja A, Senthilvelan S (2015) Development of tungsten carbide based self-lubricant cutting tool material: preliminary investigation. Int J Refract Met Hard Mater 48:89-96 3243. Muthuraja A, Senthilvelan S (2015) Adhesive wear performance of tungsten carbide based solid lubricant material. Int J Refract Met Hard Mater 52:235-244 3244. Xiao D-H, Zhang F-Q, Luo W-H (2011) Fabrication and characterization of ultra-fine WC – 8 Co – x CeB6 cemented carbides. Ceram Int 37:2795-2801 3245. Ye H, Zhang XB, Xue ZF, Fan YH, Chen K (2009) Effect of CeO2 on microstructure and properties of WC/Co coating by laser cladding. In: Yin Y, Wang X (eds) Proc. 2nd Int. conf. on multi-functional materials and structures (MFMS-2009), Qingdao, China, 9-12 Oct 2009. Adv Mater Res 79-82:795-798 3246. Wang Y, Pan Z, Wang C, Sun X, Peng Z, Wang B (2012) Cutting performance of WC-Co alloys modified by nano-additives. J Mater Sci Technol 28(3):205-213 3247. Zhang L, Tang W, Chen S, Nan Q, Xie M (2012) Synergetic migration behaviour of La and Ce and related microstructure character of Cr-V-Re co-doped WC-Co alloy. J Rare Earths 30(5):480-485 3248. Sun X, Wang Y, Peng F, Pan Z, Wang L (2013) Optimization of processing parameters for WC – 11 Co cemented carbide doped with nanocrystalline CeO2. J Mater Eng Perform 22:112-117 3249. Huang C-G (2014) Effects of rare earth elements of Y, Ce and their adding ways on microstructure and properties of WC-Co cemented carbide. Mater Sci Eng Powder Metall 19(5):701-706 (in Chinese) 3250. Liu Y, Chen H-H, Ceng S, Gou G, Wang X, Tu M, Wu X (2015) Erosion-corrosion interactional effect of CeO2 modified HVOF WC-Co coating. In: Agarwal A, Lau Y-C, Widener CA, Turunen E, Bolelli G, Concustell A, McDonald A, Toma F-L (eds) Proc. Int. thermal spray conf. and exposition (ITSC 2015), Long Beach, California, 11-14 May 2015, Vol. 2, pp. 1001-1006. ASM International, Metals Park, Ohio 3251. Ceng S, Chen H-H, Liu Y, Ma Y, Wu Y (2016) Effect of CeO2 on corrosion behaviour of WC – 12 Co coatings by high-velocity oxygen-fuel. Acta Metall Sin 52(11):1441-1448 (in Chinese) 3252. Liu Y, Hang Z, Chen H-H, Ceng S, Gou G, Wang X, Tu M, Wu X (2016) Erosioncorrosion property of CeO2-modified HVOF WC-Co coating. J Therm Spray Technol 25:815-822

752

2 Tungsten Carbides

3253. Qi X, Zhu S-G (2015) Effect of CeO2 addition on thermal shock resistance of WC – 12 % Co coating deposited on ductile iron by electric contact surface strengthening. Appl Surf Sci 349:792-797 3254. Zhang L, Chen H-H, Zhao H-Y, Cao H-Z, Lu Q-S, Nie F-L (2008) Effects of CeO2 on structure and wear resistance of laser cladding WC-Co/Ni60B coatings. Tribol 28(6):485-490 (in Chinese) 3255. Brookes KJA (2010) Key additions to WC-based hardmetals. Met Powder Rep 65(5):2027 3256. Hayashi K, Fuke Y, Suzuki H (1972) Effects of addition carbides on the grain size of WCCo alloy. J Jpn Soc Powder Powder Metall 19(2):67-71 (in Japanese) 3257. Suzuki H, Hayashi K, Taniguchi Y, Nakayama F (1979) Effects of a small amount of addition carbides on high-temperature transverse rupture strength of WC-Co cemented carbide. J Jpn Soc Powder Powder Metall 26(6):213-217 (in Japanese) 3258. Suzuki H, Tokumoto K (1984) Microstructure and mechanical properties of WC – Cr3C2 – 15 % Co cemented carbide. J Jpn Soc Powder Powder Metall 31(2):56-59 (in Japanese) 3259. Asada N, Igarashi T, Doi Y (1994) High-temperature hardness of submicron WC-Co hardmetals containing various additional carbides. J Jpn Soc Powder Powder Metall 41(7):871-876 (in Japanese) 3260. Yao L, Yang C (1992) Effect of refractory carbide additions on the characteristics of binder phase in WC-Co hard alloys. In: Advances in powder metallurgy. Proc. powder metallurgy World congress, San Francisco, California, 21-26 June 1992, Vol. 8, Part 1, pp. 61-69. Metal Powder Industries Federation, Princeton, New Jersey 3261. Banerjee D, Lal GK, Upadhyaya GS (1995) Effect of binder phase modification and Cr3C2 addition on properties of WC – 10 Co cemented carbide. J Mater Eng Perform 4:563-572 3262. Li J, Zhou G (1995) Observation and analysis on wettability of Co-Cr3C2 alloy with WC. Powder Metall Technol 13(1):44-47 (in Chinese) 3263. Roebuck B (1995) Terminology, testing, properties, imaging and models for fine-grained hardmetals. Int J Refract Met Hard Mater 13:265-279 3264. Schubert WD, Neumeister H, Kinger G, Lux B (1998) Hardness to toughness relation-ship of fine-grained WC-Co hardmetals. Int J Refract Met Hard Mater 16(2):133-142 3265. Zackrisson J, Jansson B, Upadhyaya GS, Andrén H-O (1998) WC-Co based cemented carbides with large Cr3C2 additions. Int J Refract Met Hard Mater 16:417-422 3266. Carroll DF (1999) Sintering and microstructural development in WC/Co-based alloys made with super-fine WC powder. Int J Refract Met Hard Mater 17:123-132 3267. Richter V (2001) Grain growth controlled in fine-grained tungsten carbide. Adv Mater Process 159(4):11-12 3268. Yamamoto T, Ikuhara Y, Watanabe T, Sakuma T, Taniuchi Y, Okada K, Tanase T (2001) High resolution microscopy study in Cr3C2-doped WC-Co. J Mater Sci 36:3885-3890 3269. Lay S, Hamar-Thibault S, Lackner A (2002) Location of VC in VC, Cr3C2 co-doped WCCo cermets by HREM and EELS. Int J Refract Met Hard Mater 20:61-69 3270. Shi X, Shao G, Duan X, Zhang G, Zhang W (2004) Influence of VC, Cr3C2 on sintering properties of nanocrystalline WC-Co composite powders. J Univ Sci Technol Beijing 26(6):612-615 (in Chinese) 3271. Morton CW, Wills DJ, Stjernberg K (2005) The temperature ranges for maximum effectiveness of grain growth inhibitors in WC-Co alloys. Int J Refract Met Hard Mater 23:287-293 3272. Sutthiruangwong S, Mori G (2005) Influence of refractory metal carbide addition on corrosion properties of cemented carbides. Mater Manuf Process 20:47-56 3273. Lee W-B, Kwon B-D, Jung S-B (2006) Effects of Cr3C2 on the microstructure and mechanical properties of the brazed joints between WC-Co and carbon steel. Int J Refract Met Hard Mater 24:215-221

References

753

3274. Huang SG, Li L, Vanmeensel K, Van Der Biest O, Vleugels J (2007) VC, Cr3C2 and NbC doped WC-Co cemented carbides prepared by pulsed electric current sintering. Int J Refract Met Hard Mater 25:417-422 3275. Yamanaka Y, Taniuchi T, Shirase F, Tanase T, Ikuhara Y, Yamamoto T (2007) High resolution transmission electron microscopy study of WC-Co alloy doped with other metal carbides: VC, Cr3C2 and ZrC. In: Proc. 3rd Int. conf. on recrystallization and grain growth (ReX & GG III), Jeju Island, South Korea, 10-15 June 2007. Mater Sci Forum 558559(2):993-996 3276. Hosoda Y, Sunada S, Yamamoto T, Majima K (2008) Influence of Co content on corrosion characteristics of WC-Cr3C2-Co based alloys. J Jpn Soc Powder Powder Metall 55(12):836-841 (in Japanese) 3277. Sun L, Jia C, Cao R, Lin C (2008) Effects of Cr3C2 additions on the densification, grain growth and properties of ultra-fine WC – 11 Co composites by spark plasma sintering. Int J Refract Met Hard Mater 26(4):357-361 3278. Kellner FJJ, Hildebrand H, Virtanen S (2009) Effect of WC grain size on the corrosion behaviour of WC-Co based hardmetals in alkaline solutions. Int J Refract Met Hard Mater 27:806-812 3279. Bonache V, Salvador MD, Fernández A, Borrell A (2011) Fabrication of full density nearnanostructured cemented carbides by combination of VC/Cr3C2 addition and consolidation by SPS and HIP technologies. Int J Refract Met Hard Mater 29:202-208 3280. Bonache V, Salvador MD, Rocha VG, Borrell A (2011) Microstructural control of ultrafine and nanocrystalline WC – 12 Co – VC/Cr3C2 mixture by spark-plasma sintering. Ceram Int 37:1139-1142 3281. Johansson SAE, Wahnström G (2011) A computational study of thin cubic carbide films in WC/Co interfaces. Acta Mater 59:171-181 3282. Kellner FJJ, Killian MS, Yang G, Spiecker E, Virtanen S (2011) TEM and ToF-SIMS studies on the corrosion behaviour of vanadium and chromium containing WC-Co hard metals in alkaline solutions. Int J Refract Met Hard Mater 29:376-383 3283. Ou XQ, Song M, Shen TT, Xiao DH, He YH (2011) Fabrication and mechanical properties of ultra-fine grained WC – 10 Co – 0.45 Cr3C2 – 0.25 VC alloys. Int J Refract Met Hard Mater 29:260-267 3284. Sun L, Yang T, Jia C, Xiong J (2011) VC, Cr3C2 doped ultra-fine WC-Co cemented carbides prepared by spark-plasma sintering. Int J Refract Met Hard Mater 29:147-152 3285. Lay S, Loubradou M, Johansson SAE, Wahnström G (2012) Interface structure in a WCCo alloy co-doped with VC and Cr3C2. J Mater Sci 47:1588-1593 3286. Lin N, He YH, Wu CH, Zhang QK, Zou J, Zhao ZW (2012) Fabrication of tungsten carbide – vanadium carbide core-shell structure powders and their application as an inhibitor for sintering of cemented carbides. Scripta Mater 67:826-829 3287. Zhang L, Chen S, Cheng X, Wu H-P, Ma Y, Xiong X-J (2012) Effects of cubic carbides and La additions on WC grain morphology, hardness and toughness of WC-Co alloys. Trans Nonferr Met Soc China 22:1680-1685 3288. Jin Y, Huang B, Liu C, Fu Q (2013) Phase evolution in the synthesis of WC-Co-Cr3C2-VC nanocomposite powders from precursors. Int J Refract Met Hard Mater 41:169-173 3289. Lay S (2013) HRTEM investigation of dislocation interactions in WC. Int J Refract Met Hard Mater 41:416-421 3290. Marshall JM, Kusoffsky A (2013) Binder phase structure in fine and coarse WC-Co hard metals with Cr and V carbide additions. Int J Refract Met Hard Mater 40:27-35 3291. Al-Aqeeli N, Mohammad K, Laoui T, Saheb N (2014) VC and Cr3C2 doped WC-based nano-cermets prepared by MA and SPS. Ceram Int 40:11759-11765 3292. Fu J, Song X, Wei C, Liu X, Wang H, Gao Y, Wang Y (2014) Effect of combined addition of grain growth inhibitors on the cemented carbides prepared by WC-Co composite powder. Rare Met Mater Eng 43(8):1928-1934 (in Chinese)

754

2 Tungsten Carbides

3293. Liu X-W, Song X, Wang H, Liu X-M, Zhang Q, Gao Y (2014) Ultra-fine cemented carbides with super-high fracture strength – optimization of carbon content and grain growth inhibitor. In: Chernenkoff RA, Jandeska WF, Jr (eds) Advances in powder metallurgy and particulate materials – 2014. Proc. World congress on powder metallurgy and particulate materials (PM 2014), Orlando, Florida, 18-22 May 2014, pp. 81-83. Metal Powder Industries Federation, Princeton, New Jersey 3294. Sharma S (2014) Parametric study of abrasive wear of Co-CrC based flame sprayed coatings by response surface methodology. Tribol Int 75:39-50 3295. Stanciu VI, Vitry V, Delaunois F (2014) A ready to use Cr3C2 doped cobalt powder as binder in cemented carbides. In: Kliber J, Kursa M (eds) Proc. 23rd Int. conf. on metallurgy and materials (METAL 2014), Brno, Czech Republic, 21-23 May 2014, pp. 1194-1199. Tanger Ltd., Ostrava, Czech Republic 3296. Al-Aqeeli N (2015) Characterization of nano-cemented carbides co-doped with vanadium and chromium carbides. Powder Technol 273:47-53 3297. Al-Aqeeli N, Mohammad K, Laoui T, Saheb N (2015) The effect of variable binder content and sintering temperature on the mechanical properties of WC-Co-VC/Cr3C2 nanocomposites. Mater Manuf Processes 30:327-334 3298. Buchegger C, Lengauer W, Bernardi J, Gruber J, Ntaflos T, Kiraly F, Langlade J (2015) Diffusion parameters of grain growth inhibitors in WC based hardmetals with Co, Fe/Ni and Fe/Co/Ni binder alloys. Int J Refract Met Hard Mater 49:67-74 3299. Buchegger C, Langlade J, Lengauer W (2013) Interdependencies of grain growth inhibitor diffusion in WC-Co hardmetals. In: Sigl L, Kestler H, Wagner J (eds) Proc. 18th Int. Plansee seminar, Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 3-7 June 2013, Vol. 2 – P/M hard materials, pp. HM73/1-HM73/11. Plansee Metal AG, Reutte, Austria 3300. Chen J, Gong M-F, Liu W, Zeng J-J, Wu S-H (2015) Effect of TiC and Cr3C2 addition on microstructures and properties of ultra-fine WC – 8 Co cemented carbides. J Synth Cryst 44(5):1336-1341 (in Chinese) 3301. Wang H, Webb T, Bitler JW (2015) Different effects of Cr3C2 and VC on the sintering behaviour of WC-Co materials. Int J Refract Met Hard Mater 53:117-122 3302. Guo W, Li K, Du Y, Zhang Z-J, Xu T, Yin C, Zhang Z, Zhou P, Liu X, Huang B (2016) Microstructure and composition of segregation layers at WC/Co interfaces in ultrafinegrained cemented carbides co-doped with Cr and V. Int J Refract Met Hard Mater 58:68-73 3303. Liu X-W, Song X-Y, Wang H-B, Hou C, Liu X-M, Wang X-L (2016) Reinforcement of tungsten carbide grains by nanoprecipitates in cemented carbides. Nanotechnol 27:415710 (9 pp.) 3304. Wu C-C, Chang S-H, Tang T-P, Peng K-Y, Chang W-C (2016) Study on the properties of WC – 10 Co alloys adding Cr3C2 powder via various vacuum sintering temperatures. J Alloys Compd 686:810-815 3305. Chen H, Yang Q, Yang J, Yang H, Chen L, Ruan J, Huang Q (2017) Effects of VC/Cr3C2 on WC grain morphologies and mechanical properties of WC – 6 wt.% Co cemented carbides. J Alloys Compd 714:245-250 3306. Ma R, Ju S, Chen H, Shu C (2017) Effect of cobalt content on microstructures and wear resistance of tungsten carbide – cobalt cemented carbides fabricated by spark-plasma sintering. In: Fang DJ, Jang KM, Han QS, Zhao P, Lee HV, Zhang FL (eds) Proc. 4th Int. conf. on advanced composite materials and manufacturing engineering (ACMME 2017), Xishuangbanna, Yunnan, China, 20-21 May 2017. IOP Conf Series Mater Sci Eng 207:012019 (9 pp.) 3307. Pötschke J, Richter V, Gestrich T, Säuberlich T, Meese-Marktscheffel JA (2017) Grain growth inhibition in ultra-fine hardmetals. Int J Refract Met Hard Mater 66:95-104 3308. Siwak P, Garbiec D, Rogalewicz M (2017) The effect of Cr3C2 and TaC additives on microstructure, hardness and fracture toughness of WC – 6 Co tool material fabricated by spark-plasma sintering. Mater Res 20(3):780-785

References

755

3309. Sun J, Zhao J, Li Z, Ni X, Zhou Y, Li A (2017) Effects of initial particle size distribution and sintering parameters on microstructure and mechanical properties of functionally graded WC-TiC-VC-Cr3C2-Co hard alloys. Ceram Int 43:2686-2696 3310. Takada M, Matsubara H, Kawagishi Y (2017) Lifetime in steel code wire drawing dies of WC-Co cemented carbide containing TaNbC or Cr3C2. J Jpn Soc Powder Powder Metall 64(1):17-22 (in Japanese) 3311. Tian H, Peng Y, Du Y, Qiu L, Zhang C (2017) Thermodynamic calculation designed compositions, microstructure and mechanical property of ultra-fine WC – 10 Co – Cr3C2 – TaC cemented carbides. Int J Refract Met Hard Mater 69:11-17 3312. Wang X-Z, Wang H-B, Liu X-M, Yang T, Song X-Y (2017) Grain growth inhibitor on the WC-Co cemented carbide coating. J Inorg Mater 32(8):813-818 (in Chinese) 3313. Wan L, Yang L, Zeng X, Lai X, Zhao L (2017) Synthesis of Cr-doped APT in the evaporation and crystallization process and its effect on properties of WC-Co cemented carbide alloy. Int J Refract Met Hard Mater 64:248-254 3314. Zhang X-H, Huang Z, Xu C, Li X-X, Cai Z-Y, Chen H (2017) Effect of Cr3C2 on microstructures and properties of WC – 6 Co cemented carbides prepared by SPS. Chin J Nonferr Met 27(8):1580-1588 (in Chinese) 3315. Grewe H, Exner HE, Walter P (1973) Behinderung des Kornwachstums in HartmetallLegierungen vom ISO-K10-Typ durch Zusatzkarbide (Impairment of grain growth in hard metal alloys of the ISO-K10 type by additional carbides) Z Metallkd 64(2):85-94 (in German) 3316. Liu X, Song X, Wang H, Liu X, Tang F, Lu H (2018) Complexions in WC-Co cemented carbides. Acta Mater 149:164-178 3317. Pötschke J, Säuberlich T, Vornberger A, Meese-Marktscheffel JA (2018) Solid state sintered nanoscaled hardmetals and their properties. Int J Refract Met Hard Mater 72:45-50 3318. Pötschke J, Gestrich T, Richter V (2018) Grain growth inhibition of hardmetals during initial heat-up. Int J Refract Met Hard Mater 72:117-125 3319. Yousfi MA, Norgren S, Andrén H-O, Falk LKL (2018) Chromium segregation at phase boundaries in Cr-doped WC-Co cemented carbides. Mater Charact 144:48-56 3320. Tian H, Zhang M, Peng Y, Du Y, Zhou P (2019) Sintering behaviour and mechanical properties of Cr3C2 doped ultra-fine WC-Co cemented carbides: experiment guided with thermodynamic calculations. Int J Refract Met Hard Mater 78:240-246 3321. Souza VAD, Neville A (2003) Linking electrochemical corrosion behaviour and corrosion mechanisms of thermal spray cermet coatings (WC-CrNi and WC/CrC-CoCr). Mater Sci Eng A 352:202-211 3322. Zhou W, Zhou K, Deng C, Zeng K, Li Y (2017) Hot corrosion behaviour of HVOFsprayed Cr3C2-WC-NiCoCrMo coating. Ceram Int 43:9390-9400 3323. Zhou W, Zhou K, Li Y, Deng C, Zeng K (2017) High-temperature wear performance of HVOF-sprayed Cr3C2-WC-NiCoCrMo and Cr3C2-NiCr hardmetal coatings. Appl Surf Sci 416:33-44 3324. Hulka I, Şerban VA, Secoşan I, Vuoristo P, Niemi K (2012) Wear properties of CrC – 37 WC – 18 M coatings deposited by HVOF and HVAF spraying processes. Surf Coat Technol 210:15-20 3325. Singh H, Kaur M, Prakash S (2016) High-temperature exposure studies of HVOF-sprayed Cr3C2 – 25 (NiCr) / (WC-Co) coating. J Therm Spray Technol 25:1192-1207 3326. Matikainen V, Bolelli G, Koivuluoto H, Sassatelli P, Lusvarghi L, Vuoristo P (2017) Sliding wear behaviour of HVOF and HVAF sprayed Cr3C2-based coatings. Wear 388389:57-71 3327. Srinivas V, Pathem U, Venkataramana VSN, Chebattina KRR (2019) Mechanical, anticorrosion and tribological properties of nanostructured WC-Co / Cr3C2-NiCr multilayered graded coating on aluminium substrate. Metall Mater Trans A 50:1985-1994

756

2 Tungsten Carbides

3328. Matikainen V, Koivuluoto H, Vuoristo P (2020) A study of Cr3C2-based HVOF- and HVAF-sprayed coatings: abrasion, dry particle erosion and cavitation erosion resistance. Wear 446-447:203188 (11 pp.) 3329. Carrino L, Durante M, Formisano A, Langella A, Capece-Minutolo F, Caraviello A (2014) Wear behaviour of WC-Co carbides with addition of Cr3C2 and Ni. In: Larkiola J (ed) Proc. 17th conf. Eur. scientific association on material forming (ESAFORM 2014), Espoo, Finland, 7-9 May 2014. Key Eng Mater 611-612:444-451 3330. Weidow J, Blomqvist A, Salomonsson J, Norgren S (2015) Cemented carbides based on WC pre-alloyed with Cr or Ta. Int J Refract Met Hard Mater 49:36-41 3331. Zhang L, Wu H-P, Chen S, Wang Z, Xiong X (2009) In situ formation of La containing dispersed phase on the sinter skin of La2O3 and Cr3C2 unitedly doped WC-Co cemented carbide. Int J Refract Met Hard Mater 27:991-995 3332. Zhang L, Chen S, Nan Q, Xie M-W, Wu H-P, Feng Y-P (2013) Effect of La containing phases on microscopic wear characteristics and residual stress of WC-Co cemented carbide. Int J Refract Met Hard Mater 41:7-11 3333. Nutting J, Guilemany JM, Sanchiz I (1993-1994) The topology of hard metals (Binder phase or filler phase?). Int J Refract Met Hard Mater 12:217-223 3334. Ke D, Pan Y, Xu Y, Wang P, Wu R (2017) VC and Cr3C2 doped WCoB-TiC ceramic composites prepared by hot-pressing. Int J Refract Met Hard Mater 68:24-28 3335. Uchikanezaki T, Hara H, Takashi T, Hayashi K (2010) Effects of kind of added carbides on thickness and morphology of β-free layer formed in WC-TiN-Co cemented carbide. J Jpn Soc Powder Powder Metall 57(9):618-625 (in Japanese) 3336. Zhang S-Q (2009) Sintering behaviour of ultra-fine grain cemented carbides with 0.2 μm sized grain. Mater Sci Eng Powder Metall 14(4):237-243 (in Chinese) 3337. Deng XX, Dariusz G, Torralba JM, Wang J, García-Junceda A (2019) Development and characterization of novel Cr-based hardmetals strengthened by nanosized tungsten carbide. Mater Sci Eng A 767:138413 (12 pp.) 3338. Mukha IM, Verkhoturov AD, Gnedova SV (1980) Effect of grain size of WC-Co-B alloying electrodes on the formation of a reinforced layer during electric-spark alloying. Powder Metall Met Ceram 19(11):793-795 3339. Mukha IM, Gnedova SV, Verkhoturov AD (1980) Effect of boron and chromium boride microadditions to VK6M alloy on cathode weight gain in the electric-spark alloying of steel. Powder Metall Met Ceram 19(12):818-821 3340. Lisovskii AF, Bondarenko NA, Davidenko SA (2016) Structure and properties of the diamond – WC – 6 Co composite doped by 1.5 wt.% CrSi2. J Superhard Mater 38(6):382-392 3341. Liu S, Yi DQ, Li YX, Zou D (2002) Preparing nanocrystalline La doped WC/Co powder by high-energy ball-milling. Acta Metall Sin 15(5):448-452 3342. Li J, Cheng J, Wei B, Chen P (2019) Preparation and performance of ultra-fine grained WC – 10 Co alloys with added La2O3. Ceram Int 45:3969-3976 3343. Gu D, Shen Y (2007) Effects of La2O3 addition on structure and forming property of laser sintered (WC-Co)p/Cu metal matrix composites. Acta Metall Sin 43(9):968-976 (in Chinese) 3344. Xiao YH, Liu PW, Wang Z, Wang Y, Feng KQ, Chen L (2019) La2O3 addition for improving the brazed joints of WC-Co/1Cr13. J Mater Process Technol 267:17-25 3345. Suzuki H, Hayashi K, Taniguchi Y (1980) Properties of WC-Co alloy containing molybdenum carbide. J Jpn Soc Powder Powder Metall 27(6):185-189 (in Japanese) 3346. Schmitt T, Schreiner M, Lassner E, Lux B (1983) Über das diskontinuierliche Kornwachstum in WC/Co-Hartmetallen (On the discontinuous grain growth in WC/Co hard metals). Z Metallkd 74(8):496-499 (in German) 3347. Schmitt T, Schreiner M, Ettmayer P, Lassner E, Lux B (1983) Über auflösewiederabscheidungsvorgänge beim Flüssigphasensintern von WC/Co-Hartmetallen (On solutionreprecipitation processes during the liquid phase sintering of WC/Co hard metals). Int J Refract Met Hard Mater 2(2):78-83 (in German)

References

757

3348. Ullrich H-J, Rolle S, Uhlig A, Ettmayer P, Lux B (1983) Investigation of (Mo,W)C mixed carbides by electron probe microanalysis and Kossel technique. In: Grasserbauer M, Zacherl MK (eds) Progress in materials analysis. Proc. 11th colloquium on metallurgical analysis, Vienna, Austria, 3-5 Nov 1982, Vol.1, pp. 251-260. Springer, Vienna 3349. Regmi YN, Leonard BM (2014) General synthesis method for bimetallic carbides of group VIIIA first row transition metals with molybdenum and tungsten. Chem Mater 26:2609-2616 3350. Prat O, Suarez S, García J, Sanhueza F (2016) REM- und EBSD-Charakterisierung von zweischichtigen, funktionell abgestuften Metallverbundwerkstoffen (SEM and EBSD characterization of bilayered, functionally graded hard metal composites). Prakt Metallogr 53(11):696-710 (in German) 3351. Shi K, Schwarz V, Lengauer W (2017) Preparation and properties of (W,Mo)C powders and (W,Mo)C-Co cemented carbides. In: Sigl LS, Kestler H, Pilz A (eds) Proc. 19th Int. Plansee seminar, Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 29 May – 2 June 2017, Vol. 3 – Hard materials 2, pp. HM100/1-HM100/14. Plansee Metal AG, Reutte, Austria. 3352. Bhaumik SK, Upadhyaya GS, Vaidya ML (1991) Mechanical properties and microstructure of carbide and binder modified WC – 10 Co cemented carbides. In: Pease LF, III, Sansoucy RJ (eds) Advances in powder metallurgy. Proc. powder metallurgy conf. and exhibition, Chicago, Illinois, 9-12 June 1991, Vol. 6, pp. 439-450. Metal Powder Industries Federation, Princeton, New Jersey 3353. Bhaumik SK, Upadhyaya GS, Vaidya ML (1992) Microstructure and mechanical properties of WC-TiN-Co and WC-TiN-Mo2C-Co(Ni) cemented carbides. Ceram Int 18:327336 3354. Matsugi K, Ozawa S, Hatayama T, Yanagisawa O (1997) Friction and wear characteristics of spark sintered WC-Co-MoS2 alloys. J Jpn Inst Met 61(6):519-527 (in Japanese) 3355. Zhang S, Zhang K, Hu F, Zhang C, Yan Y (2010) Frictional and wear performance of WC – 12 Co / MoS2 composite coating by detonation gun spraying. Trans China Weld Inst 31(12):49-52 (in Chinese) 3356. Yuan J, Zhu Y, Zheng X, Ji H, Yang T (2011) Fabrication and evaluation of atmospheric plasma spraying WC-Co-Cu-MoS2 composite coatings. J Alloys Compd 509(5):2576-2581 3357. Majagi SI, Upadhyaya GS (1989) Sintering of WC – 10 Co hard metal containing intermetallic compound. Int J Refract Met Hard Mater 8(2):111-113 3358. Bolelli G, Cannillo V, Lusvarghi L, Rosa R, Valarezo A, Choi WB, Dey R, Weyant C, Sampath S (2012) Functionally graded WC-Co/NiAl HVOF coatings for damage tolerance, wear and corrosion protection. Surf Coat Technol 206:2585-2601 3359. Ren S, Meng J, Lu J, Yang S, Wang J (2010) Tribo-physical and tribo-chemical aspects of WC-based cermet / Ti3SiC2 tribo-pair at elevated temperatures. Tribol Int 43:512-517 3360. Pan Q (1993) Effects of rare earth oxides on the properties of WC-Co cemented carbide. Rare Met Mater Eng 22(4):35-41 (in Chinese) 3361. Kovalchenko MS, Bronshtein DKh, Simkin ÉS, Tsypin NV (1986) Densification kinetics in the hot-pressing of a hard metal base composite material. Powder Metall Met Ceram 25(6):460-463 3362. Zhang S, Zheng K, Zheng L (1994) Study on the laser cladding hard alloy WC-SiC-Co properties. Laser J 15(1):25-28 (in Chinese) 3363. Zhao JF, Li Y, Wang L (2006) Nano-SiC particles reinforced plasma sprayed WC-Co coating by laser melting process. In: Yuan ZJ, Xu XP, Zuo DW, Yuan JL, Yao YX (eds) Proc. 8th conf. on machining and advanced manufacturing technology in China, Hangzhou, China, 15-17 Nov 2005. Key Eng Mater 315-316:575-578 3364. Oskolkova TN, Budovskikh EA (2013) Electric explosion alloying of the surface of hard alloy VK10KS with titanium and silicon carbide. Met Sci Heat Treat 55(1-2):96-99 3365. Miranda F, Rodrigues D, Nakamoto FY, Frajuca C, Santos GAD, Couto AA (2016) Microstructural evolution of composite WC – 8 (Co, Ni): effect of the addition of SiC. Defect Diff Forum 371:78-85

758

2 Tungsten Carbides

3366. Shi X, Wang M, Xu Z, Zhai W, Zhang Q (2013) Tribological behaviour of Ti3SiC2 / (WC – 10 Co) composites prepared by spark-plasma sintering. Mater Design 45:365-376 3367. Song J, Huang C, Zou B, Liu H, Liu L, Wang J (2012) Effects of sintering additives on microstructure and mechanical properties of TiB2-WC ceramic-metal composite tool materials. Int J Refract Met Hard Mater 30:91-95 3368. Bondar VT (1980) Titanonitriding kinetics of hard metals. Powder Metall Met Ceram 19(6):414-416 3369. Kim KH, Han D-S, Kim SK (2003) Adhesion properties of arc ion-plated TiN coatings with WC particle size, Co content and surface roughness. Surf Coat Technol 163-164:605610 3370. Oskolkova TN (2015) Wear-resistant coating on tungsten carbide hard alloy. In: Chinakhov DA (ed) Proc. 6th Int. scientific practical conf. on innovative technologies and economics in engineering (YIT-ITEE), Yurga, Kemerovo Area, Russian Federation, 21-23 May 2015. IOP Conf Series Mater Sci Eng 91:012020 (7 pp.) 3371. Oskolkova TN (2015) Improving the wear resistance of tungsten carbide hard alloys. Steel Transl 45(5):318-321 3372. Morks MF, Gao Y, Fahim NF, Fu Y-Q (2006) Microstructure and hardness properties of cermet coating sprayed by low power plasma. Mater Lett 60:1049-1053 3373. Li Q, Lei T-Q, Zhang Y-Z, Lu H (2002) Microstructure of laser clad (WC + W2C)p / Ni based alloy composite coatings. Mater Sci Technol 10(1):5-10 (in Chinese) 3374. Rayón E, Bonache V, Salvador MD, Roa JJ, Sánchez E (2011) Hardness and Young’s modulus distributions in atmospheric plasma sprayed WC-Co coatings using nanoindentation. Surf Coat Technol 205:4192-4197 3375. Wang H, Li Y, Gee M, Zhang H, Liu X, Song X (2020) Sliding wear resistance enhancement by controlling W2C precipitation in HVOF sprayed WC-based cermet coating. Surf Coat Technol 387:125533 (13 pp.) 3376. Kase K, Miyashita H, Kaneko A, Nishimura T, Ishibashi O (1974) Effect of WB on some properties of sintered WC – 20 Co alloys. Planseeber Pulvermetall 22(2):118-128 3377. Yan X, Wang H, Liu X, Hou C, Qiu Q, Song X (2019) High-temperature oxidation and wear resistance of WC-Co based coating with WB addition. J Eur Ceram Soc 39(10):30233034 3378. Gogova D, Gesheva K, Veneva A (1998) CVD-WC and WCxNy diffusion barrier coatings on WC/Co metalloceramics. Mater Lett 35:351-356 3379. Yeo S, Kim Y-G (2015) The enhancement of wear resistance for nitrogen-implanted tungsten carbide. J Korean Phys Soc 66(3):474-477 3380. Zhang L, Chen S, Schubert WD, Huang B-Y (2004) Microstructures and properties of WC – 20 Co – 1 Y2O3 cemented carbide by hot-press and liquid phase sintering. J Central South Univ Technol 11(2):119-123 3381. Zhang L, Chen S, Wang Y-J, Yu X-W, Xiong X-J (2008) Tungsten carbide platelet containing cemented carbide with yttrium containing dispersed phase. Trans Nonferr Met Soc China 18:104-108 3382. El-Kady OAM (2013) Effect of nano-yttria addition on the properties of WC/Co composites. Mater Design 52:481-486 3383. Feng L, Yang Y-L, Lu D-P, Peng W-Y, Lu L, Tang C-R (2014) Effects of Y2O3 on properties of reclaimed WC – 8 Co cemented carbides. Chin Rare Earths 35(1):30-34 (in Chinese) 3384. Feng Q, Wang C, Han L, Yu Q (2015) Microstructure and properties of WC/Co-Y2O3 coating fabricated by laser alloying on 38CrMoAl steel substrate. Chin J Lasers 42(8):0803001 (7 pp.) 3385. Qin Y-Q, Peng Y-Q, Tian Y, Luo L-M, Ma Y, Zan X, Zhu X-Y, Wu Y-C (2020) Effect of Y2O3 on microstructure and mechanical properties of WC-Co cemented carbides prepared via solid-liquid doping method and spark-plasma sintering. Mater Today Commun 24:101096 (9 pp.)

References

759

3386. Guo S, Bao R, Yang J, Chen H, Yi J (2017) Effect of Mo and Y2O3 additions on the microstructure and properties of fine WC-Co cemented carbides fabricated by spark-plasma sintering. Int J Refract Met Hard Mater 69:1-10 3387. An L, Han J-T, Chen J (2006) Microstructure and mechanical properties of WC – 20 wt.% Co / ZrO2 (3Y) cermet composites. J Univ Sci Technol Beijing Miner Metall Mater 13(2):174-177 3388. Zhao Z-L, An L, Wu D-M, Han J-T (2012) Wear resistance of cermet WC – 20 % Co toughened and reinforced with ZrO2 (3Y). Trans Mater Heat Treat 33(1):26-30 (in Chinese) 3389. Olubambi PA, Alaneme KK, Andrews A (2015) Mechanical and tribological characteristics of tungsten carbide cermet composites sintered with Co-based and zirconia mixed binders. Int J Refract Met Hard Mater 50:163-177 3390. Upadhyaya GS (2001) Materials science of cemented carbides – an overview. Mater Design 22:483-489 3391. Kimmari E, Hussainova I, Smirnov A, Traksmaa R, Preis I (2009) Processing and microstructural characterization of WC-based cermets doped by ZrO2. Eston J Eng 15(4):275-282 3392. Mukhopadhyay A, Chakravarty D, Basu B (2010) Spark-plasma sintered WC-ZrO2-Co nanocomposites with high fracture toughness and strength. J Am Ceram Soc 93(6):1754-1763 3393. Hamid ZA, Ghayad IM, Ibrahim KM (2005) Electrodeposition and characterization of chromium – tungsten carbide composite coatings from a trivalent chromium bath. Surf Interface Anal 37:573-579 3394. Fernandes CM, Senos AMR, Vieira MT (2007) Control of eta-carbide formation in tungsten carbide powders sputter-coated with (Fe/Ni/Cr). Int J Refract Met Hard Mater 25:310-317 3395. Brieseck M, Bohn M, Lengauer W (2010) Diffusion and solubility of Cr in WC. J Alloys Compd 489:408-414 3396. Rudy E, Chang YA (1965) Thermodynamic considerations in the selection of materials for high-temperature applications. In: Benesovsky F (ed) Metals for the space age. Proc. 5th Int. Plansee seminar, Reutte, Tyrol, Austria, 22-26 June 1964, pp. 786-818. Plansee Holding AG, Reutte, Austria 3397. Chang YA, Naujock D (1972) The relative stabilities of Cr23C6, Cr7C3 and Cr3C2 and the phase relationships in ternary Cr-Mo-C system. Metall Mater Trans B 3(7):1693-1698 3398. Gustafson P (1988) A thermodynamic evaluation of the C-Cr-Fe-W system. Metall Trans A 19(10):2547-2554 3399. Chmelik D, Cupid D, Fabrichnaya O, Kriegel M, Pavlyuchkov D, Schuster E (2012) Carbon – chromium – tungsten system. In: Franke P, Seifert HJ (eds) Ternary steel systems. Subvol. C, Part 1, pp. 109-119. Springer, Berlin, Heidelberg 3400. Bondar AA (1986) Fazovye ravnovesiya v sistemakh Mo-Cr-C i W-Cr-C (Phase equilibria in the Mo-Cr-C and W-Cr-C systems). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 3401. Eremenko VN, Velikanova TYa, Bondar AA (1990) Zakonomernosti fazovykh ravnovesii v troinykh sistemakh metallov VI gruppy s uglerodom (The regularities of phase equilibria in the ternary systems of the group VI metals with carbon). In: Eremenko VN, Velikanova TYa (eds) Fazovye ravnovesiya, struktura i svoistva splavov (The phase equilibria, structure and properties of alloys), pp. 4-17. Naukova Dumka, Kyiv (in Russian) 3402. Rezaei-Sameti M, Nadali S, Rajabi J, Rakhshi M (2012) The effects of pulse electrodeposition parameters on morphology, hardness and wear behaviour of nanostructured CrWC composite coatings. J Mol Struct 1020:23-27 3403. Rezaei-Sameti M, Nadali S, Falahatpisheh A, Rakhshi M (2013) The effects of sodium dodecyl sulphate and sodium saccharin on morphology, hardness and wear behaviour of CrWC nanocomposite coatings. Solid State Commun 159:18-21

760

2 Tungsten Carbides

3404. Rezaei-Sameti M, Rasa H, Nadali S, Rakhshi M, Jalali M (2014) The study of morphology and wear behaviour of nanocomposite Cr-WC coating produced via electrodeposition with direct and pulse current. Russ J Phys Chem A 88(7):1172-1176 3405. Xie SX, Zhang YF, Ding YH, You SJ, Yang H (2014) Study of the craft and properties on Cr/WC system hardfacing alloy with flux-cored wire. In: Xu PL, Si HZ, Wang YQ, Wang P (eds) Proc. Int. conf. on materials science and computational engineering (ICMSCE 2014), Qingdao, China, 20-21 May 2014. Adv Mater Res 926-930:366-370 3406. Sancakoğlu O, Çelik E (2016) Superhard WC-Cr composite coatings: an approach to potential wear applications. Mater Test 58(10):864-869 3407. Goldschmidt HJ (1957) Occurrence of the beta-manganese structure in transition metal alloys and some observations on chi-phase equilibria. Acta Crystallogr 10(12):769 3408. Uhrenius B, Frondell S (1977) An experimental and thermodynamic study of carbide / austenite equilibria in Fe-Cr-W-C alloys. Met Sci 11:73-81 3409. Lee B-J (1992) On the stability of Cr carbides. Calphad 16(2):121-149 3410. Kambakas K, Tsakiropoulos P (2005) Solidification of high-Cr white cast iron – WC particle reinforced composites. Mater Sci Eng A 413-414:538-544 3411. Li Z-L, Jiang Y-H, Zhou R, Chen Z-H, Shan Q (2014) Effects of Cr addition on threebody abrasive wear behaviour of WC particles reinforced iron substrate surface composites. Trans Mater Heat Treat 35(1):17-21 (in Chinese) 3412. Li Z-L, Jiang Y-H, Zhou R, Chen Z-H, Shan Q, Tan J (2014) Effects of Cr addition on the microstructure and abrasive wear resistance of WC-reinforced iron matrix surface composites. J Mater Res 29(6):778-785 3413. García-Junceda A, Sáez I, Torralba JM (2016) Novel WC hardmetal with Cr/Fe binder alloy sintered by SPS. In: Krehl M, Petzoldt F (eds) Proc. World powder metallurgy congress and exhibition (World PM 2016), Hamburg, Germany, 9-13 Oct 2016 (5 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.epma.com/publications/euro-pm-proceedings/product/ep16-3294733 Accessed 4 April 2021 3414. Deng XX, Torralba JM, García-Junceda A (2017) Field-assisted sintering of WC hard metals with Cr-based binder. In: Molinari A, Federici M, Grande MA, Vedani M (eds) Proc. Int. powder metallurgy congress and exhibition (Euro PM 2017), Milan, Italy, 1-4 Oct 2017 (5 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.epma.com/publications/euro-pm-proceedings/product/ep17-3686032 Accessed 4 April 2021 3415. García-Junceda A, Sáez I, Deng XX, Torralba JM (2018) Development of a Cr-based hard composite by spark-plasma sintering. Metall Mater Trans A 49:1363-1371 3416. Deng XX, Cinca N, Garbiec D, Torralba JM, García-Junceda A (2020) Wear resistance of nanostructured Cr-based WC hardmetals sintered by spark-plasma sintering. Int J Refract Met Hard Mater 86:105092 (11 pp.) 3417. Yang J, Chang W, Miao X, Chen H, Wang X, Yang F (2015) Influence of Mn, Mo, Ti additions on microstructure and magnetic properties of WC-FeNiCr composite coatings. Chin J Lasers 42(10):1006001 (6 pp.) (in Chinese) 3418. Yang J, Miao X, Wang X, Yang F (2014) Influence of Mn additions on the microstructure and magnetic properties of FeNiCr / 60 % WC composite coating produced by laser cladding. Int J Refract Met Hard Mater 46:58-64 3419. Yang J, Miao X, Wang X, Chen H, Yang F (2016) Microstructure, magnetic properties and empirical electron theory calculations of laser cladding FeNiCr / 60 % WC composite coatings with Mo additions. Int J Refract Met Hard Mater 54:216-222 3420. Yang J, Liu F, Miao X, Yang F (2012) Influence of laser cladding process on the magnetic properties of WC-FeNiCr metal matrix composite coatings. J Mater Process Technol 212:1862-1868 3421. Yang L, Deng L-Q, Han Y, Han Y-L (2014) Influences of heat treatment on microstructure and wear resistance of WCp / 40CrNi2Mo metal matrix composites. In: Han Y, Liu T, Zhang

References

761

Q (eds) Proc. 12th Int. conf. on advanced materials (IUMRS-ICAM 2013), Qingdao, China, 22-28 Sep 2013. Mater Sci Forum 788:632-637 3422. Guo J, Liu S, Zhou Y, Wang J, Xing X, Ren X, Yang Q (2016) Stability of eutectic carbide in Fe-Cr-Mo-W-V-C alloy. Mater Lett 171:216-219 3423. Guo J, Feng Y, Liu L, Xing X, Ren X, Yang Q (2016) Investigation of microstructural damage to eutectic carbides from scratch tests of a heat-treated Fe-Cr-W-Mo-V-C alloy. Wear 358-359:137-147 3424. Guo J, Ai L, Wang T, Feng Y, Wan D, Yang Q (2018) Microstructure evolution and micro-mechanical behaviour of secondary carbides at grain boundary in a Fe-Cr-W-Mo-V-C alloy. Mater Sci Eng A 715:359-369 3425. Sakaguchi S, Ito H, Nakamura R (1986) Some properties of iron-chromium-carbon alloy infiltrated WC-Ni skeletons. J Jpn Soc Powder Powder Metall 33(2):78-83 (in Japanese) 3426. Wang Z-H, Yang A-D, Zhang T, He D-Y (2008) Dissolution behaviour of WC in WC reinforced composite coatings. J Mater Eng (9):56-59, 63 (in Chinese) 3427. González AG, Vargas F, López ME, Toro A (2009) Influence of microstructure and mechanical properties on the tribological behaviour of flame sprayed Al2O3-TiO2 and WC NiFeCr coatings. In: Marple BR, Hyland MM, Lau Y-C, Li C-J, Lima RS, Montavon G (eds) Thermal spray – 2009. Expanding thermal spray performance to new markets and applications. Proc. Int. thermal spray conf. (ITSC 2009), Las Vegas, Nevada, 4-7 May 2009, pp. 980-985. ASM International, Metals Park, Ohio 3428. Fernandes CM, Senos AMR, Vieira MT (2012) Versatility of the sputtering technique in the processing of WC-Fe-Ni-Cr composites. Surf Coat Technol 206:4915-4921 3429. Santos AAA, Gomes UU, Furukava M (2014) A new sintered hard metal composite. In: Filho FA, Klein AN (eds) Advanced powder technology – IX. Proc. 9th Int. Latin American conf. powder technology (PTECH 2013), São Paulo, Brazil, 27-29 Oct 2013. Mater Sci Forum 802:114-119 3430. Hoshiyama Y, Yamaguchi K, Miyake H (2017) Tungsten carbide dispersed high-Cr-Ni cast iron produced by plasma spraying. In: Longauerová M, Horňak P, Zubko P (eds) Metallography – XVI. Proc. 16th Int. symp. on metallography and materials science, Stará Lesná, Slovakia, 20-22 Apr 2016. Mater Sci Forum 891:565-568 3431. Yang J, Xiao Z, Miao X, Wang X, Yang F (2015) The effect of Ti additions on the microstructure and magnetic properties of laser clad FeNiCr / 60 % WC coatings. Int J Refract Met Hard Mater 52:6-11 3432. Hinners H, Konyashin I, Ries B, Petrzhik M, Levashov EA, Park D, Weirich T, Mayer J, Mazilkin AA (2017) Novel hardmetals with nano-grain reinforced binder for hardfacings. Int J Refract Met Hard Mater 67:98-104 3433. Humphry-Baker SA, Peng K, Lee WE (2017) Oxidation resistant tungsten carbide hardmetals. Int J Refract Met Hard Mater 66:135-143 3434. Wang L, Hu S-B, Shan W-T, Hu K, Zhang L (2014) Microstructure and wear resistance of laser cladding NiCrMn-WC composite coatings. Chin J Nonferr Met 24(1):145-151 (in Chinese) 3435. Peng Z, Rohwerder M, Choi P-P, Gault B, Meiners T, Friedrichs M, Kreilkamp H, Klocke F, Raabe D (2017) Atomic diffusion induced degradation in bimetallic layer coated tungsten carbide. Corros Sci 120:1-13 3436. Roebuck B, Bennett EG, Almond EA (1986) Partitioning of molybdenum between carbide and binder phase in WC/Ni cemented carbides infiltrated with Ni-Cr-Mo alloys. J Mater Sci Lett 5:473-474 3437. Yao J, Zhang J, Wu G, Wang L, Zhang Q, Liu R (2018) Microstructure and wear resistance of laser cladded composite coatings prepared from pre-alloyed WC-NiCrMo powder with different laser spots. Optics Laser Technol 101:520-530 3438. Olivares JL, Grigorescu IC (1987) Friction and wear behaviour of thermally sprayed nichrome – WC coatings. In: Krutenat RC (ed) Proc. 14th Int. conf. on metallurgical coatings, San Diego, California, 23-27 Mar 1987. Surf Coat Technol 33:183-190

762

2 Tungsten Carbides

3439. Cooper R, Manktelow SA, Wong F, Collins LE (1988) The sintering characteristics and properties of hard metal with Ni-Cr binders. In: Proc. 3rd Int. conf. on the science of hard materials, Nassau, The Bahamas, 9-13 Nov 1987. Mater Sci Eng A 105-106:269-273 3440. Okada R, Yamada M (1994) Effect of heat treatment on hardness and wear resistance of WC-NiCr sprayed coatings. J Jpn Inst Met 58(7):763-767 (in Japanese) 3441. Stack MM, Peña D (1997) Solid particle erosion of Ni-Cr/WC metal matrix composites at elevated temperatures: construction of erosion mechanism and process control maps. Wear 203-204:489-497 3442. Stack MM, Peña D (1999) Particle size effects on the elevated temperature erosion behaviour of Ni-Cr/WC MMC-based coatings. Surf Coat Technol 113:5-12 3443. Amado JM, Tobar MJ, Yáñez A (2010) Laser cladding of NiCr-WC metal matrix composites: dependence on the matrix composition. In: Hinduja S, Li L (eds) Proc. 36th Int. MATADOR conf., Manchester, Lancashire, UK, 14-16 July 2010, pp. 459-462. SpringerVerlag, London 3444. Amado JM, Tobar MJ, Yáñez A, Amigó V, Candel JJ (2011) Crack free tungsten carbide reinforced Ni(Cr) layers obtained by laser cladding. In: Schmidt M, Zaeh M, Graf T, Ostendorf A (eds) Proc. 6th Int. WLT conf. on lasers in manufacturing (LiM 2011), Munich, Germany, 23-26 May 2011. Phys Proc 12(A):338-344 3445. Lin C-F, Du Y-G, Sun D, Chen B-J, Liu Y-H (2010) Influence of Ni and Cr on anticorrosion performance of tungsten carbide base hard alloy. Corros Protect 31(9):678-681, 728 (in Chinese) 3446. Stack MM, Mathew MT, Hodge C (2011) Micro-abrasion-corrosion interactions of NiCr/WC based coatings: approaches to construction of tribo-corrosion maps for the abrasioncorrosion synergism. Electrochim Acta 56:8249-8259 3447. Shi K-H, Zhou K-C, Li Z-Y, Zan X-Q, Xu S-Z, Min Z-Y (2013) Effect of adding method of Cr on microstructure and properties of WC – 9 Ni – 2 Cr cemented carbides. Int J Refract Met Hard Mater 38:1-6 3448. Kailash S, Praveen AS, Suresh S, Sarangan J, Murugan N (2014) Comparison of microstructural characteristics of plasma and HVOF sprayed Ni-Cr/WC coating. In: Kalainathan S (ed) Proc. Int. conf. on materials and characterization techniques, Vellore, Tamil Nadu, India, 10-12 Mar 2014. Int J Chem Tech Res 6(6):3346-3348 3449. Abioye TE, Farayibi PK, McCartney DG, Clare AT (2016) Effect of carbide dissolution on the corrosion performance of tungsten carbide reinforced Inconel 625 wire laser coating. J Mater Process Technol 231:89-99 3450. Shi K-H, Zhou K-C, Li Z-Y, Zan X-Q, Min Z-Y, Liao J (2013) Effect of additive amount of Cr on microstructure and properties of WC – 9 Ni cemented carbides. Rare Met Mater Eng 45(12):3149-3154 (in Chinese) 3451. Przestacki D, Chwalczuk T, Wojciechowski S (2017) The study on minimum uncut chip thickness and cutting forces during laser-assisted turning of WC/NiCr clad layers. Int J Adv Manuf Technol 91:3887-3898 3452. Liu G, Guo S, Li J, Chen K, Fan D (2017) Fabrication of hard cermets by in situ synthesis and infiltration of metal melts into WC powder compacts. J Asian Ceram Soc 5:418-421 3453. Wang J, Peng C, Tang J, Xie Z (2018) Friction and wear characteristics of containing a certain amount of graphene oxide (GO) for hot-pressing sintered NiCr-WC-Al2O3 composites at different temperatures. J Alloys Compd 737:515-529 3454. Singh MK, Gautam RK (2019) Structural, mechanical and electrical behaviour of ceramic reinforced copper metal matrix hybrid composites. J Mater Eng Perform 28:886-899 3455. Janka L, Berger L-M, Norpoth J, Trache R, Thiele S, Tomastik C, Matikainen V, Vuoristo P (2018) Improving the high-temperature abrasion resistance of thermally sprayed Cr3C2NiCr coatings by WC addition. Surf Coat Technol 337:296-305 3456. Janka L, Norpoth J, Tomastik C, Matikainen V, Vuoristo P (2018) Laser-induced precipitation of (W1–xCrx)2C: mixed carbide phase for improved wear resistance of thermally sprayed hardmetal coatings. Surf Coat Technol 337:177-185

References

763

3457. Li M, Han B, Wang Y, Song L, Guo L (2016) Investigation on laser cladding high hardness nanoceramic coating assisted by ultrasonic vibration processing. Optik 127:45964600 3458. Huang X-Y, Wang J-H, Zhang H-Q, Ren J, Zan Q-F, Gong Q-M, Wu B (2017) WC-NiCr-based self-lubricating composites fabricated by pulsed electric current sintering with addition of WS2 solid lubricant. Int J Refract Met Hard Mater 66:158-162 3459. Alaneme KK, Olubambi PA, Andrews A (2015) Processing and characterization of WC – 10 Ni / – 7 Ni – 3 Cr based yttria stabilized zirconia spark-plasma sintered composites. Int J Refract Met Hard Mater 48:157-166 3460. Nelson RJ, Milner DR (1971) Liquid-flow densification in the tungsten carbide – copper system. Powder Metall 14(27):39-63 3461. Flis AA, Minakova RV, Teodorovich OK, Vorona DS, Antoshina RI (1980) Tungsten carbide pseudoalloys and their potential applications. Powder Metall Met Ceram 19(2):112117 3462. Ichikawa K, Achikita M (1993) Electric conductivity and mechanical properties of carbide dispersion-strengthened copper prepared by compocasting. Mater Trans Jpn Inst Met 34(8):718-724 3463. Zimmermann G, Schievenbusch A (1999) Materials with an acoustic impedance gradient. In: Kaysser WA (ed) Proc. 5th Int. symp. on functionally graded materials (FGM ’98), Dresden, Germany, 26-29 Oct 1998. Mater Sci Forum 308-311:533-538 3464. Zhao N, Zhou F, Chen M, Wang Z, Li G (2000) Microstructure and sintering process of P/M WC reinforced copper composite. Powder Metall Technol 18(4):265-269 (in Chinese) 3465. Chen Y-B, Ren Z-A (2002) Study of processing Cu/WCp composite coatings by laser cladding. Trans China Weld Inst 23(1):19-22 (in Chinese) 3466. Bao J, Newkirk JW, Bao S (2004) Wear-resistant WC composite hard coatings by brazing. J Mater Eng Perform 13:385-388 3467. Wang M, Zhang L, Liu X (2004) Study on WC dispersion-strengthened copper. Rare Met 23(2):120-125 3468. Deshpande PK, Lin RY (2006) Wear resistance of WC particle reinforced copper matrix composites and the effect of porosity. Mater Sci Eng A 418:137-145 3469. Xie Q, Jiang Y-L, Detavernier C, Van Meirhaeghe RL, Qu X-P (2007) Tungsten carbides as a diffusion barrier for Cu metallization. In: Tang T-A, Ru G-R, Jiang Y-L (eds) Proc. 8th Int. conf. on solid state and integrated circuit technology (ICSICT-2006), Shanghai, China, 23-26 Oct 2006, pp. 342-344. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 3470. Shinoda Y, Yanagisawa Y, Akatsu T, Wakai F, Fujii H (2009) Development of creepresistant tungsten carbide – copper cemented carbide. Mater Trans Jpn Inst Met 50(9):12501254 3471. Xu D-S, Qiu X-M, Zhang H-W, Bai D-C, Chen J-H (2009) Wear behaviour of brazed WC/Cu composite coatings. Mater Sci Technol 17(S1):152-156 3472. Zuhailawati H, Jamaludin SB (2009) Studies on mechanical alloying of copper – tungsten carbide composite for spot welding electrode. J Mater Eng Perform 18:1258-1263 3473. Ardestani M, Arabi H, Razavizadeh H, Rezaie HR, Mehrjoo H (2010) Synthesis of WC – 20 wt.% Cu composite powders by co-precipitation and carburization processes. Mater Sci Poland 28(2):413-420 3474. Xie Q, Jiang Y-L, De Keyser K, Detavernier C, Deduytsche D, Ru G-P, Qu X-P, Tu KN (2010) The effect of sputtered W-based carbide diffusion barriers on the thermal stability and void formation in copper thin films. Microelectron Eng 87:2535-2539 3475. Hong E, Kaplin B, You T, Suh M-S, Kim Y-S, Choe H (2011) Tribological properties of copper alloy – based composites reinforced with tungsten carbide particles. Wear 270(910):591-597 3476. Hussain Z, Yusoff M, Othman R (2011) Phase analysis of mechanically alloyed in situ copper – tungsten carbide composite. In: Ahmad ZA, Yarmo MA, Aziz FHA, Sulaiman

764

2 Tungsten Carbides

MYM, Ahmad B, Ismail KN, Rejab NA (eds) Proc. 5th Int. conf. on X-ray and related technique in research and industry (ICXRI 2010), Langkawi Island, Kedah, Malaysia, 9-10 June 2010. Adv Mater Res 173:67-71 3477. Girish BM, Basawaraj N/A, Satish BM, Jain PK (2012) Wear behaviour of tungsten carbide particles reinforced copper alloy composites. Int J Microstruct Mater Prop 7(6):517531 3478. Girish BM, Basawaraj N/A, Satish BM, Jain PK (2012) Tungsten carbide reinforced copper composites for thermal management applications. Proc Inst Mech Eng J Mater 226(4):316-321 3479. Guo R-X, Yan F, Xia H-T (2012) Microstructure and properties of WCp/Cu layered functionally graded materials prepared by vacuum hot-pressed sintering. In: Gan B, Gan Y, Yu Y (eds) Proc. Int. conf. on applied materials and electronics (AMEE 2012), Hong Kong, 18-19 Jan 2012. Adv Mater Res 378-379:47-50 3480. Yan F, Guo R-X, Xia H-T, Yu H, Zhang Y-B (2012) Experimental investigation of tensile properties and fracture mechanism of WCp/Cu composites reinforced with different WCp volume fraction. In: Bu J, Jiang Z, Jiao S (eds) Proc 2nd Int. conf. on advances in materials and manufacturing processes (ICAMMP 2011), Guilin, China, 16-18 dec 2011. Adv Mater Res 415-417:2244-2247 3481. Xia H-T, Guo R-X, Yan F, Yu H, Zhang Y-B (2013) Investigation for the fracture process of WCp/Cu functionally graded materials under three-point bending. In: Katsuyuki K (ed) Proc. 2nd Int. conf. on advanced materials and engineering materials (ICAMEM 2012), Shanghai, China, 29-30 Dec 2012. Adv Mater Res 683:17-20 3482. Yu H, Guo R-X, Xia H-T, Yan F, Zhang Y-B (2013) Study on the effect of WC size on the thermal expansion coefficient of WC/Cu composites. In: Li G, Chen C (eds) Proc. Int. conf. on applied mechanics and materials (ICAMM 2012), Sanya, China, 24-25 Nov 2012. Appl Mech Mater 275-277:1597-1600 3483. Yu H, Guo R-X, Xia H-T, Yan F, Zhang Y-B, He T-C (2013) Application of digital image correlation method in measuring linear expansion coefficients of WC/Cu compo-sites. Optics Precis Eng 21(10):2696-2703 (in Chinese) 3484. Khosravi J, Givi MKB, Barmouz M, Rahi A (2014) Microstructural, mechanical and thermophysical characterization of Cu/WC composite layers fabricated via friction stir processing. Int J Adv Manuf Technol 74:1087-1096 3485. Radek N, Konstanty J, Scendo M (2015) The electro-spark deposited WC-Cu coatings modified by laser treatment. Arch Metall Mater 60(4):2579-2584 3486. Zhou K-C, Pei H-L, Xiao J-K, Zhang L (2015) Micro-scratch behaviour of WC particle – reinforced copper matrix composites. Rare Met (6 pp.); doi:10.1007/s12598-015-0586-2 3487. Ebrahimi-Kahrizsangi R, Mahabadi MK, Torabi O (2016) An investigation on the mechano-chemical behaviour of the Ca-C-Cu2O-WO3 quaternary system to synthesize the Cu-WC nanocomposite powder. Int J Refract Met Hard Mater 54:75-81 3488. Hashemi SR, Ardestani M, Nemati A (2016) Cold compaction behaviour and pressureless sinterability of ball-milled WC and WC/Cu powders. Sci Sinter 48:71-79 3489. Tsakiris V, Enescu E, Radulian A, Lucaci M, Lungu M, Mocioi N, Leonat L, Cirstea D, Caramitu A (2016) WC-Cu electrical contacts developed by spark-plasma sintering process. In: Hănţilă FI, Ioniţă V (eds) Proc. Int. symp. on fundamentals of electric engineering (ISFEE 2016), Bucharest, Romania, 30 June – 2 July 2016, 7803212 (5 pp.). The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 3490. Cabezas JL, Olmos L, Vergara-Hernández HJ, Garnica P, Jiménez O, Mondragón-Sánchez ML, Lemus-Ruiz J (2017) Investigation of the effect of inert inclusions on densification during solid state sintering of metal matrix composites. Sci Eng Compos Mater 24(5):755763 3491. Cabezas-Villa JL, Olmos L, Vergara-Hernández HJ, Jiménez O, Garnica P, Bouvard D, Flores M (2017) Constrained sintering and wear properties of Cu-WC composite coatings. Trans Nonferr Met Soc China 27:2214-2224

References

765

3492. Pliszka I, Radek N (2017) Corrosion resistance of WC-Cu coatings produced by electrospark deposition. In: Bujnak J, Guagliano M (eds) Proc. 12th Int. scientific conf. on sustainable, modern and safe transport (TRANSCOM 2017), High Tatras, Slovakia, 31 May – 2 June 2017. Proc Eng 192:707-712 3493. Zhang Y-B, Guo R-X, Xia H-T, Yan F, Lin Z-W (2017) Effect of WCp content on fatigue crack growth behaviour of powder metallurgy Cu/WCp composites. J Mater Eng 45(1):85-92 (in Chinese) 3494. Dias M, Guerreiro F, Tejado E, Correia JB, Mardolcar UV, Coelho M, Palacios T, Pastor JY, Carvalho PA, Alves E (2018) WC-Cu thermal barriers for fusion applications. Surf Coat Technol 355:222-226 3495. Mi P, Ye F (2018) Wear performance of the WC/Cu self-lubricating textured coating. Vacuum 157:17-20 3496. Singh MK, Gautam RK, Prakash R, Ji G (2018) Mechanical and corrosion behaviours of developed copper-based metal matrix composites. In: Rao PN (ed) Proc. Int. conf. on materials, mechanical and civil engineering (ICRAMMCE 2017), Hyderabad, India, 1-2 June 2017. IOP Conf Series Mater Sci Eng 330:012021 (12 pp.) 3497. Li J, Ni J, Huang B, Chen J, Xu Z, Liao S, Wang C, Luo W (2019) Long-term ball-milling and hot-pressing of in situ nanoscale tungsten carbides reinforced copper composite and its characterization. Mater Charact 152:134-140 3498. Şelte A, Özkal B (2019) Crystallite size and strain calculations of hard particle reinforced composite powders (Cu/Ni/Fe-WC) synthesized via mechanical alloying. Proc Estonian Acad Sci 68(1):66-78 3499. Yao G, Cao C, Pan S, Lin T-C, Sokoluk M, Li X (2019) High-performance copper reinforced with dispersed nanoparticles. J Mater Sci 54:4423-4432 3500. Yusoff M, Othman R Hussain Z (2011) Mechanical alloying and sintering of nanostructured tungsten carbide – reinforced copper composite and its characterization. Mater Design 32:3293-3298 3501. Chu JP, Hsieh YY, Lin CH, Mahalingam T (2005) Thermal stability enhancement in nanostructured Cu films containing insoluble tungsten carbides for metallization. J Mater Res 20(6):1379-1384 3502. Zhao Z, Liu J, Tang H, Ma X, Zhao W (2015) Investigation on the mechanical properties of WC-Fe-Cu hard alloys. J Alloys Compd 632:729-734 3503. Cardoso JP, Puga J, Ferro-Rocha AM, Fernandes CM, Senos AMR (2019) WC – (Cu: AISI304) composites processed from high-energy ball-milled powders. Int J Refract Met Hard Mater 84:104990 (8 pp.) 3504. Gu D, Shen Y (2009) Microstructures and properties of direct laser sintered tungsten carbide (WC) particle reinforced Cu matrix composites with RE – Si – Fe addition: a comparative study. J Mater Res 24(11):3397-3406 3505. Liu Y, Lipke DW, Zhang Y, Sandhage KH (2009) The kinetics of incongruent reduction of tungsten carbide via reaction with a hafnium-copper melt. Acta Mater 57:3924-3931 3506. Pan L, Tao J, Wu S-Q, Chen F (2002) Study on wear resistance of WC/Cu-Mn-Ni brazing coating under dry sliding. Tribol 22(1):10-13 (in Chinese) 3507. Liu J, Yang S, Xia W, Jiang X, Gui C (2016) Microstructure and wear resistance performance of Cu-Ni-Mn alloy based hardfacing coatings reinforced by WC particles. J Alloys Compd 654:63-70 3508. Liu J, Yang S, Liu K, Gui C, Xia W (2017) Effect of age-hardening treatment on microstructure and sliding wear resistance performance of WC/Cu-Ni-Mn composite coatings. Metall Mater Trans A 48:3017-3026 3509. Yang S, Meng X, Liu J, Gui C, Xia W (2019) Influence of oxidation on the hightemperature tribological properties of tungsten carbide – reinforced Cu-Ni-Mn composite coatings. Metall Mater Trans A 50:1936-1942

766

2 Tungsten Carbides

3510. Yang XG, Tan GL, Zhang XB, Wu XJ, Lei YQ, Wang QD, Zhang WK (1999) Effect of nanometer-sized WC additive on the electrochemical behaviours of AB2-type hydrogen storage alloy. Mater Chem Phys 61:130-134 3511. Cheng X-L, Tian B-H (2014) Influence of WC content on microstructure and wear resistance of (Cu – 50 Mo) – WC composites. In: Bhatnagar AK (ed) Proc. Int. conf. on materials engineering and application (ICMEA 2014), Hangzhou, China, 18-19 Oct 2014. Adv Mater Res 1052:115-119 3512. Cheng X-L, Tian B-H, Yin T, Zhang Y, Liu Y (2015) Arc erosion characteristics of Cu – 49.5 Mo – 1 WC composite. Trans Mater Heat Treat 36(8):12-16 (in Chinese) 3513. Dekhonova SZ, Stepulyak SV, Durakov VG, Gnyusov SV (2002) Structure and tribological properties of Cu-Ni-WC alloy produced by electron-beam facing. J Frict Wear 23(6):90-93 3514. Melendez N, McDonald A, Fisher G (2012) Cold-spray WC-Ni-Cu MMC coatings with improved hardness. In: Marple BR, Agarwal A, Hyland MM, Lau Y-C, Li C-J, Lima RS, McDonald A (eds) Air, land, water and the human body: thermal spray science and applications. Proc. Int. thermal spray conf. (ITSC 2012), Houston, Texas, 21-24 May 2012, pp. 515-520. ASM International, Metals Park, Ohio 3515. Yan A-R, Wang Z, Wang Z-Y (2013) High-power diode laser clad Cu-WC-Ni composite coatings on brass for wear resistance enhancement. In: Ghanbari A (ed) Proc. 4th Int. conf. on manufacturing science and technology (ICMST 2013), Dubai, United Arab Emirates, 3-4 Aug 2013. Adv Mater Res 816-817:47-53 3516. Yan A-R, Li Y-J, Wang Z-Y (2014) Development and characterization of a laser clad WC reinforced Ni-Cu alloy composite coating on brass. Laser Eng 29(5-6):365-377 3517. Cug H, Demirtas H, Erden MA, Akgul Y, Turan ME, Zengin O (2019) Influence of nanoWC addition on wear performances of Cu-Ni matrix nanocomposites. In: Proc. 8th Int. advances in applied physics and materials science congress and exhibition (APMAS 2018), Sentido Lykia Resort, Oludeniz, Turkey, 24-30 Apr 2018. Acta Phys Polon 135(5):892-894 3518. Vorotilo S, Loginov P, Mishnaevsky L, Sidorenko D, Levashov E (2019) Nanoengineering of metallic alloys for machining tools: multi-scale computational and in situ TEM investigation of mechanisms. Mater Sci Eng A 739:480-490 3519. Lim HK, Park ES, Park JS, Kim WT, Kim DH (2005) Fabrication and mechanical properties of WC particulate reinforced Cu47Ti33Zr11Ni6Sn2Si1 bulk metallic glass matrix composites. J Mater Sci 40:6127-6130 3520. Myung W-H, Yang S (1988) Crystallization of amorphous metal matrix composites. Mater Sci Eng 97:259-264 3521. Yamamoto A, Kusano T, Seki T, Okutomi T (1998) Vaporization of carbon from Cu-WC contact during arc discharge in vacuum. In: Wetzer JM (ed) Proc. 18th Int. symp. on discharges and electrical insulation in vacuum (ISDEIV 98), Eindhoven, The Netherlands, 17-21 Aug 1998, Vol. 1, pp. 349-352. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 3522. Mahamat ATZ, Abdul-Rani AM, Husain P (2011) Synthesizing and characterization of Cu-WC-Si composite prepared by using planetary ball milling. In: El-Harbawi MAAA (ed) Energy and sustainability: exploring the innovative minds. Proc. Nat. postgraduate conf., Seri Iskandar, Perak, Malaysia, 19-20 Sep 2011, ME029 (4 pp.). The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 3523. Abdul-Rani AM, Mahamat ATZ (2013) Analysis on Cu-WC-Si as electrode for advancement in electro-discharge machining. In: Tieu AK, Zhu H, Zhu Q (eds) Proc. 15th Int. conf. on advances in materials and processing technologies (AMPT 2012), Wollongong, Australia, 23-26 Sep 2012. Int J Mater Product Technol 47(1-4):241-257 3524. Wang CC, Lin CK, Lin YL, Chen JS, Jen RR, Lee PY (2005) Cu-Zr-Ti bulk metallic glass composites produced by mechanical alloying and vacuum hot-pressing. In: Zhong Z, Saka H, Kim TH, Holm EA, Han Y, Xie X (eds) Proc. 5th Pacific Rim Int. conf. on advanced

References

767

materials and processing (PRICM 5), Beijing, China, 2-5 Nov 2004. Mater Sci Forum 475479(5):3443-3450 3525. Wang CC, Chen JS, Jen RR, Lee PY (2005) In situ formed Cu-based nanocomposite by hot-pressing of mechanically alloyed Cu-Zr-Ti composites containing WC particles as a second phase. In: Inoue A (ed) Proc. 11th Int. symp. on metastable, mechanically alloyed and nanocrystalline materials (ISMANAM 2004), Sendai, Japan, 22-26 Aug 2004. J Metastable Nanocryst Mater 24-25:395-398 3526. Bodrova LE, Goida EYu, Pastukhov EA, Marshuk LA, Popova EA (2013) Interaction of tungsten with tungsten carbide in a copper melt. Russ Metall (7):491-496 3527. Zhang C, Luo G, Zhang J, Dai Y, Shen Q, Zhang L (2017) Synthesis and thermal conductivity improvement of W-Cu composites modified with WC interfacial layer. Mater Design 127:233-242 3528. Naghikhani M, Ardestani M, Moazami-Goudarzi M (2019) Microstructure, mechanical properties and wear performance of WC/brass composites produced by pressureless and spark-plasma sintering processes. Met Mater Int (10 pp); doi:10.1007/s12540-019-00564-0 3529. Grzesik Z, Dickerson MB, Sandhage KH (2003) Incongruent reduction of tungsten carbide by a zirconium-copper melt. J Mater Res 18(9):2135-2140 3530. Zhao Y, Wang Y, Zhou Y, Shen P (2011) Reactive wetting and infiltration of polycrystalline WC by molten Zr2Cu alloy. Scripta Mater 64:229-232 3531. Wang D, Wang Y (2020) Mechanism of incongruent reactions between Zr-Cu melts and solid tungsten carbide. Metall Mater Trans B 51:1603-1616 3532. Li X-J, Wang Z-L, Xie X-H, Zhao Z, Shi X-Z (2006) Experimental study on explosive compaction of WC/Al2O3/Cu powders. Explos Shock Waves 26(4):356-360 (in Chinese) 3533. Feng J, Tian B-H, Liu Y (2012) Hot deformation behaviour of Al2O3/Cu – 10 vol.% WC composite. In: Zhang H, Han Y, Chen F, Wen J (eds) Proc. Int. conf. on applied mechanics, materials and manufacturing (ICAMMM 2011), Shenzhen, China, 18-20 Nov 2011. Appl Mech Mater 117-119:921-924 3534. Feng J, Tian B-H, Sun Y-W, Liu Y, Zhang Y, Ren F-Z (2012) Hot deformation behaviour and processing maps of Al2O3/Cu-WC composites. Chin J Nonferr Met 22(12):3462-3467 (in Chinese) 3535. Feng J, Tian B-H, Sun Y-W, Liu Y, Zhang Y, Jia S-G (2012) Hot deformation behaviour and critical conditions of dynamic recrystallization of Al2O3/Cu-WC composites. Trans Mater Heat Treat 33(7):19-23 (in Chinese) 3536. Feng J, Tian B-H, Zhang Y, Liu Y, Li Q-A (2014) Effect of WC content on hot deformation behaviour of Al2O3/Cu-WC composites. Trans Mater Heat Treat 35(5):9-13 (in Chinese) 3537. Xiao H, Xiao Bing, Wu H, Xiao Bo, Yan X, Liu S (2019) Microstructure and mechanical properties of vacuum brazed CBN abrasive segments with tungsten carbide reinforced CuSn-Ti alloys. Ceram Int 45:12469-12475 3538. Yang X, Liang S, Wang X, Xiao P, Fan Z (2010) Effect of WC and CeO2 on microstructure and properties of W-Cu electrical contact materials. Int J Refract Met Hard Mater 28:305-311 3539. Zhang Y, Epshteyn Y, Chromik RR (2018) Dry sliding wear behaviour of cold-sprayed Cu-MoS2 and Cu-MoS2-WC composite coatings: the influence of WC. Tribol Int 123:296306 3540. Ernur D, Terzieva V, Schuhmacher J, Maex K (2004) Inhibition of galvanic corrosion of WNC barrier metal for reliable Cu CMP. In: Plawsky J, Martin LL (eds) Proc. 2004 AIChE annual meeting, Austin, Texas, 7-12 Nov 2004, pp. 6399-6409. The American Institute of Chemical Engineers, New York 3541. Ernur D, Terzieva V, Schuhmacher J, Sutcliffe V, Whelan CM, Maex K (2004) Corrosion and inhibition of WNxCy barrier during chemical mechanical planarization. J Electrochem Soc 152(12):B512-B518

768

2 Tungsten Carbides

3542. Singh MK, Gautam RK (2017) Synthesis of copper metal matrix hybrid composites using stir casting technique and its mechanical, optical and electrical behaviours. Trans Indian Inst Met 70(9):2415-2428 3543. Verkhoturov AD, Goryachev YuM, Ippolitov EG, Podchernyaeva IA, Rakov VI (1985) The electron nature of interaction of materials in electro-spark alloying of iron with carbides. Powder Metall Met Ceram 24(12):927-930 3544. Miyazaki K, Ito S, Koura N, Yoneba N, Asaka K (1990) Preparation of tungsten carbide – iron composite using HIP. J Jpn Soc Powder Powder Metall 37(2):219-224 (in Japanese) 3545. Zhou E, Zeng X, Wu X, Zhu B (1997) Study on laser cladding of Fe-WC ceramic-metal composite coating. Laser Technol 21(1):34-37 (in Chinese) 3546. Miyakoshi Y, Takazawa K, Tagashira K, Kamota S, Takahashi H (1998) WC-Fe alloys as stress relief layer materials for sinter-bonding between cemented carbides and steels. J Jpn Soc Powder Powder Metall 45(12):1111-1115 (in Japanese) 3547. Xu DQ, Luo J, Huang N (1999) Structures and properties of iron matrix composites with tungsten carbide particle by EPC-V process. J Iron Steel Res Int 6(2):29-32 3548. Krishna BV, Misra VN, Mukherjee PS, Sharma P (2002) Microstructure and properties of flame sprayed tungsten carbide coatings. Int J Refract Met Hard Mater 20:355-374 3549. Miyakoshi Y, Takazawa K, Tagashira K, Kamota S, Takahashi H (2002) Effect of carbon addition on mechanical properties of WC – 37 mass% Fe alloy. J Jpn Soc Powder Powder Metall 49(3):183-188 (in Japanese) 3550. Vorobev YuP (2004) Karbidy v bystrorezhushchikh stalyakh (Carbides in high-speed steels). Fiz Khim Obrabotki Mater (4):69-74 (in Russian) 3551. Kheirandish S (2001) Effect of Ti and Nb on the formation of carbides and the mechanical properties in as-cast AISI-M7 high-speed steel. ISIJ Int 41(12):1502-1509 3552. Vinokur BB (1979) Effect of tungsten on carbide formation in steel 30KhG. Met Sci Heat Treat 21(6):416-420 3553. Kalner VD, Nabutovskii LSh, Bogoslovskii ID (1976) Investigation of carbide phases in high-speed steels R18 and R6M5. Met Sci Heat Treat 18(11):944-947 3554. Tarasenko LV (2000) Rules of formation of the chemical composition of M23C6 multicomponent carbide in high-temperature steels. Met Sci Heat Treat 42(1):7-12 3555. Bunin KP, Movchan VI, Voronkina LA (1978) The carbide transformation in the Fe-V-WMo-Cr-C system. Met Sci Heat Treat 20(9):775-777 3556. Mercado WB, Cuevas J, Castro IY, Fajardo M, Pérez-Alcázar GA, Sánchez-Sthepa H (2007) Synthesis and characterization of Fe6W6C by mechanical alloying. Hyperfine Interact 175:49-54 3557. Zeng S, Li W (2007) WC particle reinforced steel/iron matrix wear-resistant composites. Spec Cast Nonferr Alloys 27(6):441-444 (in Chinese) 3558. Antoni-Zdziobek A, Shen JY, Durand-Charre M (2008) About one stable and three metastable eutectic microconstituents in the Fe-W-C system. Int J Refract Met Hard Mater 26:372-382 3559. Lugscheider E, Reimann H, Pankert R (1982) η-Carbide in den Systemen Co-W-C und FeW-C (η-carbides in the Co-W-C and Fe-W-C systems). Z Metallkd 73(5):321-324 (in German) 3560. Shtansky DV, Inden G (1997) Phase transformation in Fe-Mo-C and Fe-W-C steels. I. The structural evolution during tempering at 700 °C. Acta Mater 45:2861-2878 3561. Shtansky DV, Inden G (1997) Phase transformation in Fe-Mo-C and Fe-W-C steels. II. Eutectoid reaction of M23C6 carbide decomposition during austenitization. Acta Mater 45:2879-2895 3562. Åkesson L (1981) An experimental investigation of some phase equilibria in the Fe-W-C system. Internal Technical Report LR-2670, pp. 1-40. Sandvik Coromant Research Centre, Stockholm, Sweden

References

769

3563. Chen N, He P, Li D (2010) First principles calculation of adhesion at Fe/WC interface. In: Xie Y, Li M (eds) Proc. Int. conf. on materials and manufacturing technology (ICMMT 2010), Chongqing, China, 17-19 Sep 2010. Adv Mater Res 129-131:808-813 3564. Niu L-B, Xu Y, Wang X-G (2010) Fabrication of WC/Fe composite coating by centrifugal casting plus in situ synthesis techniques. Surf Coat Technol 205:551-556 3565. Vida-Simiti I, Jumate N, Sechel N (2010) Study on the structure of hard composite layers from iron and tungsten carbide powders. Optoelectron Adv Mater Rap Commun 4(1):77-82 3566. Zhou S, Dai X (2010) Microstructure evolution of Fe-based WC composite coating prepared by laser induction hybrid rapid cladding. Appl Surf Sci 256:7395-7399 3567. Zhou S, Zeng X (2010) Growth characteristics and mechanism of carbides precipitated in WC-Fe composite coatings by laser induction hybrid rapid cladding. J Alloys Compd 505:685-691 3568. Li L, Gui C (2011) Effect of dissolving of WC/W2C on the interface microstructure of iron matrix hardfacing alloys. In: Liu S, Zuo M (eds) Proc. 1st Int. congress on advanced materials (AM2011), Jinan, China 13-16 May 2011. Adv Mater Res 306-307:819-822 3569. Li Y, Gao Y, Xiao B, Min T, Ma S, Yi D (2011) Theoretical calculations on the adhesion, stability, electronic structure and bonding of Fe/WC interface. Appl Surf Sci 257:5671-5678 3570. Razavi M, Rahimipour MR, Yazdani-Rad R (2011) Synthesis of Fe-WC nanocomposite from industrial ferrotungsten via mechanical alloying method. Adv Appl Ceram 110(6):367374 3571. Zhang C, Qi L, Hu F, Zhang S, Wang M (2011) Study of WC particles dissolved by plasma surfacing. In: Wang J, Qi J (eds) Proc. Int. conf. on materials and manufacturing (ICMM 2011), Jinzhou, Liaoning, China, 7-9 Sep 2011. Adv Mater Res 299-300:193-196 3572. Cao G, Guo E, Feng Y, Wang L (2012) Abrasion behaviour of WC reinforced cast iron surface composite fabricated by cast-infiltration method. In: Chen W, Li Q, Chen Y, Dai P, Jiang Z (eds) Proc. 3rd Int. conf. on manufacturing science and engineering (ICMSE 2012), Xiamen, China, 27-29 Mar 2012. Adv Mater Res 476-478:555-559 3573. Huang R, Li Z, Shan Q, Jiang Y, Zhou R, Sui Y (2012) Decomposition process of casting tungsten carbide particle in steel/iron substrate. Spec Cast Nonferr Alloys 32(2):164-167 (in Chinese) 3574. Pavlina EJ, Speer JG, Van Tyne CJ (2012) Equilibrium solubility products of molybdenum carbide and tungsten carbide in iron. Scripta Mater 66:243-246 3575. Boiko VF, Vlasova NM, Zaitsev AV (2013) Evaluation of the surface tension of tungsten carbides WC and WC-W2C by the results of the laser diffraction analysis of their milling with iron powder. Russ J Non-Ferr Met 54(6):493-496 3576. Zhou S, Dai X, Zhang T (2013) Effect of binder metals on structure and properties of WC ceramic-metal composite coatings by laser-induction hybrid rapid cladding. J Compos Mater 47(12):1549-1559 3577. Niu L-B, Wang X-G, Fan Z-M (2014) Effect of process parameters on in situ synthesized of WCp/Fe composites. Trans Mater Heat Treat 35(3):24-29 (in Chinese) 3578. Álvarez EA, García JL, Benavídez ER, González-Oliver CJR (2015) Sol-gel derived Ferich matrix composites having precipitated WC. Adv Eng Mater 17(2):148-156 3579. Álvarez EA, González-Oliver CJR, García JL (2015) Densification and phase formation kinetics in composite materials of WC embedded in an Fe-matrix. In: Arce R (ed) Proc. Int. congress of science and technology of metallurgy and materials (SAM-CONAMET 2014), Santa Fe, Argentina, 21-24 Oct 2014. Proc Mater Sci 9:13-20 3580. Chumanov IV, Anikeev AN (2015) Interaction between tungsten monocarbide and an iron-based metallic melt. Russ Metall (12):1002-1004 3581. Feng Z, Li Z, Shan Q, Huang H, Jiang Y, Zhou R (2015) Thermal fatigue performance of WC particles reinforced Fe matrix surface composites. Spec Cast Nonferr Alloys 35(8):859862 (in Chinese)

770

2 Tungsten Carbides

3582. Razumovskiy VI, Ghosh G (2015) A first principles study of cementite (Fe3C) and its alloyed counterparts: structural properties, stability and electronic structure. Comput Mater Sci 110:169-181 3583. Schubert WD, Fugger M, Wittmann B, Useldinger R (2015) Aspects of sintering of cemented carbides with Fe-based binders. Int J Refract Met Hard Mater 49:110-123 3584. Feng Z-Y, Li Z-L, Shan Q, Jiang Y-H, Zhou R (2016) Effect of particle size on interface of tungsten carbide particle reinforced iron matrix composites. J Mater Eng 44(1):83-88 (in Chinese) 3585. Li Z-L, Wei H, Shan Q, Jiang Y-H, Zhou R (2016) Formation mechanism and stability of the phase in the interface of tungsten carbide particles reinforced iron matrix composites: first principles calculations and experiments. J Mater Res 31(16):2376-2383 3586. Wang G, Chang X, Tao F, Ding P, Huang Z (2016) Enhancement in the corrosion resistance of WC coatings by adding a Fe-based alloy in simulated sea water. Surf Coat Technol 305:62-66 3587. Wang J, Li L, Tao W (2016) Crack initiation and propagation behaviour of WC particles reinforced Fe-based metal matrix composite produced by laser melting deposition. Optics Laser Technol 82:170-182 3588. Wei H, Li Z-L, Shan Q, Jiang Y-H, Zhou R (2016) Effects of WC volume fraction on micro-structures and compression performances of WCp/Fe composites. Acta Mater Compos Sin 33(11):2560-2568 (in Chinese) 3589. Zhong L-S, Zhang X, Chen S, Xu Y-H, Wu H, Wang J (2016) Fe-W-C thermodynamics and in in situ preparation of tungsten carbide – reinforced iron-based surface composites by solid-phase diffusion. Int J Refract Met Hard Mater 57:42-49 3590. Zhong L-S, Zhang X, Wang X, Xu Y-H, Wu H, Fu Y-H (2016) Growth kinetics of WC-Fe layer formed at the surface iron during solid-phase diffusion. Ceram Int 42:16941-16947 3591. Cai X-L, Xu Y-H, Zhong L-S, Liu M-X (2017) Fracture toughness of WC-Fe cermet in W-WC-Fe composite by nanoindentation. J Alloys Compd 728:788-796 3592. Ojo-Kupoluyi OJ, Tahir SM, Baharudin BTHT, Azmah-Hanim MA, Anuar MS (2017) Mechanical properties of WC-based hardmetals bonded with iron alloys – a review. Mater Sci Technol 33(5):507-517 3593. Wang W, Zeng X, Li Y, Wang D, Liu Y, Yamaguchi T, Nishio K, Cao J (2017) Fabrication, microstructure and wear performance of WC-Fe composite / metal coating fabricated by resistance seam welding. Mater Charact 134:182-193 3594. Yuan Y, Li Z (2017) Microstructure and tribology behaviours of in situ WC/Fe carbide coating fabricated by plasma transferred arc metallurgic reaction. Appl Surf Sci 423:13-24 3595. Zhang X, Zhong L-S, Wang X, Xu Y-H, Wu H, Fu Y-H (2017) Fracture toughness of tungsten carbide reinforced Fe-matrix surface composites. In: Han Y, Fan R, Xiong B, Liu X, Nie Z, Zhu M, Zhao J, Zhang J, Liu X (eds) Proc. 17th IUMRS Int. conf. in Asia (IUMRSICA 2016), Qingdao, China, 20-24 Oct 2016. Mater Sci Forum 898:1453-1458 3596. Zhang Z, Chen Y, Zhang Y, Gao K, Zuo L, Qi Y (2017) Tribology characteristics of WC/Fe composites by spark-plasma sintering. Acta Mater Compos Sin 34(10):2288-2295 (in Chinese) 3597. Zou L, Liu X, Wang L, Xie H, Cai Y (2017) Effect of cast tungsten carbide powder on wear resistance of laser cladding ceramic particle reinforced iron matrix composite. Rare Met Mater Eng 46(4):1126-1131 (in Chinese) 3598. Chen FR, Li ZL, Shan Q, Jiang YH, Zhang YF, Zhang F (2018) Effects of different matrix on interface and compression fracture behaviour of WC particles reinforced iron matrix composites. In: Han YF (ed) Proc. Chinese Materials Research Society conf. (CMC 2017), Yinchuan City, Ningxia, China, 6-12 July 2018. Mater Sci Forum 913:480-489 3599. Feldshtein EE, Dyachkova LN, Adamczuk K, Legutko S, Królczyk GM (2018) Synergy effect of ultra-fine tungsten and silicon carbides and graphite microadditives on the Fe-based MMCs properties using the simplex lattice design. J Alloys Compd 757:31-38

References

771

3600. Grairia A, Beliardouh NE, Zahzouh M, Nouveau C, Besnard A (2018) Dry sliding wear investigation on tungsten carbide particles reinforced iron matrix composites. Mater Res Express 5:116528 (12 pp.) 3601. Gu D, Ma J, Chen H, Lin K, Xi L (2018) Laser additive manufactured WC reinforced Febased composites with gradient reinforcement/matrix interface and enhanced performance. Compos Struct 192:387-396 3602. Li Z, Wang P, Shan Q, Jiang Y, Wei H, Tan J (2018) The particle shape of WC governing the fracture mechanism of particle reinforced iron matrix composites. Materials 11(6):984 (10 pp.); doi:10.3390/ma11060984 3603. Pittari JJ, III, Murdoch HA, Kilczewski SM, Hornbuckle BC, Swab JJ, Darling KA, Wright JC (2018) Sintering of tungsten carbide cermets with an iron-based ternary alloy binder: processing and thermodynamic considerations. Int J Refract Met Hard Mater 76:1-11 3604. Shi Z, Liu S, Zhou Y, Yang Q (2018) First principles calculation on the relationships of hWC/γ-Fe interface. J Phys Chem Solids 123:11-18 3605. Wang M-Q, Zhou Z-H, Wu L-T, Ding Y, Wang Z-H (2018) Characterization and in situ formation mechanism of tungsten carbide reinforced Fe-based alloy coating by plasma cladding. Int J Min Metall Mater 25(4):439-443 3606. Wang M-Q, Zhou Z-H, Wu L-T, Ding Y, Xu F-L, Wang Z-H (2018) Statistical optimization of reactive plasma cladding to synthesize a WC-reinforced Fe-based alloy coating. J Therm Spray Technol 27:769-777 3607. Zhang Z, Chen Y, Zuo L, Zhang Y, Qi Y, Gao K, Liu H, Wang X (2018) In situ synthesis WC reinforced iron surface composite produced by spark-plasma sintering and casting. Mater Lett 210:227-230 3608. Zhou S, Xu Y, Liao B, Sun Y, Dai X, Yang J, Li Z (2018) Effect of laser remelting on microstructure and properties of WC reinforced Fe-based amorphous composite coatings by laser cladding. Optics Laser Technol 103:8-16 3609. Cai X, Zhong L, Xu Y, Li X, Liu M (2019) Microstructure and fracture toughness of a WC-Fe cemented carbide layer produced by a diffusion-controlled reaction. Surf Coat Technol 357:784-793 3610. Fan L, Dong Y, Chen H, Dong L, Yin Y (2019) Wear properties of plasma transferred arc Fe-based coatings reinforced by spherical WC particles. J Wuhan Univ Technol Mater Sci Ed 34(2):433-439 3611. Ku N, Pittari, JJ, III, Kilczewski S, Kudzal A (2019) Additive manufacturing of cemented tungsten carbide with a cobalt-free alloy binder by selective laser melting for high-hardness applications. JOM (J Miner Met Mater Soc) 71(4):1535-1542 3612. Pittari JJ, III, Kilczewski SM, Swab JJ, Darling KA, Murdoch HA, Hornbuckle BC (2016) Investigation into sintering of “green” tungsten carbide bodies with iron-based binders. In: Blais C, Hamilton JR (eds) Advances in powder metallurgy and particulate materials – 2016. Proc. Int. conf. on powder metallurgy and particulate materials (POWDERMET 2016), Boston, Massachusetts, 5-8 June 2016, pp. 532-551. Metal Powder Industries Federation, Princeton, New Jersey 3613. Gnyusov SF, Ivanov YuF (1998) Modifikatsiya struktury i mekhanicheskikh svoistv tverdogo splava vysokomoshchnym elektronnym puchkom (Modification of structure and mechanical properties of hard alloy by high-power electron beam). Infrared Technol 20(6):95-99 (in Russian) 3614. Song Y-P, Mao X-M, Dong Q-M, Li B-Z (2004) WCp/Fe-C composites with centrifugal casting and their application. J Funct Mater 35(6):761-762, 768 (in Chinese) 3615. Buytoz S, Ulutan M, Yildirim MM (2005) Dry sliding wear behaviour of TIG welding clad WC composite coatings. Appl Surf Sci 252:1313-1323 3616. You X-Q, Ma J-G, Song X-F, Ren H, Huang M-P (2005) Dissolution behaviour of WC particle in WC – steel matrix composites by electroslag melting and casting method. Chin J Nonferr Met 15(9):1363-1368 (in Chinese)

772

2 Tungsten Carbides

3617. Li X, Fang L, Gao Y, Xing J (2006) Evolution of reinforcing phase and microstructure in WC particle reinforced steel matrix composites. J Xian Jiaotong Univ 40(5):549-552 (in Chinese) 3618. Li Z, Jiang Y, Ye X, Zhou R (2007) Dissolution of tungsten carbide particulates (WC) in the matrix of WC reinforced gray cast iron matrix composite. Acta Mater Compos Sin 24(2):13-17 (in Chinese) 3619. Lin Y-C, Chang K-Y (2010) Elucidating the microstructure and wear behaviour of tungsten carbide multi-pass cladding on AISI 1050 steel. J Mater Process Technol 210:219225 3620. Shan Q, Li Z, Jiang Y, Zhou R, Sui Y (2012) Decomposition of two phases WC and W2C in casting tungsten carbide particles in steel/iron substrate. In: Zhang Y, Zhou L, Mao E (eds) Proc. Int. conf. on mechanics and manufacturing systems (ICMMS 2011), Ningbo, China, 1314 Nov 2011. Appl Mech Mater 109:120-124 3621. Lin Y-C, Chen Y-C (2013) Reinforcements affect mechanical properties and wear behaviours of WC clad layer by gas tungsten arc welding. Mater Design 45:6-14 3622. Chumanov IV, Anikeev AN (2018) Impregnation of tungsten carbide substrates with low carbon steel. Steel Transl 48(5):296-300 3623. Kozák J, Krejčí L, Hlavatý I, Samardžić I, Čep R (2019) An analysis of structures occurring in weld deposit of steel S235JR+N with tungsten carbide particles and martensitic matrix. Metalurgija 58(3-4):235-238 3624. Mourlas A, Pavlidou E, Vourlias G, Rodríguez J, Psyllaki P (2019) Concentrated solar energy for in situ elaboration of wear-resistant composite layers. Part II. Tungsten carbide surface enrichment of common steels. Surf Coat Technol 375:739-751 3625. Umanskii YaS, Chebotarev NT (1951) Struktura i sostav ferrovolframovykh karbidov (The structure and composition of the ferric-tungsten carbides). Izv AN SSSR Fiz 15(1):2438 (in Russian) 3626. Zhang H, Li H, Yan L, Wang C, Ai F, Li Y, Li N, Jiang Z (2019) Effect of particle size on microstructure and element diffusion at the interface of tungsten carbide / high strength steel composites. Materials 12(24):4164 (15 pp.); doi:10.3390/ma12244164 3627. Ziejewska C, Marczyk J, Szewczyk-Nykiel A, Nykiel M, Hebda M (2019) Influence of size and volume share of WC particles on the properties of sintered metal matrix composites. Adv Powder Technol 30:835-842 3628. Matějíček J, Boldyryeva H, Brožek V, Sachr P, Chráska T (2015) W-steel and W-WCsteel composites and FGMs produced by hot-pressing. Fusion Eng Design 100:364-370 3629. Zhao Z, Liu F, Zhao M, Zhong L, Xu Y, Li J (2020) A new strategy to efficiently fabricate tungsten carbide coating on tungsten: two-step interstitial carburization. Surf Coat Technol 389:125579 (9 pp.) 3630. Yan X, Huang C, Chen C, Bolot R, Dembinski L, Huang R, Ma W, Liao H, Liu M (2018) Additive manufacturing of WC reinforced maraging steel 300 composites by cold spraying and selective laser melting. Surf Coat Technol 371:161-171 3631. Sakaguchi S, Imasato S, Ito H, Nakamura R (1989) Some properties of sintered WC-(FeCr-C) alloys. J Jpn Soc Powder Powder Metall 36(8):908-912 (in Japanese) 3632. Kyubarsepp YaP, Annuka KhI, Reshetnyak KhD, Maistrenko AL, Chepovetskii GI (1990) Cracking resistance and strength of carbide steels. Powder Metall Met Ceram 29(1):83-87 3633. Kulkov SN, Gnyusov SF (1992) Shock wave fracture of composites with a structurally unstable binder. Combust Explos Shock Waves 28(4):424-425 3634. Ivanov YuF, Paul AV, Gnyusov SF, Kulkov SN, Kozlov ÉV (1993) Structural phase analysis of sintered alloy WC – 30 % steel 110G13. Russ Phys J 36(5):497-500 3635. Gnyusov SF, Kulkov SN, Paul AV, Ivanov YuF, Kozlov ÉV (1994) Study of the character of deformation of hard alloy WC – steel 110G13. Russ Phys J 37(2):130-136 3636. Paul AV, Gnyusov SF, Ivanov YuF, Kulkov SN, Kozlov ÉV (1994) Structural phase changes in hard alloy WC – steel 110G13 after dynamic loading. Russ Phys J 37(8):757-761

References

773

3637. Trueman AR, Schweinsberg DP, Hope GA (1997) The matrix corrosion of tungsten carbide / carbon steel metal matrix composites. Corros Sci 39(7):1153-1164 3638. Trueman AR, Schweinsberg DP, Hope GA (1998) The effect of chromium additions on the corrosion behaviour of tungsten carbide / carbon steel metal matrix composites. Corros Sci 40(10):1685-1696 3639. Tarraste M, Kübarsepp J, Juhani K, Mere A, Kolnes M, Viljus M, Maaten B (2018) Ferritic chromium steel as binder metal for WC cemented carbides. Int J Refract Met Hard Mater 73:183-191 3640. Yang R, Chen K, Wang K, Lu X (2005) Fracture behaviours and characteristics of WC / NiCrMo steel matrix composites. Acta Mater Compos Sin 22(3):130-134 (in Chinese) 3641. Zhang N, Qiang Y, Zhang C, Ding G (2015) Microstructure and property of WC / steel matrix composites. Emerg Mater Res 4(2):149-156 3642. Bondarenko VP, Ganopolskii AYu (1986) Development of tungsten carbide base corrosion-resistant composite materials with a binder of PKh18N15 stainless steel. Powder Metall Met Ceram 25(5):415-419 3643. Kawakami Y, Tanaka T, Enjoji T, Takashima K, Otsu M (2008) Evaluation of micro-area mechanical properties of SUS/WC surface hardened composite material prepared by pulsed current sintering process. J Jpn Soc Powder Powder Metall 55(4):239-243 (in Japanese) 3644. Laptev AV, Tolochin AI, Fomichev AS, Kovylyaev VV (2011) Osobennosti polucheniya kompozita na osnove karbida volframa i nerzhaveyushchei stali Kh17N2 (Features of fabrication of composite based on tungsten carbide and Kh17N2 stainless steel). Metallofiz Nov Tekhnol 33(3):361-373 (in Russian) 3645. Fernandes CM, Willinger M-G, Vieira MT, Senos AMR (2012) Interface exploring of tungsten carbide – stainless steel composites through HRTEM. Microsc Microanal 18(S5):109-110 3646. Marques BJ, Fernandes CM, Senos AMR (2013) Sintering, microstructure and properties of WC – AISI 304 powder composites. J Alloys Compd 562:164-170 3647. Fernandes CM, Vilhena LM, Pinho CMS, Oliveira FJ, Soares E, Sacramento J, Senos AMR (2014) Mechanical characterization of WC – 10 wt.% AISI 304 cemented carbides. Mater Sci Eng A 618:629-636 3648. Zuhailawati H, Salleh EM, Trung TB, Ahmad ZA (2014) Phase studies in WC – stainless steel AISI 347 hardmetal system with graphite addition. In: Cheong KY, Lockman Z, Zuhailawati H, Kamarulzaman N, Jaafar M, Razak KA (eds) Proc. 3rd Int. conf. on the advancement of materials and nanotechnology (ICAMN 3 2013), Penang, Malaysia, 19-21 Nov 2013. Adv Mater Res 1024:239-242 3649. Trung TB, Zuhailawati H, Ahmad ZA, Ishihara KN (2014) Sintering characteristics and properties of WC – 10 AISI 304 (stainless steel) hardmetals with added graphite. Mater Sci Eng A 605:210-214 3650. Lin C-M (2015) Functional composite metal for WC-dispersed 304L stainless steel matrix composite with alloying by direct laser: microstructure, hardness and fracture toughness. Vacuum 121:96-104 3651. Fernandes CM, Oliveira FJ, Senos AMR (2017) Reactive sintering and microstructure development of tungsten carbide – AISI 304 stainless steel cemented carbides. Mater Chem Phys 193:348-355 3652. Anijdan SHM, Sabzi M, Asadian M, Jafarian HR (2019) Effect of sub-layer temperature during HFCVD process on morphology and corrosion behaviour of tungsten carbide coating. Int J Appl Ceram Technol 16(1):243-253 3653. Fernandes CM, Rocha A, Cardoso JP, Bastos AC, Soares E, Sacramento J, Ferreira MGS, Senos AMR (2018) WC – stainless steel hardmetals. Int J Refract Met Hard Mater 72:21-26 3654. De Oro Calderon R, Agna A, Gomes UU, Schubert W-D (2019) Phase formation in cemented carbides prepared from WC and stainless steel powder – an experimental study combined with thermodynamic calculations. Int J Refract Met Hard Mater 80:225-237

774

2 Tungsten Carbides

3655. Wang C, Zhang H, Li Y, Jia H, Wang J, Meng L, Jiang Z (2019) Effect of sintering temperature on the interface of tungsten carbide / high strength steel composites. J Funct Mater 50(4):4086-4092 (in Chinese) 3656. Geller YuA, Kremnev LS, Olesova TsL (1961) High-speed steels with low carbide inhomogeneity. Met Sci Heat Treat 3(5):257-263 3657. Gnyusov SF, Kulkov SN, Paul AV, Ivanov YuF, Kozlov ÉV (1995) Fraktograficheskie i mikrostrukturnye aspekty deformirovaniya i razrusheniya tverdogo splava tipa karbid volframa – vysokomargantsevaya stal (Fractographic and microstructural aspects of deformation and fracture of a hard alloy of tungsten carbide – high manganese steel type). Izv AN SSSR Met (1):115-120 (in Russian) 3658. Molchunova LM, Gnyusov SF, Kulkov SN (2000) Study of the microstructure and phase composition of a WC alloy with a Hadfield steel binder. Russ Phys J 43(12):994-998 3659. Sevostyanova IN, Kulkov SN (2003) Fractal characteristics of the surface of tungsten carbide – manganese steel composite after plastic deformation. Tech Phys 48(2):215-218 3660. Song H-J, Zhang G-S (2005) Impact abrasive wear resistance of WC reinforced highmanganese steel matrix composites. Foundry Technol 26(6):468-469, 477 (in Chinese) 3661. Zhang G-S, Gao Y, Xing J (2005) Interfacial characteristics of tungsten carbide particle reinforced Hadfield steel matrix composite. Rare Met Mater Eng 34(S2):170 (in Chinese) 3662. Zhang G-S, Liu G, Xing J, Gao Y, Chen J (2005) Fabrication and impact wear resistance of WCp/Mn13 surface composites. J Xian Jiaotong Univ 39(7):757-761 (in Chinese) 3663. Sevostyanova IN, Savchenko NL, Kulkov SN (2010) Structural and phase binder state and behaviour during friction of WC-(Fe-Mn-C) composites. J Friction Wear 31(4):281-287 3664. Zhang G-S, Gao Y, Xing J, Wei S, Li J, Xu L (2010) Interfacial characteristics of WC particles reinforced Hadfield steel matrix composites. In: Nie J-F, Morton A (eds) Proc. 7th Pacific Rim Int. conf. on advanced materials and processing (PRICM-7), Cairns, Queensland, Australia, 2-6 Aug 2010. Mater Sci Forum 654-655:2708-2711 3665. Pascal C, Thomazic A, Antoni-Zdziobek A, Chaix J-M (2012) Investigation on pressureless co-sintering behaviour of Hadfield steel / cemented carbide biomaterials. Powder Metall 55(2):110-117 3666. Sevostyanova I, Sablina T, Fedorov D, Golub A, Kulkov S (2020) Issledovanie fazovogo sostava i ego vliyanie na mekhanicheskie svoistva karbidostalei WC-(Fe-Mn-C) (A study of the phase composition and its effect on the mechanical properties of WC-(Fe-Mn-C) carbide steels). Obrabotka Met Tekhnol Oborudov Instrum 22(2):76-88 (in Russian) 3667. Tillmann W, Vogli E, Baumann I, Krebs B, Nebel J (2010) Cermet-Schichten für den Verschleißschutz von Umformwerkzeugen (Wear-protective cermet coatings for forming tools). Materialwiss Werkstofftech 41(7):597-607 (in German) 3668. Tillmann W, Nebel J (2011) Analysis of the mechanical properties of an arc sprayed WCFeCSiMn coating: compression, bending and tension behaviour. J Therm Spray Technol 20(1-2):317-327 3669. Tillmann W, Klusemann B, Nebel J, Svendsen B (2011) Analysis of the mechanical properties of an arc-sprayed WC-FeCSiMn coating: nanoindentation and simulation. J Therm Spray Technol 20(1-2):328-335 3670. Wang X, Hu H (1998) Interface of WCp / Fe-Ni steel matrix composite. J Iron Steel Res Int 10(4):46-49 (in Chinese) 3671. Wang X, Hu H, Shi J, Sun R (1998) Behaviour of thermal fatigue resistance of WCp / FeNi steel matrix composites. J Iron Steel Res Int 10(5):44-48 (in Chinese) 3672. Wang W, Wang Z, Li Y, Wang D, Li M, Chen Q (2019) Wear behaviour of Fe-WC / metal double layer coatings fabricated by resistance seam weld method. Acta Metall Sin 55(4):537546 (in Chinese) 3673. Liu J-Y, Liu J, Gao X, Shi M (2011) Study on formation mechanism of WC in carburized layer of Fe – 1.57 W binary alloy. In: Jiang Z, Liu X, Bu J (eds) Proc. Int. conf. on advances in materials and manufacturing processes (ICAMMP 2010), Shenzhen, China, 6-8 Nov 2010. Adv Mater Res 154-155:11-18

References

775

3674. Zhan MJ, Du XD, Wang FC, Lang JW, Shi WZ (2015) Effect of rare earth on microstructure and carbides in WC-Fe composite coating. Tribol Mater Surf Interfaces 9(3):137-143 3675. Hanyaloğlu SC, Bolton JD (1999) Volfram karbür – demir/mangan sert metal alaşimlarinin toz metalurjisi metoduyla üretimi (Production of tungsten carbide – iron/manganese hard materials using powder metallurgy methods). In: Saritaş S (ed) Proc. 2nd Nat. powder metallurgy conference, Ankara, Turkey, 15-17 Sep 1999, pp. 637-643. Turkish Powder Metallurgy Association, Middle East Technical University, Ankara (in Turkish) 3676. Hanyaloğlu SC, Aksakal B, Bolton JD (2001) Production and indentation analysis of WC/Fe-Mn as an alternative to cobalt-bonded hardmetals. Mater Charact 47:315-322 3677. Hanyaloğlu SC, Aksakal B, Sen S (2003) An indentation and stress analysis of WC/Fe-Mn hardmetals. Indian J Eng Mater Sci 10:229-235 3678. Siemiaszko D, Rakowski M, Rosiński M, Michalski A (2010) WC-FeMn composites produced by pulse-plasma sintering method. In: Proc. World powder metallurgy congress and exhibition (World PM 2010), Florence, Italy, 10-14 Oct 2010, Vol. 2 (7 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 3679. Zhao Z, Liu J, Tang H, Ma X, Zhao W (2015) Effect of Mo addition on the microstructure and properties of WC-Ni-Fe hard alloys. J Alloys Compd 646:155-160 3680. Stadelmaier HH, Suchjakul C (1985) Overview of the quaternary system iron-nickeltungsten-carbon. Z Metallkd 76(3):157-161 3681. Guillermet AF (1987) Use of phase diagram calculations in selecting the composition of Fe-Ni bonded WC tools. Int J Refract Met Hard Mater 6(1):24-27 3682. Prakash LJ (1980) Weiterentwicklung von Wolframcarbid Hartmetallen unter Verwendung von Eisen-Basis-Bindelegierungen (Development of tungsten carbide hardmetals using iron-based binder alloys). Technical Report KfK-2984, pp. 1-221. Institut für Material- und Festkörperforschung, Kernforschungszentrum, Karlsruhe (in German) 3683. Emeric E (1994) Carbures cementes a liant Ni-Fe: etude et caracteristiques (Ni-Fe bonded cemented carbides: study and characteristics). Technical Report LMR-15461, pp. 1-79. CERMeP, Grenoble (in French) 3684. Moskowitz D, Ford MJ, Humenik M (1970) High-strength tungsten carbides. Int J Powder Metall 6(4):55-64 3685. Chaporova IN, Kudryavtseva VI, Sapronova ZN (1978) Structure and properties of a hard alloy based on tungsten carbide with Fe-Ni binder. Met Sci Heat Treat 20(5-6):402-404 3686. Chaporova IN, Kudryavtseva VI, Sapronova ZN, Sychkova LV (1981) An investigation of the WC-Fe-Ni system. Russ Metall (4):211-215 3687. Yan H, Zhang L, Wu C, Wu Q, Cui P (2001) Ultra-fine hard alloy powders of WC-Fe-Ni prepared by direct carbonization process. Powder Metall Technol 19(3):144-147 (in Chinese) 3688. Wang Z, Yang A, He D, Jiang J (2008) The transformation of WC in Ni-based alloy coating by vacuum melting. Rare Met Mater Eng 37(10):1869-1871 (in Chinese) 3689. Yönetken A, Erol A (2010) The effect of microwave sintering on the properties of electroless Ni plated WC-Fe-Ni composites. Sci Eng Compos Mater 17(3):191-198 3690. Guillermet AF (1986) Experimental and theoretical study of the Fe-Ni-W-C phase diagram at 1273 K. High Temp Sci 22(3):161-177 3691. Chaporova IN, Repina ÉI, Sapronova ZN, Kudryavtseva VI (1978) Structure and properties of sintered hard alloys. Met Sci Heat Treat 26(2):161-165 3692. Xu PQ, Ren JW, Zhang PL, Gong HY, Yang SL (2013) Analysis of formation and interfacial WC dissolution behaviour of WC-Co / invar laser-TIG welded joints. J Mater Eng Perform 22:613-623 3693. Gao Y, Luo B-H, Bai Z-H, Zhu B, Ouyang S-X (2016) Effect of deep cryogenic treatment on the microstructure and properties of WC-Fe-Ni cemented carbides. Int J Refract Met Hard Mater 58:42-50

776

2 Tungsten Carbides

3694. Zhu B, Bai Z-H, Gao Y, Luo B-H (2016) Effect of WC particle size on microstructure and properties of WC – 15 Fe – 5 Ni cemented carbides. Chin J Nonferr Met 26(5):1065-1074 (in Chinese) 3695. Yuan Y, Li Z (2017) A novel approach of in situ synthesis of WC particulate reinforced Fe – 30 Ni ceramic metal coating. Surf Coat Technol 328:256-265 3696. Yuan Y, Li Z (2018) Growth mechanism of in situ WC grain in Fe-Ni-W-C alloys system. J Alloys Compd 738:379-393 3697. Prywer J (2018) Comment on “Growth mechanism of in situ WC grain in Fe-Ni-W-C alloys system”. J Alloys Compd 751:335-336 3698. Walbrühl M, Linder D, Ågren J, Borgenstam A (2018) Alternative Ni-based cemented carbide binder – hardness characterization by nanoindentation and focused ion beam. Int J Refract Met Hard Mater 73:204-209 3699. Cramer CL, Preston AD, Elliot AM, Lowden RA (2019) Highly dense inexpensive composites via melt infiltration of Ni into WC/Fe preforms. Int J Refract Met Hard Mater 82:255-258 3700. Hou Z, Linder D, Hedström P, Borgenstam A, Holmström E, Ström V (2019) Effect of carbon content on the Curie temperature of WC-NiFe cemented carbides. Int J Refract Met Hard Mater 78:27-31 3701. Moreno JRS, Siqueira JF, Olivio EFT, Ferracin EM (2019) Comparative analyzes between thermal spray coating 40 Fe 30 Ni 30 WC without and with refusion and coating performed by the coated electrode process SMAW. Mater Res Express 6(6):066560 (10 pp.) 3702. Zhou P, Du Y, Lengauer W (2019) Morphology of η-phase in cemented carbides with Febased binders influenced by carbon content and nitrogen atmosphere. Ceram Int 45:2077420779 3703. Shichalin OO, Buravlev IYu, Portnyagin AS, Dvornik MI, Mikhailenko EA, Golub AV, Zakharenko AM, Sukhorada AE, Talskikh KYu, Buravleva AA, Fedorets AN, Glavinskaya VO, Nomerovskiy AD, Papynov EK (2020) SPS hard metal alloy WC – 8 Ni – 8 Fe fabrication based on mechano-chemical synthetic tungsten carbide powder. J Alloys Compd 816:152547 (8 pp.) 3704. Viswanathan A, Sastikumar D, Kumar H, Nath AK (2009) Formation of WC – iron silicide (Fe5Si3) composite clad layer on AISI 316L stainless steel by high power (CO2) laser. Surf Coat Technol 203:1618-1623 3705. Kálazi Z, Janó V, Buza G (2010) In situ produced MMC layer by laser melt injection. In: Roósz A, Mertinger V, Barkóczy P, Hoó Cs (eds) Proc. 5th Int. conf. on solidification and gravity, Miskolc-Lillafüred, Hungary, 4-5 Sep 2008. Mater Sci Forum 649:61-66 3706. Li J, Li H, Wang M, Wang S, Ji Q, Li M, Chi J (2012) Applications of WC-based composites rapid synthesized by consumable electrode in situ metallurgy to cutting pick. Int J Refract Met Hard Mater 35:132-137 3707. Tillmann W, Hagen L, Kokalj D (2017) Spray characteristics and tribo-mechanical properties of high-velocity arc-sprayed WC-W2C iron-based coatings. J Therm Spray Technol 26:1685-1700 3708. Fredriksson H, Hillert M, Nica M (1979) The decomposition of the M2C carbide in highspeed steel. Scand J Metall 8(3):115-122 3709. Zhou X-F, Liu D, Zhu W-L, Fang F, Tu Y-Y, Jiang J-Q (2017) Morphology, microstructure and decomposition behaviour of M2C carbides in high-speed steel. J Iron Steel Res Int 24:43-49 3710. Guo H-J, Jia J-H, Liang B-N, Zhang Z-Y, Lin X-J (2013) Effect of addition of nanometer powders on microstructure of Fe/WC coating. Trans Mater Heat Treat 34(9):150-154 (in Chinese) 3711. Li W, Chen Y, Wu T (2010) Phase compositions and properties of Cr3C2-WC interpenetrating networks composite coating by combustion synthesis on surface of carbon steel. J Chin Ceram Soc 38(8):1468-1472 (in Chinese)

References

777

3712. Wittmann B, Schubert W-D, Lux B (2002) WC grain growth and grain growth inhibition in nickel and iron binder hardmetals. Int J Refract Met Hard Mater 20:51-60 3713. Xu J, Li GB, Du XZ, Hao J, Tang WH, Wang HB, Zhao HY (2015) Wear resistance characterization and analysis of hard particle reinforcement in composite Fe-based alloy + WC + Cr3C2 laser cladding. In: Sheng A (ed) Energy, environment and green building materials. Proc. Int. conf. on energy, environment and green building materials (EEGBM 2014), Guilin-Guangxi, China, 28-30 Nov 2014, pp.79-84. CRC Press / Balkema, Boca Raton, London, New York 3714. Gupta DD, Paul PC, Gandhi BK, Gupta RS, Nath KA (2008) Wear behaviour of laser clad surfaces of Cr3C2, WC and Mo on austenitic AISI 304L steel. J Laser Appl 20(3):140-145 3715. He D-Y, Fu B-Y, Jiang J-M, Li X-Y (2008) Microstructure and wear performance of arc sprayed Fe-FeB-WC coatings. J Therm Spray Technol 17:757-761 3716. Shi XL, Shao G, Duan LC, Yuan R (2004) Research on rare earth and iron-rich diamondenhanced tungsten carbide composite button. Rare Met 23(4):373-376, 384 3717. Tankut A, Timuçin M (2002) Sintering of tungsten carbide in the presence of borides. In: Saritaş S, Uslan I, Usta Y (eds) Proc. 3rd Int. powder metallurgy conf., Ankara, Turkey, 4-8 Sep 2002, pp. 459-469. Turkish Powder Metallurgy Association, Gazi University, Ankara 3718. Tankut A, Timuçin M (2004) Effects of Fe-TiB2 addition as binder phase on the liquidphase sintering behaviour of tungsten carbide cermets. In: Mandal H, Öveçoğlu L (eds) Euro Ceramics VIII. Proc. 8th conf. and exhibition of the European Ceramic Society, Istanbul, Turkey, 29 June – 3 July 2003. Key Eng Mater 264-268(2):973-976 3719. Sheinberg H (1986) Sintering reactions, structure and properties of cobalt free nonconventional hard material. Int J Refract Met Hard Mater 5(4):230-236 3720. Luo J-M, Xu J-L, Zhong Z-C (2013) Microstructure and properties of Y2O3-doped steelcemented WC prepared by microwave sintering. Rare Met 32(5):496-501 3721. Rybin V, Lozanov V, Utkin A, Matvienko A, Baklanova N (2019) The formation of disordered intermetallic phase during the solid-state interaction of WC with Ir. J Alloys Compd 775:503-510 3722. Utkin A, Batraev I, Rybin V, Lozanov V, Baklanova N (2019) Hardness of promising intermetallics obtained by the solid-state reaction of refractory carbides with iridium. Ceram Int 45:2684-2688 3723. Holleck H (1979) Ternäre Carbide von Cr, Mo und W mit Platinmetallen (Ternary carbides of Cr, Mo and W with platinum metals). Z Naturforsch B 34(4):647 (in German) 3724. Holleck H (1981) Binäre und ternäre Carbide und Nitride der Übergangsmetalle und ihre Phasenbeziehungen (Binary and ternary carbides and nitrides of the transition metals and their phase relationships). Technical Report KfK-3087-B, pp. 1-340. Institut für Materialund Festkörperforschung, Kernforschungszentrum, Karlsruhe (in German) 3725. Holleck H (1983) Die Konstitution ternäre Systeme der Übergangsmetalle der 4., 5. und 6. Gruppe mit Rhenium oder Platinmetallen und Kohlenstoff. Teil. 1. (The constitution of ternary systems of the transition metals of the 4th, 5th and 6th groups with rhenium or platinum metals and carbon. Part 1). Metall 37(5):475-485 (in German) 3726. Holleck H (1983) Die Konstitution ternäre Systeme der Übergangsmetalle der 4., 5. und 6. Gruppe mit Rhenium oder Platinmetallen und Kohlenstoff. Teil. 2. (The constitution of ternary systems of the transition metals of the 4th, 5th and 6th groups with rhenium or platinum metals and carbon. Part 2). Metall 37(7):703-708 (in German) 3727. Wang Y, Deng Y, Wang Q (1987) Study on emission properties of La-WC cathode and its resistance to poisoning of oil vapour. J Electronics 4(4):282-289 3728. Wang S, Pan Q, Yong Z, Zhang W, Zhang X, Zhu J (1996) Influence of rare-earth elements on properties of WC-Ni cemented carbide. Powder Metall Technol 14(4):291-296 (in Chinese) 3729. Kumar RP, Periyasamy P, Rangarajan S, Sathish T (2020) League championship optimization for the parameter selection for Mg/WC metal matrix composition. In: Vijayan V, Lee S (eds) Proc. Int. conf. on recent trends in nanomaterials for energy, environmental

778

2 Tungsten Carbides

and engineering applications (ICONEEEA-2K19), Tiruchirappalli, India, 28-29 Mar 2019. Mater Today Proc 21(1):504-510 3730. Velikanova TYa, Eremenko VN (1974) Phase equilibria in the ternary systems formed by molybdenum and tungsten with the groups IV and V transition metals and carbon. Powder Metall Met Ceram 13(4):293-297 3731. Eremenko VN, Velikanova TYa, Artyukh LV, Vishnevskii AS (1975) Phase diagram of ternary system hafnium-tungsten-carbon. Solidus surface projection. Rev Int Hautes Temp Refract 12(3):209-213 3732. Li S, Han Z, Meng Q, Zhao X, Cao X, Liu B (2018) Effect of WC nanoparticles on the microstructure and properties of WC – bronze – Ni-Mn based diamond composites. Appl Sci 8(9):1501 (9 pp.); doi:10.3390/app8091501 3733. Wang Z, Qin L (2009) Microstructure and wear resistance of argon arc cladding Ni-MoZr-WC-B4C composite coating. Trans China Weld Inst 30(8):13-16 (in Chinese) 3734. Ghasali E, Ebadzadeh T, Alizadeh M, Razavi M (2018) Mechanical and microstructural properties of WC-based cermets: a comparative study on the effect of Ni and Mo binder phases. Ceram Int 44:2283-2291 3735. Loboda PI, Trosnikova IYu, Bilyi OI, Karasevska OP (2012) Vpliv leguvannya na strukturu ta vlastivosti splaviv WC-W2C (Effect of doping on the structure and properties of WC-W2C alloys). Metalozn Obrobka Met (2):62-67 (in Ukrainian) 3736. Trosnikova IYu, Loboda PI, Karasevska OP (2019) The structure and properties of the molybdenum-doped WC-W2C eutectic alloy depending on the production method. Powder Metall Met Ceram 58(1-2):36-41 3737. Gorshkova LV, Telegus VS, Shamrai FI, Kuzma YuB (1973) System molybdenumtungsten-carbon. Powder Metall Met Ceram 12(3):237-239 3738. Gustafson P (1988) Thermodynamic evaluation of the C-Mo-W system. Z Metallkd 79(7):397-402 3739. Rokhlin L, Dobatkina T (2010) Carbon – molybdenum – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 2, pp. 516-530. Springer, Berlin, Heidelberg 3740. Gorshkova LV, Telegus VS, Shamrai FI, Kuzma YuB (1971) Vysokotemperaturnye fazovye ravnovesiya v sisteme molibden-volfram-uglerod (High-temperature phase equilibria in the molybdenum-tungsten-carbon system) In: Ageev NV, Ivanov OS (eds) Diagrammy sostoyaniya metallicheskikh sistem (Constitution diagrams of metallic systems). Proc. 4th AllUnion conf. on constitution diagrams, Moscow, USSR, 24-26 June 1969, pp. 106-108. Nauka, Moscow (in Russian) 3741. Samsonov GV, Bogomol IV, Okhremchuk LN, Podchernyaeva LA, Fomenko VS (1975) Thermoemission von Cermets auf Basis von hochschmelzenden Carbiden (Thermoemission of cermets made on the base of high melting carbides). Rev Int Hautes Temp Refract 12:251254 (in German) 3742. Moien M, Alizadeh E (2006) Investigation of (Mo,W)C based cemented carbides. Asian J Chem 18(2):891-899 3743. Raitses VB, Volcho VI, Rutberg VP, Shcherbakova AG, Cheltsov VYa (1977) Properties of plasma-sprayed coatings based on tungsten carbide. Powder Metall Met Ceram 16(5):351353 3744. Furillo FT (1979) W-Mo carbides for hardfacing applications. In: Ludema KC, Glaeser WA, Rhee SK (eds) Wear of materials. Proc. Int. conf. on wear of materials, Dearborn, Michigan, 16-18 Apr 1979, pp. 415-426. The American Society of Mechanical Engineers, New York 3745. Furillo FT (1980) W-Mo carbides for hardfacing applications. Wear 60:183-204 3746. Barranco JM (1989) Liquid-phase sintering of carbides using a nickel-molybdenum alloy. Int J Refract Met Hard Mater 8(2):102-110

References

779

3747. Kovalchenko MS, Bogomol IV, Serebryakova TI (1972) Kinetics of the hot-pressing of titanium and tungsten carbide alloys cemented with niobium. Powder Metall Met Ceram 11(6):441-445 3748. Lyudvinskaya TA, Nizhnikovskaya PF (1976) Vzaimodeistvie poroshka karbida volframa s zhelezom (The interaction of tungsten carbide powder with iron). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 80-85. Naukova Dumka, Kyiv (in Russian) 3749. Snagovskii BM, Pirogova ÉK, Snagovskii LM, Nizhnikovskaya PF, Taran YuN (1976) Strukturoobrazovanie pri evtekticheskoi kristallizatsii splavov Fe-C-W i Fe-C-Mo (Structural formation at the eutectic crystallization of Fe-C-W and Fe-C-Mo alloys). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 73-76. Naukova Dumka, Kyiv (in Russian) 3750. Nizhnikovskaya PF, Taran YuN, Grishina ON (1976) Karbidnye prevrashcheniya v splavakh Fe-C-W i Fe-C-Mo (The carbide transformations in Fe-C-W and Fe-C-Mo alloys). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 76-80. Naukova Dumka, Kyiv (in Russian) 3751. Bergström M (1977) The eta-carbides in the quaternary system Fe-W-C-Cr at 1250 °C. Mater Sci Eng 27(3):271-286 3752. Lyudvinskaya TA (1976) Issledovanie vozmozhnosti polucheniya karbida tipa M6C v sisteme Fe-W-C (The feasibility investigation of the preparation of M6C type carbide in the Fe-W-C system). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 86-90. Naukova Dumka, Kyiv (in Russian) 3753. Tumanov VI (1971) Svoistva splavov sistemy karbid volframa – kobalt (Properties of the tungsten carbide – cobalt system alloys). Metallurgiya, Moscow (in Russian) 3754. Tumanov VI (1973) Svoistva splavov sistemy karbid volframa – karbid titana – karbid tantala – karbid niobiya – kobalt (Properties of the tungsten carbide – titanium carbide – tantalum carbide – niobium carbide – cobalt system alloys). Metallurgiya, Moscow (in Russian) 3755. Chernyavskii KS (1982) Formirovanie struktury tverdykh splavov na razlichnykh stadiyakh ikh proizvodstva (Formation of the hard alloys structure at the various stages of their production). Central Scientific and Research Institute of Economics and Information of Non-Ferrous Metallurgy, Moscow (in Russian) 3756. Perrot P, Lebrun N (2010) Carbon – niobium – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 2, pp.567-578. Springer, Berlin, Heidelberg 3757. Rudy E (1966) Constitution of niobium-tungsten-carbon alloys. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFMLTR-65-2, Contract USAF 33(615)-1249, Part 2, Vol. 18, pp. 1-61. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 3758. Eremenko VN, Velikanova TYa, Shabanova SV, Artyukh LV (1973) Continuous series of solid solutions of carbides with NaCl structure in the ternary systems Mo(W)-MeIV,V-C. Powder Metall Met Ceram 12(11):909-912 3759. Warren R, Waldron MB (1972) Microstructural development during the liquid-phase sintering of cemented carbides. I. Wettability and grain contact. II. Carbide grain growth. Powder Metall 15(30):166-201 3760. Lisovskii AF, Vishnevskii AS, Sirota KI (1977) An investigation of sintered WC-Ni hard alloys with an uneven distribution of the binder metal. Powder Metall Met Ceram 16(5):345348 3761. Suzuki H, Hayashi K, Terada O (1977) Room temperature transverse rupture strength of WC – 10 % Ni cemented carbide. J Jpn Inst Met 41(6):559-563 (in Japanese)

780

2 Tungsten Carbides

3762. Butylenko AK, Sokolovskii VN (1981) Densification of tungsten and titanium carbides and their mixtures with nickel during heating under high pressure. Powder Metall Met Ceram 20(7):466-469 3763. Ekemar S, Lindholm L, Hartzell T (1982) Nickel as a binder in WC-band cemented carbides. Int J Refract Met Hard Mater 1(1):37-40 3764. Sadahiro T, Mitsuda T, Takatsu S (1982) Fracture toughness of Ni-bonded WC base cemented carbides. J Jpn Soc Powder Powder Metall 29(6):222-226 (in Japanese) 3765. Lisovskii AF (1988) Properties of sintered hard alloys WC-Ni with inhomogeneous structure. Powder Metall Met Ceram 27(11):861-866 3766. Lisovskii AF (1989) Mass transfer of liquid phase in sintered composite materials when interacting with metal melts. Int J Refract Met Hard Mater 8(2):133-136 3767. Krawitz AD, Reichel DG, Hitterman RL (1989) Residual stress and stress distribution in a WC-Ni composite. Mater Sci Eng A 119:127-134 3768. Majumdar S, Krawitz AD (1990) Residual thermal stresses and strains in a WC-base cemented carbide composite. Mater Sci Eng A 123:L1-L3 3769. Cheburaeva RF, Chaporova IN, Rudakov YuF, Krasina TI (1992) Optimization of the composition of the nickel binder in WC-Ni cemented carbides by alloying with group IV-VI elements. Powder Metall Met Ceram 31(4):308-312 3770. Cheburaeva RF, Chaporova IN, Krasina TI (1992) Structure and properties of tungsten carbide hard alloys with an alloyed nickel binder. Powder Metall Met Ceram 31(5):423-425 3771. Tracey VA (1992) Nickel in hardmetals. Int J Refract Met Hard Mater 11(3):137-149 3772. Suzuki H, Hayashi K, Takashima Y, Nakayama F (1981) Mechanical properties of Nibonded WC base cemented carbides at elevated temperatures. J Jpn Soc Powder Powder Metall 28(2):61-66 (in Japanese) 3773. Brabyn SM, Cooper R, Peters CT (1981) The effect of substitution of nickel for cobalt in WC-based hardmetal. In: Ortner HM (ed) Trends in refractory metals, hard metals and special materials and their technology. Proc. 10th Int. Plansee seminar, Reutte, Tirol, Austria, 1-5 June 1981. High Temp High Press 13(5):675-692 3774. Vasel CH, Krawitz AD, Drake EF, Kenik EA (1985) Binder deformation in WC-(Co,Ni) cemented carbide composites. Metall Trans A 16(12):2309-2317 3775. Tracey V, Hall N (1980) Nickel matrices in cemented carbides. Powder Metall Int 12(12):132-133 3776. Gu H (1993) Laser cladding of Ni based WC alloy. Laser Technol 17(4):220-223 (in Chinese) 3777. Guilemany JM, Llorca-Isern N, Núñez MD, Garsía J (1993) Characterization of (W,Ti)C – Ni powder for thermal spraying. Surf Coat Technol 58:173-177 3778. Pelletier JM, Sallamand P, Criqui B (1994) Microstructure and mechanical properties of some metal matrix composite coatings by laser cladding. In: Moncorge R, Boulon G (eds) Proc. 3rd Int. laser M2P conf., Lyon, France, 8-10 Dec 1993. J Phys IV 4(4):93-96 3779. Chen Z, Lim LC, Qian M (1996) Laser cladding of WC-Ni composite. J Mater Process Technol 62:321-323 3780. Högberg H, Tägtström P, Lu J, Jansson U (1996) Chemical vapour deposition of tungsten carbides on tantalum and nickel substrates. Thin Solid Films 272:116-123 3781. Sobolev VV, Guilemany JM, Miguel JR, Calero JA (1996) Influence of in-flight dissolution process on composite powder particle (WC-Ni) behaviour during high-velocity oxyfuel spraying. Surf Coat Technol 81:136-145 3782. Sobolev VV, Guilemany JM, Miguel JR, Calero JA (1996) Investigation of the development of coating structure during high-velocity oxy-fuel (HVOF) spraying of WC-Ni powder particles. Surf Coat Technol 82:114-120 3783. Sobolev VV, Guilemany JM, Miguel JR, Calero JA (1996) Influence of thermal processes on coating formation during high-velocity oxy-fuel (HVOF) spraying of WC-Ni powder particles. Surf Coat Technol 82:121-129

References

781

3784. Ghosh PK, Ram N (1997) Characteristics of heat treated tungsten carbide embedded nickel base hard surfacing on structural steel produced by gas thermal spray process. Int J Join Mater 9(3):114-121 3785. Guilemany JM, Nutting J, Miguel JR, Dong Z (1997) Microstructure formation of HVOF sprayed WC-Ni coatings deposited on low alloy steel. Mater Manuf Process 12(5):901-909 3786. Liang C, Lin S-T (1997) Sintering of injection-moulded WC – 7 wt.% Ni in a hydrogen atmosphere. J Mater Sci 32:3207-3212 3787. Tu JP, Liu MS, Mao ZY (1997) Erosion resistance of Ni-WC self-fluxing alloy coating at high temperature. Wear 209:43-48 3788. Zambrano G, Prieto P, Perez F, Rincon C, Galindo H, Cota-Araiza L, Esteve J, Martinez E (1998) Hardness and morphological characterization of tungsten carbide thin films. Surf Coat Technol 108-109:323-327 3789. Whitehead K, Brownlee LD (1956) Ternary phases in the system nickel-tungsten-carbon. Planseeber Pulvermetall 4(3):62-71 3790. Salem J, Adams M (1999) Multiaxial strength of tungsten carbide. In: Ustundag E, Fischman G (eds) Proc. 23rd American Ceramic Society annual conf. on composites, advanced ceramics, materials and structures, Cocoa Beach, Florida, 25-29 Jan 1999. Ceram Eng Sci Proc 20(4):459-466 3791. Sharafat S, Kobayashi A, Chen S, Ghoniem NM (2000) Production of high-density Nibonded tungsten carbide coatings using an axially fed DC-plasmatron. Surf Coat Technol 130:164-172 3792. Jiang G, Zhuang H, Li W (2003) Mechanistic investigation of the field-activated combustion synthesis (FACS) of tungsten carbide with or without nickel additive. J Mater Sci 38:3559-3565 3793. Jiang G, Li W, Zhuang H (2003) Synthesis of tungsten carbide – nickel composites by the field-activated combustion method. Mater Sci Eng A 354:351-357 3794. Laptev AV, Tolochin AI, Ochkas LF (2003) Hard alloy WC – 24 % Ni obtained in the solid phase from ultra-fine WC, NiO and C powders. I. Density and structure of specimens. Powder Metall Met Ceram 42(11-12):614-623 3795. Laptev AV, Tolochin AI, Ochkas LF (2004) Hard alloy WC – 24 % Ni obtained in the solid phase from ultra-fine WC, NiO and C powders. II. Mechanical properties. Powder Metall Met Ceram 43(1-2):1-9 3796. Si S-H, Yuan X-M, Xu K, He Y-Z (2004) Effect of laser power on microstructures and wear properties of WCp/Ni metal ceramics coating. J Chin Soc Corros Protect 24(3):183-187 (in Chinese) 3797. Jiang G, Zhuang H, Li W, Shon I-J (2005) Parameter investigation for WC-Ni composites prepared by field-activated pressure-assisted combustion synthesis. J Chin Ceram Soc 33(3):292-298, 339 (in Chinese) 3798. Stroumbouli M, Gyftou P, Pavlatou EA, Spyrellis N (2005) Co-deposition of ultra-fine WC particles in Ni matrix composite electrocoatings. Surf Coat Technol 195:325-332 3799. Sun Y, Yu Z, Shi R, You G, Lu H (2005) Fractal characteristics of microstructure of WC, ZrO2, Cr2O3 and Al2O3 ceramic particles / nickel alloy composite coatings. Acta Mater Compos Sin 22(3):85-91 (in Chinese) 3800. Si S-H, Yuan X-M, Liu Y-L, He Y-Z, Shin K (2006) Effect of laser power on microstructure and wear resistance of WCp/Ni cermet coating. J Iron Steel Res Int 13(3):74-78 3801. Wang H, Cao J, Xu X, Liu G, Zhang X (2006) Microstructure and properties of Ni-based WC spray-welding coating on titanium alloys substrate. Lubric Eng (2):87-89, 92 (in Chinese) 3802. Erol A, Yönetken A (2009) Microwave sintering of electroless Ni plated WC powders. Gazi Univ J Sci 22(3):227-233 3803. Sandy KA, Henein H, Jaansal KM (2009) On the contact of liquid nickel with tungsten carbide or boron carbide. Can Metall Quart 48(2):133-144

782

2 Tungsten Carbides

3804. Zoikis-Karathanasis A, Pavlatou EA, Spyrellis N (2009) The effect of heat treatment on the structure and hardness of pulse electrodeposited NiP-WC composite coatings. Electrochim Acta 54:2563-2570 3805. Gu D, Meiners W (2010) Microstructure characteristics and formation mechanisms of in situ WC cemented carbide based hardmetals prepared by selective laser melting. Mater Sci Eng A 527 7585-7592 3806. Latif S, Mehmood M, Ahmad J, Aslam M, Ahmed M, Zhang Z-D (2010) Ni-WC composite coatings by carburizing electrodeposited amorphous and nanocrystalline Ni-W alloys. Appl Surf Sci 256:3098-3106 3807. Voorwald HJC, Vieira LFS, Cioffi MOH (2010) Evaluation of WC – 10 Ni thermal spraying coating by HVOF on the fatigue and corrosion AISI 4340 steel. In: Lukáš P, Kunz L, Hutař P (eds) Proc. 10th Int. fatigue congress (Fatigue 2010), Prague, Czech Republic, 6-11 June 2010. Proc Eng 2:331-340 3808. Chen J, Huang Y, Gao X, Qiao B, Yang J, He Y (2011) Experimental study on Ni-base alloy bulk reinforced by laser sintered WC particles. Adv Compos Mater 20:277-287 3809. Davoren B (2020) Additive manufacturing of tungsten carbide cemented in a nickel alloy binder utilizing the laser engineered net shaping (LENS) process. PhD thesis, University of the Witwatersrand, Johannesburg, South Africa 3810. Jones M, Waag U (2011) The influence of carbide dissolution on the erosion-corrosion properties of cast tungsten carbide / Ni-based PTAW overlays. Wear 271:1314-1324 3811. Tolochin AI, Laptev AV, Okun IYu, Kovalchenko MS (2011) Composite WC – 35 % Ni produced from ultra-fine WC + NiO powders. I. Density and structure. Powder Metall Met Ceram 50(5-6):313-321 3812. Tolochin AI, Laptev AV, Okun IYu, Kovalchenko MS (2012) Composite WC – 35 % Ni produced from ultra-fine WC + NiO powders. II. Mechanical properties. Powder Metall Met Ceram 50(9-10):625-631 3813. Varga M, Winkelmann H, Badisch E (2011) Impact of microstructure on high temperature wear resistance. In: Vergani L, Guagliano M (eds) Proc. 11th Int. conf. on the mechanical properties of materials (ICM11), Villa Erba, Como, Italy, 5-9 June 2011. Proc Eng 10:12911296 3814. Verwimp J, Rombouts M, Geerinckx, Motmans F (2011) Applications of laser cladded WC-based wear resistant coatings. In: Schmidt M, Zaeh M, Graf T, Ostendorf A (eds) Proc. 6th Int. WLT conf. on lasers in manufacturing (LiM 2011), Munich, Germany, 23-26 May 2011. Phys Proc 12:330-337 3815. Yang G, Song W, Ma Y, Lu J, Hao Y, Li Y, Wang H (2011) Microstructure of Ni/WC surface composite on gray iron substrate. J Wuhan Univ Technol Mater Sci Ed 26(5):861-866 3816. Dalfard VM (2012) Effect of particle size of tungsten carbide on weight percent of carbide in Ni-WC nanocomposite. Int J Electrochem Sci 7:3537-3542 3817. Guo C, Chen J, Zhou J, Zhao J, Wang L, Yu Y, Zhou H (2012) Effects of WC-Ni content on microstructure and wear resistance of laser cladding Ni-based alloys coating. Surf Coat Technol 206:2064-2071 3818. Liyanage T, Fisher G, Gerlich AP (2012) Microstructures and abrasive wear performance of PTAW deposited Ni-WC overlays using different Ni-alloy chemistries. Wear 274275:345-354 3819. Rong H, Peng Z, Ren X, Peng Y, Wang C, Fu Z, Qi L, Miao H (2012) Ultra-fine WC-Ni cemented carbides fabricated by spark-plasma sintering. Mater Sci Eng A 532:543-547 3820. Zhang FG, Zhu XP, Lei MK (2012) Microstructural evolution and its correlation with hardening of WC-Ni cemented carbides irradiated by high-intensity pulsed ion beam. Surf Coat Technol 206:4146-4155 3821. Zhang Z, Liu H, Zhang X, Ji S, Jiang Y (2012) Dissolution behaviour of WC reinforced particles on carbon steel surface during laser cladding process. In: Chen R, Sun D, Sung W-P (eds) Proc. Int. conf. on frontiers of advanced materials and engineering technology (FAMET 2012), Xiamen, China, 4-5 Jan 2012. Adv Mater Res 430-432:137-141

References

783

3822. Paul CP, Mishra SK, Tiwari P, Kukreja LM (2013) Solid particle erosion behaviour of WC/Ni composite clad layers with different contents of WC particles. Optics Laser Technol 50:155-162 3823. Ren X, Peng Z, Peng Y, Fu Z, Wang C, Qi L, Miao H (2013) Effect of SiC nanowhisker addition on WC-Ni based cemented carbides fabricated by hot-press sintering. Int J Refract Met Hard Mater 36:294-299 3824. Ren X, Peng Z, Fu Z, Wang C (2014) Effect of SiC nanowhisker on the microstructure and mechanical properties of WC-Ni cemented carbide prepared by spark-plasma sintering. Sci World J 2014:673276 (8 pp.) 3825. Xu J-S, Zhang X-C, Xuan F-Z, Tian F-Q, Wang Z-D, Tu S-T (2013) Tensile properties and fracture behaviour of laser cladded WC/Ni composite coatings with different contents of WC particle studies by in situ tensile testing. Mater Sci Eng A 560:744-751 3826. Amado JM, Montero J, Tobar MJ, Yáñez A (2014) Laser cladding Ni-WC layers with graded WC content. In: Schmidt M (ed) Proc. 8th Int. conf. and exhibition on photonic technologies (LANE 2014), Fürth, Germany, 8-11 Sep 2014. Phys Proc 56:269-275 3827. Gao LX, Zhou T, Zhang DQ, Lee KY (2014) Microstructure and anodic dissolution mechanism of brazed WC-Ni composite coatings. Corros Eng Sci Technol 49(3):204-208 3828. Joo HG, Zhang DQ, Gao LX, Liu T, Lee KY (2014) Corrosion resistance of tungsten carbide – based cermet coatings formed by sinter-brazing. Int J Surf Sci Eng 8(4):380-391 3829. Gu D, Jia Q (2014) Novel crystal growth of in situ WC in selective laser-melted W-C-Ni ternary system. J Am Ceram Soc 97(3):684-687 3830. Qi S, Yue J, Li YY, Huang J, Yi C, Yang BL (2014) Replacing platinum with tungsten carbide for decalin dehydrogenation. Catal Lett 144:1443-1449 3831. Wang J, Jiang X-Q, Yang Q-K (2014) Optimization of binder composition for WC-Ni cemented carbide. J Funct Mater 45:81-83, 88 (in Chinese) 3832. Farahmand P, Liu S, Zhang Z, Kovacevic R (2014) Laser cladding assisted by induction heating of Ni-WC composite enhanced by nano-WC and La2O3. Ceram Int 40(10):1542115438 3833. Farahmand P, Kovacevic R (2015) Laser cladding assisted with an induction heater (LCAIH) of Ni – 60 % WC coating. J Mater Process Technol 222:244-258 3834. Farahmand P, Frosell T, McGregor M, Kovacevic R (2015) Comparative study of the slurry erosion behaviour of laser cladded Ni-WC coating modified by nanocrystalline WC and La2O3. Int J Adv Manuf Technol 79:1607-1621 3835. Rodella CB, Barrett DH, Moya SF, Figueroa SJA, Pimenta MTB, Curvelo AAS, TeixeiraDaSilva V (2015) Physical and chemical studies of tungsten carbide catalysts: effects of Ni promotion and sulphonated carbon. RSC Adv 5(30):23874-23885 3836. Shi K-H, Zhou K-C, Li Z-Y, Zhang D, Zan X-Q (2015) Microstructure and formation process of Ni-pool defect in WC – 8 Ni cemented carbides. Trans Nonferr Met Soc China 25:873-878 3837. Shatov AV, Ponomarev SS, Firstov SA (2009) Modeling the effect of flatter shape of WC crystals on the hardness of WC-Ni cemented carbides. Int J Refract Met Hard Mater 27(2):198-212 3838. Bi Y, Zhao S, Xu X (2016) WC reinforced Ni-based composite coating prepared by highfrequency induction heating sintering on the surface of 42CrMo. Powder Metall Technol 34(6):407-412 (in Chinese) 3839. Fedorov DV, Semenov OV, Rumyantsev VI, Ordanyan SS (2016) Compaction features during sintering VN8M alloy with additives nanodimensional tungsten carbide. Russ J NonFerr Met 57(1):57-61 3840. Ma Q, Li Y, Wang J, Liu K (2016) Microstructure evolution and growth control of ceramic particles in wide-band laser clad Ni60/WC composite coatings. Mater Design 92:897-905

784

2 Tungsten Carbides

3841. Phuong DD, Trinh PV, Duong LV, Chung LD (2016) Influence of sintering temperature on microstructure and mechanical properties of WC – 8 Ni cemented carbide produced by vacuum sintering. Ceram Int 42:14937-14943 3842. Rong T, Gu D (2016) Formation of novel graded interface and its function on mechanical properties of WC1–x reinforced Inconel 718 composites processed by selective laser melting. J Alloys Compd 680:333-342 3843. Rong T, Gu D, Shi Q, Cao S, Xia M (2016) Effects of tailored gradient interface on wear properties of WC / Inconel 718 composites using selective laser melting. Surf Coat Technol 307:418-427 3844. Saks N (2016) Low-pressure cold gas dynamic spraying of tungsten carbide – nickel coatings. Met Powder Rep 71(5):356-358 3845. Weng Z, Wang A, Wu X, Wang Y, Yang Z (2016) Wear resistance of diode laser-clad Ni/WC composite coatings at different temperatures. Surf Coat Technol 304:283-292 3846. Yang G-R, Huang C-P, Song W-M, Li J, Lu J-J, Ma Y, Hao Y (2016) Microstructure characteristics of Ni/WC composite cladding coatings. Int J Min Metall Mater 23(2):184-192 3847. Yung D-L, Antonov M, Veinthal R, Hussainova I (2016) Wear behaviour of doped WC-Ni based hardmetals tested by four methods. Wear 352-353:171-179 3848. Alidokht SA, Vo P, Yue S, Chromik RR (2017) Cold spray deposition of Ni and WCreinforced Ni matrix composite coatings. J Therm Spray Technol 26:1908-1921 3849. Ramakrishnan A, Singh A, Dinda GP (2017) Microstructure and mechanical properties of laser deposited Ni/WC metal matrix composite coatings. In: TMS 2017. Proc. 146th annual meeting and exhibition supplemental, San Diego, California, 26 Feb – 2 Mar 2017, pp. 157168. Springer, Cham 3850. Shu D, Li Z, Zhang K, Yao C, Li D, Yuan Y, Dai Z (2017) Phase constituents and growth mechanism of laser in situ synthesized WC reinforced composite coating with W-C-Ni system. J Mater Res 32(3):557-565 3851. Shu D, Li Z, Zhang K, Yao C, Li D, Dai Z (2017) In situ synthesized high-volume fraction WC reinforced Ni-based coating by laser cladding. Mater Lett 195:178-181 3852. Cheniti B, Miroud D, Hvizdoš P, Balko J, Sedlák R, Csanádi T, Belkessa B, Fides M (2018) Investigation of WC decarburization effect on the microstructure and wear behaviour of WC-Ni hardfacing under dry and alkaline wet conditions. Mater Chem Phys 208:237-247 3853. Huebner J, Kata D, Rutkowski P, Petrzak P, Kusiński J (2018) Grain boundary interaction between Inconel 625 and WC during laser metal deposition. Materials 11(10):1797 (12 pp.); doi:10.3390/ma11101797 3854. Isern L, Impey S, Clouser SJ, Milosevic D, Endrino JL (2018) Particle distribution, film formation and wear performance of brush plated Ni/WC. J Electrochem Soc 165(9):D402D410 3855. Joo HG, Lee KY, Luo GM, Zhang DQ (2018) Development of WC-Ni cermet brazing process. Mater Perform 57(9):30-33 3856. Kaushal S, Gupta D, Bhowmick H (2018) On processing of Ni-WC based functionally graded composite clads through microwave heating. Mater Manuf Process 33(8):822-828 3857. Ma Z, Zhang W, Du P, Zhu X, Krishnaswamy S, Lin L, Lei M (2018) Nondestructive measurement of elastic modulus for thermally sprayed WC-Ni coatings based on acoustic wave mode conversion by small angle incidence. NDT E Int 94:38-46 3858. Nguyen QB, Zhu Z, Chua BW, Zhou W, Wei J, Nai SML (2018) Development of WCInconel composites using selective laser melting. Arch Civil Mech Eng 18:1410-1420 3859. Quazi MM, Ishak M, Arslan A, Fazal MA, Yusof F, Sazzad BS, Bashir MN, Jamshaid M (2018) Mechanical and tribological performance of a hybrid MMC coating deposited on Al – 17 Si piston alloy by laser composite surfacing technique. RSC Adv 8:6858-6869 3860. Sabzi M, Dezfuli SM, Far SM (2018) Deposition of Ni – tungsten carbide nanocomposite coating by TIG welding: characterization and control of microstructure and wear/corrosion responses. Ceram Int 44(18):22816-22829

References

785

3861. Shu D, Li Z, Yao C, Li D, Dai Z (2018) In situ synthesized WC reinforced nickel coating by laser cladding. Surf Eng 34(4):276-282 3862. Cao H, Ma W, Chen H, Wang Q, Wang Y (2019) Core-rim microstructure and properties of WC/Ni composites. Int J Refract Met Hard Mater 78:170-177 3863. Gromilov SA, Gerasimov EYu, Nikolaev RE (2019) Formation of metallic and carbide phases via co-decomposition of (NiEn3)WO4 and lithium hydride in the range 410-1060 °C. Inorg Mater 55(4):331-336 3864. Xia M, Gu D, Ma C, Zhang H, Dai D, Chen H, Li C, Zhou Z, Chen G, Kelbassa I (2019) Fragmentation and refinement behaviour and underlying thermodynamic mechanism of WC reinforcement during selective laser melting of Ni-based composites. J Alloys Compd 777:693-702 3865. Chen Y, Zheng Y, Yue X, Huang S (2020) Hydrogen evolution reaction in full pH range on nickel doped tungsten carbide nanocubes as efficient and durable non-precious metal electrocatalysts. Int J Hydrogen Energy 45:8695-8702 3866. Davoren B, Sacks N, Theron M (2020) Laser engineered net shaping of WC – 9.2 wt.% Ni alloys: a feasibility study. Int J Refract Met Hard Mater 86:105136 (10 pp.) 3867. Garcia-Ayala EM, Silvestroni L, Yus J, Ferrari B, Pastor JY, Sanchez-Herencia AJ (2021) Colloidal processing and sintering of WC-based ceramics with low Ni content as sintering aid. J Eur Ceram Soc 41:1848-1858 3868. Ilo S, Just Ch, Badisch E, Wosik J, Danninger H (2010) Effects of interface formation kinetics on the microstructural properties of wear-resistant metal-matrix composites. Mater Sci Eng A 527:6378-6385 3869. Just Ch, Badisch E, Wosik J (2010) Influence of welding current on carbide/matrix interface properties in MMCs. J Mater Process Technol 210:408-414 3870. Deng D-W, Xia H-F, Ge Y-L (2013) Influence of welding currents on microstructure and microhardness of Ni45 alloy reinforced with spherical tungsten carbides (40 mass%) by plasma transferred arc welding. Mater Trans Jpn Inst Met 54(11):2144-2150 3871. Lyu Y, Sun Y, Yang Y (2016) Non-vacuum sintering process of WC/W2C reinforced Nibased coating on steel. Met Mater Int 22(2):311-318 3872. Zhang Y, Shuai G, Huang J, Liu J, Yi J, Wang L, Wu R, Wu Y, Xie M (2016) WxC reinforced Ni-based composite coating in situ synthesis by laser cladding. Heat Treat Met 41(2):79-83 (in Chinese) 3873. Günther K, Bergmann JP (2018) Understanding the dissolution mechanism of fused tungsten carbides in Ni-based alloys: an experimental approach. Mater Lett 213:253-256 3874. Günther K, Liefeith J, Henckell P, Ali Y, Bergmann JP (2018) Influence of processing conditions on the degradation kinetics of fused tungsten carbides in hardfacing. Int J Refract Met Hard Mater 70:224-231 3875. Li C-W, Chang K-C, Yeh A-C, Yeh J-W, Lin S-J (2018) Microstructure characterization of cemented carbide fabricated by selective laser melting process. Int J Refract Met Hard Mater 75:225-233 3876. Liu F, Liu C, Chen S, Tao X (2007) Studies of W2C in situ reinforced Ni-based coating prepared by laser cladding on copper substrate. Chin J Mater Res 21(5):496-500 (in Chinese) 3877. Zhang C-H, Zhang H-F, Liu K, Tan J-Z, Zhang S (2019) Microstructure and wear resistance of in situ synthesized WxC/Ni composite coating prepared with vacuum cladding. J Shenyang Univ Technol 41(1):25-30 (in Chinese) 3878. Engleman PG, Dahotre NB, Blue CA, Harper DC, Ott R (2002) High density infrared processing of WC / Ni – 11 P composite coatings. Surf Eng 18(2):113-119 3879. Hamid ZA, El-Badry SA, Aal AA (2007) Electroless deposition and characterization of Ni-P-WC composite alloys. Surf Coat Technol 201:5948-5953 3880. Matsugi K, Abo H, Choi YB, Sasaki G, Kuramoto H, Oki T, Yanagisawa O (2009) Spark sinterability of WC – Ni (– P) powders and wear characteristics of their sintered compacts. J Jpn Soc Powder Powder Metall 56(2):51-60 (in Japanese)

786

2 Tungsten Carbides

3881. Zhao C, Yao Y (2014) Influence of tungsten carbide nanoparticles on corrosion resistance properties of electroless nickel-phosphorus coatings. Anti-Corros Method Mater 61(5):314318 3882. Zhao C, Yao Y (2014) Preparation and mechanical properties of electroless nickel – phosphorus – tungsten carbide nanocomposite coatings. J Mater Eng Perform 23:193-197 3883. Luo H, Leitch M, Behnamian Y, Ma Y, Zeng H, Luo J-L (2015) Development of electroless Ni-P / nano-WC composite coatings and investigation on its properties. Surf Coat Technol 277:99-106 3884. Liu Z, Lin Y-B (2007) Study on performance and electrodeposition process of Ni-P-WWC composite coatings. Mater Sci Technol 15(3):425-428 (in Chinese) 3885. Kimura H, Masumoto T, Ast DG (1987) Yield stress of a composite consisting of amorphous Ni78Si10B12 and μm-sized WC particles. Acta Metall 35(7):1757-1765 3886. Correa EO, Santos JN, Klein AN (2010) Microstructure and mechanical properties of WCNi-Si based cemented carbides developed by powder metallurgy. Int J Refract Met Hard Mater 28:572-575 3887. Fan D, Sun M, Sun Y-N, Zhang J-B (2008) Laser clad WCp / Ni-Si-Ti composite coatings. J Aeronaut Mater 28(1):40-44 (in Chinese) 3888. Boonyongmaneerat Y, Saengkiettiyut K, Saenapitak S, Sangsuk S (2010) Pulse coelectrodeposition and characterization of NiW-WC composite coatings. J Alloys Compd 506:151-154 3889. Genç A, Ayas E, Öveçoğlu ML, Turan S (2012) Fabrication of in situ Ni(W)-WC nanocomposites via mechanical alloying and spark-plasma sintering. J Alloys Compd 542:97-104 3890. Yung D-L, Dong M, Hussainova I (2013) Comparing tungsten carbide based composite reinforced by alumina nanofibers or zirconia. In: Christopherson D, Gasior RM (eds) Advances in powder metallurgy and particulate materials – 2013. Proc. Int. conf. on powder metallurgy and particulate materials (PowderMet 2013), Chicago, Illinois, 24-27 June 2013, pp. 824-835. Metal Powder Industries Federation, Princeton, New Jersey 3891. Farrokhzad MA, Khan TI (2016) High-temperature oxidation of nickel-based cermet coatings containing WC and Al2O3 nanosized particles. Oxid Met 86:431-451 3892. Farrokhzad MA, Khan TI (2016) Sliding wear performance of nickel-based cermet coatings composed of WC and Al2O3 nanosized particles. Surf Coat Technol 304:401-412 3893. Liu J, Ma X, Tang H, Zhao W (2012) Nanostructured Ni-bonded hard materials (W0.6Al0.4)C0.5 – Ni prepared by mechanical alloying and hot-pressing. Mater Sci Eng A 532:146-150 3894. Lee G-G, Jang K-H, Ha G-H (2012) Effect of silicon on the mechanical properties of WCNi hard metal. In: Carreño-Morelli E, Britenmoser G, Moseley S (eds) Proc. Int. European powder metallurgy congress and exhibition (Euro PM 2012), Basel, Switzerland, 16-19 Sep 2012, Vol. 2 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.epma.com/publications/euro-pm-proceedings/product/ep12415 Accessed 8 July 2021 3895. Lee G-G, Ha G-H (2013) Effect of added B4C on the mechanical properties of WC / Ni-Si hardmetal. J Korean Powder Metall Inst 20(5):366-370 (in Korean) 3896. Voyer J, Marple BR (2000) Tribological performance of thermally sprayed cermet coatings containing solid lubricants. Surf Coat Technol 127:155-166 3897. Shi K, Liu X, Zhou K, Min Z, Liao J, Zan X (2016) Effect of carbon content and CeO2 addition on thermal properties and surface morphology of ultra-fine WC – 9 Ni – 0.4 Cr3C2 cemented carbide. Rare Met Mater Eng 45(10):2593-2597 (in Chinese) 3898. Wang Y, Chen D, Piao Y, Chen X, Zhang T (2017) Influence of MgO + CeO2 on the microstructure and hardness of WC-Ni based alloy coating by vacuum melting. Surf Rev Lett 24(5):1750072 (8 pp.) 3899. Zhao T, Cai X, Wang S, Zheng S (2000) Effect of CeO2 on microstructure and corrosive wear behaviour of laser-cladded Ni/WC coating. Thin Solid Films 379:128-132

References

787

3900. Wang YN, Miao L, Geng W, Cai CB (2011) Influence of CeO2 addition on micro-structure of vacuum-melted WC-Ni base alloy coating. In: Li Y, Wang P, Ai L, Sang X, Bu J (eds) Proc. Int. conf. on advanced engineering materials and technology (AEMT 2011), Sanya, China, 29-31 July 2011. Adv Mater Res 291-294:184-187 3901. Dhakar BM, Dwivedi DK, Sharma SP (2012) Studies on remelting of tungsten carbide and rare earth modified nickel base alloy composite coating. Surf Eng 28(1):73-80 3902. Sharma S (2012) Wear study of Ni-WC composite coating modified with CeO2. Int J Adv Manuf Technol 61:889-900 3903. Lu M, Wang Y-N, Li Y-H (2013) The effect of different CeO2 addition on performance of Ni-WC composite coating by vacuum fusion sintering. In: Bu J, Kim Y-H (eds) Proc. 3rd Int. conf. on advanced engineered materials and technology (AEMT 2013), Zhangjiajie, China, 11-12 May 2013. Adv Mater Res 750-752:2052-2056 3904. He L, Tan Y, Tan H, Tu Y, Zhang Z (2014) Microstructure and tribological properties of WC – CeO2 / Ni-base alloy composite coatings. Rare Met Mater Eng 43(4):823-829 3905. Shi K-H, Zhou K-C, Li Z-Y, Liu X-H, Zan X-Q (2015) Effect of cryogenic treatment on thermal behaviour of WC – 9 Ni – x CeO2 cemented carbides. Mater Manuf Process 30:14251430 3906. Chen C, Chen Y, Shen J, Wang W (2019) Wear resistance of Ce doped Ni based – WC coating prepared by laser cladding. Heat Treat Met 14(12):192-197 (in Chinese) 3907. Tsuchiya N, Terada O, Sasaki A, Suzuki H (1989) Some properties of WC – Cr3C2 – 15 mass% Ni alloy. J Jpn Soc Powder Powder Metall 36(3):311-314 (in Japanese) 3908. Bondarenko VP, Delevi VG, Demyanchuk AV, Sirota KI, Tkachenko RK, Trunevich LV (1991) Formation of tungsten-chromium-nickel hard alloy structure. Powder Metall Met Ceram 30(4):335-338 3909. Tani K, Harada Y, Takatani Y (1995) Characterization of thermally sprayed WC-Cr3C2 cermet coating with Ni bonding. J Jpn Inst Met 59(11):1136-1142 (in Japanese) 3910. Imasato S, Tokumoto K, Sakaguchi S (2004) Microstructures, mechanical and corrosion properties of WC – (0-16) mass% Cr3C2 – 15 mass% Ni cemented carbides. J Jpn Soc Powder Powder Metall 51(1):3-9 (in Japanese) 3911. Ishikawa Y, Kuroda S, Kawakita J, Sakamoto Y, Takaya M (2007) Sliding wear properties of HVOF sprayed WC – 20 % Cr3C2 – 7 % Ni cermet coatings. Surf Coat Technol 201:47184727 3912. Fang W, Cho T-Y, Yoon J-H, Song K-O, Hur S-K, Youn S-J, Chun H-G (2009) Processing optimization, surface properties and wear behaviour of HVOF spraying WC-CrCNi coating. J Mater Process Technol 209:3561-3567 3913. Kitamura J, Osawa S, Lbe H, Mizuno H, Tawada S (2009) Improvement of impact resistance of WC-Cr3C2-Ni based coatings by means of hardness control of undercoat. In: Marple BR, Hyland MM, Lau Y-C, Li C-J, Lima RS, Montavon G (eds) Thermal spray 2009: expanding thermal spray performance to new markets and applications. Proc. Int. thermal spray conference (ITSC 2009), Las Vegas, Nevada, 4-7 May 2009, pp.963-967. ASM International, Metals Park, Ohio 3914. Zhang S-H, Cho T-Y, Yoon J-H, Li M-X, Shum P-W, Kwon S-C (2009) Investigation on microstructure, surface properties and ant-wear performance of HVOF sprayed WC-CrC-Ni coatings modified by laser heat treatment. Mater Sci Eng B 162:127-134 3915. Zhang S-H, Yoon J-H, Li M-X, Cho T-Y, Joo Y-K, Cho J-Y (2010) Influence of CO2 laser heat treatment on surface properties, electrochemical and tribological performance of HVOF sprayed WC – 24 % Cr3C2 – 6 % Ni coating. Mater Chem Phys 119:458-464 3916. Li W, Wu Q (2010) Effect of Ni addition on in situ WC-Cr3C2 cermet coating by laser controlled reactive synthesis. In: In: Lee J-H (ed) Proc. 3rd Int. conf. on multi-functional materials and structures (MFMS 2010), Jeonju, South Korea, 14-18 Sep 2010. Adv Mater Res 123-125:43-46 3917. Wu Q, Li W (2011) The microstructure and wear properties of laser-clad WC-Cr3C2 cermet coating on steel substrate. Mater Trans Jpn Inst Met 52(3):560-563

788

2 Tungsten Carbides

3918. Cho T-Y, Joo Y-K, Yoon J-H, Fang W, Zhang S-H, Chun H-G (2013) Improvement of surface properties of magnetic shaft material Inconel 718 by HVOF spray coating of WCCrC-Ni powder. In: Kim Y-H, Yarlagadda P (eds) Proc. Int. forum on mechanical and material engineering (IFMME 2013), Guangzhou, China, 13-14 June 2013. Adv Mater Res 774-776:1098-1102 3919. Thiruvikraman C, Balasubramanian V, Sridhar K (2013) Slurry erosion behaviour of HVOF sprayed WC-CrC-Ni coatings. In: Bakshi SR, Kamaraj M, Mudali UK, Sudarshan TS, Raj B, Murty BS (eds) Heat treatment and surface engineering. Proc. 1st Int. conf. and exhibition on heat treatment and surface engineering (HTSE 2013), Chennai, India, 16-18 May 2013, pp. 531-540. ASM International, Metals Park, Ohio 3920. Mayrhofer E, Janka L, Mayr WP, Norpoth J, Ripoll MR, Gröschl M (2015) Cracking resistance of Cr3C2-NiCr and WC-Cr3C2-Ni thermally sprayed coatings under tensile bending stress. Surf Coat Technol 281:169-175 3921. Nagaoka T, Kimoto Y, Watanabe H, Fukusumi M, Morisada Y, Fujii H (2015) Hardening of thermally sprayed WC-CrC-Ni cemented carbide layer by friction stir processing. J Jpn Soc Powder Powder Metall 62(5):252-257 (in Japanese) 3922. Li M, Han B, Wang Y, Song L (2016) Study on microstructure and property of laser cladded Ni-WC/Cr3C2 coating. Trans China Weld Inst 37(3):17-21 (in Chinese) 3923. Ravichandran M, Saravanan S, Balasubramaniyan V (2016) Investigations on erosion and corrosion behaviour of high-velocity oxy-fuel sprayed WC-Cr3C2-Ni coatings on AISI 1018 steel. HTM J Heat Treat Mater 71(4):163-169 3924. Somasundaram B, Kadoli R, Ramesh MR, Ramesh CS (2016) High-temperature corrosion behaviour of HVOF sprayed WC-CrC-Ni coatings. Int J Surf Sci Eng 10(4):400-413 3925. Mekgwe GN, Tuckart WR, Akinribide OJ, Langa T, Obadele BA, Olubambi PA (2019) Effect of CrC-Ni on the tribological behaviour of WC cemented carbide. In: Njuguna J, Ngo H-D (eds) Proc. 4th Int. conf. on structural nanocomposites (NANOSTRUC2018), Berlin, Germany, 23-24 May 2018. IOP Conf Series Mater Sci Eng 499:012012 (5 pp.) 3926. Bhosale DG, Rathod WS (2021) Tribo-behaviour of APS and HVOF sprayed WC-Cr3C2Ni coatings for gears. Surf Eng 37(1):80-90 3927. Yung D-L, Dong M, Hussainova I (2014) Effect of grain growth inhibitors VC/Cr3C2 on WC-ZrO2-Ni composite mechanics. In: Loca D (ed) Proc. 22nd Int. Baltic conf. on engineering materials and tribology (BALTMATTRIB 2013), Riga, Latvia, 14-15 Nov 2013. Key Eng Mater 604:106-109 3928. Wang Q, Xiang J, Wu X-B, Yang F-G, Tang Z-H (2011) Effect of fine WC powder content on the performance of WC reinforced Ni-based spray-welding coating. J Hunan Univ Nat Sci 38(12):57-61 (in Chinese) 3929. Richert M, Nejman I, Poręba M, Sieniawski J, Kuczek L (2014) Effect of plasma gases on the structure and properties of WC-CrC-Ni coatings. In: Tokarski T (ed) Proc. Int. conf. on non-ferrous metals – processing and new materials (ICNFM 2014), Wisla, Poland, 4-6 June 2014. Key Eng Mater 641:105-110 3930. Dhakar BM, Dwivedi DK, Sharma S (2012) Influence of TIG re-melting and RE (La2O3) addition on microstructure, hardness and wear of Ni-WC composite coating. In: TMS 2012. Proc. 141st annual meeting and exhibition, Orlando, Florida, 11-15 Mar 2012, Vol. 1, pp. 603-608. Wiley, Hoboken, New Jersey 3931. Wang Y, Han L, Wang X (2011) Effects of MgO addition level on microstructure and wear resistance of Ni-WC vacuum fusion sintering coating. In: Jiang Z, Liu X, Bu J (eds) Proc. Int. conf. on advances in materials and manufacturing processes (ICAMMP 2010), Shenzhen, China, 6-8 Nov 2010. Adv Mater Res 154-155:942-945 3932. Balbino NAN, Correa EO, De Carvalho-Valeriano L, Amâncio DA (2017) Microstructure and mechanical properties of 90 WC – 8 Ni – 2 Mo2C cemented carbide developed by conventional powder metallurgy. Int J Refract Met Hard Mater 68:49-53 3933. Li J, Zhang H, Li W, Zhang G (2008) Microstructure and properties of in situ synthesized TiB2 + WC reinforced composite coatings. Rare Met 27(5):451-456

References

789

3934. Song J, Huang C, Zou B, Liu H, Wang J (2012) Microstructure and mechanical properties of TiB2-WC-TiC-Ni composite tool materials. In: Gao S (ed) Proc. Int. conf. on advanced materials and engineering materials (ICAMEM 2011), Shenyang, Liaoning, China, 22-24 Nov 2011. Adv Mater Res 457-458:1191-1195 3935. Berger L-M, Saaro S, Naumann T, Kašparova M, Zahálka F (2010) Influence of feedstock powder characteristics and spray processes on microstructure and properties of WC(W,Cr)2C-Ni hardmetal coatings. Surf Coat Technol 205:1080-1087 3936. Hou G-L, An Y-L, Liu G, Zhou H-D, Chen J-M, Chen Z-J (2011) Effect of atmospheric plasma spraying power on microstructure and properties of WC-(W,Cr)2C-Ni coatings. J Therm Spray Technol 20(6):1150-1160 3937. Hou G-L, Zhou H-D, An Y-L, Liu G, Chen J-M, Chen J (2011) Microstructure and hightemperature friction and wear behaviour of WC-(W,Cr)2C-Ni coating prepared by highvelocity oxy-fuel spraying. Surf Coat Technol 206:82-94 3938. Hou G-L, An Y-L, Zhao X-Q, Chen J, Chen J-M, Zhou H-D, Liu G (2012) Effect of heat treatment on wear behaviour of WC-(W,Cr)2C-Ni coating. Surf Eng 28(10):786-790 3939. Babu PS, Rao PC, Jyothirmayi A, Phani PS, Krishna LR, Rao DS (2018) Evaluation of microstructure, property and performance of detonation sprayed WC-(W,Cr)2C-Ni coatings. Surf Coat Technol 335:345-354 3940. Genç A, Öveçoğlu ML (2010) Characterization investigations during mechanical alloying and sintering of Ni-W solid solution alloys dispersed with WC and Y2O3 particles. J Alloys Compd 508:162-171 3941. Galedari SA, Jazi MS, Azarmi F, Tangpong X, Huang Y (2015) An investigation on microstructural properties of plasma sprayed tungsten carbide enhanced with partially stabilized zirconia. In: Agarwal A, Lau Y-C, McDonald A, Bolelli G, Toma F-L, Concustell A, Widener CA, Turunen E (eds) Proc. Int. thermal spray conf. and exposition (ITSC 2015), Long Beach, California, 11-14 May 2015, Vol. 1, pp. 236-240. ASM International, Metals Park, Ohio 3942. Jazi MS, Galedari SA, Azarmi F, Tangpong X, Huang Y, Lin Z (2015) Evaluation of mechanical properties of plasma sprayed mixture of partially stabilized zirconia and tungsten carbide on low carbon steel. In: Proc. ASME Int. mechanical engineering congress and exposition (IMECE 2015), Houston, Texas, 13-19 Nov 2015, Vol. 14 – Emerging technologies, safety engineering and risk analysis, materials: genetics to structures, V014T11A017 (7 pp.). The American Society of Mechanical Engineers, New York 3943. Galedari SA, Jazi MS, Azarmi F, Tangpong X (2016) Microstructural properties of air plasma sprayed coating consisting of tungsten carbide and yttria-stabilized zirconia. Int J Appl Ceram Technol 13(3):459-468 3944. Cura ME, Voltšihhin N, Hussainova I, Viljus M, Hannula S-P (2012) Effect of carbon content on sinterability and properties of ZrO2 doped WC cermets. In: Otto T (ed) Proc. 8th Int. DAAAM Baltic conf. on industrial engineering, Tallinn, Estonia, 19-21 Apr 2012, pp. 771-776. DAAAM International, Vienna, Austria 3945. Voltšihhin N, Hussainova I, Traksmaa R, Juhani K (2012) Optimization of WC-Ni-ZrO2 structure. In: Quaresimin M, Carvelli V, Pegoretti A, Trevisan N (eds) Composites at Venice. Proc. 15th European conf. on composite materials (ECCM 2012), Venice, Italy, 24-28 June 2012 (8 pp.). University of Padova, Italy https://www.escm.eu.org/eccm15/data/assets/296.pdf Accessed 16 July 2021 3946. Hussainova I, Voltšihhin N, Cura ME, Hannula S-P (2014) Processing and properties of zirconia toughened WC-based cermets. In: Ohji T, Singh M, Kirihara S, Widjaja S (eds) Advanced processing and manufacturing technologies for structural and multi-functional materials – VII. Proc. 37th Int. conf. on advanced ceramics and composites (ICACC 2013), Daytona Beach, Florida, 27 Jan – 1 Feb 2013. Ceram Eng Sci Proc 34(8):97-103 3947. Hussainova I, Antonov M, Voltšihhin N, Kübarsepp J (2014) Wear behaviour of Co-free hardmetals doped by zirconia and produced by conventional PM and SPS routines. Wear 312:83-90

790

2 Tungsten Carbides

3948. Vasić-Anićijević DD, Nikolić VM, Marčeta-Kaninski MP, Pašti IA (2015) Structure, chemisorption properties and electrocatalysis by Pd3Au overlayers on tungsten carbide – a DFT study. Int J Hydrogen Energy 40:6085-6096 3949. Zhang Q, Mellinger ZJ, Jiang Z, Chen X, Wang B, Tian B, Liang Z, Chen JG (2018) Palladium-modified tungsten carbide for ethanol electrooxidation: from surface science studies to electrochemical evaluation. J Electrochem Soc 165(15):J3031-J3038 3950. Xiong J, Yang J-G, Guo X-H (1996) Application of rare earth elements in cemented carbide inserts, drawing dies and mining tools. Mater Sci Eng A 209:287-293 3951. Warren R (1968) The interaction between liquid platinum and some transition metal carbides. J Nucl Mater 25:117-119 3952. Ghaisas S, Ogale SB (1991) Small cluster effects in WC/Pt thin film catalyst deposited by pulsed laser co-ablation method. Mater Lett 10(11-12):540-544 3953. Lu G, Cooper JS, McGinn PJ (2006) SECM characterization of Pt-Ru-WC and Pt-Ru-Co ternary thin film combinatorial libraries as anode electrocatalysis for PEMFC. J Power Sources 161:106-114 3954. Kleykamp H, Gottschalg HD (1974) Mikrosonden-Nachuntersuchungen an (U,Pu) KarbidPrüflingen des Bestrahlungsexperiments (Microprobe follow-up examinations on (U,Pu) carbide test specimens from the irradiation experiment). Technical Report KfK-1273/4, pp. 181. Institut für Material- und Festkörperforschung, Kernforschungszentrum, Karlsruhe (in German) 3955. Lu H, Zhao C, Wang H, Liu X, Yu R, Song X (2019) Hardening tungsten carbide by alloying elements with high work function. Acta Crystallogr B 75:994-1002 3956. Zhao C, Lu H, Wang H, Tang F, Nie H, Hou C, Liu X, Song X, Nie Z (2020) Solidsolution hardening of WC by rhenium. J Eur Ceram Soc 40:333-340 3957. Zaitsev AL, Pleskachevsky YuM (1995) Inorganic tribosynthesis of solid lubricants under frictional interaction of refractory carbides and chalcogens. Wear 181-183:495-499 3958. Velikanova TYa, Eremenko VN, Artyukh LV, Bondar AA, Gordiichuk OV (1989) Phase diagrams of Sc – M (IV-VII) – C systems. Powder Metall Met Ceram 28(9):711-718 3959. Schuster JC (1993-1994) Silicon carbide and transition metals: a critical evaluation of existing phase diagram data supplemented by new experimental results. Int J Refract Met Hard Mater 12:173-177 3960. Ahuja R (2007) Nanolayered MAX phases from ab initio calculations. In: Sih GC, NaïtAbdelaziz M, Vu-Khanh T (eds) Particle and continuum aspects of mesomechanics, pp. 199204. ISTE Ltd, London, Newport Beach, California 3961. Kumar AKN, Watabe M, Kurokawa K (2012) The influence of Si on the microstructure and sintering behaviour of ultra-fine WC. Philos Mag 92(32):3950-3967 3962. Kumar AKN, Watabe M, Kurokawa K (2014) Reaction-assisted sintering and platelet growth by adiabatic heating in WC-Si cermets. Scripta Mater 75:6-9 3963. Kumar AKN, Subramanian B, Kurokawa K (2016) Defect structure evolution and abnormal grain growth during spark-plasma sintering of nano WC-Si powders. J Mater Res 31(10):1466-1476 3964. Xiao Y, Li X, Du H, Xu Y, He Y (2016) Effects of Si on microstructures and properties of in situ WC reinforced coating. Trans China Weld Inst 37(9):13-17 (in Chinese) 3965. Humphry-Baker S, Marshall J (2018) Structure and properties of high-hardness silicide coatings on cemented carbides for high-temperature applications. Coatings 8(7):247 (14 pp.); doi:10.3390/coatings8070247 3966. Ghasali E, Ebadzadeh T, Alizadeh M, Razavi M (2019) Unexpected SiC nanowires growth during spark-plasma sintering of WC – 10 Si: a comparative study on phase formation and microstructure properties against WC – 10 Co cermet. J Alloys Compd 786:938-952 3967. Shon I-J, Park J-H, Ko I-Y, Doh J-M, Yoon J-K, Nam K-S (2011) Properties and consolidation of nanocrystalline WSi2-SiC composite from mechanically activated powders by pulsed current activated combustion synthesis. Ceram Int 37:1549-1555

References

791

3968. Zhang BR, Marino F, Ferraris M (1994) Liquid-phase hot-pressing and WC particle reinforcement of SiC-Si composites. J Eur Ceram Soc 14:549-555 3969. Bochvar N, Rokhlin L, Lysova E (2010) Carbon – tantalum – tungsten system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 3, pp. 117. Springer, Berlin, Heidelberg 3970. Rudy E (1965) Ta-W-C system. In: Ternary phase equilibria in transition metal – boron – carbon – silicon systems. Technical Report AFML-TR-65-2, Contract USAF 33(615)-1249, Part 2, Vol. 8, pp. 1-141. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 3971. Eremenko VN, Velikanova TYa (1973) Stroenie diagramm sostoyaniya troinykh sistem (Mo, W) – (Ti, Zr, Hf, V, Nb, Ta) – C (Structure of phase diagrams of the (Mo, W) – (Ti, Zr, Hf, V, Nb, Ta) – C ternary systems). In: Ageev VN (ed) Obshchie zakonomernosti stroeniya diagramm sostoyaniya metallicheskikh sistem (The general regularities of the phase diagrams structures of metal systems), pp. 49-52. Nauka, Moscow (in Russian) 3972. Frisk K (1999) A thermodynamic analysis of the Ta-W-C and the Ta-W-C-N systems. Z Metallkd 90(9):704-711 3973. Weidow J, Halwax E, Schubert W-D (2015) Analysis of WC with increased Ta doping. Int J Refract Met Hard Mater 51:56-60 3974. Eremenko VN, Velikanova TYa, Bondar AA (1989) Phase equilibria at the solidus surface of the equilibrium diagram of ternary systems of technetium with carbon and d-transition metals of groups III-VII. Powder Metall Met Ceram 28(11):868-873 3975. Haldar B, Bandyopadhyay D, Sharma RC, Chakraborti N (1999) The Ti-W-C (titaniumtungsten-carbon) system J Phase Equilib 20(3):337-343 3976. Matsumoto O, Hirose H, Kawara Y, Ohue T (1977) Formation and properties of cubic solid solutions in the W-Ti-C, W-Zr-C and W-Hf-C systems. High Temp Sci 9(1):27-34 3977. Ahn SH, Yoo JH, Kim JG, Han JG (2003) On the corrosion behaviour of multilayered WC-Ti1–xAlxN coatings on AISI D2 steel. Surf Coat Technol 163-164:611-619 3978. Lin Y-C, Wang S-W, Lin Y-C (2005) Analysis of microstructure and wear performance of WC-Ti clad layers on steel produced by gas tungsten arc welding. Surf Coat Technol 200:2106-2113 3979. Jeng IK, Lee PY (2007) Mechanically alloyed tungsten carbide particle / Ti50Cu28Ni15Sn7 glassy alloy matrix composites. Mater Sci Eng A 449-451:1090-1094 3980. Li YY, Yang C, Chen WP, Li XQ (2008) Effect of WC content on glass formation, thermal stability and phase evolution of a TiNbCuNiAl alloy synthesized by mechanical alloying. J Mater Res 23(3):745-754 3981. Ghasali E, Ebadzadeh T, Alizadeh M, Razavi M (2018) Spark-plasma sintering of WCbased cermets / titanium and vanadium added composites: a comparative study on the microstructure and mechanical properties. Ceram Int 44(9):10646-10656 3982. Xiang C, Liu C, Wen X, Nie H, Hu C, Luo Z, Li Y, Luo J, Yu Z (2020) Formation of stacking faults in tungsten carbide during sintering. Ceram Int 46(10):15851-15857 3983. Guskos N, Biedunkiewicz A, Typek J, Patapis S, Maryniak M, Karkas SA (2004) Electrical conductivity of TiC and (Ti,W)C ceramic samples. Rev Adv Mater Sci 8:49-52 3984. Farr JD, Bowman MG (1963) Thermodynamic properties and phase relationships in the UC system and selected U-M-C systems. In: Russell LE, Bradbury BT, Harrison JDL, Hedger HJ, Mardon PG (eds) Carbides in nuclear energy. Proc. Int. symp. on carbides in nuclear energy, Harwell, England, 5-7 Nov 1963, Vol. 1 – Physical and chemical properties, phase diagrams, pp. 184-191. Macmillan, London 3985. Chmelik D, Cupid D, Fabrichnaya O, Kriegel M, Pavlyuchkov D, Schuster E (2012) Carbon – vanadium – tungsten system. In: Franke P, Seifert HJ (eds) Ternary steel systems. Subvol. C, Part 1, pp. 321-326. Springer, Berlin, Heidelberg 3986. Chmelik D, Cupid D, Fabrichnaya O, Kriegel M, Pavlyuchkov D, Schuster E (2012) Carbon – iron – tungsten system. In: Franke P, Seifert HJ (eds) Ternary steel systems. Subvol. C, Part 1, pp. 197-207. Springer, Berlin, Heidelberg

792

2 Tungsten Carbides

3987. Chmelik D, Cupid D, Fabrichnaya O, Kriegel M, Pavlyuchkov D, Schuster E (2012) Carbon – molybdenum – tungsten system. In: Franke P, Seifert HJ (eds) Ternary steel systems. Subvol. C, Part 1, pp. 258-269. Springer, Berlin, Heidelberg 3988. Chmelik D, Cupid D, Fabrichnaya O, Kriegel M, Pavlyuchkov D, Schuster E (2012) Carbon – nickel – tungsten system. In: Franke P, Seifert HJ (eds) Ternary steel systems. Subvol. C, Part 1, pp. 300-309. Springer, Berlin, Heidelberg 3989. Rogl P, Naik SK, Rudy E (1977) A constitutional diagram of the system VC0.88 – HfC0.98 – WC. Monatsh Chem 108(5):1213-1234 3990. Bratberg J (2005) Investigation and modification of carbide sub-systems in the multicomponent Fe-C-Co-Cr-Mo-Si-V-W system. Z Metallkd 96(4):335-344 3991. Huang S, Vleugels J, Li L, Van Der Biest O (2005) Experimental investigation and thermodynamic assessment of the V-W-C system. J Alloys Compd 395(1-2):68-74 3992. Wei W, Huang Z, Zhang H, Yang W (2019) Effect of vanadium on microstructure and performance of tungsten carbide hardfacing alloys. Trans China Weld Inst 40(6):131-136 (in Chinese) 3993. Franke P, Neuschütz D (2004) Carbon – tungsten system. In: Franke P, Neuschütz D (eds) Binary systems. Subvol. B, Part 2, pp. 165-166. Springer, Berlin, Heidelberg 3994. Jonsson S (1993) Phase relations in quaternary hard materials. PhD thesis, KTH Royal Institute of Technology, Stockholm, Sweden 3995. Wang K, Reeber RR (1998) Finite element modelling of thermal residual stress in tungsten / tungsten carbide composites. In: Bray D (ed) Proc. 22nd American Ceramic Society annual conf. on composites, advanced ceramics, materials and structures: A, Part 1, Cocoa Beach, Florida, 20-24 Jan 1998. Ceram Eng Sci Proc 19(4):177-184 3996. Gubisch M, Liu Y, Spiess L, Romanus H, Krischok S, Ecke G, Schaefer JA, Knedlik Ch (2005) Nanoscale multilayer WC/C coatings developed for nanopositioning. Part I. Microstructures and mechanical properties. Thin Solid Films 488:132-139 3997. Liu Y, Gubisch M, Hild W, Scherge M, Spiess L, Knedlik Ch, Schaefer JA (2005) Nanoscale multilayer WC/C coatings developed for nanopositioning. Part II. Friction and wear. Thin Solid Films 488:140-148 3998. Ospina R, Castillo HA, Benavides V, Restrepo E, Arango YC, Arias DF, Devia A (2006) Influence of the annealing temperature on a crystal phase W/WC bilayers grown by pulsed arc discharge. Vacuum 81:373-377 3999. Mcherzyńska B, Matsuura K (2008) Spark-plasma sintering of W-C binary hard alloys. In: Paulino GH, Pindera M-J, Dodds RH, Rochinha FA, Dave E, Chen L (eds) Proc. 9th Int. conf. on multiscale and functionally graded materials (FGM IX), Oahu Island, Hawaii, 15-18 Oct 2006. AIP Conf Proc 973:895-900 4000. Goncharov VL, Lakhotkin YuV, Kuzmin VP, Alimov VKh, Roth J (2009) Chemical vapour crystallization of hard nanocomposite tungsten carbide layers for extreme applications. In: Linsmeier Ch., Reinelt M (eds) Proc. 1st Int. conf. on new materials for extreme environments, San Sebastian, Spain, 2-4 June 2008. Adv Mater Res 59:62-65 4001. Dushik VV, Rakoch AG, Lakhotkin YuV, Gladkova AA (2013) Korrozionnostoikie i zharostoikie materialy: khimicheskoe gazofaznoe osazhdenie zashchitnykh pokrytii (Corrosion and heat resistant materials: chemical vapour deposition of protective coatings). MISIS Publishing House, Moscow (in Russian) 4002. Jipa I, Heineman FW, Schneider A, Popovska N, Siddiqi MA, Siddiqui RA, Atakan B, Marbach H, Papp C, Steinrück H-P, Zenneck U (2010) [cis-(1,3-diene)2W(CO)2] complexes as MOCVD precursors for the deposition of thin tungsten – tungsten carbide films. Chem Vap Deposition 16:239-247 4003. Chanthapan S, Kulkarni A, Singh J, Haines C, Kapoor D (2012) Sintering of tungsten powder with and without tungsten carbide additive by field assisted sintering technology. Int J Refract Met Hard Mater 31:114-120

References

793

4004. Agudelo-Morimitsu LC, De La Roche J, Escobar D, Ospina R, Restrepo-Parra E (2013) Substrate heating and post-annealing effect on tungsten / tungsten carbide bilayers grown by non-reactive DC magnetron sputtering. Ceram Int 39:7355-7365 4005. Jiang Y, Yang JF, Liu R, Wang XP, Fang QF (2014) Oxidation and corrosion resistance of WC coated tungsten fabricated by SPS carburization. J Nucl Mater 450:75-80 4006. Jin N, Yang Y, Luo X, Liu S, Xiao Z, Guo P, Huang B (2015) First principles calculation of W/WC interface: atomic structure, stability and electron properties. Appl Surf Sci 324:205-211 4007. Edin E, Blomqvist A, Lattemann M, Luo W, Ahuja R (2019) MD study of C diffusion in WC/W interfaces observed in cemented carbides. Int J Refract Met Hard Mater 85:105054 (8 pp.) 4008. Garcia-Ayala EM, Taranćon S, Gonzales Z, Ferrari B, Pastor JY, Sanchez-Herencia AJ (2019) Processing of WC/W composites for extreme environments by colloidal dispersion of powders and SPS sintering. Int J Refract Met Hard Mater 84:105026 (8 pp.) 4009. Grigoryev EG, Smirnov KL, Strizhakov EL, Neskoromniy SV (2019) Formed nano-WWC coatings on the high-speed steel substrate by the electrodischarge explosion. In: Sorokin D, Grishkov A (eds) Proc. 14th Int. conf. on gas discharge plasmas and their applications (GDP 2019), Tomsk, Russia, 15-21 Sep 2019. J Phys Conf Series 1393:012084 (5 pp.) 4010. Micallef C, Zhuk YN, Wood RJK (2019) Galling resistance of nanostructured CVD tungsten / tungsten carbide coatings. Surf Topogr Metrol Prop 7:025004 (13 pp.) 4011. Šestan A, Zavašnik J, Kržmanc MM, Kocen M, Jenuš P, Novak S, Čeh M, Dehm G (2019) Tungsten carbide as a deoxidation agent for plasma-facing tungsten-based materials. J Nucl Mater 524:135-140 4012. Zhuk YN (2019) Nanostructured CVD W/WC coating prevents galling and adhesive wear of mechanisms under dry sliding conditions. Metall Ital 111(10):45-53 4013. Ma D, Harvey TJ, Zhuk YN, Wellman RG, Wood RJK (2020) Cavitation erosion performance of CVD W/WC coatings. Wear 452-453:203276 (16 pp.) 4014. Yang L, Wirth BD (2020) First principles study of hydrogen behaviour near W/WC interfaces. J Appl Phys 127:115107 (12 pp.) 4015. Chen J-M, Papageorgopoulos CA (1970) Ditungsten carbide overlayer on W (112). Surf Sci 20(1):195-200 4016. Ollis DF, Boudart M (1970) Surface and bulk carburization of tungsten single crystals. Surf Sci 23(2):320-346 4017. Sabzi M, Anijdan SHM, Asadian M (2018) The effect of substrate temperature on microstructural evolution and hardenability of tungsten carbide coating in hot filament chemical vapour deposition. Int J Appl Ceram Technol 15:1350-1357 4018. Novak S, Kocen M, Zavašnik AŠ, Galatanu A, Galatanu M, Taranćon S, Tejado E, Pastor JY, Jenuš P (2020) Beneficial effects of a WC addition in FAST-densified tungsten. Mater Sci Eng A 772:138666 (8 pp.) 4019. Han BQ, Li N (2004) Composition of Al2O3-W-WC composite prepared by WO3-Al reaction under coke. Adv Appl Ceram 103(1):19-22 4020. Sugiyama S, Taimatsu H (2002) Preparation of WC-WB-W2B composites from B4C-WWC powders and their mechanical properties. Mater Trans Jpn Inst Met 43(5):1197-1201 4021. Ospina R, Escobar D, Restrepo-Parra E, Arango PJ, Jurado JF (2012) Substrate temperature influence on W/WCNx bilayers grown by pulsed vacuum arc discharge. Appl Surf Sci 258:5100-5104 4022. Ospina R, Escobar D, Restrepo-Parra E, Arango PJ, Jurado JF (2013) Mechanical and tribological behaviour of W/WCN bilayers grown by pulsed vacuum arc discharge. Tribol Int 62:124-129 4023. Rivera-Tello CD, Broitman E, Florez-Ruiz FJ, Jiménez O, Flores M (2016) Mechanical properties and tribological behaviour at micro- and macro-scale of WC/WCN/W hierarchical multilayer coatings. Tribol Int 101:194-203

794

2 Tungsten Carbides

4024. Hwang I, Guan Z, Li X (2018) Scalable manufacturing of zinc – tungsten carbide nanocomposites. In: Wang L (ed) Proc. 46th SME North American manufacturing research conf. (NAMRC 46), College Station, Texas, 18-22 June 2018. Proc Manuf 26:140-145 4025. Hwang I, Guan Z, Li X (2018) Fabrication of zinc – tungsten carbide nanocomposite using cold compaction followed by melting. J Manuf Sci Eng Trans ASME 140(8):084503 (6 pp.) 4026. Guan Z, Pan S, Linsley C, Li X (2019) Manufacturing and characterization of Zn-WC as potential biodegradable material. In: Fratini L, Ragai I, Wang L (eds) Proc. 47th SME North American manufacturing research conf. (NAMRC 47), Erie, Pennsylvania, 10-14 June 2019. Proc Manuf 34:247-251 4027. Guan Z, Linsley C, Hwang I, Yao G, Wu BM, Li X (2020) Novel zinc / tungsten carbide nanocomposite as bioabsorbable implant. Mater Lett 263:127282 (5 pp.) 4028. Xiong W, Du Y, Zhang W, Xu H (2010) Carbon – tungsten – zirconium system. In: Effenberg G, Ilyenko S, Dovbenko O (eds) Ternary alloy systems. Subvol. E, Part 3, pp. 3147. Springer, Berlin, Heidelberg 4029. Kuzma YuB, Fedorov TF, Shvets EA (1965) Phase equilibria in the system Zr-W-C. Powder Metall Met Ceram 4(2):106-109 4030. Shen P, Zheng X-H, Liu H-J, Jiang Q-C (2013) Wetting of WC by a Zr-base metallic glass-forming alloy. Mater Chem Phys 139:646-653 4031. Connor RD, Choi-Yim H, Johnson WL (1999) Mechanical properties of Zr57Nb5Al10Cu15.4Ni12.6 metallic glass matrix particulate composites. J Mater Res 14(8):32923297 4032. Zhou P, Peng Y, Du Y, Wang S, Wen G (2015) Thermodynamic modelling of the C-W-Zr system. Int J Refract Met Hard Mater 50:274-281 4033. Eremenko VN, Velikanova TYa, Artyukh LV (1984) Triangulyatsiya sistem s dvoinymi i troinymi fazami peremennogo sostava (Triangulation of systems with binary and ternary phases of variable compositions). In: Eremenko VN (ed) Diagrammy sostoyaniya v materialovedenii (Phase diagrams in materials science), pp. 28-37. Naukova Dumka, Kyiv (in Russian) 4034. Samsonov GV, ed (1978) Fiziko-khimicheskie svoistva okislov (Physico-chemical properties of oxides), 2nd ed. Metallurgiya, Moscow (in Russian) 4035. Shveikin GP (1962) Reaction of tungsten carbide with oxides of refractory metals in a vacuum. Powder Metall Met Ceram 1(6):454-457 4036. Josien FA, Renaud R (1965) Reduction des hémipentoxydes de vanadium de niobium et de tantale par le monocarbure de tungstene. (Reduction of vanadium, niobium and tantalum hemipentoxides by tungsten monocarbide). C R Hebd Séanc Acad Sci 260(8):2239-2242 (in French) 4037. Freundlich W, Josien FA, Erb A (1959) Types de reductions et types d’échange dans l’état solide par utilisation du monocarbure de tungstene (Types of reductions and types of exchange in the solid state using tungsten monocarbide). Bull Soc Chim France 11(1):17861787 (in French) 4038. Burykina AL, Strashinskaya LV (1966) A study of new materials operating in contact with certain solid and liquid metals and compounds. Mater Sci 1(5):385-389 4039. Fedorus VB, Kosolapova TYa, Kuzma YuB (1969) Interaction de carbures de métaux de transition des groups IV-VI du système périodique d’éléments avec l’oxyde de zirconium (Interaction of carbides of transition metals of IV-VI groups of the periodic system of elements with zirconium oxide). Rev Int Hautes Temp Refract 6(3):193-197 (in French) 4040. Samsonov GV, Burykina AL, Strashinskaya LV, Pugach ÉA (1964) Reactions between magnesium oxide or zirconium dioxide and refractory compounds at high temperatures under vacuum. Russ Metall (4):70-79 4041. Krylov YuI, Balakir ÉA (1976) Karbidno-okisnye sistemy (Carbide-oxide systems). Metallurgiya, Moscow (in Russian)

References

795

4042. Klimak ZA, Kotlyar EE, Serebryakova TI, Yukhimenko EV (1972) Character of the reactions of carbides of transition metals of groups IV-VI with ferric oxide. Inorg Mater 8(9):1404-1408 4043. Loshak MG (1984) Prochnost i dolgovechnost tverdykh splavov (The strength and durability of hard alloys). Naukova Dumka, Kyiv (in Russian) 4044. Malkov LP, Vikker IV (1936) Vzaimnaya rastvorimost tugoplavkikh karbidov metallov (Mutual solubility of the refractory metals carbides). Vestn Metalloprom (6):75-82 (in Russian) 4045. Dawihl W (1950) Über Rundkristallbildung und die Existenz des Molybdänkarbids MoC (On some crystal formation and existence of molybdenum carbide MoC). Z Anorg Allg Chem 262:212-217 (in German) 4046. Albert HJ, Norton JT (1956) Isotherme Abschnitte in den Systemen Molybdän – Wolfram – Kohlenstoff und Molybdän – Titan – Kohlenstoff (Isothermal sections in the systems molybdenum – tungsten – carbon and molybdenum – titanium – carbon). Planseeber Pulvermetall 4(1):2-6 (in German) 4047. Albert HJ (1956) Isothermal sections in the systems molybdenum – tungsten – carbon and molybdenum – titanium – carbon. PhD thesis, Massachusetts Institute of Technology, Cambridge 4048. Schuster JC, Nowotny H (1979) Molybdän- und Molybdän-Wolfram-Carbide im Temperaturbereich von 600-1600 °C (Molybdenum and molybdenum-tungsten carbides within the temperature range of 600-1600 °C). Monatsh Chem 110:321-332 (in German) 4049. Eremenko VN, Velikanova TYa, Sleptsov SV, Bondar AA (1984) Struktura i nekotorye svoistva splavov v sisteme Mo-W-C secheniya MoC0.65-WC0.62 (Structure and some properties of the alloys of the Mo-W-C system along the section MoC0.65-WC0.62). In: Eremenko VN (ed) Diagrammy sostoyaniya v materialovedenii (Phase diagrams in materials science), pp. 37-50. Naukova Dumka, Kyiv (in Russian) 4050. Trusov LI, Voskresenskii YuA, Repin IA, Novikov VI, Lapovok VN, Troitskii VN, Plotkin SS (1989) Mass transport and phase transformations in a system of small Mo-W-C particles. Powder Metall Met Ceram 28(7):519-524 4051. Throop GJ, Rogl P, Rudy E (1978) Calculation of phase equilibria in ternary alloy systems: line compounds. High Temp High Press 10:553-559 4052. Hinnüber J, Rüdiger O (1953) Hartmetall-Legierungen hoher Korrosions- und Oxidationsbeständigkeit (Hard metal alloys of high corrosion and oxidation resistance). Arch Eisenhuttenwes 24(5-6):267-274 (in German) 4053. Kiparisov SS, Nikiforov OA, Borisova NV (1968) Psevdobinarnyi razrez troinoi sistemy volfram – bor – uglerod (Pseudobinary section of the tungsten – boron – carbon ternary system). Sb Mosk Inst Stali Splavov 45:128-131 (in Russian) 4054. Sato F, Sakamoto A (2010) Effect of glass composition on interaction between alkalisilicate glass and WC mold. J Non-Cryst Solids 356:1210-1212 4055. Koontz E, Wachtel P, Musgraves JD, Richardson K, Mourad S, Huber M, Kunz A, Forrer M (2013) Interaction of N-FK5 and L-BAL35 optical glass with various carbides and other precision glass mold tooling. In: Bentley JL, Pfaff M (eds) Proc. Int. Society of Photo-Optical Instrumentation Engineers conf. (Optifab 2013), Rochester, New York, 14-17 Oct 2013. Proc SPIE 8884:8884-1Y(8884-90) 4056. Ullegaddi K, Mahesha CR, Shivarudraiah NA (2020) Influence of graphene and tungsten carbide reinforcement on tensile and flexural strength of glass fibre epoxy composites. In: Reddy ANR, Marla D, Simić M, Favorskaya MN, Satapathy SC (eds) Proc. Int. conf. on intelligent manufacturing and energy sustainability (ICIMES 2019), Hyderabad, India, 21-22 June 2019, pp. 379-389. Springer Nature, Singapore 4057. Mohan N, Mahesha CR, Rajaprakash BM (2013) Erosive wear behaviour of WC filled glass epoxy composites. In: Hassan MB (ed) Proc. Malaysian Int. tribology conf. (MITC 2013), Sabah, Malaysia, 18-20 Nov 2013. Proc Eng 68:694-702

796

2 Tungsten Carbides

4058. Deloume J-P, Marote P, Sigala C, Matei C (2003) Study of the reaction of tungsten carbide in molten alkali metal nitrates. Synthesis of divalent (s and d blocks) metal tungstates. J Solid State Chem 174:1-10 4059. Paderno Yu, Paderno V, Liashchenko A, Filipov V, Evdokimova A, Martynenko A (2006) The directional crystallization of W – B – C – d-transition metal alloys. J Solid State Chem 179:2939-2943 4060. Suetin DV, Shein IR, Ivanovskii AL (2011) Structural, electronic and magnetic properties of tungsten oxycarbides WC1–xOx and WO3–xCx from first principles calculations. Phys Stat Sol B 248(12):2884-2892 4061. Suetin DV, Shein IR, Ivanovskii AL (2009) Electronic structure of tungsten carbonitrides WC1–xNx. J Struct Chem 50(1):1-9 4062. Ivanovskii AL, Gusev AI, Shveikin GP (1996) Kvantovaya khimiya v materialovedenii: troinye Karbidy i nitridy perekhodnykh metallov i elementov IIIb, IVb podgrupp (Quantum chemistry in materials science: ternary carbides and nitrides of transition metals and groups IIIb, IVb elements). The Ural Branch of the Russian Academy of Sciences, Yekaterinburg (in Russian) 4063. Ivanovskii AL (1996) Ternary carbides and nitrides based on transition metals and subgroup IIIb and IVb elements. Russ Chem Rev 65(6):461-478 4064. Suetin DV, Shein IR, Bamburov VG, Ivanovskii AL (2009) Influence of carbon vacancies on the electronic properties of solid solutions in the W-Al-C system from first principles calculations. Dokl Phys Chem 424(1):14-16 4065. Suetin DV, Shein IR, Ivanovskii AL (2010) Structural, elastic, electronic and magnetic properties of perovskite-like Co3WC, Rh3WC and Ir3WC from first principles calculations. Solid State Sci 12(5):814-817 4066. Sun Z, Music D, Ahuja R, Li S, Schneider JM (2004) Bonding and classification of nanolayered ternary carbides. Phys Rev B 70:092102 (3 pp.) 4067. Wang Y, Heusch M, Lay S, Allibert CH (2002) Microstructure evolution in the cemented carbides WC-Co. I. Effect of the C/W ratio on the morphology and defects of the WC grains. Phys Stat Sol A 193(2):271-283 4068. Wang Y, Pauty E, Lay S, Allibert CH (2002) Microstructure evolution in the cemented carbides WC-Co. II. Cumulated effects of Cr additions and of the C/W ratio on the crystal features of the WC grains. Phys Stat Sol A 193(2):284-293 4069. Zhu S-G, Qu H-X, Ouyang C-X (2014) Hot-pressing of tungsten carbide ceramic matrix composites. In: Low IM (ed) Advances in ceramic matrix composites, pp. 190-217. Woodhead Publishing, Oxford, Cambridge, UK 4070. Maitra S, Roy J (2018) Nanoceramic matrix composites: types, processing and applications. In: Low IM (ed) Advances in ceramic matrix composites, 2nd ed., pp. 27-48. Woodhead Publishing, Duxford, UK, Cambridge, USA 4071. Zhang J, Saeed MH, Li S (2018) Recent progress in development of high-performance tungsten carbide – based composites: synthesis, characterization and potential applications. In: Low IM (ed) Advances in ceramic matrix composites, 2nd ed., pp. 307-329. Woodhead Publishing, Duxford, UK, Cambridge, USA 4072. Mukhopadhyay A, Basu B (2007) Consolidation – microstructure – property relationships in bulk nanoceramics and ceramic nanocomposites, a review. Int Mater Rev 52(5):257-288 4073. Rajaei H, Farvizi M, Mobasherpour I, Zakeri M (2018) Effect of spark-plasma sintering temperature on microstructure and mechanical properties of mullite – WC composites. Int J Refract Met Hard Mater 70:197-201 4074. Crayton PH, Greene EE (1973) Synthesis-fabrication of an Al2O3 – tungsten carbide composite. J Am Ceram Soc 56(8):423-426 4075. Belyaev AV, Zlenko AA, Chernenko AN (1990) Some properties of hot-compacted aluminium oxide with additions of tungsten carbide. Powder Metall Met Ceram 29(11):932934

References

797

4076. Endo H, Ueki M (1994) Microstructure and mechanical properties of hot-pressed and pressureless sintered WC-Al2O3 ceramic composites. In: Fauchet PM, Poker DB, Taub AI (eds) Proc. MRS Fall meeting symp., Boston, Massachusetts, 29 Nov – 2 Dec 1993. Mater Res Soc Symp Proc 327:331-336 4077. Maslov KI, Morozov AI, Sun K, Cao Z, Liu Y, Wang X (1996) Acoustic microscope studies of tool corundum ceramic Al2O3 + (Ti W)C. Russ Ultrasonics 26(1):59-63 4078. Zhang J, Lee JH, Won CW, Cho SS, Chun BS (1999) Synthesis of Al2O3-WC composite powder by SHS process. J Mater Sci 34:5211-5214 4079. Acchar W, Martinelli AE, Vieira FA, Cairo CAA (2000) Sintering behaviour of alumina – tungsten carbide composites. Mater Sci Eng A 284:84-87 4080. Schaupp D, Schneider J, Zum-Gahr K-H (2000) Einfluss der Randschicht lasermodifizierter Al2O3-Keramik auf den ungeschmierten oszillierenden Gleitverschleiß (Influence of lasermodified Al2O3-ceramic surface layers on unlubricated oscillating sliding contact). Keram Z 52(9):776-784 (in German) 4081. Schaupp D, Schneider J, Zum-Gahr K-H (2001) Wear mechanisms on multi-phase Al2O3 ceramics during running-in period in unlubricated oscillating sliding contact. Tribol Lett 9(34):125-131 4082. Wang L, Shi J-L, Gao J-H, Yan D-S (2001) Influence of tungsten carbide particles on resistance of alumina matrix ceramics to thermal shock. J Eur Ceram Soc 21:1213-1217 4083. Wang L, Shi J-L, Hua Z-L, Gao J-H, Yan D-S (2001) The influence of addition of WC particles on mechanical properties of alumina matrix composite. Mater Lett 50:179-182 4084. Tavares ECS, Costa FA, Gomes UU, Acchar W (2003) Mechanical characterization of alumina-doped tungsten carbide. Mater Sci Forum 416-418(1):616-620 4085. Motoc Ş, Abagiu A, Neagu R, Volceanov E, Gurban AM, Motoc AM (2004) Influence of forming conditions on characteristics of alumina composite reinforced with non-oxide particles. In: Mandal H, Öveçoğlu L (eds) Euro Ceramics VIII. Proc. 8th conf. and exhibition of the European Ceramic Society, Istanbul, Turkey, 29 June – 3 July 2003. Key Eng Mater 264-268(2):853-856 4086. Acchar W, Cairo CAA, Segadães AM (2005) Effect of tungsten carbide additions on the microstructure and properties of hot-pressed alumina. Mater Sci Eng A 406:74-77 4087. El-Eskandarany MS (2005) Fabrication and characterizations of new nanocomposite WC/Al2O3 materials by room temperature ball milling and subsequent consolidation. J Alloys Compd 391:228-235 4088. Acchar W, Zollfrank C, Greil P (2006) Microstructure of alumina reinforced with tungsten carbide. Mater Sci 41:3299-3302 4089. Faryna M (2006) Microbeam studies of alumina-based composite. In: Proc. workshop on progress in microstructure characterization by electron microscopy, Zakopane, Poland, 30 Sep – 2 Oct 2005. Arch Metall Mater 51(1):75-81 4090. Sztwiertnia K, Faryna M, Sawina G (2006) Quantitative misorientation characteristics of interphase boundaries in composites. J Microsc 224(1):4-7 4091. Grabowski G, Pędzich Z (2007) Residual stresses in particulate composites with alumina and zirconia matrices. J Eur Ceram Soc 27:1287-1292 4092. Pallone EMJA, Martin DR, Tomasi R, Filho WJB (2007) Al2O3-WC synthesis by highenergy reactive milling. Mater Sci Eng A 464:47-51 4093. Pędzich Z (2007) The abrasive wear of alumina matrix particulate composites at different environments of work. In: Zhang D, Pickering K, Gabbitas B, Cao P, Langdon A, Torrens R, Verbeek J (eds) Proc. 4th Int. conf. on advanced materials and processing (ICAMP-4), Hamilton, New Zealand, 10-13 Dec 2006. Adv Mater Res 29-30:283-286 4094. Pędzich Z (2007) The microstructure and Weibull statistic of alumina-WC particulate composites. In: Kageyama K, Ishikawa T, Takeda N, Hojo M, Sugimoto S, Ogasawara T (eds) A giant step towards environmental awareness: from green composites to aerospace. Proc. 16th Int. conf. on composite materials (ICCM-16), Kyoto, Japan, 8-13 July 2007, Po-05 (6 pp.). Japan Society for Composite Materials, Japan Aerospace Exploration Agency, Tokyo

798

2 Tungsten Carbides

https://www.iccm-central.org/Proceedings/ICCM16proceedings/contents/pdf/Poster/Po05ge_pedzichz224124p.pdf Accessed 16 October 2021 4095. Pędzich Z (2009) Fracture of oxide matrix composites with different phase arrangement. In: Dusza J, Danzer R, Morrell R, Quinn GD (eds) Proc. 3rd Int. conf. on fractography of advanced ceramics, Stara Lesna, Slovakia, 7-10 Sep 2008. Key Eng Mater 409:244-251 4096. Yang FZ, Ai X, Zhao J (2009) Preparation and characterization of WC matrix nanocomposite cermet. In: Guo D, Wang J, Jia Z, Kang R, Gao H, Wang X (eds) Advances in materials manufacturing science and technology XIII. Proc. 13th Int. manufacturing conf. in China (IMCC 2009), Dalian, China, 21-23 Sep 2009. Mater Sci Forum 628-629:459-464 4097. Huang S, Vanmeensel K, Van Der Biest O, Vleugels J (2010) Pulsed electric current sintering and characterization of ultra-fine Al2O3-WC composites. Mater Sci Eng A 527:584589 4098. Zakeri M, Rahimipour MR, Sadrnezhad SKh, Yazdanni-Rad R (2010) Preparation of alumina – tungsten carbide nanocomposite by mechano-chemical reduction of WO3 with aluminium and graphite. J Alloys Compd 491:203-208 4099. Boonpo J, Buggakupta W, Chuankrerkkul N (2011) Microstructure and mechanical properties of Al2O3/WC composites with Ca-PSZ addition. Malaysian J Microsc 7(1):26-30 4100. Pędzich Z, Maziarz W (2011) Nanocomposites in the ZrO2-Al2O3-WC system. Acta Metall Slovaca 17(2):84-89 4101. Acchar W, Da Camara CRF, Cairo CAA, Filgueira M (2012) Mechanical performance of alumina reinforced with NbC, TiC and WC. Mater Res 15(6):821-824 4102. Niyomwas S (2012) Synthesis of alumina – tungsten carbide composites by self-propagating high-temperature synthesis process. In: Bu JL, Jiang ZY, Jiao SH (eds) Advanced materials. Proc. 2nd Int. conf. on advances in materials and manufacturing processes (ICAMMP 2011), Guilin, China, 16-18 Dec 2011. Adv Mater Res 415-417:226-231 4103. Qu H-X, Zhu S-G (2012) Phase transformation during the hot-pressing of WC – 40 vol.% Al2O3 composites. In: Jin W (ed) Mechanical engineering and materials. Selected papers from Int. conf. on mechanical engineering and materials (ICMEM 2012), Melbourne, Australia, 15-16 Jan 2012. Appl Mech Mater 152-154:260-265 4104. Qu H-X, Zhu S-G, Li Q, Ouyang C-X (2012) Influence of sintering temperature and holding time on the densification, phase transformation, microstructure and properties of hotpressed WC – 40 vol.% Al2O3 composites. Ceram Int 38:1371-1380 4105. Qu H-X, Zhu S-G, Li Q, Ouyang C-X (2012) Microstructure and mechanical properties of hot-pressing sintered WC – x vol.% Al2O3 composites. Mater Sci Eng A 543:96-103 4106. Zakeri M, Rahimipour MR (2012) Effect of cup and ball types on alumina – tungsten carbide nanocomposite powder synthesized by mechanical alloying. Adv Powder Technol 23:31-34 4107. Zheng D, Li X, Ai X, Yang C, Li Y (2012) Bulk WC-Al2O3 composites prepared by sparkplasma sintering. Int J Refract Met Hard Mater 30(1):51-56 4108. Landfried R, Kern F, Gadow R, Burger W, Leonhardt W (2013) Development of electrical discharge machinable ZTA ceramics with 24 vol.% of TiC, TiN, TiCN, TiB2 and WC as electrically conductive phase. Int J Appl Ceram Technol 10(3):509-518 4109. Nayak PK, Lin H-T, Chang M-P, Chen W-H, Huang J-L (2013) Microstructure analysis and mechanical properties of a new class of Al2O3-WC nanocomposites fabricated by sparkplasma sintering. J Eur Ceram Soc 33:3095-3100 4110. Pei Y, Zhu S-G, Qu H-X (2013) Two-step hot-pressing sintering of composite WC – 40 vol.% Al2O3 compacts. Acta Mater Compos Sin 30(6):127-134 (in Chinese) 4111. Qu H-X, Zhu S-G, Di P, Ouyang C-X, Li Q (2013) Microstructure and mechanical properties of WC – 40 vol.% Al2O3 composites hot-pressed with MgO and CeO2 additives. Ceram Int 39:1931-1942 4112. Qu H-X, Zhu S-G (2013) Two-step hot-pressing sintering of dense fine-grained WC-Al2O3 composites. Ceram Int 39:5415-5425

References

799

4113. Qu H-X, Zhu S-G, Gu W, Li Q, Ouyang C-X (2013) Microstructure and mechanical properties of hot-pressed WC matrix composites toughened by commercial Al2O3 and αAl2O3 particulates. J Ceram Process Res 14(3):363-370 4114. Sakaki M, Bafghi MSh, Vahdati-Khaki J, Zhang Q, Saito F (2013) Conversion of W2C to WC phase during mechano-chemical synthesis of nanosized WC-Al2O3 powder using WO3 – 2Al – (1 + x)C mixtures. Int J Refract Met Hard Mater 36:116-121 4115. Bafghi MSh, Sakaki M, Vahdati-Khaki J, Zhang Q, Saito F (2014) Evaluation of process behaviour and crystallite specifications of mechano-chemically synthesized WC-Al2O3 nanocomposites. Mater Res Bull 49:160-166 4116. Chen W-H, Lin H-T, Nayak PK, Huang J-L (2014) Material properties of tungsten carbide – alumina composites fabricated by spark-plasma sintering. Ceram Int 40:15007-15012 4117. Chuankrerkkul N, Buggakupta W, Surawatthana J (2014) Role of tungsten carbide reinforcement in alumina matrix composites fabricated by powder injection moulding. In: Sirisoonthorn S, Jiemsirilers S, Nilpairach S, Wasanapianpong T, Sujaridworakun P, Chuankrerkkul N (eds) Proc. Int. conf. on traditional and advanced ceramics (ICTA 2013), Bangkok, Thailand, 11-13 Sep 2013. Key Eng Mater 608:230-234 4118. Dong W-W, Zhu S-G, Wang Y, Bai T (2014) Influence of VC and Cr3C2 as grain growth inhibitors on WC-Al2O3 composites prepared by hot-pressing sintering. Int J Refract Met Hard Mater 45:223-229 4119. Sakaki M, Karimzadeh-Behnami A, Bafghi MSh (2014) An investigation of the fabrication of tungsten carbide – alumina composite powder from WO3, Al and C reactants through microwave-assisted SHS process. Int J Refract Met Hard Mater 44:142-147 4120. Chen W-H, Nayak PK, Lin H-T, Lee AC, Huang J-L (2015) Enhanced mechanical properties of WC-reinforced Al2O3 ceramics via spark-plasma sintering. Ceram Int 41:13171321 4121. Chen W-H, Lin H-T, Nayak PK, Chang M-P, Huang J-L (2015) Sintering behaviour and mechanical properties of WC-Al2O3 composites prepared by spark-plasma sintering (SPS). Int J Refract Met Hard Mater 48:414-417 4122. Dong W-W, Zhu S-G, Bai T, Luo Y (2015) Influence of Al2O3 whisker concentration on mechanical properties of WC – Al2O3 whisker composite. Ceram Int 41:13685-13691 4123. Sakaki M, Bafghi MSh, Vahdati-Khaki J (2015) Effect of heat absorbing alumina addition on mechano-chemical synthesis of WC-Al2O3 nanocomposites. Adv Appl Ceram 114(3):144149 4124. Sharma SK, Kumar BVM, Kim Y-W (2015) Effect of WC addition on sliding wear behaviour of SiC ceramics. Ceram Int 41:3427-3437 4125. Chen W-H, Lin H-T, Chen J, Nayak PK, Lee AC, Lu H-H, Huang J-L (2016) Microstructure and wear behaviour of spark-plasma sintering sintered Al2O3/WC-based composite. Int J Refract Met Hard Mater 54:279-283 4126. Dong W-W, Zhu S-G, Qu H-X, Liu X (2016) Microstructural evolution and mechanical properties of hot-pressed WC – α-Al2O3 with Y2O3 and CeO2. Adv Appl Ceram 115(6):316321 4127. Gao X-H, Wang C-B, Guo Z-M, Geng Q-F, Theiss W, Liu G (2016) Structure, optical properties and thermal stability of Al2O3-WC nanocomposite ceramic spectrally selective solar absorbers. Optic Mater 58:219-225 4128. Luo Y, Liu X, Dong W-W, Zhu S-G (2016) Friction and wear properties of WC-Al2O3 composite. Acta Mater Compos Sin 33(11):2584-2590 (in Chinese) 4129. Ma N, Wu H, Lu G, Guo L, Ye F (2016) Design and preparation of WC composite powders and coatings with in situ synthesis Al2O3. Rare Met Mater Eng 45(4):1012-1017 (in Chinese) 4130. Oh S-J, Kim B-S, Yoon J-K, Hong K-T, Shon I-J (2016) Enhanced mechanical properties and consolidation of the ultra-fine WC-Al2O3 composites using pulsed current activated heating. Ceram Int 42:9304-9310

800

2 Tungsten Carbides

4131. Xia X, Li X, Li J, Zheng D (2016) Microstructure and characterization of WC – 2.8 wt.% Al2O3 – 6.8 wt.% ZrO2 composites produced by spark-plasma sintering. Ceram Int 42:1418214188 4132. Karimzadeh-Behnami A, Sakaki M, Bafghi MSh, Yanagisawa K (2017) Facile microwave-assisted fabrication of WC-Al2O3 composite powder from WO3-Al-C mixture. Trans Nonferr Met Soc China 27:2630-2637 4133. Heidarpour A, Shahin N, Kazemi Sh (2017) A novel approach to in situ synthesis of WCAl2O3 composite by high-energy reactive milling. Int J Refract Met Hard Mater 64:1-6 4134. Pötschke J, Berger C, Vornberger A (2017) Carbide-oxide composites made from nanoscaled tungsten carbide, alumina and zirconia powders. In: Goto R, Strauss JT (eds) Advances in powder metallurgy and particulate materials. Proc. Int. conf. on powder metallurgy and particulate materials (PowderMet 2017), Las Vegas, Nevada, 13-16 June 2017, pp. 693-700. Metal Powder Industries Federation, Princeton, New Jersey 4135. Sun J, Zhao J, Chen M, Ni X, Li Z, Gong F (2017) Determination of microstructure and mechanical properties of VC/Cr3C2 reinforced functionally graded WC-TiC-Al2O3 micronano composite tool materials via two-step sintering. J Alloys Compd 709:197-205 4136. Vornberger A, Pötschke J, Berger C (2017) Manufacturing and properties of tungsten carbide – oxide composites. In: Herrmann AS (ed) Proc. 21st symp. on composites, Bremen, Germany, 5-7 July 2017. Key Eng Mater 742:223-230 4137. Bai T, Xie T (2018) Influence of TiO2 contents and sintering temperature on the microstructure and mechanical properties of WC-Al2O3 cemented carbide reinforced by multi-wall carbon nanotubes. J Alloys Compd 745:562-568 4138. Sun J, Zhao J, Ni X, Gong F, Li Z (2018) Fabrication of dense nanolaminated tungsten carbide materials doped with Cr3C2/VC through two-step sintering. J Eur Ceram Soc 38:3096-3103 4139. Su Q, Zhu S-G, Ding H, Bai Y, Di P (2018) Effect of the additive VC on tribological properties of WC-Al2O3 composites. Int J Refract Met Hard Mater 64:111-117 4140. Shao T-Q, Ma H, Feng M-D, Wang J, Yan M-B, Wang J-F, Zhao S-X, Qu S-B (2020) A thin dielectric ceramic coating with good absorbing properties composed by tungsten carbide and alumina. J Alloys Compd 818:152851 (9 pp.) 4141. Li J, Li X, Xia X (2022) Effects of Al2O3-ZrO2 content on the densification, microstructure and mechanical properties of cemented tungsten carbides. Mater Chem Phys 276:125330 (11 pp.) 4142. Tang HG, Ma XF, Zhao W, Yan XW, Yan JM (2004) Synthesis, reactive mechanism and thermal stability of W1–xAlxC (x = 0.33, 0.5, 0.75, 0.86) nanocrystalline. Mater Res Bull 39:707-713 4143. Schneider JM, Sun Z, Music D (2005) Theoretical investigation of the bonding and solubility in Nb2–xWxAlC. J Phys Condens Matter 17:6047-6056 4144. Music D, Sun Z, Ahuja R, Schneider JM (2005) Coupling in nanolaminated ternary carbides studied by theoretical means: the influence of electronic potential approximations. Phys Rev B 73:134117 (5 pp.) 4145. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2006) Crystallization and characterization of substoichiometric compound (W0.5Al0.5)C0.5 obtained by solid state reaction. Metall Mater Trans A 37(5):1692-1695 4146. Emmerlich J, Music D, Houben A, Dronskowski R, Schneider JM (2007) Systematic study on the pressure dependence of M2AlC phases (M = Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W). Phys Rev B 76:224111 (7 pp.) 4147. Yan JM, Ma XF, Zhao W, Tang HG, Zhu CJ, Cai SG (2007) High-pressure sintering study of a novel hard material (W0.5Al0.5)C0.5 without binder metal. Int J Refract Met Hard Mater 25:62-66 4148. Suetin DV, Shein IR, Ivanovskii AL (2008) Structural, elastic and electronic properties and formation energies for hexagonal (W0.5Al0.5)C in comparison with binary carbides WC and Al4C3 from first principles calculations. Phys B 403:2654-2661

References

801

4149. Lee HY, Han JG, Baeg SH, Yang SH (2002) Structure and properties of WC-CrAlN superlattice films by cathodic arc ion plating process. Thin Solid Films 420-421:414-420 4150. Lee HY, Han JG, Baeg SH, Yang SH (2003) Characterization of WC-CrAlN heterostructures obtained using a cathodic arc ion plating process. Surf Coat Technol 174-175:303309 4151. Ren X, Peng Z, Peng Y, Wang C, Fu Z, Qi L, Miao H (2013) Ultra-fine binderless WCbased cemented carbides with varied amounts of AlN nanopowder fabricated by sparkplasma sintering. Int J Refract Met Hard Mater 41:308-314 4152. Stanishevsky AV, Walock MJ, Zou Y, Imhoff L, Zairi A, Nouveau C (2013) Growth of WC-Cr-N and WC-Al-N coatings in a RF-magnetron sputtering process. Vacuum 90:129-134 4153. Wen G, Li SB, Zhang BS, Guo ZX (2000) Processing of in situ toughened B-W-C composites by reaction hot-pressing of B4C and WC. Scripta Mater 43:853-857 4154. Dash T, Nayak BB (2016) Preparation of multi-phase composite of tungsten carbide, tungsten boride and carbon by arc-plasma melting: characterization of melt-cast product. Ceram Int 42:445-459 4155. Radev D, Avramova I, Kovacheva D, Gautam D, Radev I (2016) Synthesis of boron carbide by reactive pulsed electric current sintering in the presence of tungsten boride. Int J Appl Ceram Technol 13(6):997-1007 4156. Rahimi A, Baharvandi H (2017) Effect of tungsten carbide nanoparticles on mechanical properties and sinterability of B4C-WC nanocomposites using pressureless sintering method. Int J Refract Met Hard Mater 66:220-225 4157. Shanholtz ER, LaSalvia JC, Behler KD, Walck SD, Giri A, Kuwelkar K (2017) Chemical interactions in B4C/WC powder mixtures heated under inert and oxidizing atmospheres. In: LaSalvia JC, Narayan R, Colombo P (eds) Advances in ceramic armour, bioceramics and porous materials. Proc. 14th armour ceramics symp. at 40th Int. conf. on advanced ceramics and composites (ICACC 2016), Daytona Beach, Florida, 24-29 Jan 2016. Ceram Eng Sci Proc 37(4):57-64 4158. Felba J, Friedel KP, Krull P, Pobol IL, Wohlfahrt H (2001) Electron beam activated brazing of cubic boron nitride to tungsten carbide cutting tools. Vacuum 62:171-180 4159. Prakash LJ (1995) Application of fine grained tungsten carbide based cemented carbides. Int J Refract Met Hard Mater 13:257-264 4160. Li X, Cao T, Zhang M, Qiu H, Huang Y, Qu S, Liang L, Song T (2020) Ultra-fine porous boron nitride nanofiber – toughened WC composites. Int J Appl Ceram Technol 17(3):941948 4161. Cao T, Li X, Li J, Huang Y, Qu S, Yang C, Liang L, Song T (2021) Mechanical properties of WC-Si3N4 composites with ultra-fine porous boron nitride nanofiber additive. Front Mater 8:534407 (9 pp.) 4162. Zhao J, Lin D-Q, Yao S-J (2009) Expansion and hydrodynamic properties of β-cyclodextrin polymer / tungsten carbide composite matrix in an expanded bed. J Chromatogr A 1216:7840-7845 4163. Zhao J, Lin D-Q, Wang Y-C, Yao S-J (2010) A novel β-cyclodextrin polymer / tungsten carbide composite matrix for expanded bed adsorption: preparation and characterization of physical properties. Carbohydrate Polym 80:1085-1090 4164. Xia H-F, Lin D-Q, Yao S-J (2007) Preparation and characterization of macroporous cellulose – tungsten carbide composite beads for expanded bed applications. J Chromatogr A 1175:55-62 4165. Xia H-F, Lin D-Q, Yao S-J (2008) Chromatographic performance of macroporous cellulose – tungsten carbide composite beads as anion-exchanger for expanded bed adsorption at high fluid velocity. J Chromatogr A 1195:60-66 4166. Phottraithip W, Wang Z-Y, Lin D-Q, Yao S-J (2010) Preparation of cellulose / tungsten carbide composite beads with direct dissolution method for expanded bed application. J Zhejiang Univ Eng Sci 44(5):998-1002 (in Chinese)

802

2 Tungsten Carbides

4167. Vogler TJ, Alexander CS, Wise JL, Montgomery ST (2010) Dynamic behaviour of tungsten carbide and alumina filled epoxy composites. J Appl Phys 107:043520 (13 pp.) 4168. Canel A, Korkut H, Korkut T (2019) Improving neutron and gamma flexible shielding by adding medium-heavy metal powder to epoxy based composite materials. Radiat Phys Chem 158:13-16 4169. Gavrish V, Baranov G, Velyaev Yu, Gavrish O (2019) Study on production of composite based on epoxy matrix modified by hard alloy waste processing products. In: Bratan S, (ed) Proc. Int. conf. on modern trends in manufacturing technologies and equipment (ICMTMTE 2018), Sevastopol, Crimea, Ukraine, 10-14 Sep 2018. Mater Today Proc 11(1):548-553 4170. Li W, Meng F, Li YF, Huang X (2019) Topological design of 3D phononic crystals for ultra-wide omnidirectional bandgaps. Struct Multidisc Optim 60:2405-2415 4171. Ullegaddi K, Shivarudraiah NA, Mahesha CR (2019) Significance of tungsten carbide filler reinforcement on ultimate tensile strength of basalt fiber epoxy composites. Int J Recent Technol Eng 8(3):7913-7916 4172. Ullegaddi K, Shivarudraiah NA, Mahesha CR (2019) Flexural strength of basalt fiber reinforced with tungsten carbide filler filled epoxy composites. J Emerg Technol Innov Res 6(6):791-795 4173. Reddy MK, Babu VS, Srinadh KV (2020) Microhardness and erosive wear behaviour of tungsten carbide filled epoxy polymer nanocomposites. Int J Math Eng Manag Sci 5(3):405410 4174. Huang H, Guo Z-C (2010) Synthesis and polymerization mechanism of polyaniline / tungsten carbide composites. Acta Polym Sin (10):1180-1185 (in Chinese) 4175. Huang H, Guo Z-C, Li J-K, Chen B-M (2010) Structural change and failure behaviour of polyaniline / tungsten carbide anode during electrowinning of zinc. Chin J Process Eng 10(5):1020-1024 (in Chinese) 4176. Huang H, Guo Z-C (2011) Conductive composite of polyaniline and tungsten carbide. Polym Sci 53(1-2):31-34 4177. Huang H, Fu R-C, Guo Z-C (2012) Thermal degradation behaviour of polyaniline in polyaniline / tungsten carbide composite. In: Kao J (CM), Sung W-P, Chen R (eds) Frontiers of materials, chemical and metallurgical technologies. Proc. Int. conf. on chemical engineering, metallurgical engineering and metallic materials (CMMM 2012), Kun Ming, China, 12-13 Oct 2012. Adv Mater Res 581-582(1):719-722 4178. Adesina AY, Khan MF, Azam MU, Samad MA, Sorour AA (2019) Characterization and corrosion resistance of ultra-high molecular weight polyethylene composite coatings reinforced with tungsten carbide particles in hydrochloric acid medium. J Polym Eng 39(10):861-873 4179. Clarizia G, Torchia AM, Drioli E (2004) Influence of additives on CO2 transport in PEEKWC membranes. In: Plawsky J, Martin LL (eds) Proc. 2004 AIChE annual meeting, Austin, Texas, 7-12 Nov 2004, pp. 6411-6414. The American Institute of Chemical Engineers, New York 4180. Sharma S, Joshi P, Mehtab S, Zaidi MGH, Singhal K, Siddiqi TI (2020) Development of non-enzymatic cholesterol electrochemical sensor based on polyindole / tungsten carbide nanocomposite. J Anal Test 4(1):13-22 4181. Du Y, Chen J, Liu X, Lu C, Xu J, Paul B, Eklund P (2018) Flexible n-type tungsten carbide / polylactic acid thermoelectric composites fabricated by additive manufacturing. Coatings 8(1):25 (7 pp.); doi:10.3390/coatings8010025 4182. Abbas B, Hashim A (2019) Novel X-ray attenuation by PMMA-PS-WC new nanocomposites: fabrication, structural, optical characterizations and X-ray shielding application. Int J Emerg Trends Eng Res 7(8):131-144 4183. Derradji M, Zegaoui A, Medjahed A, Liu W, Henniche A (2020) Hybrid phthalonitrilebased materials with advanced mechanical and nuclear shielding performances. Polym Compos 41(1):134-141

References

803

4184. Xu C, Fan G, Qu Y, Liu Y, Zhang Z, Fan R (2020) Core-shell structured tungsten carbide / polypyrrole metacomposites with tailorable negative permittivity at the radio frequency. Polymer 188:122125 (8 pp.) 4185. Moskała N, Pyda W (2006) Thermal stability of tungsten carbide in 7 mol.% calcia – zirconia solid solution matrix heat treated in argon. J Eur Ceram Soc 26:3845-3851 4186. Huang SG, Vanmeensel K, Van Der Biest O, Vleugels J (2007) Development of ZrO2-WC composites by pulsed electric current sintering. J Eur Ceram Soc 27:3269-3275 4187. He L, Tan Y, Wang X, Tan H, Zhou C (2014) Tribological properties of WC and CeO2 particles reinforced in situ synthesized NiAl matrix composite coatings at elevated temperature. Surf Coat Technol 244:123-130 4188. Jin L, Huang H, Fei Y, Yang H-T, Zhang H-Y, Guo Z-C (2018) Polymer anode used in hydrometallurgy: anodic behaviour of PANI / CeO2 / WC anode sulphate electrolytes. Hydrometall 176:201-207 4189. Myslivchenko AN, Laptev AV, Tolochin AI, Karpets MV (2019) Fazoobrazovanie v sisteme WC-Fe2O3-NiO-Co3O4-C pri nagreve v raznyh sredakh (Phase formation in the WCFe2O3-NiO-Co3O4-C system upon heating in different media). Metallofiz Nov Tekhnol 41(8):1003-1015 (in Russian) 4190. Fu C-T, Lai C-P, Li A-K (1996) Densification and mechanical properties of WC particulate reinforced Cr3C2 matrix composites. J Mater Sci 31:3475-3479 4191. Taimatsu H, Sugiyama S, Komatsu M (2009) Effects of Cr3C2 and V8C7 on the microstructure and mechanical properties of WC – SiC whisker ceramics. Mater Trans Jpn Inst Met 50(10):2435-2440 4192. Poetschke J, Richter V, Holke R (2012) Influence and effectivity of VC and Cr3C2 grain growth inhibitors on sintering binderless tungsten carbide. Int J Refract Met Hard Mater 31:218-223 4193. Taimatsu H, Sugiyama S (2012) Study on the syntheses and mechanical properties of WCSiC hard ceramics. J Jpn Soc Powder Powder Metall 59(8):459-464 (in Japanese) 4194. Ouyang C-X, Zhu S-G, Dong W-W, Qu H-X (2013) Microstructure and mechanical properties of hot-pressed WC-MgO composites with Cr3C2 or VC addition. Int J Refract Met Hard Mater 41:41-47 4195. Nino A, Takahashi N, Sugiyama S, Taimatsu H (2014) Effects of carbide grain growth inhibitors on the microstructures and mechanical properties of WC-SiC-Mo2C hard ceramics. Int J Refract Met Hard Mater 43:150-156 4196. Poetschke J, Richter V, Gestrich T, Michaelis A (2014) Grain growth during sintering of tungsten carbide ceramics. Proc. 18th Int. Plansee seminar and Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 3-7 June 2013. Int J Refract Met Hard Mater 43:309-316. 4197. Zheng D, Li X, Li Y, Qu S, Yang C (2014) Zirconia-toughened WC with/without VC and Cr3C2. Ceram Int 40:2011-2016 4198. Poetschke J, Richter V, Michaelis A (2015) Fundamentals of sintering nanoscaled binderless hardmetals. Int J Refract Met Hard Mater 49:124-132 4199. Nino A, Sekine T, Sugawara K, Sugiyama S, Taimatsu H (2015) Effect of added Cr3C2 on the microstructure and mechanical properties of WC-SiC ceramics. In: Chen J-C, Hiroshi U, Lee S-W, Fuh Y-K (eds) Proc. Int. conf. on machining, materials and mechanical technologies (IC3MT 2014), Taipei City, Taiwan, China, 31 Aug – 5 Sep 2014. Key Eng Mater 656-657:33-38 4200. Jin H, Ju X (2017) Consolidation of Cr3C2 doping WC – 1 TiN – 5 MgO micro-nano composites by two-step sintering. Mater Manuf Process 32(12):1403-1408 4201. Chen Y, Zhang L, Zhu J-J, Zhang H-D, Zhou L, Xiao Q-P, Luo G-K (2018) Phase interfaces between AlTiN and WC/Mo2C in WC – Mo2C substrate and the related characteristics. Int J Refract Met Hard Mater 72:323-331 4202. Vinokur BB, Braun MP, Khilchevskaya TV, Petrenko PV, Shiyanovskii VI, Pakchanin LM, Kulichenko VP (1973) Obrazovanie karbidov pri otpuske khromistoi kompleksno-

804

2 Tungsten Carbides

legirovannoi stali (Formation of carbides during tempering of complexly-alloyed chromium steel). Fiz Met Metalloved 35(4):785-790 (in Russian) 4203. Rutkowski P, Stobierski L (2009) Ewolucja mikrostruktury tworzyw kompozytowych z węglików metali przejściowych (Microstructure evolution of composite materials based on transition metal carbides). Mater Ceram 61(2):140-145 (in Polish) 4204. Lee H-S, Lee D-B (2008) High-temperature oxidation of WC-CrN superhard nanocomposite film. In: Jun B, Kim H, Lee C, Lee SW (eds) Eco-materials processing and design IX. Proc. 9th Int. symp. on eco-materials processing and design, Changwon City, South Korea, 7-9 Jan 2008. Mater Sci Forum 569:57-60 4205. Lee D-B (2009) High-temperature oxidation of WC-CrN nano-multilayered film at 700 and 800 °C. J Nanosci Nanotechnol 9(12):7416-7421 4206. Zhang S-H, He Y-S, Li M-X, He Y-Z, Kwon S-C, Yoon J-H, Cho T-Y (2010) Synthesis and characterization of Cu3N-WC nanocomposite films prepared by direct current magnetron sputtering. Thin Solid Films 518:5227-5232 4207. Yaghobizadeh O, Baharvandi H, Alizadeh A (2014) Investigation of effect of acrylate gel maker parameters on properties of WC preforms for the production of W-ZrC composite. Int J Refract Met Hard Mater 45:130-136 4208. Khoee AAN, Habibolahzadeh A, Qods F, Baharvandi H (2014) Study on rheological behaviour of WC slurry in gel-casting process and reactive infiltration of produced foam by molten Zr2Cu alloy. Int J Refract Met Hard Mater 46:30-34 4209. Ghosh G (2015) A first principles study of cementite (Fe3C) and its alloyed counterparts: elastic constants, elastic anisotropies and isotropic elastic moduli. AIP Adv 5:087102 (19 pp.) 4210. Kobayashi K, Miwa K, Fukunaga M, Machida M (1994) Preparation of hard metal bonded with Fe-Al alloy. J Jpn Soc Powder Powder Metall 41(1):14-17 (in Japanese) 4211. Schneibel JH, Carmichael CA, Specht ED, Subramanian R (1997) Liquid-phase sintered iron aluminide – ceramic composites. Intermetallics 5:61-67 4212. Subramanian R, Schneibel JH (1997) Intermetallic bonded WC-based cermets by pressureless melt infiltration. Intermetallics 5:401-408 4213. Schneibel JH, Becher PF (1999) Iron and nickel aluminide composites. J Chin Inst Eng / Trans Chin Inst Eng A 22(1):1-12 4214. Fukunaga M, Machida M, Kobayashi K, Ozaki K (2000) Preparation of cemented carbide with FeAl binder phase by pulsed current sintering process. J Jpn Soc Powder Powder Metall 47(5):510-514 (in Japanese) 4215. Matsumoto A, Kobayashi K, Ozaki K, Nishio T (2001) Fabrication of FeAl-WC composite using mechanical alloying. J Jpn Soc Powder Powder Metall 48(10):986-989 (in Japanese) 4216. Mosbah A, Wexler D, Calka A (2001) Tungsten carbide – iron aluminide hardmetals: nanocrystalline vs. microcrystalline. In: Schumacher P, Warren P, Cantor B (eds) Proc. Int. symp. on metastable, mechanically alloyed and nanocrystalline materials (ISMANAM-2000), Oxford, UK, 9-14 July 2000. Mater Sci Forum 360-362:649-654 4217. Ahmadian M, Wexler D, Calka A, Chandra T (2003) Liquid-phase sintering of WC-FeAl and WC-Ni3Al composites with and without boron. In: Chandra T, Torralba JM, Sakai T (eds) Proc. Int. conf. on processing and manufacturing of advanced materials (THERMEC’2003), Madrid, Spain, 7-11 July 2003. Mater Sci Forum 426-432(3):1951-1956 4218. Matsumoto A, Kobayashi K, Nishio T, Ozaki K (2005) Synthesis of Fe – 40 at.% Al + WC powders by mechanical alloying and the mechanical property of the composites. J Jpn Soc Powder Powder Metall 52(3):146-150 (in Japanese) 4219. Mosbah AY, Wexler D, Calka A (2005) Abrasive wear of WC-FeAl composites. Wear 258:1337-1341 4220. Kobayashi K, Ozaki K, Tada S, Nishio T, Yasui S (2008) Effects of WC particle size and the FeAl amount on mechanical property of WC-FeAl hard metal. J Jpn Soc Powder Powder Metall 55(8):593-598 (in Japanese)

References

805

4221. Huang S, Van Der Biest O, Vleugels J (2009) Pulsed electric current sintered Fe3Al bonded WC composites. Int J Refract Met Hard Mater 27:1019-1023 4222. Huang S, Van Der Biest O, Vleugels J (2009) Microstructure and mechanical properties of Fe3Al bonded WC composites obtained by pulsed electric current sintering. In: Proc. European Int. powder metallurgy congress and exhibition (Euro PM 2009), Copenhagen, Denmark, 12-14 Oct 2009, Vol. 3 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 4223. Xiang J-H, Zhu X-H, Chen G, Duan Z, Lin Ya, Liu Yi (2009) Oxidation behaviour of Fe 40 Al – x WC composite coatings obtained by high-velocity oxygen-fuel thermal spray. Trans Nonferr Met Soc China 19:1545-1550 4224. Matsumoto A, Kato K, Shimojima K, Hosokawa H, Takada M, Hiramatsu T (2010) preparation and mechanical property for WC – 25 vol.% FeAl using wet milling process. J Jpn Soc Powder Powder Metall 57(12):764-768 (in Japanese) 4225. Ozaki K, Tada S, Kobayashi K, Mabari M, Sasaki K (2010) Near-net-shaping of rod compact of WC-FeAl alloy by travelling zone sintering. J Jpn Soc Powder Powder Metall 57(8):565-569 (in Japanese) 4226. Xiang J-H, Liu Y-W, Hu G-H, Bai L-Y, Wang J (2010) Oxidation behaviour of FeAl – 20 WC composite coating obtained by HVOF thermal spray. J Northeast Univ 31(S1):293-296 (in Chinese) 4227. Furushima R, Katou K, Nakao S, Sun ZM, Shimojima K, Hosokawa H, Matsumoto A (2013) Relationship between microstructure and mechanical properties of sintered WC-FeAl composites prepared from wet powder milling. In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2013), Gothenburg, Sweden, 15-18 Sep 2013, 110976 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 4228. Wang H-T, Ji G-C, Wang R-Y (2013) Characterization of WC particle – reinforced in situ FeAl intermetallic matrix composite coating by cold spraying. In: Innovative coating solutions for the global economy. Proc. Int. thermal spray conf. and exposition (ITSC 2013), Busan, South Korea, 13-15 May 2013, pp. 677-683. ASM International, Metals Park, Ohio 4229. Furushima R, Katou K, Nakao S, Sun ZM, Shimojima K, Hosokawa H, Matsumoto A (2014) Effect of oxygen content in WC-FeAl powders on microstructure and mechanical properties of sintered composites fabricated by pulse current sintering technique. J Jpn Soc Powder Powder Metall 61(6):281-289 (in Japanese), also – Mater Trans Jpn Soc Powder Powder Metall 55(12):1792-1799 4230. Furushima R, Katou K, Nakao S, Sun ZM, Shimojima K, Hosokawa H, Matsumoto A (2014) Relationship between hardness and fracture toughness in WC-FeAl composites fabricated by pulse current sintering technique. Int J Refract Met Hard Mater 42:42-46 4231. Matsumoto A, Kato K, Shimojima K, Hosokawa H, Furushima R (2014) Microstructure and mechanical properties of WC-FeAl composites using wet milling followed by pulse current sintering process. In: Chernenkoff RA, Jandeska WF, Jr (eds) Advances in powder metallurgy and particulate materials – 2014. Proc. World congress on powder metallurgy and particulate materials (PM 2014), Orlando, Florida, 18-22 May 2014, pp. 843-850. Metal Powder Industries Federation, Princeton, New Jersey 4232. Wang H-T, Wang R-Y, Chen X, Bai X-B, Dong Z-X, Ji G-C (2014) Structural Fe – 50 Al / WC composite powder during mechanical alloying process. In: Li J-F (ed) Proc. 3rd Int. conf. on machinery electronics and control engineering (ICMECE 2013), Jinan, Shandong, China, 29-30 Nov 2013. Appl Mech Mater 441:3-6 4233. Furushima R, Katou K, Shimojima K, Hosokawa H, Mikami M, Matsumoto A (2015) Effect of η-phase and FeAl composition on the mechanical properties of WC-FeAl composites. Intermetallics 66:120-126 4234. Furushima R, Katou K, Shimojima K, Hosokawa H, Matsumoto A (2015) Mechanical properties of WC-FeAl double layer composite fabricated by pressure-assisted sintering technique. In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2015), Reims,

806

2 Tungsten Carbides

France, 4-7 Oct 2015, 124663 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 4235. Furushima R, Katou K, Shimojima K, Hosokawa H, Matsumoto A (2015) Control of WC grain sizes and mechanical properties in WC-FeAl composite fabricated by vacuum sintering technique. Int J Refract Met Hard Mater 50:16-22 4236. Furushima R, Katou K, Shimojima K, Hosokawa H, Mikami M, Matsumoto A (2015) Changes in constituents and FeAl composition with oxygen content in WC-FeAl composites. Int J Refract Met Hard Mater 50:298-303 4237. Katou K, Matsumoto A, Shimojima K, Hosokawa H, Furushima R (2015) Preparation of WC-FeAl hard metal using FeAl2 and FeAl powder. J Jpn Soc Powder Powder Metall 62(9):478-494 (in Japanese) 4238. Matsumoto A, Katou K, Shimojima K, Hosokawa H, Furushima R (2015) Microstructure and mechanical properties of WC-FeAl compacts using wet milling followed by vacuum sintering. In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2015), Reims, France, 4-7 Oct 2015, 124663 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 4239. Shon I-J (2016) Rapid consolidation of nanostructured WC-FeAl hard composites by highfrequency induction heating and its mechanical properties. Int J Refract Met Hard Mater 61:185-191 4240. Furushima R, Shimojima K, Hosokawa H, Matsumoto A (2017) Oxidation-enhanced wear behaviour of WC-FeAl cutting tools used in dry machining oxygen-free copper bars. Wear 374-375:104-112 4241. Shon I-J, Lee S-J (2017) Rapid consolidation of nanostructured WC-FeAl3 by pulsed current activated heating and its mechanical properties. Int J Refract Met Hard Mater 65:6975 4242. Ybarra LAC, Chimanski A, Gama S, Da Silva RAG, Machado IF, Yoshimura HN (2017) development of WC-Fe3Al composites by spark-plasma sintering process. In: Dos SantosOrtega F (ed) Proc. 59th Brazilian ceramic conf. (CBC 59), Barra dos Coqueiros, Brazil, 1720 May 2015. Mater Sci Forum 881:307-312 4243. Karimi H, Hadi M, Ebrahimzadeh I, Farhang MR, Sadeghi M (2018) High-temperature oxidation behaviour of WC-FeAl composite fabricated by spark-plasma sintering. Ceram Int 44:17147-17153 4244. Furushima R, Hyuga H (2019) Improvement of thermal conductivity of WC-FeAl hard materials by elimination of oxide materials. Int J Refract Met Hard Mater 82:1-6 4245. Mostajeran A, Shoja-Razavi R, Hadi M, Erfanmanesh M, Barekat M, Firouzabadi MS (2020) Evaluation of the mechanical properties of WC-FeAl composite coating fabricated by laser cladding method. Int J Refract Met Hard Mater 88:105199 (10 pp.) 4246. Ni D-W, Liu J-X, Zhang G-J (2012) Pressureless sintering of HfB2-SiC doped with WC. J Eur Ceram Soc 32:3627-3635 4247. Hu D-L, Zheng Q, Gu H, Ni D-W, Zhang G-J (2014) Role of WC additive on reaction, solid solution and densification of HfB2-SiC ceramics. J Eur Ceram Soc 34:611-619 4248. Binner J, Porter M, Baker B, Zou J, Venkatachalam V, Diaz VR, D’Angio A, Ramanujam P, Zhang T, Murthy TSRC (2020) Selection, processing, properties and applications of ultrahigh temperature ceramic matrix composites, UHTCMCs – a review. Int Mater Rev 65(7):389-444 4249. Zhang G-J, Liu H-T, Wu W-W, Zou J, Ni D-W, Guo W-M, Liu J-X, Wang X-G (2014) Reactive processes for diboride-based ultra-high temperature ceramics. In: Fahrenholtz WG, Wuchina EJ, Lee WE, Zhou Y-C (eds) Ultra-high temperature ceramics: materials for extreme environment applications, 1st ed., pp. 33-59. The American Ceramic Society, Westerville, Ohio 4250. Liu J-X, Zhang G-J, Xu F-F, Wu W-W, Liu H-T, Sakka Y, Nishimura T, Suzuki TS, Ni DW, Zou J (2015) Densification, microstructure evolution and mechanical properties of WC doped HfB2-SiC ceramics. J Eur Ceram Soc 35:2707-2714

References

807

4251. Zhang G-J, Ni D-W, Zou J, Liu H-T, Wu W-W, Liu J-X, Suzuki TS, Sakka Y (2018) Inherent anisotropy in transition metal diborides and microstructure/property tailoring in ultra-high temperature ceramics – a review. J Eur Ceram Soc 38:371-389 4252. Carney CM, Parthasarathy TA, Cinibulk MK (2011) Oxidation resistance of hafnium diboride ceramics with additions of silicon carbide and tungsten boride or tungsten carbide. J Am Ceram Soc 94(8):2600-2607 4253. Knizhnik AA, Safonov AA, Iskandarova IM, Bagaturyants AA, Potapkin BV, Fonseca LRC, Stoker MW (2006) First principles investigation of the WC/HfO2 interface properties. J Appl Phys 99:084104 (5 pp.) 4254. Zhang Y, Ma J, Di P, Zhu S-G (2010) Effects of La2O3 on microstructure and mechanical properties of hot-pressing sintered WC-MgO composite material. Chin J Nonferr Met 20(10):1982-1988 (in Chinese) 4255. Ma J, Zhu S-G, Di P, Zhang Y (2011) Influence of La2O3 addition on hardness, flexural strength and microstructure of hot-pressing sintered WC-MgO bulk composites. Mater Design 32:2125-2129 4256. Zhao X, Yuan X, Liu S, Zhao C, Wang C, Zhou Y, Yang Q (2017) Investigation on WC/LaAlO3 heterogeneous nucleation interface by first principles. J Alloys Compd 695:1753-1762 4257. Kondrashov AI (1974) Reactions of lanthanum hexaboride with carbides and borides of refractory metals. Powder Metall Met Ceram 13(11):911-913 4258. Xiao D, Li X, Shen T, Song M (2015) Effect of LaB6 addition on microstructure and mechanical properties of ultra-fine grained WC-Ni3Al alloys. J Central South Univ Sci Technol 46(1):81-87 (in Chinese) 4259. El-Eskandarany MS (2000) Fabrication of nanocrystalline WC and nanocomposite WCMgO refractory materials at room temperature. J Alloys Compd 296:175-182 4260. Zhang M-L, Zhu S-G, Ma J, Wu C-X (2008) Preparation of WC/MgO composite nanopowders by high-energy reactive ball-milling and their plasma-activated sintering. Powder Metall Met Ceram 47(9-10):525-530 4261. Ma J, Zhu S-G, Wu C-X, Zhang M-L (2009) Application of back-propagation neutral network technique to high-energy planetary ball-milling process for synthesizing nanocomposite WC-MgO powders. Mater Design 30:2867-2874 4262. Wu C-X, Zhu S-G, Ma J, Zhang M-L (2009) Synthesis and formation mechanisms of nanocomposite WC-MgO powders by high-energy reactive milling. J Alloys Compd 478:615-619 4263. Zhu S-G, Wu C-X, Luo Y-L (2009) Effects of stearic acid on synthesis of nanocomposite WC-MgO powders by mechanical alloying. J Mater Sci 45:1817-1822 4264. Ma J Zhu S-G, Ouyang C-X (2011) Two-step hot-pressing sintering of nanocomposite WC-MgO compacts. J Eur Ceram Soc 31:1927-1935 4265. Ouyang C-X, Zhu S-G, Qu H-X (2012) VC and Cr3C2 doped WC-MgO compacts prepared by hot-pressing sintering. Mater Design 40:550-555 4266. Ouyang C-X, Zhu S-G, Ma J, Qu H-X, Li Q (2012) Effect of two-step hot-pressing sintering technique on microstructure and mechanical properties of WC-MgO nanocomposite. Chin J Nonferr Met 22(12):3395-3401 (in Chinese) 4267. Ouyang C-X, Zhu S-G (2012) Densification process of WC-MgO nanocomposite based on master sintering curve. In: Jin W (ed) Mechanical engineering and materials. Selected papers from Int. conf. on mechanical engineering and materials (ICMEM 2012), Melbourne, Australia, 15-16 Jan 2012. Appl Mech Mater 152-154:232-238 4268. Ouyang C-X, Zhu S-G, Ma J, Qu H-X (2012) Master sintering curve of nanocomposite WC-MgO powder compacts. J Alloys Compd 518:27-31 4269. Ouyang C-X, Zhu S-G, Li D-Y (2013) Experimental and simulation studies on the solidparticle erosion of WC-MgO composites. Tribol Lett 52:501-510 4270. Ouyang C-X, Zhu S-G, Li D-Y (2014) Corrosion and corrosive wear behaviour of WCMgO composites with and without grain growth inhibitors. J Alloys Compd 615:146-155

808

2 Tungsten Carbides

4271. Radajewski M, Schimpf C, Krüger L (2017) Study of processing routes for WC-MgO composites with varying MgO contents consolidated by FAST/SPS. J Eur Ceram Soc 37:2031-2037 4272. Zou J, Ma H-B, D’Angio A, Zhang G-J (2018) Tungsten carbide: a versatile additive to get trace alkaline-earth oxide impurities out of ZrB2 based ceramics. Scripta Mater 147:40-44 4273. Tang C-B, Lu Y-X, Wang F, Niu H, Yu L-H, Xue J-Q (2020) Influence of a MnO2-WC interlayer on the stability and electrocatalytic activity of titanium based PbO2 anodes. Electrochim Acta 331:135381 (20 pp.) 4274. Skarvelis P, Papadimitriou GD, Perraki M (2010) Self-lubricating composite coatings containing TiC-MnS or WC-MnS compounds prepared by the plasma transferred arc (PTA) technique. J Tribol 132(3):1-8 4275. Kupalova IK, Baikov AM, Kabaev MM (1972) Investigation of carbide transformations during tempering of the solid solutions of tungsten and tungsten-molybdenum high-speed steels. Phys Met Metallogr 33(1):175-185 4276. Sevastyanova LG, Velikodnyi YuA, Zubova EV, Kovba LM, Krutskikh VM, Kudrya NA (1976) Poluchenie kubicheskogo karbida volframa pod vysokim davleniem (Production of cubic tungsten carbide under high pressure). Doklady AN SSSR 229(2):357-359 (in Russian) 4277. Silberberg E, Reniers F, Buess-Herman C (1999) Quantitative analysis of mixed (Mo,W) carbides by means of least-squares minimization performed on Auger spectra simulations. Surf Interface Anal 27:43-51 4278. Tanaka K, Hayashi K (2000) Synthesis of new (W,Mo)(C,N) powder by heating W-Mo alloy powder in CH4 + NH3 mixed gas of normal pressure. J Jpn Soc Powder Powder Metall 47(9):946-950 4279. Asada N, Yamamoto Y, Igarashi T, Doi Y, Hayashi K (2002) Synthesis of new monocarbonitride (W,Mo)(C,N) powder by heating W-Mo alloy + C mixed powder in high pressure nitrogen gas. J Jpn Soc Powder Powder Metall 49(4):270-278 4280. Liu C, Nino A, Sugiyama S, Taimatsu H (2012) Preparation of (W,Mo)C-SiC ceramics and their mechanical properties. J Jpn Soc Powder Powder Metall 59(8):484-488 4281. Waki T, Terazawa S, Umemoto Y, Tabata Y, Murase Y, Kato M, Hirota K, Nakamura H (2012) Magnetic susceptibility of η-carbide-type molybdenum and tungsten carbides and nitrides. In: Murase M, Nishimura K, Yoshimura K, Ohta H (eds) Proc. Int. and interdisciplinary workshop on novel phenomena in integrated complex sciences: from non-living to living systems (IIW-NPICS 2010), Kyoto, Japan, 11-14 Oct 2010. J Phys Conf Series 344:012017 (4 pp.) 4282. Kushkov KhB, Kardanov AL, Adamokova MN (2013) Electrochemical synthesis of binary molybdenum-tungsten carbides (Mo,W)2C from tungstate-molybdate-carbonate melts. Russ Metall (2):79-85 4283. Liu C (2016) The development and prospect of binderless carbide. Mater China 35(8):622628 (in Chinese) 4284. Maier H, Rasinski M, Von Toussant U, Greuner H, Böswirth B, Balden M, Elgeti S, Ruset C, Matthews GF (2016) Kinetics of carbide formation in the molybdenum-tungsten coatings used in the ITER-like wall. Phys Scripta T 167:014048 (4 pp.) 4285. Nino A, Nakaibayashi Y, Sugiyama S, Taimatsu H (2017) Effect of Mo2C addition on the microstructures and mechanical properties of WC-SiC ceramics. Int J Refract Met Hard Mater 64:35-39 4286. Taimatsu H (2018) Study on binderless cemented carbides and their related high-temperature reactions between different phases. J Jpn Soc Powder Powder Metall 65(9):533-538 (in Japanese) 4287. Hatzl G, Fürst M, Lengauer W (2021) (W,Mo)C-based hardmetals with Ni-rich binders In: Proc. Int. powder metallurgy congress and exhibition (Euro PM 2021), Session 37 – Alternative hardmetals, 18-21 Oct 2021, online (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.researchgate.net/publication/356378834_WMoCbased_hardmetals_with_Ni-rich_binders Accessed 20 November 2021

References

809

4288. Chan TY, Hu Y, Gharbi MM, Politis DJ, Wang L (2016) The friction coefficient evolution of a MoS2/WC multi-layer coating system during sliding wear. In: Cardoso RRR, Neto ES, Cesar De Sa JMA, Adetoro OB (eds) Proc. 10th Int. conf. and workshop on numerical simulation of 3D sheet metal forming processes (Numisheet 2016), Bristol, UK, 4-9 Sep 2016. J Phys Conf Series 734(3):032081 (4 pp.) 4289. Domínguez-Meister S, Rojas TC, Brizuela M, Sánchez-López JC (2017) Solid lubricant behaviour of MoS2- and WSe2-based nanocomposite coatings. Sci Technol Adv Mater 18(1):122-133 4290. Rudy E, Kieffer BF, Baroch E (1978) HfN coatings for cemented carbides and new hardfacing alloys on the basis (Mo,W)C-(Mo,W)2C. Planseeber Pulvermetall 26(2):105-115 4291. Schwarz V, Shi K, Lengauer W (2016) Metallurgy and properties of Mo-doped WC-Co and (W,Mo)C-Co hardmetals. In: Krehl M, Petzoldt F (eds) Proc. World powder metallurgy congress and exhibition (World PM 2016), Hamburg, Germany, 9-13 Oct 2016 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.epma.com/publications/euro-pm-proceedings/product/ep16-3307171 Accessed 21 November 2021 4292. Zhang C, Yin H, Lv J, Du Y, Tan Z, Liu Y (2019) Thermodynamic investigation of phase equilibria on the (W,Mo)C-(Co,Ni) cemented carbides. Calphad 67:101664 (8 pp.) 4293. Zhou P, Peng Y, Buchegger C, Du Y, Lengauer W (2016) Experimental investigation and thermodynamic assessment of the C-Co-Fe-Ni-W system. Int J Refract Met Hard Mater 54:60-69 4294. Dalbauer V, Jewett T (2014) Hardmetals: Mo and Mo2C additions on the microstructure of sintered WC-Co components. In: Proc. Int. conf. and exhibition on powder metallurgy (Euro PM 2014), Salzburg, Austria, 21-24 Sep 2014, 117821 (8 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 4295. Jewett T (2017) Effects of doping WC-Co hardmetals with Mo and Mo2C. In: Sigl LS, Kestler H, Pilz A (eds) Proc. 19th Int. Plansee seminar, Int. conf. on refractory metals and hard materials, Reutte, Tyrol, Austria, 29 May – 2 June 2017, Vol. 2 – Hard materials 1, pp. HM12/1-HM12/10. Plansee Metal AG, Reutte, Austria. 4296. Mobin M, Malik AU (1991) High-temperature interactions of transition metal carbides with Na2SO4. J Less-Common Met 170:243-254 4297. Branagan DJ, Kramer MJ, McCallum RW (1996) Transition metal carbide formation in the Nd2Fe14B system and potential as alloying additions. J Alloys Compd 244:27-39 4298. Tumanov AV, Gostev YuV, Panov VS, Kots YuF (1986) Wetting of TiC-WC system carbides with molten Ni3Al. Powder Metall Met Ceram 25(5):428-430 4299. Kots YuF, Panov VS, Shipkov NV, Filimonova AA (1990) Oxidation of WC-Ni-Al system alloys. Powder Metall Met Ceram 29(10):816-819 4300. Panov VS, Kots YuF, Filimonova AA (1990) Interaction between phases in the WC-Ni3Al system. Powder Metall Met Ceram 29(10):564-567 4301. Kulkov SN, Gnyusov SF, Molchunova LM (1994) Formation of the microstructure of a composite during its dynamic loading. J Appl Mech Tech Phys 35(5):735-738 4302. Tiegs TN, Menchhofer PA, Plucknett KP, Alexander KB, Becher PF, Waters SB (1995) Hardmetals based on Ni3Al as the binder phase. In: Froes FH (ed) Proc. 4th Int. conf. on powder metallurgy in aerospace, defence and demanding applications, Anaheim, California, 8-10 May 1995, pp. 211-218. Metal Powder Industries Federation, Princeton, New Jersey 4303. Plucknett KP, Tiegs TN, Becher PF, Waters SB, Menchhofer PA (1996) Ductile intermetallic toughened carbide matrix composites. In: Wachtman JB, Greenhut V (eds) Proc. 20nd American Ceramic Society annual conf. on composites, advanced ceramics, materials and structures: A, Cocoa Beach, Florida, 7-11 Jan 1996. Ceram Eng Sci Proc 17(3):314-321 4304. Tiegs TN, Alexander KB, Plucknett KP, Menchhofer PA, Becher PF, Waters SB (1996) Ceramic composites with a ductile Ni3Al binder phase. Mater Sci Eng A 209:243-247 4305. Timuçin M, Aydoğan ME (1999) WC bazh sert maden uçlarinda yeni bir bağlayiei: NiAl (NiAl: new binder for WC-based cemented carbides). In: Saritas S (ed) Proc. 2. Ulusal toz

810

2 Tungsten Carbides

metalurjisi konf. uluslararasi katilimli (2nd Nat. powder metallurgy conf. with international participation), Ankara, Turkey, 15-17 Sep 1999, pp. 661-668. Turkish Powder Metallurgy Association, Middle East Technical University, Ankara (in Turkish) 4306. Suo J-P, Feng D, Qian X-L, Cui K (2001) Improvement of Ni3Al welding property with addition of WC. Trans China Weld Inst 22(6):11-14 (in Chinese) 4307. Suo J-P, Feng D, Luo H-L, Cui K (2002) Effect of WC content on the structure of Ni3AlWC composites. Mater Sci Technol 10(2):131-135 (in Chinese) 4308. Xu XY, Liu WJ, Zhong ML, Sun HQ (2003) Synthesis and fabrication of WC particulate reinforced Ni3Al intermetallic matrix composite coating by laser powder deposition. J Mater Sci Lett 22:1369-1372 4309. Talanova GV, Padalko AG, Panov VS, Veselov AN, Shvorneva LI (2008) Effect of barothermal processing on the structure and properties of a WC-Ni3Al alloy. Inorg Mater 44(3):244-247 4310. Panov VS, Shugaev VA, Goldberg MA (2009) The possibility of utilization of Ni3Al as the binding material for hard alloys. Russ J Non-Ferr Met 50(3):317-320 4311. Panov VS, Goldberg MA (2009) Interaction of tungsten carbide with aluminium nickelide Ni3Al. Powder Metall Met Ceram 48(7-8):445-448 4312. Janas A, Fras E, Kolbus A, Olejnik E (2010) Cast in situ composites of Ni3Al/MeC type. In: Proc. 69th World foundry congress (WFS 2010), Hangzhou, China, 16-20 Oct 2010, Vol. 3, pp. 1045-1049. World Foundry Organization, Kington, UK 4313. Li X, Chen J, Zheng D, Qu S, Xiao Z (2012) Preparation and mechanical properties of WC – 10 Ni3Al cemented carbides with plate-like triangular prismatic WC grains. J Alloys Compd 544:134-140 4314. Long J-Z, Xu T, Peng W, Lu B-Z (2012) Microstructure and properties of WC-Ni3Al composites by powder metallurgy. Mater Sci Eng Powder Metall 17(1):63-68 (in Chinese) 4315. Kim W, Suh C-Y, Roh K-M, Cho S-W, Na K-I, Shon I-J (2013) Mechanical properties of (W,Ti)C and (W,Ti)C-NiAl3 cermet consolidated by the high-frequency induction-heating method. J Alloys Compd 568:73-77 4316. Long J-Z, Zhang Z-J, Xu T, Lu B-Z (2013) Microstructure, mechanical properties and fracture behaviour of WC – 40 vol.% Ni3Al composites with various carbon contents. Int J Refract Met Hard Mater 40:2-7 4317. Zhang K, Zhang Z-J, Lu X-X, Li K, Du Y, Long J-Z, Xu T, Zhang H, Chen L, Kong Y (2014) Microstructure and composition of the grain/binder interface in WC-Ni3Al composites. Int J Refract Met Hard Mater 44:88-93 4318. Liang L, Liu X, Li X-Q, Li Y-Y (2015) Wear mechanisms of WC – 10 Ni3Al carbide tool in dry turning of Ti-6Al-4V. Int J Refract Met Hard Mater 48:272-285 4319. Li X, Zhang M, Zheng D, Cao T, Chen J, Qu S (2015) The oxidation behaviour of the WC – 10 wt.% Ni3Al composite fabricated by spark-plasma sintering. J Alloys Compd 629:148154 4320. Gostishchev VV, Astapov IA, Khimukhin SN (2017) Exothermic synthesis of cast nickel aluminide alloys with tungsten and molybdenum carbides. Inorg Mater 53(2):160-163 4321. Katou K, Shimojima K, Hosokawa H (2017) Preparation for WC-Ni3Al hard metal by vacuum sintering. J Jpn Soc Powder Powder Metall 64(11):615-620 (in Japanese) 4322. Yuan J, Zhang X, Li B, Wang X, Sun K (2017) Microstructure and tribological behaviour of NiAl/WC composites fabricated by thermal explosion reaction at 800 °C. J Alloys Compd 693:70-75 4323. Krylova TA, Chumakov YuA, Domarov EV, Korchagin AI (2019) Investigation of composite coatings based on the intermetallic matrix Ni3Al with refractory WC inclusions. In: Panin VE, Psakhie SG, Fomin VM (eds) Proc. Int. conf. on advanced materials with hierarchical structure for new technologies and reliable structures, Tomsk, Russian Federation, 1-5 Oct 2019. AIP Conf Proc 2167:020185 (8 pp.)

References

811

4324. Zarezadeh-Mehrizi M, Momeni MR, Beygi R, Eisaabadi GB, Kim B-H, Kim S-K (2019) Reaction pathway of NiAl/WC nanocomposite synthesized from mechanical activated Ni-AlW-C powder system. Ceram Int 45:11833-11837 4325. Grigorev ON, Chugunova SI, Shatokhin AM, Yaroshenko VP (1981) Mechanical properties of silicon nitride composite materials. Powder Metall Met Ceram 20(7):502-505 4326. Huang J-L, Lin C-J (1993) The role of elastic property mismatch in the failure of ceramic composites. J Mater Sci 28:1074-1080 4327. Iizuka T, Kita H, Hyuga H, Hirai T, Osumu K (2004) In situ synthesis and microstructures of tungsten carbide nanoparticle – reinforced silicon nitride matrix composites. J Am Ceram Soc 87(3):337-341 4328. Li Y, Zheng D, Li X, Qu S, Yang C (2013) Cr3C2 and VC doped WC-Si3N4 composites prepared by spark-plasma sintering. Int J Refract Met Hard Mater 41:540-546 4329. Zheng D, Li X, Li Y, Qu S, Yang C (2013) In situ elongated β-Si3N4 grains toughened WC composites prepared by one/two-step spark-plasma sintering. Mater Sci Eng A 561:445-451 4330. Zheng D, Li X, Tang Y, Cao T (2015) WC-Si3N4 composites prepared by two-step sparkplasma sintering. Int J Refract Met Hard Mater 50:133-139 4331. Liu J, Zhu T, Xie Z-P, Wu W (2017) New route to improve the flexural strength of silicon nitride ceramics by introducing tungsten carbide nanoparticles. Int J Appl Ceram Technol 14:860-865 4332. Wang Z, Jia J, Cao L, Sun N, Wang Y (2019) Microstructure and mechanical properties of spark-plasma sintered Si3N4/WC ceramic tools. Materials 12(11):1868 (11 pp.); doi: 10.3390/ma12111868 4333. Ayas E, Kara A, Mandal H, Turan S, Kara F (2004) Decolouration effect of WC addition on gas pressure sintered α-β SiAlON ceramics. Mater Lett 58:1498-1501 4334. Biswas M, Sarkar S, Halder R, Bysakh S, Muraleedharan K, Bandyopadhyay S (2020) Sintering and characterization of hard-to-hard configured composite: spark-plasma sintered WC reinforced α-SiAlON. J Phys Chem Solids 145:109548 (14 pp.) 4335. Sarkar S, Biswas M, Halder R, Bandyopadhyay S (2020) Spark-plasma sintering processed α-SiAlON bonded tungsten carbide: densification, microstructure and tribomechanical properties. Mater Chem Phys 248:122955 (10 pp.) 4336. Chen L, Goto T, Hirai T (1993) Preparation of SiC-W2C nanocomposite powders by chemical vapour deposition of the SiH4-CH4-WF6-H2 system. J Mater Sci 28:5543-5547 4337. Martin H-P, Müller E, Dachselt U (1999) Formation process of mixed silicon and tungsten carbide from co-pyrolysis of polysilane and metallic tungsten. Part I. J Mater Sci 34:26652670 4338. Romanus H, Cimalla V, Ahmed SI, Schaefer JA, Ecke G, Avci R, Spiess L (1999) Preparation of conductive tungsten carbide layers for SiC high-temperature applications. In: Binari S, Burk A, Melloch M, Nguyen C (eds) Proc. MRS spring meeting symp. on widebandgap semiconductors for high-power, high-frequency and high-temperature applications, San Francisco, California, 5-8 Apr 1999. Mater Res Soc Symp Proc 572:99-104 4339. Endrino JL, Krzanowski JE (2002) Nanostructure and mechanical properties of WC-SiC thin films. J Mater Res 17(12):3163-3167 4340. Chamberlain AL, Fahrenholtz WG, Hilmas GE (2004) High-strength zirconium diboride – based ceramics. J Am Ceram Soc 87(6):1170-1172 4341. Zhou S, Xiao H, Yang Q (2004) Self-lubrication properties at elevated temperatures and mechanism of SiC and SiC-WC composites. J Chin Ceram Soc 32(12):1470-1475 (in Chinese) 4342. Krzanowski JE, Wormwood J (2005) Structural disordering in WC thin films induced by SiC additions. Metall Mater Trans A 36:3055-3063 4343. Krzanowski JE, Palacín S, Gutiérrez A, Schäfers F, Mertin M, Endrino JL, Soriano L (2007) X-ray absorption spectroscopy study at the Si K-edge of tungsten carbide – silicon carbide thin films. Scripta Mater 56:1011-1014

812

2 Tungsten Carbides

4344. Pang J, Li J (2009) Low thermal expansion porous SiC-WC composite ceramics. Ceram Int 35:3517-3520 4345. Li Q, Xiao H-N, Gao P-Z, Hu J-L, Guo W-M, Tang J-X (2011) Properties and sintering mechanism of RSiC-WC composite ceramics. Chin J Nonferr Met 21(6):1359-1366 (in Chinese) 4346. Zou J, Sun S-K, Zhang G-J, Kan Y-M, Wang P-L, Ohji T (2011) Chemical reactions, anisotropic grain growth and sintering mechanisms of self-reinforced ZrB2-SiC doped with WC. J Am Ceram Soc 94(5):1575-1583 4347. Zhang SC, Hilmas GE, Fahrenholtz WG (2006) Pressureless densification of zirconium diboride with boron carbide additions. J Am Ceram Soc 89(5):1544-1550 4348. Fernández-Perea M, Pivovaroff MJ, Soufli R, Alameda J, Mirkarimi P, Descalle M-A, Baker SL, McCarville T, Ziock K, Hornback D, Romaine S, Bruni R, Zhong Z, Honkimäki V, Ziegler E, Christensen FE, Jakobsen AC (2013) Ultra-short-period WC/SiC multilayer coatings for X-ray applications. Nucl Instrum Meth A 710:114-119 4349. Shin D-G, Cho K-Y, Jin E-J, Kim Y, Kim S-R, Kwon W-T, Lee Y-J, Hong J-S, Riu D-H (2013) Tungsten carbide – silicon carbide nanocomposite fibres prepared from tungsten nanoparticle dispersed polycarbosilane by electrospinning. J Ceram Process Res 14(4):463467 4350. Sharma SK, Kumar BVM, Lim K-Y, Kim Y-W, Nath SK (2014) Erosion behaviour of SiC-WC composites. Ceram Int 40:6829-6839 4351. Rogowski J, Kubiak A, Andrzejczuk M (2015) Carbothermal reduction of SiO2 promoted with tungsten and morphology of WC – W2C – β-SiC nanostructured composite material. Appl Surf Sci 359:177-187 4352. Guo L-J, Peng J, Kou G, Huo C-X, Li H-J, Li K-Z (2016) Ablation mechanism of WC-SiC double layer coating under oxyacetylene torch test. Ceram Int 42:16804-16812 4353. Knoll L, Teodorescu V, Minamisawa RA (2016) Ultra-thin epitaxial tungsten carbide Schottky contacts in 4H SiC. IEEE Electron Devise Lett 37(10):1318-1320 4354. Ma H-B, Zou J, Zhu J-T, Lu P, Xu F-F, Zhang G-J (2017) Thermal and electrical transport in ZrB2-SiC-WC ceramics up to 1800 °C. Acta Mater 129:159-169 4355. Shirani M, Rahimipour M, Zakeri M, Safi S, Ebadzadeh T (2017) ZrB2-SiC-WC coating with SiC diffusion bond coat on graphite by spark-plasma sintering process. 43(16):1451714520 4356. Ma H-B, Zou J, Zhu J-T, Liu L-F, Zhang G-J (2018) Segregation of tungsten atoms at ZrB2 grain boundaries in strong ZrB2-SiC-WC ceramics. Scripta Mater 157:76-80 4357. Zou J, Zhang G-J, Hu C-F, Nishimura T, Sakka Y, Vleugels J, Van Der Biest O (2012) Strong ZrB2-SiC-WC ceramics at 1600 °C. J Am Ceram Soc 95(3):874-878 4358. Zhang SC, Fahrenholtz WG, Hilmas GE (2009) Oxidation of ZrB2 and ZrB2-SiC ceramics with tungsten additions. In: Proc. 214th Electrochemical Society meeting, Honolulu, Hawaii, 12-17 Oct 2008 (Technical Report AFRL-RX-WP-TP-2009-4126, Contract FA8650-04-C5704, pp. 1-16). ESC Trans 16(44):137-145 4359. Hu D-L, Gu H, Zou J, Zheng Q, Zhang G-J (2021) Core-rim stricture, bi-solubility and a hierarchical phase relationship in hot-pressed ZrB2-SiC-MC ceramics (M = Nb, Hf, Ta, W). J Materiomics 7:69-79 4360. Zou J (2011) ZrB2-based ultra-high temperature ceramics: densification, microstructure tailoring and performance improving. Shanghai Institute of Ceramics, Chinese Academy of Sciences (in Chinese) 4361. Hu D-L (2014) Study on microstructure and quantitative phase relation of diboride-based ultra-high temperature ceramics. Shanghai Institute of Ceramics, Chinese Academy of Sciences (in Chinese) 4362. Sharma SK, Kumar BVM, Zugelj BB, Kalin M, Kim Y-W (2017) Room and hightemperature reciprocated sliding wear behaviour of SiC-WC composites. Ceram Int 43:16827-16834

References

813

4363. Sharma SK, Kumar BVM, Kim Y-W (2017) Effect of impingement angle and WC content on high-temperature erosion behaviour of SiC-WC composites. Int J Refract Met Hard Mater 68:166-171 4364. Prasciolu M, Bajt S (2018) On the properties of WC/SiC multilayers. Appl Sci 8(4):571 (15 pp.); doi:10.3390/app8040571 4365. Sharma SK, Kumar BVM, Kim Y-W (2019) Tribology of WC reinforced SiC ceramics: influence of counter body. Friction 7(2):129-142 4366. Colque S, Grange P, Delmon B (1993) Preparation of tungsten carbides on silica – evidence of coupling effects during reduction/carburization of tungsten oxide. Solid States Ionics 63-65:122-127 4367. Chaira D, Chaudhuri MG, Das GC, Mukherjee S, Mitra MK, Bhattachariya A (2007) Leaching kinetics of tungstic acid and in situ synthesis of tungsten carbide in silica gel matrix. Trans Indian Ceram Soc 66(4):167-170 4368. Hu L, Ji S, Jiang Z, Song H, Wu P, Liu Q (2007) Direct synthesis and structural characteristics of ordered SBA-15 mesoporous silica containing tungsten oxides and tungsten carbides. J Phys Chem C 111:15173-15184 4369. Roy SK, Dey R, Mitra A, Mukherjee S, Mitra MK, Das GC (2007) Optimization of process parameters for the synthesis of silica gel – WC nanocomposite by design of experiment. Mater Sci Eng C 27:725-728 4370. Burykina AL, Struk LI, Manzhurnet KV (1967) Stability of refractory compounds in fused basalt. Powder Metall Met Ceram 6(2):122-123 4371. Gavrish V, Chayka T, Baranov G, Fedorova S, Gavrish O (2019) Effect of additives being WC, TiC, TaC nanopowder mixtures on strength property of concrete. In: Glezer A, Gorbatyuk S (eds) Proc. Int. conf. on modern trends in manufacturing technologies and equipment (ICMTMTE 2019), Sevastopol, Crimea, Ukraine, 9-13 Sep 2019. Mater Today Proc 19(5):1961-1964 4372. Jenkins RO, Trodden WG (1959) Evaporation of thorium from carburized thoriated tungsten cathodes. Brit J Appl Phys 10:10-15 4373. Jenkins RO, Trodden WG (1961) The poisoning of thoriated tungsten cathodes. J Electron Control 12(1):1-12 4374. Jenkins RO (1969) A review of thermionic cathodes. Vacuum 19(8):353-359 4375. Iwakawa T, Hattori H, Yamamoto S (1966) Decarburizing phenomena of carburized thoriated tungsten filaments. J Vac Soc Jpn 9(7):269-273 (in Japanese) 4376. Liu Y, Huang C, Liu H, Zou B, Shi Q (2012) Microstructure and mechanical properties of Ti(C,N)-TiB2-WC composite ceramic tool materials. In: Huang C, Zhu H, Wang J, Li X (eds) Advances in materials processing – X. Proc. 10th Asia-Pacific conf. on materials processing (APCMP 2012), Jinan, China, 14-17 June 2012. Adv Mater Res 500:673-678 4377. Zhao Y, Huang C, Zou B, Fei Y, Liu H, Zhu H, Wang J (2012) The effects of sintering process on microstructure and mechanical properties of TiB2-Ti(C0.5N0.5)-WC composite tool materials. In: Huang C, Zhu H, Wang J, Li X (eds) Advances in materials processing – X. Proc. 10th Asia-Pacific conf. on materials processing (APCMP 2012), Jinan, China, 14-17 June 2012. Adv Mater Res 500:640-645 4378. Song J, Huang C, Zou B, Liu H, Wang J (2012) Microstructure and mechanical properties of TiB2-TiC-WC composite ceramic tool materials. Mater Design 36:69-74 4379. Liu Y, Huang C, Liu H, Zou B, Yao P, Xu L (2014) Effect of nano-additives on microstructure and mechanical properties of Ti(C,N)-TiB2-WC composite ceramic cutting tool materials. In: Xu X, Huang C, Zuo D, Chen M (eds) Proc. 12th conf. on machining and advanced manufacturing technology (CMAMT 2013), Xiamen, China, 24-27 July 2013. Key Eng Mater 589-590:337-341 4380. Tanaka K, Nishiyama K (2014) Fabrication and mechanical properties of TiB2-WC composites. J Jpn Soc Powder Powder Metall 61(7):362-368 (in Japanese) 4381. Li J, Zhang Y, Luo H, Gong S, Li P, Huo Y (2016) Surface modification of Ti alloys with WC-TiB2-reinforced laser composite coatings. Sci Eng Compos Mater 23(6):737-741

814

2 Tungsten Carbides

4382. Zhang C, Song J, Jiang L, Gao J, Liang G, Lei C, Xie J, Wang S, Lv M (2017) Fabrication and tribological properties of WC-TiB2 composite cutting tool materials under dry sliding condition. Tribol Int 109:97-103 4383. Telle R (2019) Analysis of pressureless sintering of titanium diboride ceramics with nickel, cobalt and tungsten carbide additives. J Eur Ceram Soc 39:2266-2276 4384. Zhang S, Li D, Yoon J, Cho T (2010) Synthesis and evaluation of TiN-WC/TiN nanocomposite by the hybrid technique with arc ion plating and magnetron sputtering. Curr Appl Phys 10:842-847 4385. Gren M, Fransson E, Ångqvist M, Erhart P, Wahnström G (2021) Modelling of vibrational and configurational degrees of freedom in hexagonal and cubic tungsten carbides at high temperatures. Phys Rev Mater 5:033804 (14 pp.) 4386. Ratov BT, Bondarenko MO, Mechnik VA, Strelchuk VV, Prikhna TA, Kolodnitskyi VM, Nikolenko AS, Lytvyn PM, Danylenko IM, Moshchil VE, Gevorkyan ES, Kosminov AS, Borash AR (2021) Structure and properties of WC-Co composites with different CrB2 concentrations, sintered by vacuum hot pressing for drill bits. J Superhard Mater 43(5):344354 4387. Nowotny H, Kieffer R, Benesovsky F, Laube E (1957) Zur Kenntnis der Teilsysteme: UCTiC, -ZrC, -VC, -NbC, -TaC, -Cr3C2, -Mo2C und -WC (To the knowledge of the subsystems: UC-TiC, -ZrC, -VC, -NbC, -TaC, -Cr3C2, -Mo2C and -WC). Monatsh Chem 88(3):336-343 (in German) 4388. Ugajin M (1973) The U0.8Pu0.2C – W system. J Nucl Mater 47(2):205-218 4389. Ugajin M, Takahashi I (1970) The phase reaction in the UC-W system. J Nucl Mater 35(3):303-313 4390. Suzuki Y, Shiozawa K, Handa M (1984) Solubility of tungsten in uranium monocarbide. J Nucl Sci Technol 21(8):608-613 4391. Brukl CE (1972) Der Einfluß von Vanadin und Niob auf feste Subcarbidlösungen in den Systemen Tantal – Wolfram – Kohlenstoff und Tantal – Molybdän – Kohlenstoff (The influence of vanadium and niobium on solid semicarbide solutions in the tantalum – tungsten – carbon and tantalum – molybdenum – carbon systems). Monatsh Chem 103:820-830 (in German) 4392. Paul AV, Gnyusov SF, Ivanov YuF, Kulkov SN, Kozlov ÉV (1992) Deformation processes in tungsten carbide powder ground in a ball mill. Russ Phys J (5):447-451 4393. Romanus H, Cimalla V, Schaefer JA, Spieβ L, Ecke G, Pezoldt J (2000) Preparation of single-phase tungsten carbide by annealing of sputtered tungsten-carbon layers. Thin Solid Films 359:146-149 4394. Kovalchenko MS, Paustovskii AV, Botvinko VP (2001) Phase composition of electrospark tungsten carbide – based coatings after heat treatment and isothermal soaking. Powder Metall Met Ceram 40(3-4):179-182 4395. Zheng Q, Banerjee D, Huston WR, Stark R (2011) Wear resistant ultra-fine double-phase binderless tungsten carbide. In: Proc. 8th Int. conf. on tungsten, refractory and hard materials, San Francisco, California, 18-21 May 2011, pp. 308-313. Metal Powder Industries Federation, Princeton, New Jersey 4396. Poluboyarov VA, Zhdanok AA, Korotaeva ZA, Kuznetsov VA (2014) Preparation of WC and W2C by self-propagating high-temperature synthesis using a mixture of tungsten, titanium and carbon black powders. Inorg Mater 50(5):469-472 4397. Trosnikova IYu, Loboda PI, Karasevska OP, Bilyi OI (2014) Effect of the cooling rate during melt solidification on the structure and properties of WC-W2C. Powder Metall Met Ceram 52(11-12):674-679 4398. Chen W-T, Dickey EC (2016) Crystallographic orientation relationships and interfaces in laser-processed directionally solidified WC-W2C eutectoid ceramics. J Mater Sci 51:43714378 4399. Chen W-T, Dickey EC (2017) Indentation-induced deformation mechanisms in laserprocessed directionally solidified WC-W2C eutectoids. J Mater Sci 52:5511-5519

References

815

4400. Tillman W, Hagen L, Kokalj D (2017) Embedment of eutectic tungsten carbides in arc sprayed steel coatings. Surf Coat Technol 331:153-162 4401. Mühlbauer G, Kremser G, Bock A, Weidow J, Schubert W-D (2018) Transition of W2C to WC during carburization of tungsten metal powder. Int J Refract Met Hard Mater 72:141-148 4402. Andreev PV, Smetanina KE, Lantsev EA (2019) X-ray powder diffraction analysis of a tungsten carbide – based ceramic. In: Alymov MI, Moskovskikh DO, Rogachev AS (eds) Proc. Int. conf. on synthesis and consolidation of powder materials (SCPM-2018), Chernogolovka, Moscow Region, Russian Federation, 23-26 Oct 2018. IOP Conf Series Mater Sci Eng 558:012003 (5 pp.) 4403. Trosnikova IYu, Loboda PI (2019) Composition and properties of eutectic alloy of WCW2C system. J Superhard Mater 41(1):49-52 4404. Friedemann M, Klostermann H (2016) Composition and mechanical properties of B-C-W and B-C-Ti thin films prepared by pulse magnetron sputtering. Surf Coat Technol 308:115120 4405. Wang H, Yan X, Liu X, Lu H, Hou C, Song X, Nie Z (2018) Microstructure, mechanical and tribological properties of WC-WCoB coating. J Eur Ceram Soc 38:4874-4881 4406. Haschke H, Nowotny H, Benesovsky F (1966) Untersuchungen in den Dreistoffen: (Mo, W) – (Fe, Co, Ni) – B (Investigations in the ternary systems: (Mo, W) – (Fe, Co, Ni) – B). Monatsh Chem 97(5):1459-1468 (in German) 4407. Suzuki H, Hayashi K (1983) Some properties of β – W and β – WC sintered compacts containing nitrogen. J Jpn Soc Powder Powder Metall 30(6):243-248 (in Japanese) 4408. Asada N, Yamamoto Y, Igarashi T, Doi Y, Hayashi K (1999) Synthesis of new carbonitride W(C,N) powder by heating W + C mixed powder in high-pressure nitrogen gas. J Jpn Soc Powder Powder Metall 46(4):373-377 4409. Tanaka K, Hayashi K (1999) Synthesis of new W(C,N) powder by heating W + C and WO3 + C mixed powders in NH3 + H2 and CH4 + NH3 mixed gases. J Jpn Soc Powder Powder Metall 46(11):1154-1161 4410. Gromilov SA, Shubin YuV, Kinelovskii SA, Trishin YuA, Popov YuN (2001) Obrazovanie faz v sisteme W-C pri kumulyativnom nanesenii pokrytii (Formation of phases in the W-C system upon cumulative deposition of coatings). Poverkhnost Rentgen Sinkhrotron Neitron Issled (6):82-84 (in Russian) 4411. Kinelovskii SA, Gromilov SA (2001) Specific features of the formation of crystalline phases of the W-C-N system in a cumulative process. Combust Explos Shock Waves 37(2):243-246 4412. Gerasimov AF, Konev VN, Timofeeva NF (1961) Study of reaction diffusion in “metal – complex gas” systems. VI. Tungsten-carbon-nitrogen system. Phys Met Metallogr 11(4):106110 4413. Li W-M, Elers K, Kostamo J, Kaipio S, Huotari H, Soininen M, Soininen PJ, Tuominen M, Haukka S, Smith S, Besling W (2002) Deposition of WNxCy thin films by ALCVDTM method for diffusion barriers in metallization. In: Proc. IEEE Int. interconnect technology conf. (IITC 2002), Burlingame, California, 3-5 June 2002, 1014930, pp. 191-193. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 4414. Tanaka K, Asada N, Hayashi K (2003) Proposal of atomic models for formation process of carbonitride W(C,N) synthesized by normal- and high-pressure methods. J Jpn Soc Powder Powder Metall 50(7):534-544 4415. Hoyas AM, Schuhmacher J, Shamiryan D, Waeterloos J, Besling W, Celis JP, Maex K (2004) Growth and characterization of atomic layer deposited WC0.7N0.3 on polymer films. J Appl Phys 95(1):381-388 4416. Ajmera HM, Anderson T, Reitfort LL, McElwee-White L (2005) Deposition of WNxCy using allylimido complexes Cl4(RCN)W(NC3H5): effect of NH3 on film properties. In: Sinno TR, Koberstein J, Harris MT, Narasimhan B (eds) Proc. 2005 AIChE annual meeting and fall showcase, Cincinnati, Ohio, 30 Oct – 4 Nov 2005, pp. 4624-4632. The American Institute of Chemical Engineers, New York

816

2 Tungsten Carbides

4417. Ajmera HM, Heitsch AT, Bchir OJ, Norton DP, Reitfort LL, McElwee-White L, Anderson TJ (2008) Deposition of WNxCy using the allylimido complexes Cl4(RCN)W(NC3H5): effect of NH3 on film properties. J Electrochem Soc 155(10):H829-H835 4418. Kim S-H, Oh SS, Kim K-B, Kang D-H, Li W-M, Haukka S, Tuominen M (2003) Atomiclayer-deposited WNxCy thin films as diffusion barrier for copper metallization. Appl Phys Lett 82(25):4486-4488 4419. Koh W, Kumar D, Li W-M, Sprey H, Raaijmakers IJ (2005) Meeting the Cu diffusion barrier challenge using ALD tungsten nitride carbide. Solid State Technol 48(6):54-58 4420. Chuang S-H, Chiu H-T, Chou Y-H, Chen S-F (2006) Growth of ternary WCxNy thin films from a single-source precursor W(NtBu)2(Net2)2. J Chin Chem Soc 53(6):1391-1395 4421. Kim S-H, Oh SS, Kim H-M, Kang D-H, Kim K-B, Li W-M, Haukka S, Tuominen M (2004) Characterization of atomic layer deposited WNxCy thin film as a diffusion barrier for copper metallization. J Electrochem Soc 151(4):C272-C282 4422. Hoyas AM, Travaly Y, Schuhmacher J, Sajavaara T, Whelan CM, Eyckens B, Richard O, Giangrandi S, Brijs B, Vandervorst W, Maex K, Celis, JP, Jonas AM, Vantomme A (2006) The impact of the density and type of reactive sites on the characteristics of the atomic layer deposited WNxCy films. J Appl Phys 99:063515 (8 pp.) 4423. Hoyas AM, Schuhmacher J, Whelan CM, Landaluce TF, Vanhaeren D, Maex K, Celis, JP (2006) Using scaling laws to understand the growth mechanism of atomic layer deposited WNxCy films on methyl-terminated surfaces. J Appl Phys 100:114903 (6 pp.) 4424. Kim K-S, Lee M-S, Yim S-S, Kim H-M, Kim K-B, Park H-S, Koh W, Li W-M, Stokhof M, Sprey H (2006) Evaluation of integrity and barrier performance of atomic layer deposited WNxCy films on plasma-enhanced chemical vapour deposited SiO2 for Cu metallization. Appl Phys Lett 89:081913 (3 pp.) 4425. Ajmera HM, Anderson TJ, Koller J, McElwee-White L, Norton DP (2008) Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2–) tungsten complex (CH3CN)Cl4W(NNMe2). Thin Solid Films 517:6038-6045 4426. Su YD, Hu CQ, Wang C, Wen M, Liu DS, Zheng WT (2009) Stress induced preferred orientation and phase transition for ternary WCxNy thin films. Appl Surf Sci 255:8164-8170 4427. Su YD, Hu CQ, Wen M, Wang C, Liu DS, Zheng WT (2009) Effects of bias voltage and annealing on the structure and mechanical properties of WC0.75N0.25 thin films. J Alloys Compd 486:357-364 4428. Kang Y, Kang S (2010) WC-reinforced (Ti,W)(C,N). J Eur Ceram Soc 30:793-798 4429. Ospina R, Escobar-Rincón, Arango PJ, Restrepo-Parra E, Jurado JF (2013) Structural and chemical composition analysis of WCN produced by pulsed vacuum arc discharge. Surf Coat Technol 232:96-100 4430. Kim H, Park J, Jeon He, Jang W, Jeon Hy, Yuh J (2015) Characteristics of WNxCy films deposited using remote plasma atomic layer deposition with (MeCp)W(CO)2(NO) for Cu diffusion barrier. J Vac Sci Technol A 33(5):05E111 (8 pp.) 4431. Zhao H, Ye F (2016) Investigation of sputtered WCN coating for diesel engine pistons applications. Vacuum 126:5-9 4432. Zhao H, Ni Z, Ye F (2016) Effect of carbon content on structure and properties of WCN coatings prepared by RF magnetron sputtering. Surf Coat Technol 287:129-137 4433. Kim H, Jang W, Shin K, Lee K, Lim H, Kim M, Yuh J, Jeon Hy (2017) The annealing effect on work function variation of WNxCy films deposited by remote plasma atomic layer deposition. Phys Stat Sol A 214(7):1700010 (5 pp.) 4434. Restrepo-Parra E, Escobar D, Ospina R, Quintero JH, Londoño RM (2018) Plasma diagnostic and microstructural study of WCN coatings growth by pulsed vacuum arc discharge. Contrib Plasma Phys 58:827-837 4435. Zhao H, Yu L, Ye F (2018) Comparison study on the oxidation behaviour of WN and WCN ceramic coatings during heat treatment. Mater Chem Phys 206:144-149 4436. Zonensain O, Fadida S, Fisher I, Gao J, Chattopadhyay K, Harm G, Mountsier T, Danek M, Eizenberg M (2015) Working function tuning of plasma-enhanced atomic layer deposited

References

817

WCxNy electrodes for metal/oxide/semiconductor devices. Appl Phys Lett 106(8):082107 (4 pp.) 4437. Kiparisov SS, Pankevich AP (1978) Production of high-density sintered parts from tungsten carbide powder. Powder Metall Met Ceram 17(7):565-567 4438. Xiao T, Hanif A, York APE, Sloan J, Green MLH (2002) Study on preparation of high surface area tungsten carbides and phase transition during the carburisation. Phys Chem Chem Phys 4:3522-3529 4439. Krzanowski JE, Endrino JL (2004) The effects of substrate bias on phase stability and properties of sputter-deposited tungsten carbide. Mater Lett 58:3437-3440 4440. Soares DM, Vicentini R, Peterlevitz AC, Rodella CB, Da Silva LM, Zanin H (2019) Tungsten oxide and carbide composite synthesized by hot filament chemical deposition as electrodes in aqueous-based electrochemical capacitors. J Energy Storage 26:100905 (11 pp.) 4441. Zekonyte J, Polcar T (2015) Friction force microscopy analysis of self-adaptive W-S-C coatings: nanoscale friction and wear. ACS Appl Mater Interfaces 7:21056-21064 4442. Luković J, Milovanović D, Kumar R, Kijevčanin M, Radović I, Matović B, VolkovHusović T (2018) Synthesis and characterization of porous tungsten carbide with added tungsten silicides. Int J Refract Met Hard Mater 72:9-14 4443. Shiono T, Fuke A (1996) Preparation and mechanical properties of ZrO2-WC composites by slip-casting technique. J Jpn Soc Powder Powder Metall 43(7):885-889 (in Japanese) 4444. Pȩdzich Z, Haberko K (1997) Toughening mechanisms in the TZP-WC particulate composites. In: Abélard P, Baxter J, Bortzmeyer D, Baumard J-F, Cauville R (eds) Euro Ceramics V. Proc. 5th conf. and exhibition of the European Ceramic Society, Versailles, France, 22-26 June 1997. Key Eng Mater 132-136(3):2076-2079 4445. Pȩdzich Z, Haberko K, Piekarczyk J, Faryna M, Lityńska L (1998) Zirconia matrix – tungsten carbide particulate composites manufactured by hot-pressing technique. Mater Lett 36:70-75 4446. Faryna M, Bischoff E, Sztwiertnia K (2002) Crystal orientation mapping applied to the Y-TZP/WC composite. Mikrochim Acta 139:55-59 4447. Haberko K, Pȩdzich Z, Róg G, Bućko M, Faryna M (1995) The TZP matrix – WC particulate composites. Eur J Solid State Inorg Chem 32(7-8):593-601 4448. Pȩdzich Z, Haberko K, Faryna M (1996) Tetragonal zirconia – tungsten carbide composites: manufacturing, microstructure and properties. In: Adali S, Verijenko VE (eds) Proc. 1st Int. conf. on composite science and technology (ICCST/1), Durban, South Africa, 18-20 June 1996, pp. 379-384. University of Natal, South Africa 4449. Haberko K, Pȩdzich Z (1999) Particulate composites in the TZP – carbide systems. Bull Polish Acad Sci Tech Sci 47(4):379-395 4450. Haberko K, Pȩdzich Z, Dutkiewicz J, Faryna M, Kowal A (1998) Microstructure of the particulate composites in the (Y)TZP-WC system. In: Tomsia AP, Glaeser AM (eds) Ceramic microstructures: control at the atomic level. Proc. Int. materials symp. on ceramic microstructures ’96, Berkeley, California, 24-27 June 1996, pp. 741-748. Plenum Press, New York, London 4451. Faryna M, Pȩdzich Z, Lityńska L, Haberko K (1997) Microstructure of the TZP particulate composites. In: Scott ML (ed) Proc. 11th Int. conf. on composite materials (ICCM 11), Gold Coast, Queensland, Australia, 14-18 July 1997, Vol. 2 – Fatigue, fracture and ceramic matrix composites, pp. 751-756. Woodhead Publishing, Australian Composite Structures Society, Port Melbourne, Victoria, Australia 4452. Pȩdzich Z (2012) Tungsten carbide as an reinforcement in structural oxide-matrix https://www.intechopen.com/chapters/41528 Accessed 28 December 2021 4453. Pȩdzich Z, Wajler C (2005) Influence of second phase particles addition on reliability of composites with 3Y-TZP matrix. In: Nie JF, Barnett M (eds) Materials Forum, Vol. 29 –

818

2 Tungsten Carbides

Advanced materials processing, pp. 336-339. The Institute of Materials Engineering Australasia, Melbourne, Victoria, Australia 4454. Ünal N, Kern F, Öveçoglu ML, Gadow R (2009) Properties of zirconia – tungsten carbide composites produced by hot-pressing. In: Proc. European Int. powder metallurgy congress and exhibition (Euro PM 2009), Copenhagen, Denmark, 12-14 Oct 2009, Vol. 3 (1 p.). The European Powder Metallurgy Association, Shrewsbury, UK 4455. Basu B, Venkateswaran T, Sarkar D (2005) Pressureless sintering and tribological properties of WC-ZrO2 composites. J Eur Ceram Soc 25:1603-1610 4456. Biswas K, Mukhopadhyay A, Basu B, Chattopadhyay K (2007) Densification and microstructure development in spark-plasma sintering WC – 6 wt.% ZrO2 nanocomposites. J Mater Res 22(6):1491-1450 4457. Venkateswaran T, Sarkar D, Basu B (2005) Tribological properties of WC-ZrO2 nanocomposites. J Am Ceram Soc 88(3):691-697 4458. Basu B, Lee J-H, Kim D-Y (2004) Development of WC-ZrO2 nanocomposites by sparkplasma sintering. J Am Ceram Soc 87(2):317-319 4459. Jiang D, Van Der Biest O, Vleugels J (2007) ZrO2-WC nanocomposites with superior properties. J Eur Ceram Soc 27:1247-1251 4460. Huang SG, Vleugels J, Van Der Biest O (2007) Pulsed electric current sintering of WC based hardmetals and ZrO2 based ceramic composites. In: Proc. European Int. powder metallurgy congress and exhibition (Euro PM 2007), Toulouse, France, 15-17 Oct 2007, Vol. 1, pp. 257-262. The European Powder Metallurgy Association, Shrewsbury, UK 4461. Ünal N, Kern F, Öveçoglu ML, Gadow R (2010) Processing of yttria stabilized zirconia / tungsten carbide composites by ceramic injection molding. In: Proc. World powder metallurgy congress and exhibition (World PM 2010), Florence, Italy, 10-14 Oct 2010, Vol. 4 (6 pp.). The European Powder Metallurgy Association, Shrewsbury, UK 4462. Ünal N, Kern F, Öveçoglu ML, Gadow R (2011) Influence of WC particles on the microstructural and mechanical properties of 3 mol.% Y2O3 stabilized ZrO2 matrix composites produced by hot pressing. J Eur Ceram Soc 31:2267-2275 4463. Zheng D, Li X, Li Y, Qu S, Yang C (2013) ZrO2(3Y) toughened WC composites by sparkplasma sintering. J Alloys Compd 572:62-67 4464. Nasser A, Kassem MA, Elsayed A, Gepreel MA, Moniem AA (2016) Influence of grain refinement on microstructure and mechanical properties of tungsten carbide / zirconia nanocomposites. J Mater Eng Perform 25(11):5065-5075 4465. Wang J, Zuo D, Zhu L, Li W, Tu Z, Dai S (2018) Effects and influence of Y2O3 addition on the microstructure and mechanical properties of binderless tungsten carbide fabricated by spark-plasma sintering. Int J Refract Met Hard Mater 71:167-174 4466. Zhang SC, Hilmas GE, Fahrenholtz WG (2008) Improved oxidation resistance of zirconium diboride by tungsten carbide additions. J Am Ceram Soc 91(11):3530-3535 4467. Zou J, Zhang G-J, Kan Y-M (2009) Formation of tough interlocking microstructure in ZrB2-SiC-based ultra-high temperature ceramics by pressureless sintering. J Mater Res 24(7):2428-2434 4468. Zhang SC, Hilmas GE, Fahrenholtz WG (2011) Oxidation of zirconium diboride with tungsten carbide additions. J Am Ceram Soc 94(4):1198-1205 4469. Zou J, Zhang G-J, Sun S-K, Liu H-T, Kan Y-M, Liu J-X, Xu C-M (2009) ZrO2 removing reactions of groups IV-VI transition metal carbides in ZrB2 based composites. J Eur Ceram Soc 31:421-427 4470. Zou J, Rubio V, Binner J (2017) Thermoablative resistance of ZrB2-SiC-WC ceramics at 2400 °C. Acta Mater 133:293-302 4471. Lee D-B, Shapovalov YA (2006) High-temperature oxidation of WC-ZrN superhard nanocomposite film. In: Eco-materials processing & design VII. Proc. 7th Int. symp. on ecomaterials and design (ISEPD-7), Chengdu, China, 8-11 Jan 2006. Mater Sci Forum 510511:414-417

References

819

4472. Lee H-S, Kim S-J, Bak S-H, Lee D-B (2008) High-temperature oxidation of WC-ZrN superhard nanolayered film. J Ceram Process Res 9(5):517-521 4473. Put S, Anné G, Vleugels J, Van Der Biest O (2002) Functionally graded ZrO2-WC composites processed by electrophoretic deposition. In: Kermel C, Lardot V, Libert D, Urbain I (eds) Euro Ceramics VII. Proc. 7th conf. of the European Ceramic Society, Brugge, Belgium, 9-13 Sep 2001. Key Eng Mater 206-213(1):189-192 4474. Guo M-H, Duan Z-L (2004) Microstructure of ZrO2 + WC made by ceramic coating melting-spraying. Trans China Weld Inst 25(1):13-16, 20 (in Chinese) 4475. Pȩdzich Z, Wajler C (2004) Reliability of zirconia based composites. In: Mandal H, Öveçoğlu L (eds) Euro Ceramics VIII. Proc. 8th conf. and exhibition of the European Ceramic Society, Istanbul, Turkey, 29 June – 3 July 2003. Key Eng Mater 264-268(2):837-840 4476. Anné G, Put S, Vanmeensel K, Jiang D, Vleugels J, Van Der Biest O (2005) Hard, tough and strong ZrO2-WC composites from nanosized powders. J Eur Ceram Soc 25:55-63 4477. Venkateswaran T, Sarkar D, Basu B (2006) WC-ZrO2 composites: processing and unlubricated tribological properties. Wear 260:1-9 4478. Lauwers B, Brans K, Liu W, Vleugels J, Salehi S, Vanmeensel K (2008) Influence of the type and grain size of the electro-conductive phase in the Wire-EDM performance of ZrO2 ceramic composites. CIRP Annals Manuf Technol 57:191-194 4479. Yang F-Z, Ai X, Zhao J, Zhou J-Q (2008) Effect of microstructures om mechanical properties of WC-ZrO2 ceramic composites. J Synth Cryst 37(4):814-818 (in Chinese) 4480. Bonny K, De Baets P, Vleugels J, Salehi A, Van Der Biest O, Lauwers B, Liu W (2009) EDM machinability and frictional behaviour of ZrO2-WC composites. Int J Adv Manuf Technol 41:1085-1093 4481. Malek O, Lauwers B, Perez Y, De Baets P, Vleugels J (2009) Processing of ultra-fine ZrO2 toughened WC composites. J Eur Ceram Soc 29:3371-3378 4482. Malek O, Vleugels J, Perez Y, De Baets P, Liu J, Van Der Berghe S, Lauwers B (2010) Electrical discharge machining of ZrO2 toughened WC composites. Mater Chem Phys 123:114-120 4483. Malek O, Vleugels J, Lauwers B (2010) Wire EDM of WC-ZrO2 composites. In: Zhao W, Ye J, Zhu D (eds) Proc. 16th Int. symp. on electromachining (ISEM XVI), Shanghai, China, 19-23 Apr 2010, pp. 243-248. Shanghai Jiatong University Press, Shanghai, China 4484. Ünal N, Kern F, Öveçoglu ML, Gadow R (2011) Optimization of processing conditions and characterization investigations of ceramic injection molded and sintered ZrO2/WC composites. J Alloys Compd 509:4797-4804 4485. Ma J, Xu C-H, Yi M-D, Xiao G-C, Wang X-H (2014) Friction and wear property of Ti(C,N)/ZrO2/WC nanocomposite cermet die material. In: Yarlagadda P, Kim Y-H (eds) Proc. 3rd Int. conf. on materials and products manufacturing technology (ICMPMT 2013), Guangzhou, China, 25-26 Sep 2013. Adv Mater Res 834-836:23-28 4486. Karbaum J, Zwick M, Müller A, Scheidt K (2017) Entwicklung und anwendung keramischer ZrO2/WC-verbundwerkstoff-mahlkugeln (Development and application of ceramic ZrO2/WC composite materials grinding balls). Keram Z 69(5):112-114 (in German) 4487. Magano M (2017) Development, production and application of new composite ceramic materials for engineering. J Jpn Soc Powder Powder Metall 64(11):609-614 (in Japanese) 4488. Mohan K, Strutt PR (1996) Observation of Co nanoparticle dispersions in WC nanograins in WC-Co cermets consolidated from chemically synthesized powders. Nanostruct Mater 7(5):547-555 4489. Mohan K, Strutt PR (1996) Microstructure of spray converted nanostructured tungsten carbide – cobalt composite. Mater Sci Eng A 209:237-242 4490. McCandlish LE, Kear BH, Kim BK (1990) Chemical processing of nanophase WC-Co composite powders. Mater Sci Technol 6(10):953-957 4491. Sluiter MHF (2009) Interstitials in tetrahedrally close-packed phases: C, N, O and F in β-tungsten from first principles. Phys Rev B 80(22):220102(R) (4 pp.)

820

2 Tungsten Carbides

4492. Trpčevská J, Ganev N, Żórawski W, Jakubeczyová D, Briančin J (2009) Effect of powder particle size on the structure of HVOF WC-Co sprayed coatings. Powder Metall Prog 9(1):42-48 4493. Kumar AKN, Kurokawa K (2012) Spark-plasma sintering of ultra-fine WC powders: a combined kinetic and microstructural study. In: Liu K (ed) Tungsten carbide: processing and https://www.intechopen.com/chapters/41530 Accessed 3 January 2022 4494. Madej M (2012) Tungsten carbide as an addition to high speed steel based composites. In: 51-5024-4, doi:10.5772/51243 https://www.intechopen.com/chapters/41529 Accessed 3 January 2022 4495. Zhu E-T, Zhang J-X, Guo S-D, Yang X-Y, Zhang X, Yang J-G (2019) Effect of Co on morphology and preparation of in situ synthesis of WC-Co composite powders. Mater Res Express 6:086522 (14 pp.) 4496. Cheng Y, Zhu T, Zhang J, Li Y, Sang S, Xie Z (2020) Oscillatory pressure sintering of binderless tungsten carbide. Ceram Int 46:25603-25607 4497. Ghasali E, Orooji Y, Tahamtan H, Asadian K, Alizadeh M, Ebadzadeh T (2020) The effects of metallic additives on the microstructure and mechanical properties of WC-Co cermets prepared by microwave sintering. Ceram Int 46:29199-2906 4498. Karimi H, Hadi M (2020) Effect of sintering techniques on the structure and dry sliding wear behaviour of WC-FeAl composite. Ceram Int 46:18487-18497 4499. Sivkov AA, Shanenkov II, Shanenkova YL, Rakhmatullin IA, Ivashutenko AS, Nikitin DS, Nasyrbaev AR (2020) Plasma dynamic synthesis of nanocrystalline γ-WC1–x and the dependence of the product structure on the ratio of precursors. Tech Phys 65(12):2007-2015 4500. Sivkov AA, Nasyrbaev AR, Nikitin DS, Shanenkov II, Rakhmatullin IA (2021) Plasma jet synthesis of cubic tungsten carbide of variable stoichiometry. Inorg Mater 57(4):337-342 4501. Sivkov AA, Shanenkov II, Shanenkova YL, Nikitin DS, Rakhmatullin IA, Tsimmerman AI, Shanenkova NS (2021) Plasma dynamic synthesis of cubic tungsten carbide and the influence of the gas atmosphere parameters. J Surf Investig 15(2):361-370 4502. Su W, Zou J, Sun L (2020) Effects of nano-alumina on mechanical properties and wear resistance of WC – 8 Co cemented carbide by spark-plasma sintering. Int J Refract Met Hard Mater 92:105337 (10 pp.) 4503. Liu R, Zhang D, Tang Y, Tang X, Humphries E, Li D (2021) (W1–xMx)C carbides with desired combinations of compatible density and properties – a first principles study. J Am Ceram Soc 104(8):4239-4256 4504. Solodkyi I, Bogomol I, Loboda P (2021) High-speed electron beam sintering of WC – 8 Co under controlled temperature conditions. Int J Refract Met Hard Mater 102:105730 (12 pp.) 4505. Konyashin I, Ries B (2022) Cemented carbides, 1st ed. Elsevier, Amsterdam, Berlin 4506. Pugach ÉA (1969) Issledovanie vysokotemperaturnogo okisleniya karbidov i boridov perekhodnykh metallov IV-VI grupp periodicheskoi sistemy (A study of high-temperature oxidation of carbides and borides of the periodic system groups IV-VI transition metals). PhD thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 4507. Voitovich RF (1976) Issledovanie vysokotemperaturnogo okisleniya splavov perekhodnykh metallov i ikh tugoplavkikh soedinenii (A study of high-temperature oxidation of the alloys of transition metals and their refractory compounds). DSc thesis, Institute for Problems of Materials Science, Ukrainian SSR Academy of Sciences, Kyiv (in Russian) 4508. Samsonov GV, Épik AP (1966) Coatings of high-temperature materials. Some properties of high-temperature compounds. In: Hausner HH (ed) Coatings of high-temperature materials, pp. 7-111. Springer, Plenum Press, New York 4509. Reed EL (1958) Report on tungsten carbide. Technical Report AECU-110, pp. 1-121. United States Atomic Energy Commission, Washington, DC

References

821

4510. Webb WW, Norton JT, Wagner C (1956) Oxidation studies in metal-carbon systems. J Electrochem Soc 103(2):112-117 4511. Samsonov GV, ed (1962) Analiz tugoplavkikh soedinenii (The analysis of refractory compounds). Metallurgizdat, Moscow (in Russian) 4512. Mashkovich LA, Kuteinikov AF, Maslova TP (1964) Phase analysis of tungsten and tungsten carbide materials. Indust Lab 30(5):651-654 4513. Ohlinger LA (1948) The stability of tungsten carbide in hydrogen at elevated temperatures. Technical Report NRR-164 (AD-145616). Northrop Aircraft, Hawthorne, California 4514. May CE, Koneval D, Fryburg GC (1959) Stability of ceramics in hydrogen between 4000 °F and 4500 °F. NASA Memorandum 3-5-59E. National Aeronautics and Space Administration, Washington, DC, pp. 1-18. 4515. May CE, Hoekstra PD (1961) Stability of refractory compounds in hydrogen between 4000 °F and 4500 °F and their compatibility with tungsten. Technical Report NASA-TN-D844. National Aeronautics and Space Administration, Washington, DC, pp. 1-18. 4516. Garbiec D, Laptev AM, Leshchynsky V, Wiśniewska M, Figiel P, Biedunkiewicz A, Siwak P, Räthel J, Pötschke J (2022) Spark-plasma sintering of WC-Ti powder mixtures and properties of obtained composites. J Eur Ceram Soc 42(5):2039-2047 4517. Newkirk AE (1955) The oxidation of tungsten carbide. J Am Chem Soc 77(17):4521-4522 4518. Simons EL, Fagel JE, Jr, Balis EW (1955) Combustion of tungsten carbide by highfrequency induced radiant heating. Anal Chem 27(7):1123-1125 4519. Hauffe K (1965) Oxidation of metals. Plenum Press, New York 4520. Okuyama F (1979) Decarburization of monocrystalline ditungsten carbide as revealed by field electron microscopy. Appl Surf Sci 3:1-12 4521. Kang SG, Fromm E (1981) Reactions of molybdenum and tungsten carbides with oxygen at high temperatures. Metall Trans A 12(12):1993-1998 4522. Kang SG, Fromm E (1982) Reaktion von Mo2C, W2C, WC und WC-Co-Hartmetallen mit Sauerstoff bei hohen Temperaturen (Reaction of Mo2C, W2C, WC and WC-Co with oxygen at high temperatures). High Temp High Press 14(2):209-218 (in German) 4523. Dufour LC, Simon J (1968) Cinétique d’oxydation à très basse pression d’O2 d’échantillons pulvérulents de ZrC, WC et Mo2C (Kinetics of oxidation at very low O2 pressures of powdered samples of ZrC, WC and Mo2C). Bull Soc Chem France 9:3643-3649 (in French) 4524. Roebuck B, Bennett EG, Almond EA, Gee MG (1986) Dependence of oxidation rate of WC powder on particle size. J Mater Sci 21:2033-2042 4525. Roebuck B (1988) Isochronal oxidation experiments on WC powders. Int J Refract Met Hard Mater 7(1):41-46 4526. Aizawa T, Hayami W, Souda R, Otani S, Tanaka T, Ishizawa Y (1996) Molecular adsorption of oxygen on transition metal carbide. Surf Sci 357-358:645-650 4527. Warren A, Nylund A, Olefjord I (1996) Oxidation of tungsten and tungsten carbide in dry and humid atmospheres. Int J Refract Met Hard Mater 14:345-353 4528. Gimelfarb FA, Zelikman AN (1967) Kinetika okisleniya karbida volframa (The kinetics of oxidation of tungsten carbide). Izv Vyssh Uchebn Zaved Tsvet Metall (3):63-66 (in Russian) 4529. Brillo J, Kuhlenbeck H, Freund H-J (1998) Interaction of O2 with WC (0001). Surf Sci 409:199-206 4530. Preiss H, Meyer B, Olschewski C (1998) Preparation of molybdenum and tungsten carbides from solution derived precursors. J Mater Sci 33:713-722 4531. Kudin VG, Makara VA (2004) Oxidation resistance of B, W2B5 and WC powders. Powder Metall Met Ceram 43(1-2):67-71 4532. Ribeiro CA, De Souza WR, Crespi MS, Neto JAG, Fertonani FL (2007) Non-isothermal kinetic of oxidation of tungsten carbide. J Therm Anal Calorim 90(3):801-805 4533. Kurlov AS, Gusev AI (2011) Effect of particle size on the oxidation of WC powders during heating. Inorg Mater 47(2):133-138 4534. Göthelid M, Haglund S, Ågren J (2000) Influence of O and Co on the early stages of sintering of WC-Co: a surface study by AES and STM. Acta Mater 48:4357-4362

822

2 Tungsten Carbides

4535. Håkansson KL, Johansson HI, Johansson LI (1994) High-resolution core-level study of hexagonal WC (0001). Phys Rev B 49(3):2035-2039 4536. Kurlov AS, Gusev AI (2013) Oxidation of tungsten carbide powders in air. Int J Refract Met Hard Mater 41:300-307 4537. Humphry-Baker SA, Lee WE (2016) Tungsten carbide is more oxidation resistant than tungsten when processed to full density. Scripta Mater 116:67-70 4538. Kieffer R, Kölbl F (1950) Über das Zunderverhalten und den Oxydationsmechanismus warm- und zunder-fester Hartlegierungen, insbesondere solcher auf Titancarbid-Basis (On scaling behaviour and oxidation mechanism of heat- and scale-resistant hard alloys, especially those based on titanium carbide). Z Anorg Allg Chem 262(1-5):229-247 (in German) 4539. Liu Y, Wang Z, Sun Q, Yin B, Cheng J, Zhu S, Yang J, Qiao Z, Liu W (2018) Tribological behaviour and wear mechanism of pure WC at wide range temperature from 25 to 800 °C in vacuum and air environment. Int J Refract Met Hard Mater 71:160-166 4540. Kieffer R, Nowotny H, Ettmayer P, Freudhofmeier M (1970) Über die Beständigkeit von Übergangsmetallcarbiden gegen Stickstoff bis zu 300 at (On the stability of transition metal carbides in nitrogen up to 300 atm). Monatsh Chem 101(1):65-82 (in German) 4541. Bi K, Liu J, Dai Q (2012) First principles study of boron and nitrogen adsorption on WC (100) surface. Appl Surf Sci 258:4581-4587 4542. Wetzel M, Wawrzik S, Buchegger C, Gierl C, Lengauer W (2012) Interaction of nitrogen with WC and nitrogen-assisted sintering of hardmetals. In: Carreño-Morelli E, Britenmoser G, Moseley S (eds) Proc. Int. European powder metallurgy congress and exhibition (Euro PM 2012), Basel, Switzerland, 16-19 Sep 2012, Vol. 2 (8 pp.). The European Powder Metallurgy Association, Shrewsbury, UK https://www.epma.com/publications/euro-pm-proceedings/product/ep12507 Accessed 17 January 2022 4543. Spriggs GE (1961) A preliminarily study of the reactions between tungsten carbide and tungsten carbide – 6 % cobalt powders and wet and dry hydrogen. Powder Metall 4(7):296311 4544. Ko EI, Madix RJ (1981) Effect of oxygen and sulphur on the bonding and reactivity of CO, H2, H2CO and CH3OH on tungsten and tungsten carbide surfaces. J Phys Chem 85:40194025 4545. Van Duyn W, Van Lochem B (1989) Chemical and mechanical characterization of WC:H amorphous layers. Thin Solid Films 181:497-503 4546. Bewilogua K, Dimigen H (1993) Preparation of W-C:H coatings by reactive magnetron sputtering. Surf Coat Technol 61:144-150 4547. Cohron J, Zee R, Chin B (1994) Degradation of refractory carbides by hot hydrogen. J Nucl Mater 212-215:1488-1491 4548. Cohron J, Ozaki Y, Chin B, Zee R (1994) Reactivity of refractory carbides with hot hydrogen. In: El-Genk MS, Hoover MD (eds) Proc. 11th symp. on space nuclear power and propulsion, Albuquerque, New Mexico, 9-13 Jan 1994. AIP Conf Proc 301(1):939-944 4549. Hofmann D, Schuessler H, Bewilogua K, Hübsch H, Lemke J (1995) Plasma-boosterassisted hydrogenated W-C coatings. In: McGuire GE, Sartwell BD, Jehn HA (eds) Proc. 21st Int. conf. on metallurgical coatings and thin films, San Diego, California, 25-29 Apr 1994. Surf Coat Technol 73:137-141 4550. Trefilov VI, Morozov IA, Morozova RA, Satanin SV, Yurchenko DZ (1996) Effect of hydrogen on improving purity of WC and AlN powders. Int J Hydrogen Energy 21(1112):1097-1099 4551. Bondarenko VP, Pavlotskaya EG (1997) Hydrogen-containing chemically active gas medium for controlling carbon content of tungsten-base hard alloys. Int J Hydrogen Energy 22(2-3):205-212 4552. Strondl C, Carvalho NM, De Hosson JThM, Krug TG (2005) Influence of energetic ion bombardment on W-C:H coatings deposited with W and WC targets. Surf Coat Technol 200:1142-1146

References

823

4553. Luo J, Guo Z-M, Lin T, Hu X-S (2007) Study on removing free carbon of nanosized WC by heat processing in flowing hydrogen atmosphere. Trans Mater Heat Treat 28(1):38-41 (in Chinese) 4554. Marinelli F, Jelea A, Allouche A (2007) Interactions of H with tungsten carbide surfaces: an ab initio study. Surf Sci 601:578-587 4555. Mireles OR, Anghaie S, Cunningham B, Dooies B (2009) Material performance evaluation of TaC, WC and ZrC under prototypic nuclear thermal propulsion hot hydrogen environment. In: Bragg-Sitton S, Houts M, Howe SD, Scott J (eds) Proc. 3rd topical meeting on nuclear and emerging technologies for space (NETC 2009), Atlanta, Georgia, 14-18 June 2009, pp. 99106. American Nuclear Society, La Grange Park, Illinois 4556. Ma C-A, Liu T, Chen L-T (2010) CO and H adsorption on Pt / WC (0001) surface. Acta Phys Chim Sin 26(1):155-162 (in Chinese) 4557. Czyżniewski A, Gulbiński W, Radnóczi G, Szerencsi M, Pancielejko M (2011) Microstructure and mechanical properties of W-C:H coatings deposited by pulsed reactive magnetron sputtering. Surf Coat Technol 205:4471-4479 4558. Guo P, Ke P, Wang A (2013) Incorporated W roles on microstructure and properties of WC:H films by a hybrid linear ion beam systems. J Nanomater 2013:530959 (8 pp.) 4559. Jansen SA, Hoffmann R (1987) Summary abstract: a theoretical analysis of the deactivation of metal surfaces upon carburization. J Vac Sci Technol A 5(4):637-640 4560. Brillo J, Sur R, Kuhlenbeck H, Freund H-J (1998) Interaction of CO and NO with WC (0001). Surf Sci 397:137-144 4561. Brillo J, Sur R, Kuhlenbeck H, Freund H-J (1998) Electron spectroscopic study of the interaction of WC (0001) with different adsorbates (C6H6, CO and NO). J Electron Spectrosc Relat Phenom 88-91:809-815 4562. Brillo J, Hammoudeh A, Kuhlenbeck H, Panagiotides N, Schwegmann S, Freund H-J (1998) Structural studies of WC (0001) and the adsorption of benzene. J Electron Spectrosc Relat Phenom 96:53-60 4563. Kelly TG, Stottlemyer AL, Ren H, Chen JG (2011) Comparison of O-H, C-H and C-O bond scission sequence of methanol on tungsten carbide surfaces modified by Ni, Rh and Au. J Phys Chem C 115:6644-6650 4564. Lewis MWJ (1987) Tribological coatings for nuclear applications in the United Kingdom. J Vac Sci Technol A 5(5):2930-2940 4565. Andersson KM, Bergström L (2000) Oxidation and dissolution of tungsten carbide powder in water. Int J Refract Met Hard Mater 18:121-129 4566. Jia X, Chen X, Zhang X (2011) Study on oxidation and dissolution of tungsten carbide in water. In: Proc. 2nd Int. conf. on mechanic automation and control engineering (MACE 2011), Hohhot, Inner Mongolia, China, 15-17 July 2011, pp.1679-1682. The Institute of Electrical and Electronics Engineers, Piscataway, New Jersey 4567. Zheng W, Chen L, Ma C (2014) Density functional study of H2O adsorption and dissociation on WC (0001). Comput Theor Chem 1039:75-80 4568. Jimenez-Orozco C, Flórez E, Montoya A, Rodriguez JA (2019) Binding and activation of ethylene on tungsten carbide and platinum surfaces. Phys Chem Chem Phys 21(31):1733217342 4569. Schumb WC, Aronson JR (1959) The fluorination of carbides. J Am Chem Soc 81(4):806807 4570. González-García P, Urones-Garrote E, Ávila-Brande D, Gómez-Herrero A, Otero-Díaz LC (2010) Structural study of carbon nanomaterials prepared by chlorination of tungsten carbide and bis(cyclopentadienyl)tungsten dichloride. Carbon 48:3667-3675 4571. Presser V, Heon M, Gogotsi Y (2011) Carbide-derived carbons – from porous networks to nanotubes and graphene. Adv Funct Mater 21:810-823 4572. Tallo I, Thomberg T, Kontturi K, Jänes A, Lust E (2011) Nanostructured carbide-derived carbon synthesized by chlorination of tungsten carbide. Carbon 49:4427-4433

824

2 Tungsten Carbides

4573. Zelikman AN, Leonova LM (1978) Khlorirovanie karbidnykh sostavlyayushchikh tverdykh splavov (Chlorination of carbide components of hard alloys). Tsvet Met (5):54-56 (in Russian) 4574. Urbonaite S, Wachtmeister S, Mirguet C, Coronel E, Zou WY, Csillag S, Svensson G (2007) EELS studies of carbide-derived carbons. Carbon 45:2047-2053 4575. Wu OKT, Burns RP (1980) Silicon production from the interaction between a SiO molecular beam and a tungsten carbide surface. J Phys Chem 84:1445-1448 4576. Samsonov GV, Panasyuk AD, Kozina GK (1968) Wetting of refractory carbides with liquid metals. Powder Metall Met Ceram 7(11):874-878 4577. Eremenko VN, Naidich YuV (1958) Zmochuvannya ridkymy metallamy poverkhen tugoplavkikh spoluk (The wetting of surface of refractory compounds by rare metals). UkrSSR Academy of Sciences, Kyiv (in Ukrainian) 4578. Ramqvist L (1965) Wettability of metallic carbides by liquid copper, nickel, cobalt and iron. Int J Powder Metall 1(4):2-21 4579. Warren R (1980) Solid-liquid interfacial energies in binary and pseudo-binary systems. J Mater Sci 15(10):2489-2496 4580. Samsonov GV, Panasyuk AD, Kozina GK, Dyakonova LV (1976) Kontaktnoe vzaimodeistvie karbida tsirkoniya s nikelevymi splavami (The contact interaction of zirconium carbide with nickel alloys). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 56-59. Naukova Dumka, Kyiv (in Russian) 4581. Tumanov VI, Funke VF, Belenkaya LI (1962) Nekotorye dannye po smachivaemosti okisi alyuminiya i karbidov metallami gruppy zheleza (Some data on the wettability of aluminium oxide and carbides by metals of the iron group). Zh Fiz Khim 36(7):1575-1577 (in Russian) 4582. Samsonov GV, Kozina GK, Panasyuk AD, Bondarchuk SN (1974) The reaction of refractory carbides with molten steels and cast irons. In: Samsonov GV (ed) Refractory carbides, pp. 433-440. Consultants Bureau, New York, London 4583. Livey DT, Murray P (1956) The wetting properties of solid oxides and carbides by liquid metals. In: Benesovsky F (ed) Sintered high-temperature and corrosion resistance materials. Proc. 2nd Plansee seminar, Reutte, Tyrol, 19-23 June 1955, pp. 375-404. Metallwerk Plansee AG, Reutte, Tyrol, Austria 4584. Vishnyakov LR, Grudina TV, Kadyrov VKh, Karpinos DM, Oleynik VI, Sapozhnikova AB, Tuchinskii LI (1985) Kompozitsionnye materialy (Composite materials). Naukova Dumka, Kyiv (in Russian) 4585. Naidich YuV (1981) The wettability of solids by liquid metals. Prog Surf Membr Sci 14:353-484 4586. Eustathopoulos N, Nicholas MG, Drevet B (1999) Wettability at high temperatures. Elsevier Science, Oxford 4587. Chumanov IV, Anikeev AN (2014) Issledovanie smachivaemosti karbida volframa metallicheskim rasplavom. Chast I. (A study of wettability of tungsten carbide with metallic melt. Part I.) Elektrometall (1):32-35 (in Russian) 4588. Chumanov IV, Anikeev AN (2014) Issledovanie smachivaemosti karbida volframa metallicheskim rasplavom. Chast II. (A study of wettability of tungsten carbide with metallic melt. Part II.) Elektrometall (2):34-36 (in Russian) 4589. Kislyi PS (ed), Bodnaruk NI, Borovikova MS, Zaverukha OV, Kozina GK, Kryl YaA, Kuzenkova MA, Kushtalova IP, Prikhodko LI, Storozh BD (1985) Kermety (Cermets). Naukova Dumka, Kyiv (in Russian) 4590. Eso OO, Fang ZZ, Griffo A (2005) Liquid-phase sintering of functionally graded WC-Co composites. Int J Refract Met Hard Mater 23:233-241 4591. Eso OO, Fang ZZ, Griffo A (2005) Kinetics of cobalt gradient formation during the liquidphase sintering of functionally graded WC-Co. Int J Refract Met Hard Mater 25:286-292 4592. Eso OO, Fan P, Fang ZZ (2008) A kinetic model for cobalt gradient formation during liquid-phase sintering of functionally graded WC-Co. Int J Refract Met Hard Mater 26:91-97

References

825

4593. Samsonov GV, Épik AP (1962) On the problem of parameters of the reactive diffusion of boron and carbon into refractory transition metals. Phys Met Metallogr 14(3):144-145 4594. Samsonov GV, Épik AP (1964) Pro reaktsiinu difuziyu boru ta vugletsyu u tugoplavki perekhidni metaly (On the reactive diffusion of boron and carbon into refractory transition metals). Dopov Akad Nauk Ukr RSR (1):67-70 (in Ukrainian) 4595. Samsonov GV, ed (1976) Svoistva elementov (Properties of elements), 2nd ed., Vol. 1. Metallurgiya, Moscow (in Russian) 4596. Becker JA, Becker EJ, Brandes RG (1961) Reactions of oxygen with pure tungsten and tungsten containing carbon. J Appl Phys 32(3):411-414 4597. Rawlings KJ, Foulias SD, Hopkins BJ (1981) The diffusion of carbon to and from W (100). Surf Sci 109(3):513-521 4598. Eremeev VS, Gruzin PL, Panov AS (1971) Issledovanie reaktsionnoi diffuzii ugleroda v sistemakh W-C i Mo-C (A study of the reactive diffusion of carbon in the W-C and Mo-C systems). In: Spitsyn VI (ed) Metod izotopnykh indikatorov v nauchnykh issledovaniyakh i v promyshlennom proizvodstve (Isotope tracer method in scientific research and industrial production), pp. 60-65. Atomizdat, Moscow (in Russian) 4599. Kalinovich DF, Kovenskii II, Smolin MD (1964) Podvizhnost ugleroda v volframa pri vysokih temperaturakh (Mobility of carbon in tungsten at high temperatures) Ukr Fiz Zh 9:920-921 (in Russian) 4600. Krasnov AN, Burykina AL (1971) Diffusion saturation of spherical metals powders with carbon and boron. Rev Int Hautes Temp Refract 8(1):15-24 4601. Nakonechnikov AI, Pavlinov LV, Bykov VN (1966) Diffusion of carbon in refractory metals with a bcc lattice. Phys Met Metallogr 22(2):73-76 4602. Shepela A (1972) The diffusion of carbon-14 in tungsten and tungsten-rhenium alloys. J Less-Common Met 26(1):33-43 4603. Treheux D, Dubois J, Fantozzi G, Guiraldenq P (1979) Détermination du coefficient volumique de diffusion du 14C dans le carbure de tungstène W2C (Determination of the volume coefficient of diffusion of 14C in tungsten carbide W2C). C R Hebd Séanc Acad Sci B 288(11):183-185 (in French) 4604. Treheux D, Dubois J, Fantozzi G (1981) Bulk and grain boundary diffusion of 14C in tungsten hemicarbide. Ceram Int 7(4):142-148 4605. Samsonov GV, Kushtalova IP (1973) Issledovanie protsessov deformatsii i rekristallizatsii tugoplavkikh soedinenii (A study of the deformation and recrystallization processes of refractory compounds). Izv AN SSSR Neorg Mater 9(1):46-47 (in Russian) 4606. Baskin ML, Tretyakov VI, Chaporova IN (1962) Diffuziya volframa v monokarbidakh volframa, tantala, titana i v tverdykh rastvorakh TiC-WC i TiC-WC-TaC (Diffusion of tungsten in tungsten, tantalum and titanium monocarbides and solid solutions of TiC-WC and TiC-WC-TaC). Fiz Met Metalloved 14(3):422-427 (in Russian) 4607. Aleksandrov LN, Shchelkonogov VYa (1964) The diffusion of carbon into tungsten and molybdenum at low carbon concentrations. Powder Metall Met Ceram 3(4):288-291 4608. Matzke Hj, Rondinella VV (1999) Diffusion in carbides, nitrides, hydrides and borides. In: Beke DL (ed) Diffusion in non-metallic solids. Subvol. B, Part 1, pp. 5/1-5/29. Springer, Berlin, Heidelberg 4609. May W, Krämer E (1974) Volumendiffusion im System WC-TiC und ihr Einfluß auf die Mischarbidbildung (Volume diffusion in the WC-TiC system and its influence on mixed carbide formation). Planseeber Pulvermetall 22:107-117 4610. Kovenskii II (1965) Diffusion of carbon in tungsten at high temperatures. In: Diffusion in body-centred cubic metals. Proc. Int. conf. on diffusion in body-centred cubic materials, Gatlinburg, Tennessee, 16-18 Sep 1964, pp. 283-287. The American Society for Metals, Metals Park, Ohio 4611. Épik AP, Bovkun GA, Golubchik IV, Sinitsina LP (1965) Nekotorye svoistva diffusionnykh karbidnykh i boridnykh pokrytii na tugoplavkih metallakh (Some properties of diffusion carbide and boride coatings on refractory metals). In: Samsonov GV (ed) Diffuzionnye

826

2 Tungsten Carbides

pokrytiya na metallakh (Diffusion coatings on metals), pp. 127-139. Naukova Dumka, Kyiv (in Russian) 4612. Kreimer GS, Efros LD, Voronkova EA (1952) O reaktivnoi diffusii ugleroda v volframa. Chast I. (On the reactive diffusion of carbon into tungsten. Part I.). Zh Tekh Fiz 22(5):858873 (in Russian) 4613. Kreimer GS, Efros LD, Voronkova EA (1952) O reaktivnoi diffusii ugleroda v volframa. Chast II. Issledovanie diffuzii ugleroda v nedeformirovannom volframa (On the reactive diffusion of carbon into tungsten. Part II. A study of the diffusion of carbon in unstrained tungsten). Zh Tekh Fiz 22(5):874-876 (in Russian) 4614. Samsonov GV, Épik AP (1964) Issledovanie uslovii poverkhnostnogo nasyshcheniya tugoplavkikh perekhodnykh metallov uglerodom i borom (A study of conditions of surface saturation of refractory transition metals with carbon and boron). In: Oding IA (ed) Issledovanie stalei i splavov (The studies of steels and alloys), pp. 132-139. Nauka, Moscow (in Russian) 4615. Pirani M., Sandor J (1947) Diffusion of carbon into tungsten. J Inst Met 73(5):385-395 4616. Yang Q, Yang J, Yang H, Ni G, Ruan J (2017) Synthesis of ultra-fine WC – 10 Co composite powders with carbon boat added and densification by sinter-HIP. Int J Refract Met Hard Mater 62:104-109 4617. Shchelkonogov VYa, Aleksandrov LN, Piterimov VA, Mordyuk VS (1968) Internal friction method of studying diffusion mobility of carbon in tungsten and molybdenum. Phys Met Metallogr 25(1):68-71 4618. Fries RJ, Cummings JE, Hoffman CG, Daily SA (1968) The chemical diffusion of carbon in the group VI-B metal carbides. Technical Report TR-USAEC-LA-3795-MS, Contract W7405-eng-36, pp. 1-32. Los Alamos Scientific Laboratory, New Mexico 4619. Fries RJ, Cummings JE, Hoffman CG, Daily SA (1969) The chemical diffusion of carbon in the group VI-B metal carbides. In: Benesovsky F (ed) High-temperature materials. Proc. 6th Int. Plansee seminar on high-temperature materials, fundamental and developments, Reutte, Tyrol, Austria, 24-28 June 1968, Vol. 2, pp. 568-585. Springer-Verlag, Vienna, New York 4620. Fries RJ, Cummings JE, Hoffman CG, Daily SA (1971) Carbide layer growth rates on tungsten-molybdenum and tungsten-rhenium alloys. J Nucl Mater 39:35-48 4621. Gale WF, Totemeir TC, eds (2004) Smithells metals reference book, 8th ed. Elsevier Butterworth Heinemann, ASM International Materials Information Society, Amsterdam, Boston 4622. Askill J (1970) Tracer diffusion data for metals, alloys and simple oxides. IFI/Plenum, New York, London 4623. Krasnov AN, Burykina AL (1968) Karbidizatsiya sfericheskikh poroshkov niobiya, molibdena, volframa (The carburization of spherical powders of niobium, molybdenum, tungsten). In: Samsonov GV (ed) Zashchitnye pokrytiya na metallakh (Protective coatings on metals), Vol. 2, pp.261-268. Naukova Dumka, Kyiv (in Russian) 4624. Peterson NL (1960) Diffusion in refractory metals. Technical Report WADD-TR-60-793, Contract USAF 33(616)-7382, pp. 1-164. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 4625. Klein R (1954) The surface migration of carbon on tungsten. J Chem Phys 22(8):14061413 4626. Frantsevich IN, Kovenskii II (1961) Pro stan vugletsyu v titani, tantali ta volframa (The state of carbon in titanium, tantalum and tungsten). Dopov Akad Nauk Ukr RSR (11):14711474 (in Ukrainian) 4627. Kushtalova IP, Ristič MM (1984) Recrystallization of refractory materials. I. Physical essence of recrystallization. Sci Sinter 16:111-113 4628. Kushtalova IP, Ristič MM (1984) Recrystallization of refractory materials. II. Kinetics of recrystallization. Sci Sinter 16:115-117

References

827

4629. McCarty LV, Donelson R, Hehemann RF (1987) A diffusion model for tungsten powder carburization. Metall Trans A 18(6):969-974 4630. Schmid K, Roth J (2002) Concentration dependent diffusion of carbon in tungsten. J Nucl Mater 302:96-103 4631. Kharatyan SL, Chatilyan HA, Arakelyan LH (2008) Kinetics of tungsten carbidization under non-isothermal conditions. Mater Res Bull 43:897-906 4632. Kharatyan SL, Chatilyan HA, Merzhanov AG (1990) Kinetics of tungsten – methane interaction. Sov J Chem Phys 6(2):404-419 4633. Kharatyan SL, Chatilyan HA, Merzhanov AG (1991) Kinetics of tungsten carburization with methane. Sov J Chem Phys 7(6):1341-1357 4634. Liu Y-L, Zhou H-B, Zhang Y, Lu G-H (2010) Dissolution and diffusion properties of carbon in tungsten. J Phys Condens Matter 22:445504 (6 pp.) 4635. Shohoji N, Magalhães T, Oliveira FAC, Rosa LG, Fernandes JC, Rodríguez J, Cañadas I, Martínez D (2010) Heterogeneity along the height in disc specimens of graphite/tungsten powder mixtures with sub-stoichiometric carbon atom ratios heated by concentrated solar beam to 1600 °C. Mater Trans Jpn Inst Met 51(2):381-388 4636. Demirskyi D, Ragulya A, Agrawal D (2011) Initial stage sintering of binderless tungsten carbide powder under microwave radiation. Ceram Int 37:505-512 4637. Demirskyi D, Borodianska H, Agrawal D, Ragulya A, Sakka Y, Vasylkiv O (2012) Peculiarities of the neck growth process during initial stage of spark-plasma, microwave and conventional sintering of WC spheres. J Alloys Compd 523:1-10 4638. Kumar AKN, Watabe M, Kurokawa K (2011) The sintering kinetics of ultra-fine tungsten carbide powders. Ceram Int 37:2643-2654 4639. Le Claire AD, Neumann G (1990) Diffusion of C, N and O in metals. In: Mehrer H (ed) Diffusion in solid metals and alloys, pp. 471-503. Springer-Verlag, Berlin, Heidelberg 4640. Covington L, Munirathinam K, Islam AW, Roberts KL (2012) Synthesis and characterization of nanostructured molybdenum & tungsten carbide materials and study of diffusion model. Polish J Chem Technol 14(1):28-34 4641. Kovalchenko MS (2013) Pressure sintering kinetics of tungsten and titanium carbides. Int J Refract Met Hard Mater 39:32-37 4642. Innocent AJ, Hlatshwayo TT, Njoroge EG, Malherbe JB (2018) Interface interaction of tungsten film deposited on glassy carbon under vacuum annealing. Vacuum 148:113-116 4643. Innocent AJ, Hlatshwayo TT, Njoroge EG, Ntsoane TP, Madhuku M, Ejeh EO, Mlambo M, Ismail MYA, Theron CC, Malherbe JB (2020) Evaluation of diffusion parameters and phase formation between tungsten films and glassy carbon. Vacuum 175:109245 (8 pp.) 4644. Jehn H, Bär G, Best E, Koch E (1993) Tungsten. Suppl. Vol. A, Part 5b – Metal, chemical reactions with non-metals nitrogen to arsenic. In: Von Jouanne J, Koch El, Koch E (eds) Gmelin handbook of inorganic and organometallic chemistry – Gmelin Handbuch der Anorganischen Chemie, 8th ed. Springer-Verlag, Berlin, Heidelberg 4645. Kashin VI, Klibanov EL, Tsilosani AG, Tylkina MA, Konieva LZ (1972) Saturation of liquid molybdenum, tungsten and rhenium with carbon in an arc furnace. Russ Metall (2):2934 4646. Andrews MR (1923) Production and characteristics of the carbides of tungsten. J Phys Chem 27(3):270-283 4647. Andrews MR, Dushman S (1925) Diffusion of carbon thru tungsten and tungsten carbide. J Phys Chem 29(4):462-472 4648. Shchelkonogov VYa (1978) Energiya aktivatsii diffuzii ugleroda v volframa i molibdene (Activation energy for carbon diffusion in tungsten and molybdenum). In: Margulis AD (ed) Elektronnye svoistva tverdykh tel i fazivye prevrashcheniya (Electron properties of solids and phase transformations), pp. 115-121. Ogarev Mordovia State University, Saransk (in Russian) 4649. Aleksandrov LN (1962) O diffuzionnom zagryaznenii volframa uglerodom iz grafitovoi smazki (On the diffusion contamination of tungsten with carbon from graphite lubricant). Inzh Fiz Zh 5(9): 53-58 (in Russian)

828

2 Tungsten Carbides

4650. Klopp WD, Barth VD (1960) Diffusion rates and solubilities of interstitials in refractory metals. Technical Report DMIC-Memo-50, pp. 1-10. Battelle Memorial Institute, Defence Metals Information Centre, Columbus, Ohio 4651. Foulias SD, Rawlings KJ, Hopkins BJ (1981) A reversible phase transition in carbon segregation to W (110). J Phys C 14(34):5403-5409 4652. Rawlings KJ, Foulias SD, Hopkins BJ (1981) A model for carburized W (100) and W (110). J Phys C 14(34):5411-5416 4653. Piquet A, Pralong G, Roux H, Uzan R, Drechsler M (1977) Adsorption et segregation du carbone sur le tungstène et influence de cet adsorbat sur l’autodiffusion en surface (Adsorption and segregation of carbon on tungsten and influence of this adsorbate on surface self-diffusion). In: Actes 3-ème colloque Int. on physique et chimie der surfaces solides, Grenoble, France, 1-3 June 1977, pp. 376-386. Société Française du Vide, Paris (in French) 4654. Piquet A, Roux H, Pralong G, Dupin JP (1980) Dosage d’une couche adsorbée sur une pointe à émission de champ à l’aide de méthodes de microanalyse nucléaire (Pd ou C adsorbé sur W) (Assay of an adsorbed layer on a field emission tip using nuclear microanalysis methods (Pd or C adsorbed on W)). Rev Phys Appl 15(1):67-73 (in French) 4655. Anastasiadi GP, Girshov VL, Gulyaev BB, Sheyanova EV (1977) The effect of free energy of grain boundaries on the distribution of carbon in cast tungsten. Phys Met Metallogr 44(2):99-103 4656. Ostermayer FW, Jr, Koch FB (1980) Carbon segregation and arc damage of tungsten electrodes. Appl Phys Lett 36(4):266-268 4657. Bas EB (1977) LEED and emission electron microscopic investigations of carbon segregations on W (001) surface. In: Dobrozemsky R, Rüdenauer F, Viehboeck FP, Breth A (eds) Proc. 7th Int. vacuum congress and 3rd Int. conf. on solid surfaces of the Int. Union for vacuum science, technique and applications, Vienna, Austria, 12-16 Sep 1977, Vol. 2, pp. 1233-1236. Österreichische Studiengesellschaft für Atomenergie, Vienna, Austria 4658. Joyner RW, Rickman J, Roberts MW (1973) Study of the preparation of atomically clean tungsten surfaces by Auger electron spectroscopy. Surf Sci 39(2):445-449 4659. Samsonov G.V., Burykina AL, Épik AP (1972) Zashchitnye pokrytiya iz tugoplavkikh soedinenii na metallakh i grafite (Protective coatings made from refractory compounds on metals and graphite). In: Samsonov GV (ed) Zashchitnye pokrytiya na metallakh (Protective coatings on metals), Vol. 6, pp.5-21. Naukova Dumka, Kyiv (in Russian) 4660. Kopylova VP (1961) Khimicheskaya ustoichivost karbidov perekhodnykh elementov IV, V i VI grupp (The chemical stability of transition element carbides IV, V and VI groups). Zh Prikl Khim 34(9):1936-1939 (in Russian) 4661. Booss H-J (1957) Über das Verhalten von Hartstoffen und hochschmelzenden Metallen in alkalischen Trikaliumhexacyanoferrat (III) – Lösungen (On the behaviour of hard materials and refractory metals in alkaline tripotassium hexacyanoferrate (III) solutions). Z Anorg Allg Chem 292(4):232-241 (in German) 4662. Fedorus VB, Kosolapova TYa, Kuzma YuB, Kugai LN (1974) A study of the reaction of zirconium dioxide with the carbides of group VI metals. In: Samsonov GV (ed) Refractory carbides, pp. 423-431. Consultants Bureau, New York, London 4663. Kushtalova IP (1974) A study of recrystallization processes in refractory compounds. In: Samsonov GV (ed) Refractory carbides, pp. 311-313. Consultants Bureau, New York, London 4664. Solodkyi I, Teslia S, Bezdorozhev O, Trosnikova I, Yurkova O, Bogomol I, Loboda P (2022) Hardmetals prepared from WC-W2C eutectic particles and AlCrFeCoNiV highentropy alloy as a binder. Vacuum 195:110630 (10 pp.) 4665. Evans BS, Box FW (1943) A process for the analysis of tungsten carbide tips. Analyst 68(808):203-206 4666. Kudo T, Okamoto H, Matsumoto K, Sasaki Y (1986) Peroxopolytungstic acids synthesized by direct reaction of tungsten or tungsten carbide with hydrogen peroxide. Inorg Chim Acta 111(2):L27-L28

References

829

4667. Jansson B (1990) Thermodynamic calculations for tungsten carbide tools with an ironbased binder. High Temp High Press 22(4):465-478 4668. Kardonskii VM, Samoilova OV (1990) High-strength austenitic steels with tungsten. Met Sci Heat Treat 32(8):627-630 4669. Kanashvili RSh, Gorbatov IN, Rezvanov GF, Kartvelishvili IM, Terentev AE, Ilchenko NS (1990) Autoclave cladding of aluminium and tungsten carbide powders with nickel. Powder Metall Met Ceram 29(6):433-435 4670. Azuma S, Kusaba Y (1995) Effect of pH and calcium (II) ion on the corrosion of tungsten carbide bearing hard alloy in water at elevated temperatures. Corros Eng 44:399-404 (in Japanese) 4671. Nakajima H, Kudo T (1999) Reaction of metal, carbide and nitride of tungsten with hydrogen peroxide characterized by 183W nuclear magnetic resonance and Raman spectroscopy. Chem Mater 11:691-697 4672. Jain M, Sadangi RK, Cannon WR, Kear BH (2001) Processing of functional graded WC/Co/diamond nanocomposites. Scripta Mater 44:2099-2103 4673. Lee J, Kim S, Kim B (2017) A new recycling process for tungsten carbide soft scrap that employs a mechanochemical reaction with sodium hydroxide. Metals 7(7):230 (9 pp.); doi:10.3390/met7070230 4674. Davis JR, ed (1995) ASM specialty handbook: tool materials. ASM International, Metals Park, Ohio 4675. Walker P, Tarn WH, eds (1991) CRC handbook of metal etchants. CRC Press, Boca Raton, Boston, London 4676. Deng H, Biesuz M, Vilémova M, Kermani M, Veverka J, Tyrpekl V, Hu C, Grasso S (2021) Ultra-high temperature flash sintering of binderless tungsten carbide within 6 s. Materials 14(24):7655 (11 pp.); doi:10.3390/ma14247655 4677. Elliott RP (1965) Constitution of binary alloys, first supplement. McGraw-Hill, New York, London

Addendum A.1 Structures Summarized general data on the structural properties (atomic or molecular weights, phase homogeneity regions, crystal systems, types, space groups and lattice parameters, calculated and experimental densities) of the high-melting chemical elements (carbon and refractory metals) and highly refractory compounds (carbides of Hf, Nb, Ta, Ti, V, W and Zr), which were considered separately and comprehensively in the main chapters of volumes I, II, III and IV, are given (in alphabetical order) in Table A.1 [1-52, 67-68, 90, 236, 239, 245, 255, 257-258, 262263-269, 271, 274-281, 284-285, 288-289, 295, 299-300].

A.2 Thermal Properties The most important thermodynamic properties (standard heat of formation, standard molar entropy, molar and specific heat capacities, molar and specific enthalpies (heats) of melting (fusion) and vaporization, molar and specific enthalpy differences HT – H298) of the ultra-high temperature materials considered separately and comprehensively in the volumes I, II, III and IV of the book series are summarized below in Tables A.2-A.3 [1-3, 7-9, 13-20, 28-33, 36-41, 43-44, 5366, 85, 90, 236, 249-253, 275, 277, 281-283, 286-287, 295-296]. For the general comparison, some other thermal properties (melting and boiling points, coefficients of linear thermal expansion, relative thermal expansion, thermal conductivity, vapour pressure and vaporization rate) of ultra-high temperature materials (graphite, refractory metals and Hf, Nb, Ta, Ti, V, W and Zr refractory carbides) are given below in Tables A.4-A.5 [1-3, 6-21, 23-32, 35-44, 46-47, 50-57, 66, 6970, 72-75, 79-90, 247-248, 256, 258, 261, 268, 270-271, 274-277, 279, 281-289, 295-296]. The values of the heat capacities, enthalpy differences, thermal expansion and thermal conductivity properties and vaporizations parameters of the materials are presented there in the wide range from room (or moderate) to ultra-high temperatures.

A.3 Electro-Magnetic & Optical Properties For the general comparison, the main electro-magnetic and optical properties (specific electrical resistance, temperature coefficient of electroresistance, integral and monochromatic emittances, thermoionic emission characteristics and molar © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 I. L. Shabalin, Ultra-High Temperature Materials IV, https://doi.org/10.1007/978-3-031-07175-1

831

832

Addendum

magnetic susceptibility) of carbon (graphite), refractory metals and Hf, Nb, Ta, Ti, V, W and Zr refractory carbides are given in Table A.6 [1, 3-4, 6-9, 11-15, 18-21, 23, 31-41, 43-47, 56, 90-92, 236-237, 254, 258, 267-268, 275, 281, 288-289, 291, 295-296]. The values of the electrical resistance and integral and monochromatic emittances of the high-melting elements and compounds are summarized in the wide range from room (or moderate) to ultra-high temperatures.

A.4 Physico-Mechanical Properties The relative comparison of some physico-mechanical properties (hardness, tensile and compressive strengths and Young’s modulus) of ultra-high temperature materials (graphite, refractory metals and Hf, Nb, Ta, Ti, V, W and Zr carbides), which were considered separately and comprehensively in the main chapters of the volumes I, II, III and IV of the book series, can be carried out on the basis of the data presented in Table A.7 [1, 4, 6-15, 18-21, 23, 29-41, 43-47, 57, 83, 90, 93-94, 236, 238-239, 242-246, 258-260, 264-265, 268, 270-272, 275-277, 279, 281, 288-289, 292-298]. The values of the hardness, strength and elasticity of all the ultra-high temperature materials are summarized there for the wide range from room to ultrahigh temperatures.

A.5 Nuclear Physical Properties Nuclear physical properties (isotopic mass range, total number of isotopes, thermal neutron macroscopic cross sections, moderating ability and capture resonance integral) of the chemical elements (carbon and refractory metals) and compounds (Hf, Nb, Ta, Ti, V, W and Zr refractory carbides) are summarized in Table A.8 [12, 95-100, 220, 273, 290].

A.6 Chemical Properties For the cubic refractory carbides of Hf, Nb, Ta, Ti, V, W and Zr (NaClstructured), considered in the volumes II, III and IV of the book series, the interaction with various isomorphic compounds (carbides, nitrides, oxides, phosphides and sulphides) is reviewed in Table A.9 [1, 8, 14-21, 24, 28-33, 35-44, 48-50, 64, 67, 90, 230-235, 240-241, 275-277]. For all the ultra-high temperature materials (elements and refractory compounds), considered in detail in the volumes I, II, III and IV of the book series, the characters of interaction with some chemical reagents in the aqueous solutions at room temperature are summarized in the Table

Addendum

833

A.10 [2-3, 7, 9, 11, 13, 17, 19, 23, 32. 36, 38, 43-44, 56, 90, 101-104, 220-229, 236, 245, 275-277, 289].

A.7 Porosity-Property Relationships The methods of powder metallurgy and particulate technologies, such as conventional sintering, hot pressing, hot isostatic pressing, spark plasma sintering and others, are widely spread for the preparation and production of ultra-high temperature materials, especially for those based on Hf, Nb, Ta, Ti, V, W and Zr carbides considered in volumes II, III and IV of the book series. The effect of porosity on physical properties (thermal conductivity, electrical resistance, strength and elastic characteristics) of sintered metallic and ceramic materials has been the subject of numerous experimental and theoretical studies. Some of the formalae proposed by various researchers for the descrption of physical properties and characteristics of the materials with residual porosity are given in Table A.11 [105-219]. The diversity of the formulae is associated with the necessity to consider the shape, size and number of pores, the surface conditions of the test samples, the grain size in the materials, the degree of their local inhomogeneity, the presence of residual stresses and some other factors.

NaCl NiAs NaCl NiAs NaCl NaCl NaCl W2C i

183.84

200.62-262.87 0.03 ≤ x ≤ 0.70 Hexagonal f

100.60-104.44 0.04 ≤ x ≤ 0.36 Cubic (fcc)

341.34-527.72 −0.18 ≤ x ≤ 0.85 Hexagonal g

187.80-192.72 0.02 ≤ x ≤ 0.43 Cubic (fcc)

0.12 ≤ x ≤ 0.39 Cubic (fcc)

180.95

184.74-190.26 0.02 ≤ x ≤ 0.48 Cubic (fcc)

0.02 ≤ x ≤ 0.53 Cubic (fcc)

186.21

53.51-59.64

58.27-61.51

353.95-535.95 −0.14 ≤ x ≤ 0.85 Hexagonal h

Ta

W

HfC1−x

Nb2+xC

NbC1−x

Ta2±xC

TaC1−x

TiC1−x

VC1−x

W2±xC

–

–

–

–

190.23

Re Cubic (bcc)

Cubic (bcc) W

W

Hexagonal (hcp) Mg

Hexagonal (hcp) Mg

W

W

Os

Cubic (bcc)

–

Cubic (bcc)

–

95.94

Cu

Graphite

92.91

Cubic (fcc)

Hexagonal

Type

Nb

–

192.22

Ir

System

Mo

–

C (graphite)e 12.01

Materials Atomic or mo- Phase homogeformula lecular weight neity region a

P63/mmc

Fm(–3)m

Fm(–3)m

Fm(–3)m

P63/mmc

Fm(–3)m

P63/mmc

Fm(–3)m

Carbides

Im(–3)m

Im(–3)m

P63/mmc

P63/mmc

Im(–3)m

Im(–3)m

Fm(–3)m

P63/mmc

Elements

Space group

0.3001

0.4166

0.4330

0.4457

0.3105

0.4470

0.3127

0.4640

0.3165

0.3303

0.2762

0.2734

0.3301

0.3147

0.3839

0.2464

a

0.4736

–

–

–

0.4935

–

0.4972

–

–

–

0.4457

0.4320

–

–

–

0.6711

c

1.578

1.589

1.590

1.614

1.580

–

–

–

–

–

–

–

–

–

–

2.7236

c/a

Lattice parameters b, nm

Crystal structure

1

4

4

4

1

4

1

4

2

2

2

2

2

2

4

4

Zc

17.35

5.65

4.90

14.50

15.05

7.80

7.80

12.65

19.25

16.68

21.01

22.60

8.578

10.22

22.56

2.267

17.25 (continued)

5.60

4.90

14.45

14.90

7.75

7.80

12.60

19.20

16.60

21.00

22.48

8.59

10.24

22.45

2.26

Calculated Experi(XRD) mental d

Density, g cm−3

Table A.1 Structural properties (atomic or molecular weight, phase homogeneity region, system, type and space group of crystal structure, calculated and experimental densities)

834 Addendum

195.25-196.09 −0.05 ≤ x ≤ 0.02 Hexagonal

δ-WC1±x

P(–6)m2

l

WC

Fm(–3)m

NaCl 0.2906

0.4215 k 0.2837

– 0.9736

– 1

4 15.70

17.20 15.65

–

ZrC1−x 97.95-102.99 0.02 ≤ x ≤ 0.44 Cubic (fcc) – – 4 6.60 6.60 NaCl Fm(–3)m 0.4700 a The maximum variation in the non-metal content of refractory compounds within their temperature intervals of thermal stability according to the phase diagrams b Concerning the refractory compounds, it is given for the phase compositions with the minimum deviation from the stoichiometry c Number of formula units per lattice d Pycnometric density e 2H-Graphite (or α-carbon, α-graphite) f The data are given for the high-temperature modification (Nb semicarbide phases undergo the phase transformations: α-Nb2C ↔ β-Nb2+xC at ~ 1200-1230 °C and β-Nb2+xC ↔ γ-Nb2±xC at ~ 2450-2575 °C, the temperatures of transformations depend on the phase compositions, see section II-4.1) g The data are given for the high-temperature modification (Ta semicarbide phases undergo the phase transformation: α-Ta2+xC ↔ β-Ta2±xC at ~ 1930-2270 °C, the temperatures of transformations depend on the phase compositions, see section II-2.1) h The data are given for the high-temperature modification (W semicarbide phases undergo the phase transformation: α-W2+xC ↔ β-W2+xC at ~2100 °C, β-W2+xC ↔ γ-W2±xC at ~ 2385-2500 °C and ε-W2+xC ↔ γ-W2±xC at ~2480 °C (?), the temperatures of transformations depend on the phase compositions, see section 2.1) i Or anti-NiAs structure type j The γ-WC1−x phase is thermodynamically stable only in the range of temperatures from 2535 °C to 2780 °C (at lower temperatures γ-WC1−x decomposes forming γ-W2±xC and δ-WC1±x, so a quenching does not allow to prepare pure single-phase samples of γ-WC1−x); however, it can be stabilized by the addition of some transition metals forming NaCl-structured carbides k Experimentally determined content C – 45.1 at.% l Proposed to be a partially disordered NiAs structure type

191.05-192.50 0.28 ≤ x ≤ 0.40 Cubic (fcc)

γ-WC1−x j

Table A.1 (continued)

Addendum 835

28.6

36.5

–

–

–

–

–

–

Mo

Nb

Os

Re

Ta

W

37.3

141

208

145

184

106

NbC1−x

Ta2±xC

TaC1−x

TiC1−x

VC1−x

28.3

24.3

42.3

81.6

64.0

195

Nb2+xC

41.2

235

HfC1−x

32.8

41.5

36.5

32.6

35.5

–

5.74

–

Ir

Standard heat Standard moof formation lar entropy S°298, –ΔH°298, J mol–1 K–1 kJ mol–1

C (graphite)

Materials formula

32.5

34.7

36.8

61.0

36.8

63.5

37.5

24.3

25.4

25.5

24.9

24.7

24.0

25.0

8.5

52.6

51.8

51.1

79.5

51.2

81.1

51.6

27.6

27.9

29.0

27.5

27.7

28.7

29.2

21.0

61.3

59.8

59.1

94.1

60.0

88.3

58.0

32.3

31.0

34.9

31.2

31.8

36.9

35.2

25.0 –

69.5

68.4

66.9

108.1

66.7

94.2

63.6

Carbides a

37.2

44.1

42.3

34.9

33.5

41.8

26.5

Elements

3000 (2730)

74.2

72.5

69.2

41.8

46.0

37.7

–

–

–

–

–

–

–

–

–

4000 (3730)

528

582

191

163

352

317

197

132

140

138

130

265

250

130

700

855

869

267

213

490

404

271

150

154

156

145

300

300

153

1750

1000 (730)

997

1003

307

252

575

440

305

176

171

188

164

340

385

191

2100

2000 (1730)

1130

1147

347

289

639

470

336

202

244

227

183

360

435

2200 –

3000 (2730)

–

–

–

–

–

(continued)

385

694

364

227

247

198

–

–

–

–

4000 (3730)

298 (25)

2000 (1730)

298 (25)

1000 (730)

Specific heat capacity c, J kg–1 K–1, at temp., K (°C)

Molar heat capacity cp, J mol–1 K–1, at temp., K (°C)

Table A.2 Thermodynamic properties (standard heat of formation, standard molar entropy, molar and specific heat capacities)

836 Addendum

40.2

δ-WC1±x

32.4

56.1

35.4

76.6 50.1

99.2 56.3

111.1 77.1

122.2

ZrC1−x 197 33.3 37.9 53.4 57.4 60.9 a All the data are given for the pure near-stoichiometric phase compositions

26.4

W2±xC

Table A.2 (continued)

76.2

–

– 368

180

202 518

255

261 557

288

293 591

394

322 740

–

–

Addendum 837

Enthalpy (heat) of vaporization b

52.3

W

–

VC1−x

–

1.404d

83.7d

TiC1−x

–

0.545g

Ta2±xC

–

0.881g

105.0g

–

NbC1−x

–

0.220

0.200

0.178

TaC1−x

–

92.0g

Nb2+xC

–

36.6

Ta

HfC1−x

34.1

Re

0.304

0.315

30.0

57.9

Nb

0.290

37.5

Mo

Os

12.2

0.214

41.1

Ir

0.71

59.1

~0.6

d

~0.6d

12.8

32.5

51.0

32.6

52.4

32.7

18.3

19.0

19.2

18.4

18.5

18.5

18.9

~9.8d 36.8

~10.1d 37.2

–

6.63d

2.48d

–

~6.7h

~0.7h

–

8.24d

1.57d

–

4.33

4.15

3.74

3.84

7.32

6.16

3.14

0.80

0.75

0.70

0.73

0.69

0.60

0.60

36.6

93.9

93.0

87.7

137.9

88.4

139.7

87.7

48.1

48.2

51.0

47.7

48.2

51.0

52.0

62.8

159.2

156.8

150.6

239.0

151.4

229.6

f

148.5

83.8

83.6

89.5

80.7

108.2

123.6

118.2

–

293.2

221.0

353.7e

313.6

–

214.8e

Carbides

158.6

150.6

167.9

149.4

141.7

165.4

160.1

–

Elements

c

360

285

386

200

186

214

187

175

799

–

–

–

–

–

–

427

352

458

962

892

856

–

–

–

–

–

–

–

–

–

2000 3000 4000 5000 6000 (1730) (2730) (3730) (4730) (5730)

Molar enthalpy differences HT – H298, kJ mol–1, at temp., K (°C)

molar, specific, molar, specific, 1000 kJ mol–1 MJ kg–1 MJ mol–1 MJ kg–1 (730)

Enthalpy (heat) of melting a

C (graphite) 146

Materials formula

598.4

623.8

168.7

136.4

312.3

261.2

171.8

99.3

104.9

103.0

96.6

198.5

192.2

98.3

1067

1000 (730)

1527

1560

455

369

847

696

461

262

266

274

251

518

531

271

3050

2000 (1730)

2589

2630

782

639

1450

1144

780

456

462

481

424

1164

1288

615

5230

–

–

4917

1147

946

2998

–

1128

867

832

902

786

1525

1723

833

–

6037

1479

–

3697

–

–

1090

1029

1149

983

1884

8324

–

–

7161

1827

–

4387

–

–

–

–

–

5058

9598

8920

–

–

6000 (5730)

– (continued)

3000 4000 5000 (2730) (3730) (4730)

Specific enthalpy differences HT – H298, kJ kg–1, at temp., K (°C)

Table A.3 Thermodynamic properties (molar and specific enthalpies (heats) of melting/vaporization, molar and specific enthalpy differences)

838 Addendum

–

δ-WC1±x

–

–

4.03

i

i

0.79

2.13i

0.81i 31.9

64.5 85.3

169.9 173.7

286.6 –

– –

– –

– 190.6

170.0 516

448 887

755 –

– –

–

–

–

ZrC1−x 83.7g, j 0.813g 0.61d, k 5.92d 34.3 89.9 149.0 291.0 408 487 333.0 873 1447 2825 3961 4720 a For refractory metals molar and specific enthalpies (heats) of melting are given at the melting points b For refractory metals molar and specific enthalpies (heats) of vaporization are given at the boiling points c All the data are given for the pure near-stoichiometric phase compositions d At 298.15 K e Extrapolated data f Extrapolated data (for middle-temperature modification β-Nb2+xC) g At the melting point h The approximate value for the vaporization (dissociation) process of NbC1–x (crystal) = NbC1–x−y (crystal) + yC (gas) at 2800 K (2530 °C) i Data for the congruent vaporization (calculated on the basis of thermodynamical data) j Molar enthalpy (heat) of melting at 298.15 K is 79.5 kJ mol–1 k Molar enthalpy (heat) of vaporization (dissociation) is 1.52 kJ mol–1 (the value was measured on the basis of Langmuir mode, but also calculated in accordance to the second law of thermodynamics as a sum of average partial enthalpies (heats) of vaporization of C1 (gas) and Zr (gas) from ZrC~1.0)

–

W2±xC

Table A.3 (continued)

Addendum 839

3320 (3050) 5300 (5030) 6.1

3450 (3180) 5870 (5600) 6.6

3270 (3000) 5700 (5430) 6.5

3680 (3410) 6000 (5730) 4.3

4220 (3950) 5670 (5400) 5.7

3350 (3080)

3870 (3600) 5275 (5000) 6.4

3610 (3335) 5740 (5465) 4.2/2.7k

4260 (3990) 5770 (5500) 5.8

3340 (3070) 4570 (4300) 6.8

Os

Re

Ta

W

HfC1−x

Nb2+xC

NbC1−x

Ta2±xC

TaC1−x

TiC1−x

–

8.9

2740 (2470) 5020 (4750) 7.1

Nb

8.6

7.0

7.3 –

3.4/9.9/5.7 8.6/9.8

7.0

5.0

7.7

7.0

j

6.7

2890 (2620) 5100 (4830) 5.4

Mo

i

9.2

2720 (2450) 4700 (4430) 6.8

Ir

~9

1.5-25

0.54

0.44

–

0.46

–

0.47

0.32

0.50

0.47 0.52

0.88

0.85

–

1.02

0.74

0.98

0.192.40

0.500.58

0.88

1.32

0.97

0.80

–

0.84

–

0.82

–

–

1.52

1.15

1.55

0.323.60

0.800.92

Elements

1.47

1.20

–

1.28

–

1.19

Carbidesh

0.32 (?)

0.56

0.38

0.52

0.081.30

0.250.30

2.60

1.65

–

1.77

–

1.56

1.20

1.82

–

–

2.00

–

2.14

–

2.32

–

1.98

1.60

2.40

–

–

–

–

–

2.18d 1.66

–

1.471.70

0.494.90

1.131.28

at room 1000 1500 2000 2500 3000 20-1700 °C temperature (730) (1230) (1730) (2230) (2730)

Average coefficient of Relative thermal expansion, %, affected linear thermal expan- by heating from room temp. to T, K (°C) sion, 10–6 K–1

C (graphitec) 4200 (3930)b 4200 (3930)b 0-20

Boiling point, K (°C)

5.1-5.8

Melting point, K (°C)

C (graphitea) 4200 (3930)b 4200 (3930)b 2.5-3.5

Materials formula

60-70

f

30

25

35

18

12 (?)

15

160

60

70

88

50

135

145

36

30

25

21

–

–

120

f

40

34

32

27

–

–

105

76

50 70

84

85

56g

70

95

115e

f

60

115

130

f

44

37

38

33

–

–

100

80

45

85

80

80

110

48

39

43

39

95

84

42

–

–

~80

90

70

100d

–

–

–

(continued)

48

41

47

45

92

–

–

–

–

–

–

45-60 35-50 35-45 35-45

1000 1500 2000 2500 3000 (730) (1230) (1730) (2230) (2730)

3-1000 1.5-200 1-150 0.7-100 0.5-70

100200

290 (20)

Thermal conductivity, W m–1 K–1, at temperature, K (°C)

Table A.4 Thermal properties (melting and boiling points, coefficients of linear thermal expansion, relative thermal expansion and thermal conductivity)

840 Addendum

3760 (3490) 5370 (5100) 4.5

ZrC1−x

–

–

7.1

5.5

5.6

7.0 – 0.45

0.35

–

0.33

0.46

0.85

0.64

–

0.62

0.71

1.30

0.95

–

0.96

1.15

1.77

1.25

–

1.30

1.80

2.27

–

–

–

–

35

29

30

38 – 25

42

32

37 – 30

48

34 –

–

32

52

38 –

–

35

55

45 –

–

40

–

–

–

–

High quality pure industrial polycrystalline (quasi-isotropic) graphite b Total gas pressure over the solid/liquid surface – 10 MPa c Highly oriented pyrolitic graphite (HOPG) d Extrapolated values e Interpolated value f Average values; in different directions the minimal and maximal values are 76 and 111 W m–1 K–1 at 1000 (730) K (°C), 75 and 110 W m–1 K–1 at 1500 (1230) K (°C), 77 and 107 W m–1 K–1 at 2000 (1730) K (°C) g Average value; in different directions the minimal and maximal values are 54 and 60 W m–1 K–1 h All the data are given for the pure near-stoichiometric phase compositions i The experimental data for the low-temperature modification α-Nb2C are given for its main crystallographic directions: a/b/c, respectively j The experimental data for the middle-temperature modification β-Nb2+xC given for its main crystallographic directions (for a – in the numerator and for c – in the denominator, respectively) were extrapolated to the region of higher temperatures k The experimental data for the low-temperature modification α-Ta2+xC are given for its main crystallographic directions: for a – in the numerator and for c in the denominator, respectively l The W2±xC phases are thermodynamically unstable at temperatures < 1250 °C m The γ-WC1−x phase is thermodynamically unstable at temperatures < 2535 °C

a

3050 (2780) 6270 (6000) 5.2

δ-WC1±x

–

3060 (2790) 6270 (6000)

3070 (2800) 4170 (3900) 6.5

3050 (2780)

l

γ-WC1−x m

W2±xC

VC1−x

Table A.4 (continued)

Addendum 841

10–7

10–5

10–3

0.1

10

103

105 Elements

10–10

10–8

10–6

10–4

10–2

Temperature, K (°C), corresponding to vapour pressure over Temperature, K (°C), corresponding to materials surface, Pa surface vaporization rate, kg m–2 s–1 10–14

10–12

10–10

10–8

10–6

Temperature, K (°C), corresponding to surface vaporization rate, m s–1

2250 2500 2820 3220 3760 4520 5800 2230 2480 2810 3220 (1980) (2230) (2550) (2950) (3490) (4250) (5530) (1960) (2210) (2540) (2950)

–

–

–

(continued)

2270 2520 2860 3290 (2000) (2250) (2590) (3020)

2130 2360 2670 3070 (1860) (2090) (2400) (2800)

–

–

W

–

–

2110 2350 2650 3050 3590 4350 ~5700 2100 2340 2650 3020 (1840) (2080) (2380) (2780) (3320) (4080) (~5430) (1830) (2070) (2380) (2750)

–

2100 2350 2680 3120 (1830) (2080) (2410) (2850)

–

Ta

–

–

2070 2320 2630 3040 3610 4460 ~5920 2060 2300 2620 3040 (1800) (2050) (2360) (2770) (3340) (4190) (~5650) (1790) (2030) (2350) (2770)

–

Re

–

~1880 ~2090 ~2370 ~2700 ~3160 ~3850 ~4880 ~1870 ~2080 ~2350 ~2700 >3150 ~1910 ~2120 ~2410 ~2780 ~3270 (~1610) (~1820) (~2100) (~2430) (~2890) (~3580) (~4610) (~1600) (~1810) (~2080) (~2430) (>2880) (~1640) (~1850) (~2140) (~2510) (~3000)

–

Os

–

1930 2120 2380 2720 3220 3940 ~4530 1930 2130 2400 2750 3250 1930 2130 2390 2740 3230 (1660) (1850) (2110) (2450) (2950) (3670) (~4260) (1660) (1860) (2130) (2480) (2980) (1660) (1860) (2120) (2470) (2960)

–

Nb

–

1750 1960 2210 2550 3010 3770 ~5100 1750 1960 2230 2560 3020 1750 1960 2220 2560 3030 (1480) (1690) (1940) (2280) (2740) (3500) (~4830) (1480) (1690) (1960) (2290) (2750) (1480) (1690) (1950) (2290) (2760)

–

Mo

–

1750 1940 2190 2510 (1480) (1670) (1920) (2240)

Ir

C (graphite) 1790 1950 2160 2410 2740 3170 3790 2000 2200 2450 2800 3300 1950 2130 2360 2700 3100 (1520) (1680) (1890) (2140) (2470) (2900) (3520) (1730) (1930) (2180) (2530) (3030) (1680) (1860) (2090) (2430) (2830)

Materials formula

Table A.5 Thermal properties (vapour pressure and vaporization rate)

842 Addendum

–

–

–

–

–

–

–

–

–

–

– –

–

2940 (2670)/ / 2830 (2560)c

–

–

–

–

~2440 ~2760 ~3170 ~3710 (~2170) (~2490) (~2900) (~3440)

~1950 2220 2590 ~3090 (~1680) (1950) (2320) (~2820)

–

–

–

–

– ~6270 (~6000)

~6270 (~6000) –

– –

–

–

–

–

–

–

–

–

–

–

–

–

–

–

–

–

–

3550 4570 1720 1950 2200 2530 2980 1690 1890 2150 2480 2920 (3280)/ (4300) (1450) (1680) (1930) (2260) (2710) (1420) (1620) (1880) (2210) (2650) / ~3380 (~3110)c

–

~2420 ~2730 ~3130 ~3660 (~2150) (~2460) (~2860) (~3390)

~1940 2210 2570 ~3070 (~1670) (1940) (2300) (~2800)

–

–

~1690 1990 2440 ~3120 (~1420) (1720) (2170) (~2850)

~1970 ~2190 2480 2850 ~3340 – ~5370 ~1960 2190 2460 ~2820 ~3330 ~1940 2160 2440 ~2790 ~3250 (~5100) (~1690) (1920) (2190) (~2550) (~3060) (~1670) (1890) (2170) (~2520) (~2980) (~1700)/ (~1920)/ (2210)/ /(2580)/ (~3070)/ / ~1950 / ~2170 2460 / 2810 / ~3280 (~1680)c(~1900)c(2190)c (2540)c (~3010)c a All the data are given for the pure near-stoichiometric phase compositions

–

δ-WC1±x

ZrC1−x (C/Zr)

–

W2±xC

2500 (2230)/ / 2430 (2160)c

–

–

–

–

–/ –/ –/ –/ –/ –/ –/ ~1520 ~1710 1930 2200 2600 ~1530 ~1740 ~1970 2250 2670 / ~1550 / ~1730 / ~1960 / 2230 / 2640 / ~3230 / ~4170 (~1250) (~1440) (1660) (1930) (2330) (~1260) (~1470) (~1700) (1980) (2400) (~1280)c(~1460)c(~1690)c(1960)c (2370)c (~2960)c(~3900)c

2170 (1900)/ / 2120 (1850)c

–

–

–

VC1−x (C/V)

–

2910 ~3540 (2640)/ (~3270) / 3550 (3280)c

–

–

~1720 1920 (~1450)/ (1650)/ / ~1690 / 1890 (~1420)c(1620)c

–

–

~5275 ~1710 2020 2460 ~3140 (~5000) (~1440) (1750) (2190) (~2870)

–

~5670 2070 2260 2530 2910 3400 2030 2270 2550 2920 3410 (~5400) (1800) (1990) (2260) (2640) (3130) (1760) (2000) (2280) (2650) (3140)

TiC1−x (C/Ti)

–

–

–

–

~1890 ~2140 2470 (~1620)/ (~1870)/ (2200)/ / 2490 / 2760 / 3100 (2220)c (2490)c (2830)c

–

~1790 ~2050 ~2400 2770 3570 (~1520) (~1780) (~2130) (2500) (3300)

–

2080 2270 2550 2920 3410 (1810) (2000) (2280) (2650) (3140)

Carbides a

TaC1−x (C/Ta)

Ta2±xC

NbC1−x

Nb2+xCb

HfC1−x

Table A.5 (continued)

Addendum 843

c

No data on the vaporization of Nb2+xC phases are available The vapour pressures over TaC1−x TiC1−x VC1−x and ZrC1−x materials surface are given separately: in the numerator – for C and in the denominator – for metals Ta, Ti, V and Zr, respectively

b

844 Addendum

0.55

0.09

0.18

0.135 0.44

0.055 0.245

Os

Re

Ta

W

0.64

0.38

0.43

f

0.15

Nb

0.40

0.62

0.84

0.55

0.57

0.79

1.0

–

0.70

0.45

0.36

0.75

0.95

1.1

–

0.83

0.55

> 0.6

0.055 0.22

0.34

Mo

0.20

0.48

12

0.05

11

Ir

9.5

3.54.01.3×103 0.7×103

8.5

C 2.52.50.5-104 (graphited) 3.5×103 2×103

C 10 (graphitec)

–

–

–

–

–

–

–

–

2.8

2.4

~4.2

1.9

3.6

5.1

0.925 5.5

1.1

13

0.21 –

–

0.11

0.26

~0.10 0.23

0.30

0.28

~0.15 ~0.25 0.29

–

0.25

0.26

0.33

0.33

0.33

–

–

–

–

~0.18e 0.21

– –

– –

0.730.86

0.720.84

~0.10 0.22

0.06

–

0.600.75

0.590.78

Elements

0.45

0.46

0.43

–

0.38

0.39

–

0.770.92

0.780.94

–

0.740.88

0.43

0.42

0.40

~0.4

0.37

0.35

0.42

0.40

0.38

~0.4

0.36

0.34

~0.25e 0.215

0.770.92

0.750.89

0.41

0.38

0.36

–

–

–

–

–

–

–

(–3200) -(–75)

–

(continued)

4.2-5.8 60-200 +665

3.9-4.8 ~40-120 +1935

4.7-5.3 ~50-700 +840

4.7-5.9 ~105 (?) +140

3.9-4.9 ~ 35-70 +2615

4.0-5.0 55-115 +905

4.7-5.7 100-120 +315

–

4.0-5.0 ~ 15-60

Specific electrical resistance (resistivity), μΩ m, Integral emittance εT a Monochromatic emittance Thermionic Thermal (spectral emissivity) ελ (λ = emission charac- Molar at temperature, K (°C) at temperature, K (°C) coef. of magnetic Materials teristics 0.665 μm) a at temp., K (°C) electrosuscepformula Electron Richard- tibility resistance work son con- χmol(SI)b, 290 1000 1500 2000 2500 3000 at 20- 1000 2000 2500 3000 1000 2000 2500 3000 function, stant, 10–6 cm3 1700 °C , (20) (730) (1230) (1730) (2230) (2730) (730) (1730) (2230) (2730) (730) (1730) (2230) (2730) eV 104 A mol–1 10–3 K–1 m–2 K–1

Table A.6 Electro-magnetic and optical properties (specific electrical resistance, temperature coefficient of electroresistance, integral and monochromatic emittances, thermoionic emission characteristics and molar magnetic susceptibility)

Addendum 845

0.50

0.70

0.75

TiC1−x

VC1−x

W2±xC

0.25

δ-WC1±x 0.20

–

–

~0.30

–

~2.5

1.5

1.3

0.95

1.0

1.2

–

–

~0.35

–

~3.3

~2.0

1.6

1.2

1.2

1.5

–

–

–

~0.4

~4

~3

2.0

1.5

1.4

1.8

–

–

2.2

–

–

–

–

1.75

1.7

2.2 – –

~0.50

–

~1.95

0.6

1.1

1.1

0.85

1.4

–

0.44

–

0.37

–

0.46

–

0.45

0.44

–

0.50

–

0.48

–

–

–

–

~0.25

–

~0.30

–

–

–

–

–

0.75

0.90

0.53

–

0.33 0.73

– 0.69

–

0.46

0.75

0.90

0.48

– 0.39

–

0.61

–

–

+500 –

> +200

3.1-4.7 0.2-140 +200

4.1-4.7

2.2-4.2 70-400 +200

4.1-5.2

~0.75 2.0-4.5 15-230 –400

–

–

–

–

– – 3.8-4.6 3-240

4.4-4.8

4.3-4.6 190

3.8-4.2

~0.42i ~0.40i 2.1-4.8 1-360

–

0.35

0.45

–

–200

+145

–

–

+300

~0.75 ~0.70 2.3-4.1 2.5-115 +250

0.42

–

0.62

~0.66h 0.63 –

–

0.70

–

–

~0.55 0.65

~0.40 0.48

–

~0.40 ~0.50 ~0.60 0.75

~0.30 0.36

–

0.42

–

~0.25h 0.44

Carbides g

ZrC1−x 0.40 1.0 1.5 1.8 2.2 2.6 1.2 ~0.68 0.59 0.55 ~0.50 ~0.60h 0.48 a Measured on non-oxidized surfaces b Measured at room temperature c High quality industrial polycrystalline (quasi-isotropic) graphite with high purity d Highly oriented pyrolitic graphite (HOPG) e Interpolated data f Average value; in different directions the minimal and maximal values are 270 and 430 nΩ m, respectively g All the data are given for the pure near-stoichiometric compositions h The experimental data were extrapolated to the region of lower temperatures i The experimental data were extrapolated to the region of higher temperatures

–

1.8

1.2

1.0

0.75

–

0.75

–

0.85

–

γ-WC1−x

0.45

0.40

0.45

NbC1−x

TaC1−x

1.4 (?)

Nb2+xC

Ta2±xC

0.45

HfC1−x

Table A.6 (continued)

846 Addendum

Ultimate tensile strength b, MPa, at temperature, K (°C) Ultimate compressive strength, MPa, at temperature, K (°C)

Young’s modulus, GPa, at temperature, K (°C)

0.43.0

1.46.0

W

0.91.6

0.61.2

~0.5g ~0.2

0.30.5

−

−

~0.1

−

−

−

~20 −

−

~20

25-80 ~7

~75

~35

300- 180- 100- 601900 800 350 140

200~190 ~85 1000

−

68

70

70

75

1 and for compression b < 1) and a′ – parameter that determines the inhomogeneity of stresses within a crosssection (for most of sintered materials a′ ≈ 2)

a – constant and m – Weibull modulus

(A.34) Krasulin et al.

k – the coefficient of concentration of stresses in welding ligament formed due to sintering and ξ ≈ r/R, where r – welding (sintered) neck radius and R – particle radius

σ = 3σ0(ξ 2/k)(1 – P)2/3(1 – P0)

(applied for ultra-high temperature oxide materials produced from microspheres)

(A.33) Millard

a, n and p – empirically determined (applied for the evaluation of compressive strength of gypsum based materials) constants

σ = σ0[1 – (P/P0)n][1 + a(P/P0)p]

n – exponential constant (n = 3 for (A.32) Schiller (applied for the evaluation of compressive strength of gypsum based materials) spherical pores and n = 2 for cylindrical pores) and P0 – percolation limit of solid (the porosity value corresponding to σ = 0)

σ = σ0[1 – (P/P0)n]

(proposed for sintered ceramic materials)

σ = σ0[E(1 – P)/E0 ]1/2

(proposed for sintered metallic materials)

σ = σ0(1 – P2)2exp(– aP)

(in an approximate form for the practical application)

or σ = σ0[(1 – 1.5P)/(1 + 1.5a′P)]

(proposed for sintered metallic materials)

σ = σ0{1 – [1.5abP(6P/πb – 36P/π2)1/2]}

(proposed for materials with low porosity (P < 0.1) and spherical pores)

σ = σ0(1 – P)/(1 – 6.25P + aP/2mπ)1/m

Table A.11 (continued)

(continued)

860 Addendum

E = E0(1 – P)

(universal formula, for P ≤ 0.5)

E = E0exp(– aP)

(proposed for highly porous materials)

E = E0a(1 – P)n

(A.35) Balshin

a – constant (1.4 ≤ a ≤ 9.0, determined experimentally, without a clear correlation to the porosity structure; for β-SiC: a = 2.73; for B4±xC: a = 5.46±0.30; for AlN: a = 2.44; for α-HfO2−x: a = 4.17; for MgO: a = 4.75; for UO2+x: a = 2.51; for α-Al2O3: a = 1.60÷4.35)

(A.38) Spriggs

a – proportionality constant depend- (A.37) Ashby ent on the pore geometry and n – exponential constant dependent on the pore morphology (for cellular materials with open pores (cells) n = 2 and with closed pores (cells) n = 3)

n – exponential constant (0.5 ≤ n ≤ 4, (A.36) Wagh et al. dependent on the tortuosity of the porous structure; for hot-pressed SiC: n = 3.80; for Si3N4 based materials: n = 2.6÷5.5; for UO2+x: n = 2.27; for RE oxide materials: n = 2.0÷2.5, α-Al2O3: n = 2.14; β-Al2O3: n = 4.12)

E0 – Young’s modulus of poreless materials

Young’s modulus, E

(based on porous body modelling approach and applied for refractory materials)

E = E0(1 – P)n

(proposed for sintered metallic materials)

3

Table A.11 (continued)

(continued)

Addendum 861

a, b and c – constants dependent on (based on the dependence of sound velocity on the elastic properties of materi- the shape and size of the average pore and the properties of poreless als) materials

E = E0(1 + aP + bP2)/(1 + cP)

(in an approximate form applied for refractory materials)

or E = E0exp[– (aP + bP2)]

(based on a model for packing equal-sized spheres)

(A.43) Kupkova

(A.42) Wang

a, b, c… – non-negative constants (additional high-order terms can be included in the exponential polynomial for wider porosity ranges and for improved accuracy; for α-Al2O3 (0.05 ≤ P ≤ 0.32): a = 1.46 and b = 9.82)

E = E0exp[– (aP + bP2 + cP3 + ...)]

(universal formula)

a and b – constants (determined ex- (A.41) Hasselman perimentally, without a clear correlation to the porosity structure)

a – constant (determined experimen- (A.40) Rice tally, without a clear correlation to the porosity structure)

a – constant (determined experimen- (A.39) Hasselman tally, without a clear correlation to the porosity structure; for UC1±x: a = 1.9÷2.3; for UN1−x: a = 2.0÷2.7; for UO2+x: a = 2.28; for α/β-Hf(Y)O2−x: a = 2.60; for β-Hf(Er)O2−x: a = 2.17; for MgO: a = 2.7÷4.9; for RE oxide materials: a = 2.4÷2.5; for glass materials: a = 2.06)

E = E0(1 – aP)/(1 + bP)

(universal formula, for P ≥ 0.5)

E = E0exp[– a(1 – P)]

(universal formula)

E = E0(1 – aP)

Table A.11 (continued)

(continued)

862 Addendum

(A.45) Ondracek

“

“

(A.48) Frantsevich

(continued)

(A.47) Boccaccini and Ondracek

a = z/x – the shape factor, defined by (A.46) Ondracek the axial ratio of the substitutional spheroids, and b = cos2α – the orientation factor, where α is the angle between the stress direction and the rotational axis of the substitutional spheroid (for isotropically oriented porosity: a = 4.5 and b = 0.33)

a = 1.21 and n = 2/3

a and n – semi-empirical constants: (A.44) Phani and Niyogi packing geometry factor and grain morphology / pore geometry parameter, respectively (for SiC: a = 1.0 and n = 3.8; for Si3N4 based materials: a = 1.0÷2.3 and n = 1.1÷2.6; for UO2+x: a = 1.0 and n = 4.1; for α-Al2O3: a = 1.0÷3.9 and n = 0.7÷3.4; for β-Al2O3: a = 1.0 and n = 4.1; for RE oxide materials: a = 1.9÷2.7 and n = 0.7÷1.3)

a and n – empirical constants con(proposed for materials prepared from refractory compounds (carbides, nitrides, sidering the effect of concentration of stresses by pores borides and silicides) by powder metallurgy methods)

E = E0(1– P2/3)/(1 + aPn)

(proposed for the pores of various shapes in isotropic materials)

E = E0(1 – P2/3)1.21Γ with Γ = a1/3[1 + b(1/a2 – 1)]1/2

(proposed for the pores of various shapes in isotropic materials)

E = E0{1 – πb(9aP2/16π2)1/3[1 + (1/a2 – 1)]1/2}

(universal formula, for spherical pores, P ≤ 0.5)

E = E0(1 – aPn)

(based on porous body modelling approach and applied for refractory materials)

E = E0(1 – aP)n

Table A.11 (continued)

Addendum 863

E = E0[1 – 15P(1 – ν0)/(7 – 5ν0)]

(based on physico-mechanical approach and applied for ceramic materials)

E = E0(1 – P)/[1 + (1 + ν0)(13 – 15ν0)/2P(7 – 5ν0)]

(based on physico-mechanical approach with the assumption of independence of Poisson’s ratio on porosity)

E = E0[1 – 3P(9 + 5ν0)(1 – ν0)/2(7 – 5ν0)]

(based on physico-mechanical approach with the assumption of independence of Poisson’s ratio on porosity, applied for ultra-high temperature carbide materials)

– (A.50) Knudsen et. al

(A.49) Paul

(A.52) Boccaccini and Fan

“

“

“

“

“

“

(A.56) Weil

(A.55) Hill

(A.54) Plyatt et al.

ν0 – Poisson’s ratio of poreless mate- (A.53) Hashin

a – constant (parameter of structure, 0.4 ≤ a ≤ 1.0)

a – constant (determined experimen- (A.51) Hasselman tally; for BeO: a = – 2.0÷2.8)

a and b – constants (without a clear correlation to the porosity structure, to be determined experimentally; for carbide materials: a ≈ 1.9÷2.0 and b ≈ 0.9÷1.0, e.g. for ZrC1–x: a = 1.9 and b = 0.9; for ThO2−x: a = 2.3÷2.7; for Y2O3−x: a = 1.5 and b = –2.7)

(based on physico-mechanical approach, applied for ultra-high temperature car- rials bide and carbide-carbon materials)

E = E0{1 – 15P(1 – ν0)/[(7 – 5ν0) + 2P(4 – 5ν0)]}

(proposed and applied for refractory materials)

E = E0a(1 – P)2/[P + a(1 – P)]

(proposed and applied for refractory materials)

E = E0{1 + aP/[1 – (a + 1)P]}

(based on a model for packing equal-sized spheres and applied for ultra-high temperature carbide and oxide materials)

E = E0(1 – aP + bP2)

(based on physico-mechanical analysis for a matrix-inclusion model)

E = E0(1 – P2/3)/(1 + P – P2/3)

Table A.11 (continued)

(continued)

864 Addendum

“

(universal formula)

G = G0(1 – aP)/(1 + bP)

(universal formula)

G = G0(1 – aP)

Coulomb’s (shear) modulus, G

a and b – constants (determined ex- (A.62) Hasselman perimentally, without a clear correlation to the porosity structure)

a – constant (determined experimen- (A.61) Hasselman tally, without a clear correlation to the porosity structure; for UC1±x and UN1−x: a = 1.92; for α/β-Hf(Y)O2−x: a = 2.60; for β-Hf(Er)O2−x: a = 2.15; for glass: a = 1.94)

(A.60) Spriggs

(continued)

(A.58) Ramakrishnan and Arunachalam

a and b – constants, which express (A.59) Ordanyan et al. the influence of the shape, size distribution and relative orientation of the pores on the stress conditions (for ZrC0.91: a = 3.26 and b = 1.06; for ZrC0.95: a = 3.49 and b = 1.08; for NbC0.98: a = 2.30 and b = 1.18)

“

ν0 – Poisson’s ratio of poreless mate- (A.57) Nielsen rials

G0 – Coulomb’s (shear) modulus of (universal formula, applied for sintered ultra-high temperature oxide materials, poreless materials, a – constant (determined experimentally, without a for P ≤ 0.5) clear correlation to the porosity structure; for MgO a = 3.90; for α-Al2O3: a = 1.7÷3.3)

G = G0exp(– aP)

(applied for ultra-high temperature carbide materials)

E = 3E0exp[– aP/(1 – P)]/{2(1 + ν0)exp[– bP/(1 – P)] + (1 – ν0)}

(based on numerical experiments using the finite element method)

E = E0(1 – P)2/[1 + P(2 – 3ν0)]

(proposed for an isolated spherical pore geometry)

E = E0(1 – P)2/[1 + (1 – 5ν0)(3ν0 – 1)P/2(7 – 5ν0)]

Table A.11 (continued)

Addendum 865

(based on physico-mechanical approach and applied for ceramic materials)

G = G0(1 – P)/[1 + 2(4 – 5ν0)/P(7 – 5ν0)]

(universal formula)

G = G0[1 – 5P(3K + G)/(9K + 8G)]

(for spherical pores, applied for sintered high-temperature materials)

G = G0[1 – 5P(3K0 + 4G0)/(9K0 + 8G0) + AP2]

(applied for refractory materials)

G = G0{1 – aP/[1 – (a + 1)P]}

(applied for ultra-high temperature oxide materials)

G = G0(1 – aP + bP2)

(based on physico-mechanical approach)

G = G0(1 – 5P/3)

(based on porous body modelling approach and applied for refractory materials)

G = G0(1 – aP)n

(applied for ultra-high temperature carbide materials)

G = G0exp[– aP/(1 – P)]

Table A.11 (continued)

(A.66) Knudsen et. al

(A.65) Dewey

(A.64) Phani and Niyogi

(A.69) Kerner ν0 – Poisson’s ratio of poreless mate- (A.70) Weil rials

–

K0 – bulk (compression) modulus of (A.68) MacKenzie poreless materials, A – proportionality coefficient for higher powers of porosity, determined by setting G = 0 at P = 1

a – constant (determined experimen- (A.67) Hasselman tally; for BeO: a = 2.0÷2.8)

a and b – constants (without a clear correlation to the porosity structure, to be determined experimentally; for ThO2−x: a = 2.5÷2.9)

–

a and n – semi-empirical constants: packing geometry factor and grain morphology / pore geometry parameter, respectively (for Si3N4: a = 1.0 and n = 2.9)

a – constant, which express the in(A.63) Ordanyan et al. fluence of the shape, size distribution and relative orientation of the pores on the stress conditions (for ZrC0.91: a = 2.20; for ZrC0.95: a = 2.41; for NbC0.98: a = 2.12)

(continued)

866 Addendum

(universal formula)

K = K0[1 – P(1 + 3K/4G)]

(applied for ultra-high temperature carbide materials)

K = K0exp[– aP/(1 – P)]

(applied for refractory materials)

K = K0{1 – aP/[1 – (a + 1)P]}

(universal formula)

K = K0(1 – aP)/(1 + bP)

(universal formula)

K = K0(1 – aP)

“

“ “

“

(A.74) Hasselman

−

(A.78) Kerner

a – constant, which express the in(A.77) Ordanyan et al. fluence of the shape, size distribution and relative orientation of the pores on the stress conditions (for ZrC0.91: a = 3.26; for ZrC0.95: a = 3.49; for NbC0.98: a = 2.30)

a – constant (determined experimen- (A.76) Hasselman tally)

(continued)

(A.73) Ramakrishnan and Arunachalam

(A.72) Nielsen

a and b – constants (determined ex- (A.75) Hasselman perimentally, without a clear correlation to the porosity structure)

K0 – bulk (compression) modulus of poreless materials, a – constant (determined experimentally, without a clear correlation to the porosity structure; for UC1±x: a = 2.52; for UN1−x: a = 2.51)

Bulk (compression) modulus, K

(based on numerical experiments using the finite element method)

G = G0(1 – P)2/[1 + P(11 – 19ν0)/4(1 + ν0)]

(proposed for an isolated spherical pore geometry)

G = G0(1 – P)2/[1 + (1 – 5ν0)P/(7 – 5ν0)]

ν0 – Poisson’s ratio of poreless mate- (A.71) Hill (based on physico-mechanical approach with the assumption of independence rials of Poisson’s ratio on porosity)

G = G0[1 – 15P(1 – ν0)/(7 – 5ν0)]

Table A.11 (continued)

Addendum 867

“

“

“

“

“

“

“

“

“

“

“

“

“

“

“

“

(A.88) MacKenzie

(continued)

(A.87) Boccaccini and Ondracek

(A.86) Ondracek

(A.85) Zimmerman

(A.84) Hill and Budiansky

(A.83) Ramakrishnan and Arunachalam

(A.82) Nielsen

(A.81) Plyatt et al.

(A.80) Weil

ν0 – Poisson’s ratio of poreless mate- (A.79) Hashin rials

A – proportionality coefficient for (proposed for spherical pores, applied for sintered high-temperature materials) the higher powers of porosity

K = 1/[1/K0(1 – P) + 3P/4G0(1 – P) + AP3]

(proposed for the materials with spherical pores for the whole porosity range)

with s = 1/{1 + exp[– 100(P – 0.4)]}

K = 2(1 – s)K0(1 – 2ν0)(3 – 5P)(1 – P)/[2(3 – 5P)(1 – 2ν0) + 3P(1 + ν0)] + + 2sK0(1 – 2ν0)(1 – P)/3(1 – ν0)

(proposed for the materials with low concentration of spherical pores)

K = 2K0(1 – 2ν0)(3 – 5P)(1 – P)/[2(3 – 5P)(1 – 2ν0) + 3P(1 + ν0)]

(based on the differential method of mechanics of composites)

K = 2K0G(1 – 2ν0)/G0(1 + ν0)[1 + (G/G0)3/5(1 – 5ν0)/(1 + ν0)]

(based on the self-consistent method of mechanics of composites)

K = K0(1 – P)/[1 + PG0(1 + ν0)/2G(1 – 2ν0)]

(based on numerical experiments using the finite element method)

K = K0(1 – P)2/[1 + P(1 + ν0)/2(1 – 2ν0)]

(proposed for an isolated spherical pore geometry)

K = K0(1 – P)2/[1 + P(5ν0 – 1)/2(1 – 2ν0)]

(based on physico-mechanical approach with the assumption of independence of Poisson’s ratio on porosity)

K = K0[1 – 15P(1 – ν0)/(7 – 5ν0)]

(based on physico-mechanical approach and applied for ceramic materials)

K = K0(1 – P)/[1 + (1 + ν0)/2P(1 – 2ν0)]

(based on physico-mechanical approach)

K = K0{1 – 3P(1 – ν0)/[2(1 – 2ν0) + P(1 + ν0)]}

Table A.11 (continued)

868 Addendum

(proposed for the isotropic materials with spherical pores for the whole porosity range) a Most of formulae in this section can be applied for the description of resistivity as well

with s = 1/{1 + exp[– 100(P – 0.4)]}

ν = 0.5 – (1 – P2/3)1.21/4{(1 – s)(3 – 5P)(1 – P)/[2(3 – 5P)(1 – 2ν0) + 3P(1 + ν0)] + s(1 – P)/3(1 – ν0)}

(proposed for spherical pores in isotropic materials)

ν = 0.5 – (1 – P2/3)1.21[2(3 – 5P)(1 – 2ν0) + 3P(1 + ν0)]/4(3 – 5P)(1 – P)

(based on numerical experiments using the finite element method)

ν = (4ν0 + 3P – 7ν0P)/4(1 + 2P – 3ν0P)

(proposed for an isolated spherical pore geometry)

–

–

–

–

(A.93) Boccaccini and Ondracek

(A.92) Boccaccini and Ondracek

(A.91) Ramakrishnan and Arunachalam

(A.90) Nielsen

ν0 – Poisson’s ratio of poreless mate- (A.89) Spriggs rials, a – constant (determined experimentally, without a clear correlation to the porosity structure; for UC1±x: a = 0.17÷0.29; for UN1−x: a = 0.10÷0.37; for α-Al2O3: a = 0.30÷0.35)

Poisson’s ratio, ν

ν = [2ν0(7 – 5ν0) + P(1 – 5ν0)(3 – ν0)]/[2(7 – 5ν0) + P(1 – 5ν0)(3ν0 – 1)]

(universal formula, applied for sintered ceramic materials, for P ≤ 0.5)

ν = ν0 – aP

Table A.11 (continued)

Addendum 869

870

Addendum

References 1. Kotelnikov RB, Bashlykov SN, Galiakbarov ZG, Kashtanov AI (1968) Osobo tugoplavkie elementy i soedineniya (Extra refractory elements and compounds). Metallurgiya, Moscow (in Russian) 2. Lide DR, ed (2010) CRC handbook of chemistry and physics, 90th ed. CRC Press, Boca Raton, New York 3. Samsonov GV, ed (1976) Svoistva elementov (Properties of elements), 2nd ed., Vol. 1. Metallurgiya, Moscow (in Russian) 4. Bushuev YuG, Persin MI, Sokolov VA (1994) Uglerod-uglerodnye kompozitsionnye materialy (Carbon-carbon composite materials). Metallurgiya, Moscow (in Russian) 5. Steurer W (1996) Crystal structure of the metallic elements. In: Cahn RW, Haasen P (eds) Physical metallurgy, 4th ed., Vol. 1, pp. 1-46. Elsevier Science BV, Amsterdam 6. Martienssen W (2005) The elements. In: Martienssen W, Warlimont H (eds) Springer handbook of condensed matter and materials data, pp. 45-158. Springer, Berlin, Heidelberg 7. Goodwin F, Guruswamy S, Kainer KU, Kammer C, Knabl W, Koethe A, Leichtfried G, Schlamp G, Stickler R, Warlimont H (2005) Metals. In: Martienssen W, Warlimont H (eds) Springer handbook of condensed matter and materials data, pp. 161-430. Springer, Berlin, Heidelberg 8. Marmer ÉN, Gurvich OS, Maltseva LF (1967) Vysokotemperaturnye materialy (Hightemperature materials). Metallurgiya, Moscow (in Russian) 9. Portnoi KI, Chubarov VM (1967) Svoistva tugoplavkikh metallov i soedinenii (The properties of refractory metals and compounds). In: Tumanov AT, Portnoi KI (eds) Tugoplavkie materialy v mashinostroenii (Refractory materials in machinery construction), pp. 7-124. Mashinostroenie, Moscow (in Russian) 10. Tumanov AT, ed (1964) Konstruktsionnye materialy (Structural materials). Sovetskaya Entsiklopediya, Moscow (in Russian) 11. Cardarelli F (2008) Materials handbook, 2nd ed. Springer, London 12. Emsley J (1991) The elements, 2nd ed. Clarendon Press, Oxford 13. Gale WF, Totemeir TC, eds (2004) Smithells metals reference book, 8th ed. Elsevier Butterworth Heinemann, ASM International Materials Information Society, Amsterdam, Boston 14. Umanskii YaS (1947) Karbidy tverdykh splavov (Carbides of hard alloys). Metallurgizdat, Moscow (in Russian) 15. Kieffer R, Schwarzkopf P (1953) Hartstoffe und Hartmetalle (Refractory hard metals). Springer, Vienna (in German) 16. Storms EK (1964) A critical review of refractories. Report LA-TR-2942, Contract W-7405ENG-36, pp. 1-255. Los Alamos Scientific Laboratory, New Mexico 17. Storms EK (1967) The refractory carbides. Academic Press, New York, London 18. Toth LE (1971) Transition metal carbides and nitrides. Academic Press, New York, London 19. Goldschmidt HJ (1967) Interstitial alloys. Butterworths, London 20. Lengauer W (2000) Transition metal carbides, nitrides and carbonitrides. In: Riedel R (ed) Handbook of ceramic hard materials, pp. 202-252. Wiley-VCH, Weinheim, New York 21. Sheipline VM, Runck RJ (1956) Carbides. In: Campbell IE (ed) High-temperature technology, pp. 114-130. Wiley, New York 22. Ramqvist L (1968) Variation of lattice parameter and hardness with carbon content of group 4b metal carbides. Jernkontoret Ann 152(10):517-523 23. Warlimont H (2005) Ceramics. In: Martienssen W, Warlimont H (eds) Springer handbook of condensed matter and materials data, pp. 431-476. Springer, Berlin, Heidelberg 24. Rudy E (1969) Compendium of phase diagram data. In: Ternary phase equilibria in transition metal-boron-carbon-silicon systems. Report AFML-TR-65-2, Contracts USAF 33(615)-1249

References

871

and USAF 33(615)-67-C-1513, Part 5, pp. 1-689. Air Force Materials Laboratory, WrightPatterson Air Force Base, Ohio 25. Hansen M, Anderko K (1958) Constitution of binary alloys, 2nd ed. McGraw-Hill, New York, London 26. Massalski TB, Subramanian PR, Okamoto H, Kacprzak L, eds (1990) Binary alloy phase diagrams, 2nd ed. ASM International, Metals Park, Ohio 27. Lyakishev NP, ed (1996) Diagrammy sostoyaniya dvoinykh metallicheskikh sistem (Phase diagrams of binary metal systems), Vol. 1. Mashinostroenie, Moscow (in Russian) 28. Andrievskii RA, Umanskii YaS (1977) Fazy vnedreniya (Interstitial phases). Nauka, Moscow (in Russian) 29. Andrievskii RA, Lanin AG, Rymashevskii GA (1974) Prochnost tugoplavkikh soedinenii (Strength of refractory compounds). Metallurgiya, Moscow (in Russian) 30. Andrievskii RA, Spivak II (1989) Prochnost tugoplavkikh soedinenii i materialov na ikh osnove (Strength of refractory compounds and materials based on them). Metallurgiya, Chelyabinsk (in Russian) 31. Shaffer PTB (1964) Handbooks of high-temperature materials: No. 1 – Materials index. Plenum Press, Springer, New York 32. Samsonov GV (1964) Handbooks of high-temperature materials: No. 2 – Properties index. Plenum Press, Springer Science, New York 33. Samsonov GV (1953) Fizicheskie svoistva nekotorykh faz vnedreniya (Physical properties of certain interstitial phases). Doklady AN SSSR 93(4):689-692 (in Russian) 34. Samsonov GV, Naumenko VY, Okhremchuk LN (1971) Herstellung und Eigenschaften von Karbiden der Übergangsmetalle in ihren Homogenitätsbereichen (Synthesis and properties of carbides of transition metals in their homogeneity range). Phys Stat Sol A 6(1):201-211 (in German) 35. Samsonov GV, Umanskii YaS (1957) Tverdye soedineniya tugoplavkikh metallov (Hard compounds of refractory metals). Metallurgizdat, Moscow (in Russian) 36. Samsonov GV (1964) Refractory transition metal compounds. Academic Press, New York 37. Samsonov GV, Portnoy KI (1961) Splavy na osnove tugoplavkikh soedineniy (Alloys based on refractory compounds). Oborongiz, Moscow (in Russian) 38. Samsonov GV, Vinitskii IM (1980) Handbook on refractory compounds. IFI/Plenum, New York 39. Samsonov GV, Épik AP (1973) Tugoplavkie pokrytiya (Refractory coatings). Metallurgiya, Moscow (in Russian) 40. Samsonov GV, Upadhyaya GS, Neshpor VS (1974) Fizicheskoe materialovedenie karbidov (Physical materials science of carbides). Naukova Dumka, Kyiv (in Russian) 41. Upadhyaya GS (1996) Nature and properties of refractory carbides. Nova Science, Commack, New York 42. Holleck H (1984) Binäre und ternäre Carbid- und Nitridsysteme der Ubergangsmetalle (Binary and ternary carbide and nitride systems of the transition metals). Gebrüder Bornträeger, Berlin, Stuttgart (in German) 43. Kosolapova TYa (1971) Carbides: properties, production and applications. Plenum Press, New York 44. Kosolapova TYa, ed (1990) Handbook of high-temperature compounds: properties, production and applications. Hemisphere, New York 45. Eisenmann B, Schäfer H (1988) Carbides. In: Hellwege K-H, Hellwege AM (eds) Structure data of elements and intermetallic phases. Subvol. A – Elements, borides, carbides, hydrides, pp. 197-318. Springer, Berlin, Heidelberg 46. Krajewski A, D’Alessio L, De Maria G (1998) Physico-chemical and thermophysical properties of cubic binary carbides. Cryst Res Technol 33(3):341-374 47. Tulhoff H (2005) Carbides. In: Ullmann’s encyclopedia of industrial chemistry. Wiley, Weinheim 48. Shveikin GP, Alyamovskii SI, Zainulin YuG, Gusev AI, Gubanov VA, Kurmaev ÉZ (1985) Soedineniya peremennogo sostava i ikh tverdye rastvory (Compounds of variable composi-

872

Addendum

tion and their solid solutions). USSR Academy of Sciences Ural Scientific Centre, Sverdlovsk (in Russian) 49. Gusev AI (1991) Fizicheskaya khimiya nestekhiometricheskikh tugoplavkikh soedinenii (Physical chemistry of non-stoichiometric refractory compounds). Nauka, Moscow (in Russian) 50. Gusev AI, Rempel AA, Magerl AJ (2001) Disorder and order in strongly nonstoichiometric compounds. Springer, Berlin 51. Savitskii EM, Burkhanov GS (1971) Metallovedenie splavov tugoplavkikh i redkih metallov (Metallography of refractory and less-common metal alloys), 2nd ed. Nauka, Moscow (in Russian) 52. Kalin BA (ed), Platonov PA, Chernov II, Shtrombakh YaI (2008) Fizicheskoe materialovedenie (Physical materials science). Vol. 6, Part 1 – Konstruktsionnye materially yadernoi tekhniki (Structural materials of nuclear engineering). National Research Nuclear University MEPhI, Moscow (in Russian) 53. Chirkin VS (1959) Teplofizicheskie svoistva materialov. (Thermophysical properties of materials) Fizmatgiz, Moscow (in Russian) 54. Chirkin VS (1968) Teplofizicheskie svoistva materialov yadernoi tekhniki (Thermophysical properties of nuclear materials). Atomizdat, Moscow (in Russian) 55. Zefirov AP (ed), Veryatin UD, Mashirev VP, Ryabtsev NG, Tarasov VI, Rogozkin BD, Korobov IV (1965) Termodinamicheskie svoistva neorganicheskikh veschestv (Thermodynamic properties of inorganic substances). Atomizdat, Moscow (in Russian) 56. Krzhizhanovskii RE, Shtern ZYu (1977) Teplofizicheskie svoistva nemetallicheskikh materialov (karbidy) (Thermophysical properties of non-metallic materials (carbides)). Energiya, Leningrad (in Russian) 57. Hague JR, Lynch JF, Rudnick A, Holden FC, Duckworth WH (1964) Refractory ceramics for aerospace. Battelle Memorial Institute, The American Ceramic Society, Columbus, Ohio 58. Leider HR, Krikorian OH, Young DA (1973) Thermodynamic properties of carbon up to the critical point. Carbon 11:555-563 59. Barriault RJ, Bender SL, Dreikorn RE, Einwohner TH, Feber RC, Gannon RE, Hanst PL, Ihnat ME, Phaneuf JP, Schick HL, Ward CH (1962) Thermodynamics of certain refractory compounds. Report ASD-TR-61-260, Part 1, Vol. 1, pp. 1-404. Air Force Materials Laboratory, Wright-Patterson Air Force Base, Ohio 60. Schick HL, ed (1966) Thermodynamics of certain refractory compounds, Vol. 1-2. Academic Press, New York, London 61. Barin I (1995) Thermochemical data of pure substances, 3rd ed. VCH, Weinheim, New York 62. Chase MW, Jr, ed (1998) NIST-JANAF thermochemical tables, 4th ed. J Phys Chem Ref Data Monograph No. 9. American Institute of Physics, New York (see also http://webbook.nist.gov/chemistry Accessed 21 October 2016) 63. Bolgar AS, Turchanin AG, Fesenko VV (1973) Termodinamicheskie svoistva karbidov (Thermodynamic properties of carbides). Naukova Dumka, Kyiv (in Russian) 64. Turchanin AG, Turchanin MA (1991) Termodinamika tugoplavkikh karbidov i karbonitridov (Thermodynamics of refractory carbides and carbonitrides). Metallurgiya, Moscow (in Russian) 65. Kulikov IS (1988) Termodinamika karbidov i nitridov (Thermodynamics of carbides and nitrides). Metallurgiya, Chelyabinsk (in Russian) 66. Savvatimskii A (2015) Carbon at high temperatures. Springer Nature, Cham, Switzerland 67. Senczyk D (1984) The lattice parameters of MeC-type carbides, nitrides and carbonitrides of transition metals of IV and V groups of the periodic system. In: Proc. 11th conf. applied crystallography, Vol. 1, pp. 234-240. Kozubnik, Poland 68. Vishwanadh B, Murthy TSRCh, Arya A, Tewari R, Dey GK (2016) Synthesis and phase transformation mechanism of Nb2C carbide phases. J Alloys Compd 671:424-434 69. Goldsmith A, Waterman TE, Hirschhorn HJ (1961) Handbook of thermophysical properties of solid materials. Vol. 1 – Elements. Pergamon Press, Oxford, New York

References

873

70. Goldsmith A, Waterman TE, Hirschhorn HJ (1961) Handbook of thermophysical properties of solid materials. Vol. 3 – Ceramics. Pergamon Press, Oxford, New York 71. Wicks CE, Block FE (1963) Thermodynamic properties of 65 elements – their oxides, halides, carbides and nitrides. Bulletin N 605, pp. 1-146. US Bureau of Mines, US Department of the Interior, Washington, DC 72. Touloukian YS, Powell RW, Ho CY, Klemens PG (1970) Thermophysical properties of matter. Vol. 1 – Thermal conductivity – metallic elements and alloys. IFI/Plenum Data Corporation, New York, Washington 73. Touloukian YS, Powell RW, Ho CY, Klemens PG (1970) Thermophysical properties of matter. Vol. 2 – Thermal conductivity – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington 74. Touloukian YS, Buyco EH (1970) Thermophysical properties of matter. Vol. 4 – Specific heat – metallic elements and alloys. IFI/Plenum Data Corporation, New York, Washington 75. Touloukian YS, Buyco EH (1970) Thermophysical properties of matter. Vol. 5 – Specific heat – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington 76. Touloukian YS, DeWitt DP (1970) Thermophysical properties of matter. Vol. 7 – Thermal radiative properties – metallic elements and alloys. IFI/Plenum Data Corporation, New York, Washington 77. Touloukian YS, DeWitt DP (1972) Thermophysical properties of matter. Vol. 8 – Thermal radiative properties – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington 78. Touloukian YS, DeWitt DP, Hernicz RS (1972) Thermophysical properties of matter. Vol. 9 – Thermal radiative properties – coatings. IFI/Plenum Data Corporation, New York, Washington 79. Touloukian YS, Powell RW, Ho CY, Nicolaou MC (1973) Thermophysical properties of matter. Vol. 10 – Thermal diffusivity. IFI/Plenum Data Corporation, New York, Washington 80. Touloukian YS, Kirby RK, Taylor RE, Desai PD (1975) Thermophysical properties of matter. Vol. 12 – Thermal expansion – metallic elements and alloys. IFI/Plenum Data Corporation, New York, Washington 81. Touloukian YS, Kirby RK, Taylor RE, Lee TYR (1977) Thermophysical properties of matter. Vol. 13 – Thermal expansion – nonmetallic solids. IFI/Plenum Data Corporation, New York, Washington 82. Touloukian YS, Ho CY (1979) Thermophysical properties of matter. Vol. 14 – Master index to materials and properties. IFI/Plenum Data Corporation, New York, Washington 83. Lynch JF (1979) Engineering property data on selected ceramics. Vol. 2 – Carbides. Report MCIC-HB-07, pp. 1-136. Metals and Ceramics Information Centre, Battelle Columbus Laboratories, Ohio 84. Waseda Y, Hirata K, Ohtani M (1975) High-temperature thermal expansion of platinum, tantalum, molybdenum and tungsten measured by X-ray diffraction. High Temp High Pressures 7:221-226 85. Panish MB, Reif L (1961) Vaporization of iridium and rhodium. J Chem Phys 34:1915-1918 86. Samsonov GV, Bolgar AS, Guseva EA, Klochkov LA, Kovenskaya BA, Serebryakova TI, Timofeeva II, Turchanin AG, Fesenko VV (1973) Thermophysical properties of transition metal carbides and diborides. High Temp High Press 5(1):29-33 87. Fesenko VV, Bolgar AS (1963) Evaporation rate and vapour pressures of carbides, silicides, nitrides and borides. Powder Metall Met Ceram 2(1):11-17 88. Fesenko VV, Bolgar AS (1965) Isparenie tugoplavkikh soedinenii (Vaporization of refractory compounds). Metallurgiya, Moscow (in Russian) 89. Fesenko VV, Bolgar AS (1969) Study of evaporation rates of carbides of titanium, zirconium, hafnium, niobium and tantalum at high temperatures. High Temp 7(2):226-233 90. Pierson HO (1996) Handbook of refractory carbides and nitrides. Noyes Publications, Westwood, New Jersey

874

Addendum

91. Fomenko VS, Podchernyaeva IA (1975) Emissionnye i adsorbtsionnye svoistva veshchestv i materialov (The thermoionic emission and absorptance properties of substances and materials). Atomizdat, Moscow (in Russian) 92. Fomenko VS (1981) Emissionnye svoistva materialov (The thermoionic emission properties of materials). Naukova Dumka, Kyiv (in Russian) 93. Gao X-P, Jiang Y-H, Liu Y-Z, Zhou R, Feng J (2014) Stability and elastic properties of NbxCy compounds. Chin Phys B 23(9):097704 94. Wu L, Wang Y, Yan Z, Zhang J, Xiao F, Liao B (2013) The phase stability and mechanical properties of Nb-C system: using first-principles calculations and nano-indentation. J Alloys Compd 561:220-227 95. Mattes M, Keinert J (2005) Status of thermal neutron scattering data for graphite. IAEA Nuclear Data Section, Vienna 96. Mughabghab SF (2003) Thermal neutron capture cross sections resonance integral and Gfactors. IAEA Nuclear Data Section, Vienna 97. Gordeev NV, Kardashev DA, Malyshev AV (1963) Yaderno-fizicheskie konstanty (Nuclear physics constants). Gosatomizdat, Moscow (in Russian) 98. DoE Fundamentals Handbook (1993) Nuclear physics and reactor theory. US Department of Energy, Washington, Oak Ridge 99. Sears VF (1992) Neutron scattering lengths and cross sections. Neutron News 3(3):26-37 100. Munter A (2013) Neutron scattering lengths and cross sections. NIST Centre for Neutron Research, National Institute of Standards and Technology, Gaitherburg, Maryland https://www.ncnr.nist.gov/resources/n-lengths/ Accessed 17 March 2020 101. Robin A, Rosa JL (2000) Corrosion behaviour of niobium, tantalum and their alloys in hot hydrochloric and phosphoric acid solutions. Int J Refract Met Hard Mater 18(1):13-21 102. Walker P, Tarn WH (1991) CRC handbook of metal etchants. CRC Press, Boca Raton, Boston, London 103. Samsonov GV (1962) Analiz tugoplavkikh soedinenii (The analysis of refractory compounds). Metallurgizdat, Moscow (in Russian) 104. Kopylova VP (1961) Khimicheskaya ustoichivost karbidov perekhodnykh elementov IV, V i VI grupp (The chemical stability of transition element carbides IV, V and VI groups). Zh Prikl Khim 34(9):1936-1939 (in Russian) 105. Maxwell JC (1954) A treatise on electricity and magnetism, 3rd ed. Dover Publications, New York 106. Eucken A (1940) Allgemeine Gesetzmäβigkeiten für das Wärmeleitvermögen verschiedener Stoffarten und Aggregatzustände (General laws for the thermal conductivity of different types of substances and states of aggregation). Forsch Gebiete Ing 11(1):6-20 107. Loeb AL (1954) Thermal conductivity. VIII. A theory of thermal conductivity of porous materials. J Am Ceram Soc 37(2):96-99 108. Francl J, Kingery WD (1954) Thermal conductivity. IX. Experimental investigation of effect of porosity on thermal conductivity. J Am Ceram Soc 37(2):99-107 109. Kingery WD, Francl J, Coble RL, Vasilos T (1954) Thermal conductivity. X. Data for several pure oxide materials corrected to zero porosity. J Am Ceram Soc 37(2):107-110 110. Vasilos T, Kingery WD (1954) Thermal conductivity. XI. Conductivity of some refractory carbides and nitrides. J Am Ceram Soc 37(9):409-414 111. Kulcinski GL, Wagner P, Cowder LR (1964) The effect of porosity and pore interconnection on the thermal conductivity and electrical resistivity of tungsten. J Less-Common Met 7(5):383-392 112. Moore JP, McElroy DL (1971) Thermal conductivity of nearly stoichiometric single-crystal and polycrystalline UO2. J Am Ceram Soc 54(1):40-46 113. Storms EK, Wagner P (1973) Thermal conductivity of sub-stoichiometric ZrC and NbC. High Temp Sci 5(6):454-462 114. Taylor RE, Storms EK (1976) Thermal transport in refractory carbides. In: Klemens PG, Chu TK (eds) Thermal conductivity – 14. Proc. 14th Int. conf. on thermal conductivity, University of Connecticut, Storrs, 2-4 June 1975, pp. 161-174. Plenum Press, New York

References

875

115. Vishnevetskaya IA, Kudryasheva LV, Ordanyan SS, Petrov VA (1983) The effect of processing factors on the thermal and electrical conductivity of zirconium carbides at high temperatures. In: Larsen DC (ed) Thermal conductivity – 16. Proc. 16th Int. conf. on thermal conductivity, IIT Research Institute, Chicago, 7-9 Nov 1979, pp. 351-365. Plenum Press, New York 116. Odelevskii VI (1951) Raschet obobshchennoi provodimosti geterogennykh system. 1. Matrichnye dvukhfaznye sistemy s nevytyanutymi vklyucheniyami. (Calculation of the summarized conductivity of heterogeneous systems. 1. Matrix two-phase systems with nonlengthened inclusions). Zh Tekh Fiz 21(6):667-677 (in Russian) 117. Odelevskii VI (1951) Raschet obobshchennoi provodimosti geterogennykh system. 2. Statisticheskie smesi nevytyanutykh chastits. (Calculation of the summarized conductivity of heterogeneous systems. 2. Statistical mixtures of non-lengthened particles). Zh Tekh Fiz 21(6):678-685 (in Russian) 118. Odelevskii VI (1951) Raschet obobshchennoi provodimosti geterogennykh system. 3. Polikristall. (Calculation of the summarized conductivity of heterogeneous systems. 3. A polycrystal). Zh Tekh Fiz 21(11):1379-1382 (in Russian) 119. Aivazov MI, Domashnev IA (1968) Influence of porosity on the conductivity of hot-pressed titanium nitride specimens. Powder Metall Met Ceram 7(9):708-710 120. Ondracek G, Schulz B (1973) The porosity dependence of the thermal conductivity for nuclear fuels. J Nucl Mater 46:253-258 121. Ondracek G (1978) Zum Zusammenhang zwischen Eigenschaften und Gefügestruktur mehrphasiger Werstoffe (On the relationship between the properties and microstructure of multiphase materials). KfK 2688. Institut für Material- und Festkörperforschung, Kernforschungszentrum Karlsruhe (in German) 122. Kämpf H, Karsten G (1970) Effects of different types of void volumes on radial temperature distribution of fuel pins. Nucl Appl Technol 9(3):288-299 123. Nikolopoulos P, Ondracek G (1983) Field property bounds for porous sintered ceramics. J Am Ceram Soc 66(4):238-241 124. Ondracek G (1986) Microstructure – thermomechanical property correlations of two-phase and porous materials. Mater Chem Phys 15:281-313 125. Dulnev GN, Zarichnyak YuP (1974) Teploprovodnost smesei i kompozitsionnykh materialov (Thermal conductivity of mixtures and composite materials). Energiya, Leningrad (in Russian) 126. Dulnev GN, Novikov VV (1991) Protsessy perenosa v neodnorodnykh sredakh (The processes of transfer in inhomogeneous media). Energoatomizdat, Leningrad (in Russian) 127. Boccacini AR, Fan Z (1997) A new approach for the Young’s modulus – porosity correlation of ceramic materials. Ceram Int 23:239-245 128. Andrievskii RA (1982) Properties of sintered solids. Powder Metall Met Ceram 21(1):33-38 129. Balshin MYu (1948) Poroshkovoe metallovedenie (Powder metals science). Metallurgizdat, Moscow (in Russian) 130. Balshin MYu (1949) Zavisimost mekhanicheskikh svoistv poroshkovykh materialov ot poristosti i predelnye svoistva poristykh metallokeramicheskikh materialov (Relation of mechanical properties of powder materials and their porosity and the ultimate properties of porous sintered materials). Doklady AN SSSR 67(5):831-834 (in Russian) 131. Pines BI, Sukhinin NI (1956) Some laws of mechanical strength in bodies produced by sintering powdered metals. Sov Phys Tech Phys 1(9):2014-2022 132. Pines BI, Sirenko AF, Sukhinin NI (1957) Some correlations regarding the mechanical strength of materials obtained by sintering of powdered metals. 3. Case when powder mixtures contain easily fusible components. Sov Phys Tech Phys 2(8):1773-1779 133. Plyatt ShN, Rapoport YuM, Chofnus EG (1958) K voprosu zavisimosti modulei uprugosti nekotorykh geterogennykh sistem ot poristosti (On the problem of the dependence of elastic moduli of some heterogeneous materials on porosity). Inzh Fiz Zh 1(6):96-99 (in Russian)

876

Addendum

134. Skorokhod VV (1959) Ob elektroprovodnosti dispersnykh smesei provodnikov s neprovodnikami (On electrical conductivity of the disperse mixtures of conductors with nonconductors). Inzh Fiz Zh 2(8):51-59 (in Russian) 135. Skorokhod VV (1977) Fiziko-mekhanicheskie svoistva poristykh materialov (Physicomechanical properties of porous materials). In: Frantsevich IN (ed) Poroshkovaya metallurgiya – 77 (Powder metallurgy – 77), pp. 120-129. Naukova Dumka, Kyiv (in Russian) 136. Troshchenko VT (1960) Nekotorye voprosy prochnosti metallokeramicheskikh materialov na osnove karbida kremniya (Some problems of the strength of sintered materials based on silicon carbide). Inzh Fiz Zh 3(1):103-108 (in Russian) 137. Troshchenko VT (1964) Statystychni teorii mitsnosti ta ih zastosuvannya do spechennyh materialiv (Statistical theories of strength and their application to sintered materials). Ukrainian RSR Academy of Sciences, Kyiv (in Ukrainian) 138. Shcherban NI (1973) Effect of porosity on the mechanical properties of materials produced by powder metallurgy techniques. Powder Metall Met Ceram 12(9):736-748 139. Shcherban NI (1973) Effect of technological factors upon the mechanical properties of porous materials produced by powder metallurgy techniques. Powder Metall Met Ceram 12(10):834-840 140. Wachtman JB, Jr (1969) Elastic deformation of ceramics and other refractory materials. In: Wachtman JB, Jr (ed) Mechanical and thermal properties of ceramics. Proc. symp. on mechanical and thermal properties of ceramics, Gaithersburg, Maryland, 1-2 Apr 1968, Special Publication 303, pp. 139-168. National Bureau of Standards, US Government Printing Office, Washington, DC 141. Ryshkewitch E (1953) Compression strength of porous sintered alumina and zirconia. 9th communication to ceramography. J Am Ceram Soc 36(2):65-68 142. Duckworth W (1953) Discussion of Ryshkewitch paper. J Am Ceram Soc 36(2):68 143. MacKenzie JK (1950) Elastic constants of a solid containing spherical holes. Proc Phys Soc Lond B 63(1):2-11 144. Coble RL, Kingery WD (1956) Effect of porosity on physical properties of sintered alumina. J Am Ceram Soc 39(11):377-385 145. Kingery WD, Bowen HK, Uhlmann RD (1976) Introduction to ceramics. Wiley, New York 146. Dewey JM (1947) The elastic constants of materials loaded with non-rigid fillers. J Appl Phys 18(6):578-581 147. Spriggs RM (1961) Expression for effect of porosity on elastic modulus of polycrystalline refractory materials, particularly aluminium oxide. J Am Ceram Soc 44(12):628-629 148. Spriggs RM, Brissette LA (1962) Expression for shear modulus and Poisson’s ratio of porous refractory oxides. J Am Ceram Soc 45(4):198-199 149. Knudsen FP (1959) Dependence of mechanical strength of brittle polycrystalline specimens on porosity and grain size. J Am Ceram Soc 42(8):376-387 150. Knudsen FP (1962) Effect of porosity on Young’s modulus of alumina. J Am Ceram Soc 45(2):94-95 151. Spinner S, Knudsen FP, Stone L (1963) Elastic constant – porosity relations for polycrystalline thoria. J Res Nat Bur Stan C 67(1):39-46 152. Fryxell RE, Chandler BA (1964) Creep, strength, expansion and elastic moduli of sintered BeO as a function of grain size, porosity and grain orientation. J Am Ceram Soc 47(6):283291 153. Hill R (1952) The elastic behaviour of a crystalline aggregate. Proc Phys Soc Lond A 65(5):349-355 154. Hill R (1965) A self-consistent mechanics of composite materials. J Mech Phys Solids 13(4):213-222 155. Budiansky B (1965) On the elastic moduli of some heterogeneous materials. J Mech Phys Solids 13(4):223-227 156. Wu T (1966) The effect of inclusion shape on the elastic moduli of a two-phase material. Int J Solids Struct 2(1):1-8

References

877

157. Dean EA (1983) Elastic moduli of porous sintered materials as modelled by a variableaspect-ratio self-consistent oblate-spheroidal-inclusion theory. J Am Ceram Soc 66(12):847854 158. Kerner EH (1956) The elastic and thermo-elastic properties of composite media. Proc Phys Soc Lond B 69(8):808-813 159. Hashin Z (1962) Elastic moduli of heterogeneous materials. J Appl Mech 29:143-150 160. Hashin Z, Shtrikman S (1963) A variational approach to the theory of the elastic behaviour of multiphase materials. J Mech Phys Solids 11(2):127-140 161. Hasselman DPH (1962) On the porosity dependence of the elastic moduli of polycrystalline refractory materials. J Am Ceram Soc 45(9):452-453 162. Hasselman DPH (1963) Relation between effects of porosity on strength and on Young’s modulus of elasticity of polycrystalline materials. J Am Ceram Soc 46(11):564-565 163. Hasselman DPH, Fulrath RM (1964) Effect of small fraction of spherical porosity on elastic moduli of glass. J Am Ceram Soc 47(1):52-53 164. Brown SD, Biddulph RB, Wilcox PD (1964) A strength-porosity relation involving different pore geometry and orientation. J Am Ceram Soc 47(7):320-322 165. Buch A, Goldschmidt S (1970) Influence of porosity on elastic moduli of sintered materials. Mater Sci Eng 5(2):111-118 166. Paul B (1960) Prediction of elastic constants of multiphase materials. Trans AIME 218(1):36-41 167. Paul B (1960) The elastic moduli of heterogeneous materials. J Appl Mech Trans ASME 29(4):765-766 168. Frantsevich IN, Zhurakovskii EA, Lyashchenko AB (1967) Elastic constants and characteristics of the electron structure of certain classes of refractory compounds obtained by the metal-powder method. Inorg Mater 3(1):6-12 169. Frantsevich IN, Voronov FF, Bakuta SA (1982) Uprugie postoyannye i moduli uprugosti metallov i nemetallov (The elastic constants and elasticity moduli of metals and non-metals). Naukova Dumka, Kyiv (in Russian) 170. Kats SM (1981) Vysokotemperaturnye teploizolyatsionnye materially (High-temperature thermal insulation materials). Metallurgiya, Moscow (in Russian) 171. Rice RW (1977) Microstructure dependence of mechanical behaviour of ceramics. In: McCrone R (ed) Treatise on materials science and technology, pp. 199-381. Academic Press, New York 172. Rice RW (1998) Porosity of ceramics. Marcel Dekker, New York, Basel 173. Rice RW (2005) Mechanical properties. In: Scheffler M, Colombo P (eds) Cellular ceramics: structure, manufacturing, properties and applications, pp. 291-312. Wiley, Weinheim, Germany 174. Gibson LJ, Ashby MF (1999) Cellular solids: structure and properties, 2nd ed. Cambridge University Press, Cambridge, UK 175. Ashby MF (2005) Cellular solids – scaling properties. In: Scheffler M, Colombo P (eds) Cellular ceramics: structure, manufacturing, properties and applications, pp. 3-17. Wiley, Weinheim, Germany 176. Ashby MF (2006) The properties of foams and lattices. Philos Trans Royal Soc A 364(1838):15-30 177. Baranov VM, Knyazev VI, Korostin OS (1973) The temperature dependence of the elastic constants of nonstoichiometric zirconium carbides. Strength Mater 5(9):1074-1077 178. Avgustinik AI, Ordanyan SS, Fishchev VN, Kudryashova LV (1973) Elastic properties of zirconium and niobium carbides in their homogeneity regions. Inorg Mater 9(7):1039-1041 179. Ordanyan SS, Fishchev VN (1976) Porosity as a factor in the elastic modulus of zirconium and niobium monocarbides. Refract Indust Ceram 17(1-2):111-113 180. Kotelnikov RB, Bashlykov SN, Kashtanov AI, Menshikova TS (1978) Vysokotemperaturnoe yadernoe toplivo (High-temperature nuclear fuel). Atomizdat, Moscow (in Russian)

878

Addendum

181. Padel A, De Novion Ch. (1969) Constantes elastiques des carbures, nitrures et oxydes d’uranium et de plutonium (Elastic constants of carbides, nitrides and oxides of uranium and plutonium). J Nucl Mater 33:40-51 (in French) 182. Haglund JA, Hunter O, Jr (1973) Elastic properties of polycrystalline monoclinic Gd2O3. J Am Ceram Soc 56(6):327-330 183. Hunter O, Jr, Graddy GE, Jr (1976) Porosity dependence of elastic properties of polycrystalline cubic Lu2O3. J Am Ceram Soc 59(1-2):82 184. Scheidecker RW, Hunter O, Jr, Calderwood FW (1979) Elastic properties of partiallystabilized HfO2 compositions. J Mater Sci 14(10):2284-2288 185. Dole SL, Hunter O, Jr, Calderwood FW (1980) Elastic properties of stabilized HfO2 compositions. J Am Ceram Soc 63(3-4):136-139 186. Dole SL, Hunter O, Jr (1983) Elastic properties of hafnium and zirconium oxides stabilized with praseodymium or terbium oxides. J Am Ceram Soc 66(3):C47-C49 187. Wang JC (1984) Young’s modulus of porous materials. Part 1. Theoretical derivation of modulus-porosity correlation. J Mater Sci 19(3):801-808 188. Wang JC (1984) Young’s modulus of porous materials. Part 2. Young’s modulus of porous alumina with changing pore structure. J Mater Sci 19(3):809-814 189. Phani KK, Niyogi SK (1986) Porosity dependence of ultrasonic velocity and elastic modulus in sintered uranium dioxide – a discussion. J Mater Sci Lett 5(4):427-430 190. Phani KK, Niyogi SK (1987) Elastic modulus – porosity relationship for Si3N4. J Mater Sci Lett 6(5):511-515 191. Phani KK, Niyogi SK (1987) Elastic modulus – porosity relation in polycrystalline rareearth oxides. J Am Ceram Soc 70(12):C362-C366 192. Phani KK, Niyogi SK (1987) Young’s modulus of porous brittle solids. J Mater Sci 22(1):257-263 193. Wagh AS, Poeppel RB, Singh JP (1991) Open pore description of mechanical properties of ceramics. J Mater Sci 26(14):3862-3868 194. Boccaccini AR, Ondracek G, Mazilu P, Windelberg D (1993) On the effective Young’s modulus of elasticity for porous materials: microstructure modelling and comparison between calculated and experimental values. J Mech Behav Mater 4(2):119-128 195. Arnold M, Boccaccini AR, Ondracek G (1996) Prediction of the Poisson’s ratio of porous materials. J Mater Sci 31:1643-1646 196. Boccaccini AR, Fan Z (1997) A new approach for the Young’s modulus – porosity correlation of ceramic materials. Ceram Int 23:239-245 197. Boccaccini DN, Boccaccini AR (1997) Dependence of ultrasonic velocity on porosity and pore shape in sintered materials. J Nondestruct Eval 16(4):187-192 198. Janowski KR, Rossi RC (1967) Elastic behaviour of MgO matrix composites. J Am Ceram Soc 50(11):599-603 199. Fate WA (1974) Density dependence of shear modulus of Si3N4. J Am Ceram Soc 57(8):372 200. Nielsen LF (1982) Elastic properties of two-phase materials. Mater Sci Eng 52(1):39-62 201. Norris AN (1985) A differential scheme for the effective moduli of composites. Mech Mater 4:1-16 202. Zimmerman RW (1991) Elastic moduli of a solid containing spherical inclusions. Mech Mater 12:17-24 203. Ramakrishnan N, Arunachalam VS (1993) Effective elastic moduli of porous ceramic materials. J Am Ceram Soc 76(11):2745-2752 204. Ramakrishnan N, Arunachalam VS (1990) Effective elastic moduli of porous solids. J Mater Sci 25(9):3930-3937 205. Kupková M (1993) Porosity dependence of materials elastic moduli. J Mater Sci 28(19):5265-5268 206. Kupková M, Kupka M (1997) Elastic-wave velocities for porous media with power-law distribution of pore sizes. Geol Rundsch 86(1):156-159

References

879

207. Kupková M, Parilák L (1997) Young’s modulus calculations for systems with periodically distributed identical spheroidal pores of various size, orientation and shape anisotropy. Kovove Mater 35(4):237-246 208. Kupková M, Kupka M (2004) Theoretical bounds on the electrical conductivity of sintered materials and their relation to bounds on the Young’s modulus. Metalurgija 43(2):97-100 209. Kral C, Lengauer W, Rafaja D, Ettmayer P (1998) Critical review on the elastic properties of transition metal carbides, nitrides and carbonitrides. J Alloys Compd 265:215-233 210. Gong L, Wang Y, Cheng X, Zhang R, Zhang H (2014) A novel effective medium theory for modelling the thermal conductivity of porous materials. Int J Heat Mass Transfer 68:295-298 211. Jana DC, Sundararajan G, Chattopadhyay K (2017) Effect of porosity on structure, Young’s modulus and thermal conductivity of SiC foams by direct foaming and gelcasting. J Am Ceram Soc 100(1):312-322 212. Peras AYa, Dauknis VI (1971) The effect of small porosity on the strength of brittle ceramic materials. Strength Mater 3(8):921-925 213. Peras AYa, Dauknis VI (1977) Prochnost ogneupornoi keramiki i metody ee issledovaniya (The strength of refractory ceramics and methods of its investigation). Mokslas, Vilnius (in Russian) 214. Schiller KK (1958) Porosity and strength of brittle solids (with particular reference to gypsum). In: Warson WH (ed) Mechanical properties of non-metallic brittle materials, pp. 35-49. Interscience, New York 215. Carniglia SC (1972) Working model for porosity effects on the uniaxial strength of ceramics. J Am Ceram Soc 55(12):610-618 216. Krasulin YuL, Timofeev VN, Barinov SM, Ivanov AB (1980) Strength and fracture of porous ceramics sintered from spherical particles. J Mater Sci 15:1402-1406 217. Krasulin YuL, Timofeev VN, Barinov SM, Ivanov AB, Asonov AN, Shnyrev GD (1980) Poristaya konstruktsionnaya keramika (Porous structural ceramics). Metallurgiya, Moscow (in Russian) 218. Krasulin YuL, Barinov SM, Ivanov VS (1985) Struktura i razrushenie materialov iz poroshkov tugoplavkikh soedinenii (Microstructure and fracture of materials prepared from the powders of refractory compounds). Nauka, Moscow (in Russian) 219. Carson JK, Sekhon JP (2010) Simple determination of the thermal conductivity of the solid phase of particulate materials. Int Commun Heat Mass Transfer 37:1226-1229 220. Katoh Y, Vasudevamurthy G, Nozawa T, Snead LL (2013) Properties of zirconium carbide for nuclear fuel applications. J Nucl Mater 441:718-742 221. Brynza AP, Khmelovskaya SA, Fedorus VB, Silina ZR (1976) Issledovanie khimicheskoi stoikosti i elektrokhimicheskogo povedeniya karbidov (A study of the chemical resistance and electrochemical behaviour of carbides). In: Samsonov GV, Kosolapova TYa, Gnesin GG, Fedorus VB, Domasevich LG (eds) Karbidy i splavy na ikh osnove (Carbides and alloys based on them), pp. 199-208. Naukova Dumka, Kyiv (in Russian) 222. Kotlyar EE, Nazarchuk TN (1966) O nekotorykh khimicheskikh svoistvakh karbidov perekhodnykh metallov IV, V grupp periodicheskoi sistemy (On certain chemical properties of the transition metal carbides of IV, V groups of the periodic table). Izv AN SSSR Neorg Mater 2(10):1778-1780 (in Russian) 223. Philipp WH (1966) Chemical reactions of carbides, nitrides and diborides of titanium and zirconium and chemical bonding in these compounds. Report NASA-TN-D-3533, pp. 1-23. National Aeronautics and Space Administration, Washington DC 224. Lukashenko TA, Tikhonov KI (1998) Korrozionnaya stoikost ryada karbidov i nitridov perekhodnykh metallov 4-6 grupp v kontsentrirovannykh rastvorakh sernoi i fosfornoi kislot (Corrosion resistance of a number of carbides and nitrides of group 4-6 transition metals in concentrated solutions of sulfuric and phosphoric acids). Zh Prikl Khim 71(12):2017-2020 (in Russian) 225. Kopylova VP, Kornilova VI, Nazarchuk TN, Fedorus VB (1980) Reactions of powders of zirconium and niobium carbides in their homogeneity with some acids. Powder Metall Met Ceram 19(1):9-12

880

Addendum

226. Kotlyar EE, Nazarchuk TN (1972) Interaction of the carbides of group IV and V transition metals with various acids. In: Samsonov GV (ed) Chemical properties and analysis of refractory compounds, pp. 1-5. Consultants Bureau, New York, London 227. Georgieva GG, Lashko NF, Sorokina KP (1972) Chemical and electrochemical methods of separating the carbides MeC and the carbonitrides Me(C,N) of group IV and V metals. In: Samsonov GV (ed) Chemical properties and analysis of refractory compounds, pp. 72-76. Consultants Bureau, New York, London 228. Ball MC, Brown DS, Page D, Thurman RRT (1967) The action of alkali on transition metal carbides. Trans Brit Ceram Soc 66:307-313 229. Loskutov VF, Khizhnyak VG, Kunitskii YuA, Kindrachuk MV (1991) Diffuzionnye karbidnye pokrytiya (Diffusion carbide coatings). Tékhnika, Kyiv (in Russian) 230. Kieffer R, Benesovsky F (1968) Hartstoffe (Hard materials). Springer, Vienna (in German) 231. Kieffer R (1971) Sondermetalle (Special metals). Springer, Wien (in German) 232. Kieffer R, Nowotny H, Neckel A, Ettmayer P, Usner L (1968) Zur Entmischung von kubischen Mehrstoffcarbiden (On the miscibility of multicomponent cubic carbides). Monatsh Chem 99(3):1020-1027 (in German) 233. Kieffer R, Benesovsky F (1968) Hartstoffe (Hard materials). Springer, Vienna (in German) 234. Kieffer R, Kölbl F (1949) Tungsten carbide – free hard metals. Powder Metall Bull 4(1):417 235. Kieffer R, Ettmayer P, Nowotny H, Dufek G (1972) Neue Ermittlungen zur Mischbarkeit von Übergangsmetallnitride und -carbide (New investigations concerning miscibility of transition metal nitrides and carbides). Metall 26(7):701-708 (in German) 236. Kiparisov SS, Levinskii YuV, Petrov AP (1987) Karbid titana: poluchenie, svoistva, primenenie (Titanium carbide: production, properties, application). Metallurgiya, Moscow (in Russian) 237. Petrov VA (1969) Izluchatelnaya sposobnost vysokotemperaturnykh materialov (The emissivity of high-temperature materials). Nauka, Moscow (in Russian) 238. Andrievskii RA (1979) Prochnost tugoplavkikh soedinenii (Strength of high-melting compounds). Zh Vsesoyuz Khim Obshchestva im D I Mendeleev 24(3):258-262 (in Russian) 239. Fedorchenko IM, Frantsevich IN, Radomyselskii ID, Kovalchenko MS, Kislyi PS, Kosolapova TYa, Mai VK, Shcherban NI (1985) Poroshkovaya metallurgiya (Powder metallurgy). Naukova Dumka, Kyiv (in Russian) 240. Alekseeva ZM (1987) Dvoinye tugoplavkie karbidy urana (Binary refractory uranium carbides). Nauka, Moscow (in Russian) 241. Alyamovskii SI, Zainulin YuG, Shveikin GP (1981) Oksikarbidy i oksinitridy metallov IVA i VA podgrupp (Oxycarbides and oxynitrides of IVA and VA subgroups metals). Nauka, Moscow (in Russian) 242. Kashtalyan YuA (1970) Kharakteristiki uprugosti materialov pri vysokikh temperaturakh (Elasticity characteristics of materials at high temperature). Naukova Dumka, Kyiv (in Russian) 243. Khusainov MA (1979) Termoprochnost tugoplavkikh materialov, poluchennykh gazofaznym osazhdeniem (Thermal strength of refractory materials manufactured by gasphase deposition). Leningrad State University, Leningrad (in Russian) 244. Ivanko AA (1968) Tverdost (The hardness). Naukova Dumka, Kyiv (in Russian) 245. Samsonov GV, Portnoi KI (1961) Splavy na osnove tugoplavlikh soedinenii (The alloys on the basis of refractory compounds). Oborongiz, Moscow (in Russian) 246. Bukatov VG (1979) Issledovanie fiziko-mekhanicheskikh svoistv karbidov tugoplavkikh metallov i nekotorykh splavov na ikh osnove (Studies of physico-mechanical properties of refractory metal carbides and some alloys on their basis). PhD thesis, Moscow Institute of Steels and Alloys (in Russian) 247. Bolgar AS, Verkhoglyadova TS, Samsonov GV (1961) Davlenie para i teplota ispareniya TiC, ZrC i HfC v vakuume pri vysokikh temperaturakh (Vapour pressure and heat of vaporization of TiC, ZrC and HfC in vacuum at high temperatures). Izv AN SSSR OTN Metall Toplivo (1):142-145 (in Russian)

References

881

248. Lvov SN, Nemchenko VF, Samsonov GV (1961) Teploprovodnost tugoplavkikh boridov, karbidov i niridov (Heat conduction of refractory borides, carbides and nitrides). Poroshkovaya Metall (6):68-74 (in Russian) 249. Glushko VP, Medvedev VA, eds (1974) Termicheskie konstanty veshchestv (Thermal constants of substances), Vol. 7, Part 1. USSR Academy of Sciences All-Union Institute of Scientific and Technical Information, Moscow (in Russian) 250. Glushko VP, Gurvich LV, eds (1982) Termodinamicheskie svoistva individualnukh veshchestv (Thermodynamic properties of individual substances), Vol. IV, Parts 1-2. Nauka, Moscow (in Russian) 251. Karapetyants MKh, Karapetyants ML (1968) Osnovnye termodinamicheskie konstanty neorganicheskikh i organicheskikh veshchestv (General thermodynamic constants of inorganic and organic substances). Khimiya, Moscow (in Russian) 252. Fesenko VV, Turchanin AG, Guseva EA (1971) Termodinamicheskie svoistva karbida titana v oblasti temperatur 0-3000 K (Thermodynamic properties of titanium carbide in the range of temperatures 0-3000 K). Zh Fiz Khim 45(8):1966-1968 (in Russian) 253. Coltters RG (1985) Thermodynamics of binary metallic carbides: a review. Mater Sci Eng 76(1-2):1-50 254. Samsonov GV, Fomenko VS, Podchernyaeva IA, Okhremchuk LN (1974) Thermionic emission properties of refractory compounds and materials based on them (a review). Powder Metall Met Ceram 13(10):836-842 255. De Laeter JR, Bohlke JK, De Bievre P, Hidaka H, Peiser HS, Rosman KJR, Taylor PDP (2003) Atomic weights of the elements. Review 2000 (IUPAC Technical report). Pure Appl Chem 75(6):683-800 256. Wallace TC, Sr, Butt DP (1996) Review of diffusion and vaporization of group 4 and 5 transition metal carbides. In: Oyama ST (ed) The chemistry of transition metal carbides and nitrides, pp. 53-90. Chapman & Hall, London, Glasgow 257. Weinberger CR, Thompson GB (2018) Review of phase stability in the group IVB and VB transition metal carbides. J Am Ceram Soc 101(10):4401-4424 258. Mukhopadhyay A, Raju GB, Basu B (2013) Ultra-high temperature ceramics: processing, properties and applications. In: Low I-M, Sakka Y, Hu C (eds) MAX phases and ultra-high temperature ceramics for extreme environments, pp. 49-99. IGI Global, Hershey, Pennsylvania 259. Basu B, Balani K (2011) Advanced structural ceramics. The American Ceramic Society, Wiley, Hoboken, New Jersey 260. Maity TN, Gopinath NK, Biswas K, Basu B (2019) Spark-plasma sintering of ultra-high temperature ceramics. In: Cavaliere P (ed) Spark-plasma sintering of materials, pp. 369-440. Springer Nature, Cham, Switzerland 261. Williams WS (1990) Thermal conductivity of transition metal carbides. In: Freer R (ed) The physics and chemistry of carbides, nitrides and borides, pp. 625-637. Kluwer Academic, Dordrecht 262. Gorshkov VS, Savelev VG, Fedorov NF (1988) Fizicheskaya khimiya silikatov i drugikh tugoplavkikh soedinenii (Physical chemistry of silicates and other refractory compounds). Vysshaya shkola, Moscow (in Russian) 263. Gurevich YuG, Narva VK, Frage NR (1988) Karbidostali (Carbide steels). Metallurgiya, Moscow (in Russian) 264. McColm IJ (1990) Ceramic hardness. Plenum Press, New York, London 265. Gubanov VA, Ivanovsky AL, Zhukov VP (1994) Electronic structure of refractory carbides and nitrides. Cambridge University Press, Cambridge, New York 266. Telle R (1994) Boride and carbide ceramics. In: Swain MV (ed) Materials science and technology, Vol. 11 – Structure and properties of ceramics, pp. 175-266. Wiley – VCH, Weinheim 267. Oyama ST (1996) Introduction to the chemistry of transition metal carbides and nitrides. In: Oyama ST (ed) The chemistry of transition metal carbides and nitrides, pp. 1-27. Chapman & Hall, London, Glasgow

882

Addendum

268. Kumashiro Y (2000) High-temperature characteristics. In: Kumashiro Y (ed) Electric refractory materials, pp. 191-222. Marcel Dekker, New York, Basel 269. Jeitschko W, Pöttgen R, Hoffmann R-D (2000) Structural chemistry of hard materials. In: Riedel R (ed) Handbook of ceramic hard materials, pp. 3-40. Wiley-VCH, Weinheim, New York 270. Fergus JW, Hoffmann WP (2014) Refractory metals, ceramics and composites for hightemperature structural and functional applications. In: Bar-Cohen Y (ed) High-temperature materials and mechanisms, pp. 39-68. CRC Press, Boca Raton, London, New York 271. Wuchina EJ, Opeka M (2014) The group IV carbides and nitrides. In: Fahrenholtz WG, Wuchina EJ, Lee WE, Zhou Y (eds) Ultra-high temperature ceramics, pp. 361-390. The American Ceramic Society, Wiley, Hoboken, New Jersey 272. Pelleg J (2014) Mechanical properties of ceramics. Springer Nature, Cham, Switzerland 273. Pritychenko B, Mughabghab SF (2012) Neutron thermal cross sections, Westcott factors, resonance integrals, Maxwellian averaged cross sections and astrophysical reaction rates calculated from the ENDF/B-VII.1, JEFF-3.1.2, JENDL-4.0, ROSFOND-2010, CENDL-3.1 and EAF-2010 evaluated data libraries. Brookhaven National Laboratory Report BNL-984032012-JA. Nucl Data Sheets 113(12):3120-3144 274. Kurlov AS, Gusev AI (2013) Tungsten carbides. Structure, properties and application in hardmetals. Springer, Heidelberg 275. Samsonov GV, Vitryanyuk VK, Chaplygin FI (1974) Karbidy volframa (Tungsten carbides). Naukova Dumka, Kyiv (in Russian) 276. Upadhyaya GS (1998) Cemented tungsten carbides. Production, properties and testing. Noyes Publications, Westwood, New Jersey 277. Tretyakov VI (1976) Osnovy metallovedeniya i tekhnologii proizvodstva spechennykh tverdykh splavov (Fundamentals of metal science and production technology of sintered hard alloys). Metallurgiya, Moscow (in Russian) 278. Eckerlin P, Kandler H (1971) Structural data for elements and intermetallic phases. Springer, Berlin 279. Holleck H (1986) Material selection for hard coatings. J Vac Sci Technol A 4(6):2661-2669 280. Pearson WB (1958) Lattice spacings and structures of metals and alloys. Pergamon Press, London 281. Berg G, Friedrich C, Broszeit E, Berger C (2000) Data collection of properties of hard materials. In: Riedel R (ed) Handbook of ceramic hard materials, pp. 965-995. Wiley – VCH, Weinheim 282. Kubaschewski O, Evans EL (1958) Metallurgical thermochemistry. Pergamon Press, Oxford 283. Kubaschewski O, Alcock CB (1979) Metallurgical thermochemistry, 5th ed. Pergamon Press, Oxford 284. Elliott RP (1965) Constitution of binary alloys, first supplement. McGraw-Hill, NewYork, London 285. Shunk FA (1969) Constitution of binary alloys, second supplement. McGraw-Hill, New York, London 286. Nesmeyanov AN (1963) Vapour pressure of the chemical elements. Elsevier, New York 287. Kulikov IS (1969) Termicheskaya dissotsiatsiya soedinenii (Thermal dissociation of compounds), 2nd ed. Metallurgiya, Moscow (in Russian) 288. Shackelford JF, Han Y-H, Kim S, Kwon S-H (2016) CRC materials science and engineering handbook, 4th ed. CRC Press, Boca Raton, London, New York 289. Schwarzkopf P, Kieffer R (1960) Cemented carbides. Macmillan, New York 290. Kikoin IK (1976) Tablitsy fizicheskikh velichin (Tables of physical values). Atomizdat, Moscow (in Russian) 291. Samsonov GV (ed), Fomenko VS (1966) Handbook of thermionic properties. Plenum Press, New York 292. Mott BW (1956) Micro indentation hardness testing. Butterworth, London

References

883

293. Borisenko VA (1984) Tverdost i prochnost tugoplavkikh materialov pri vysokikh temperaturakh (Hardness and strength of refractory materials at high temperatures). Naukova Dumka, Kyiv (in Russian) 294. Habig K-H (1980) Verschleiß und Härte von Werkstoffen (Wear and hardness of materials). Hanser, München (in German) 295. Hornbogen E (1987) Werkstoffe: Aufbau und Eigenschaften von Keramik, Metallen, Polymer- und Verbundwerkstoffen (Materials: structure and properties of ceramics, metals, polymer and composite materials). Springer, Berlin (in German) 296. Westbrook JH, Stover ER (1967) Carbides for high-temperature materials. In: Campbell IE, Sherwood EM (eds) High-temperature materials and technology, pp. 312-348. Wiley, New York 297. Pisarenko GS, Rudenko VN, Tretyachenko GN, Troshchenko VT (1966) Prochnost materialov pri vysokikh temperaturakh (Strength of materials at high temperatures). Naukova Dumka, Kyiv (in Russian) 298. Kreimer GS (1968) Strength of hard alloys. Consultants Bureau, New York 299. Kurlov AS, Gusev AI (2006) Phase equilibria in the W-C system and tungsten carbides. Russ Chem Rev 75(7):617-636 300. Kurlov AS, Gusev AI (2006) Tungsten carbides and W-C phase diagram. Inorg Mater 42(2):121-127

Index (Physical Properties)

A

I

Atomic weights 831, 834-835

Integral emittances 54, 831-832, 845-846 Isotopic mass ranges 123, 832, 850-851

B Boiling points 36, 38, 831, 839-841

L

C

Lattice parameters 12-31, 33, 41, 117, 123128, 367, 517-518, 542, 831, 834-835

Coefficients of linear thermal expansion 46-49, 121, 525, 831, 840-841

Lattice point defects 27, 33, 44, 123-125, 130, 275, 321, 357, 364, 545, 573

Crystal systems 13, 15, 20-22, 831, 834835

M

Crystal types 13, 15, 20-22, 831, 834-835

D Densities 13-17, 20-23, 33-34, 831, 834835, 851 — calculated (XRD) 13-17, 20-23, 33, 831, 834-835, 851 — experimental (pycnometric) 33-34, 831, 834-835 Diffusion rate in species pairs (diffusivity) 566-573

Macroscopic thermal neutron cross sections — capture (absorption) 123-124, 832, 850-851 — scattering 123-124, 832, 850-851 Melting points 12, 34, 36-39, 831, 839-841 Microscopic thermal neutron cross sections — capture (absorption) 123-124, 832, 850-851 — scattering 123-124, 832, 850-851 Molar enthalpy differences 37, 831, 838839

E

Molar enthalpy of atomization from solid state 36-38

Electron work functions 54, 56-58, 845846

Molar entropy 35, 37-39, 831, 837

Enthalpies (heat) of melting 831, 838-839

Molar heat capacities 34-35, 37-41, 831, 836-837

Enthalpies (heat) of vaporization 36-37, 831, 838-839

H

Molar magnetic susceptibilities 52-53, 58, 831-832, 845-846 Monochromatic emittances 54-55, 831832, 845-846

Hardnesses 58-86, 89, 92-93, 95, 97, 122, 130, 832, 847-849

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 I. L. Shabalin, Ultra-High Temperature Materials IV, https://doi.org/10.1007/978-3-031-07175-1

885

886 N Neutron moderating abilities (macroscopic slowing down power) 123-124, 832, 850851

P Phase homogeneity regions 11, 25-27, 3334, 39, 41, 83, 85, 116-117, 831, 834835 Porosity — property-porosity relationships 833, 857-869 — — for bulk (compression) modulus 867-868 — — for Coulomb’s (shear) modulus 865-867 — — for electrical resistivity 857858 — — for Poisson’s ratio 869 — — for strength characteristics 859-860 — — for thermal conductivity 857858 — — for Young’s modulus 861865

R Relative thermal expansion 48-49, 831, 840-841 Resonance integral for neutron capture 123, 832, 850-851 Richardson constants 54, 56-58, 831-832, 845-846

S Space groups 13, 15, 20-22, 831, 834-835 Specific electrical resistances 49-51, 58, 123, 127-128, 831-833, 845-846, 858 Specific enthalpy differences 831, 838-839 Specific heat capacities 36-37, 39, 831, 836-837

Index (Physical Properties) Standard molar entropies 35, 37, 831, 836837

T Thermal coefficients of electroresistance 49-51, 831, 845-846 Thermal conductivity 44-45, 49, 121, 831, 833, 840-841, 857-858 Total numbers of isotopes 123, 832, 850851 Tungsten monocarbide (cubic) γ-WC1−x — chemical properties and materials design 6, 131, 140, 159, 183-186, 191, 212-214, 216, 225-229, 232-235, 239242, 253, 255, 258-259, 261, 263-264, 276-277, 280-282, 285-287, 317, 348, 357, 367-368, 370-371, 374, 394, 403404, 408-409, 418, 427-430, 433-434, 436, 438-439, 442-445, 447, 450-451, 467, 469, 471, 475, 483, 485, 491-492, 498, 506, 508-510, 512, 514-522, 530, 532-537, 539-541, 543, 545, 548-549, 552-556, 565, 832-833, 852 — — catalytic activity 6, 131, 552556 — — chemical interaction and compatibility 140, 159, 183-186, 191, 212-214, 216, 225-229, 232235, 239-242, 253, 255, 258-259, 261, 263-264, 276-277, 280-282, 285-287, 317, 348, 357, 367-368, 370-371, 374, 394, 403-404, 408409, 418, 427-430, 433-434, 436, 438-439, 442-445, 447, 450-451, 467, 469, 471, 475, 483, 485, 491492, 498, 506, 508-510, 512, 514522, 530, 532-537, 539-541, 543, 545, 548-549, 556-557, 565, 832833, 852 — — — with elements (solid and liquid metals / non-metals) 140, 159, 183-186, 191, 212214, 216, 225-229, 232-235,

Index (Physical Properties) 239-242, 253, 255, 258-259, 261, 263-264, 276-277, 280282, 285-287, 317, 348, 357, 367-368, 370-371, 374, 394, 403-404, 408-409, 418, 427430, 433-434, 436, 438-439, 442-445, 447, 565 — — — with refractory and other compounds 450-451, 467, 469, 471, 475, 483, 485, 491492, 498, 506, 508-510, 512, 514-522, 530, 832-833, 852 — — — with gaseous media 131, 532-537, 539-541, 543, 545, 548-549 — — — — oxidation resistance 131, 543, 545, 548549 — — electrochemical behaviour 556-557 — — quasi-binary systems 183186, 225, 228, 235, 239-242, 282, 367, 370, 394, 427-428, 433-434, 438, 443, 451, 467, 471, 483, 485, 491-492, 498, 506, 509, 512, 515, 517-521, 530, 832-833, 852 — electro-magnetic and optical properties 51-54, 56-58, 831-832, 846 — — molar magnetic susceptibility 52-53 — — normal monochromatic emittance (spectral emissivity) 54, 831832, 846 — — optical spectra 53 — — — spectra in the infrared (IR) ranges 53 — — superconductivity 51 — — thermoionic emission characteristics 54, 56-58, 831-832, 846 — — — work function 54, 5658, 831-832, 846 — nuclear physical properties 123, 128, 130 — — under ion bombardment 128, 130

887 — physico-mechanical properties 1517, 19, 33, 69, 85-86, 93, 100-101, 108109, 116-120, 122, 831-833, 835, 848, 859-869 — — bulk (compression) modulus 100, 108-109, 117-119, 122, 833, 867-868 — — Coulomb’s (shear) modulus 100, 108-109, 117-119, 122, 833, 865-867 — — density 15-17, 19, 33, 831, 835 — — elastic constants 100-101, 108-109, 116-119, 122, 832-833, 848, 861-869 — — hardness characteristics 69, 85-86, 832, 848 — — — microhardness 69, 832, 848 — — Poisson’s ratio 100, 108-109, 117-119, 122, 833, 869 — — sound velocities 120 — — — average 120 — — — longitudinal 120 — — — transversal 120 — — stiffness coefficients 100, 108-109, 116-119, 122 — — volume compressibility 108, 117 — — Young’s modulus 100-101, 108-109, 116-119, 122, 832-833, 848, 860-865 — structures 11-12, 15-17, 19, 25-26, 28-30, 32-33, 831, 835 — — chemical bonding 11-12 — — crystal system 15, 831, 835 — — crystal type 15, 831, 835 — — densities 15-17, 19, 33, 831, 835 — — — XRD density 15-17, 19, 33, 831, 835 — — homogeneity region 11, 34, 39, 831, 835 — — lattice parameters 15-17, 19, 25-26, 28-29, 33, 831, 835

888 — — metal-carbon phase diagram 11 — — nanostructures 15-16, 19, 27, 29-33, 51-52, 69-70, 85-86, 100, 109, 130, 159, 183-185, 191, 213214, 225, 228, 232, 258, 348, 367368, 370, 403-404, 427-428, 430, 433, 437, 439, 498, 517-522, 539542 — — — nanoparticles 15, 19, 29-30, 33, 183-185, 228, 437 — — — nanotubes 29, 32, 539 — — — nanowires 16, 19, 3132, 51, 522 — — — thin films/coatings 16, 19, 32-33, 51-52, 69-70, 85-86, 100, 109, 130, 159, 191, 213214, 225, 228, 232, 258, 348, 367-368, 370, 403-404, 427428, 430, 433, 439, 498, 517522, 540-542 — — radii ratio of Me in Me/MeC 12 — thermal properties 11, 34, 39, 41, 831, 841 — — melting point 11, 34, 39, 831, 841 — — molar heat capacity 39, 41 — — formation energy 39 Tungsten monocarbide (hexagonal) δ-WC1±x — chemical properties and materials design 6, 131-580, 832-833, 856 — — catalytic activity 6, 131, 552556 — — chemical interaction and compatibility 131-553, 832-833, 856 — — — with elements (solid and liquid metals / non-metals) 131-448 — — — with reagents (acids, alkalies and salts) in aqueous so-

Index (Physical Properties) lutions 574-578, 580, 832-833, 856 — — — with refractory and other compounds 131, 449-532 — — — with gaseous media 131, 532-553 — — — — oxidation resistance 131, 543-553 — — diffusion characteristics 566573 — — — hetero-diffusion characteristics 572 — — — self-diffusion characteristics 566-573 — — electrochemical behaviour 556-557 — — quasi-binary systems 132, 136-138, 159-160, 182-191, 254283, 348-349, 357-359, 367-371, 394-398, 402-409, 425-429, 431445, 447-455, 461-471, 474-481, 483-500, 503-524, 529-532 — — quasi-ternary and multicomponent systems 132-136, 138159, 161-182, 191-254, 283-357, 359-367, 371-401, 409-426, 428432, 436-437, 441, 445-447, 449451, 455-463, 465-469, 472-476, 479, 481-494, 496-497, 500-506, 508-513, 521-530, 532 — — recommended chemical etching agents 576-578 — — wettability with liquid metals and alloys 557-565 — electro-magnetic and optical properties 49-55, 57-58, 127-128, 831-833, 846, 858 — — colour at the common conditions 54 — — Hall coefficient 51-52 — — integral (total) emittance 54, 831-832, 846 — — molar magnetic susceptibility 52-53, 831-832, 846

Index (Physical Properties) — — normal monochromatic emittance (spectral emissivity) 54-55, 831-832, 846 — — — isosbestic points (Xpoints) 54-55 — — optical spectra 53-54 — — — reflectance spectra 53 — — — spectra in the infrared (IR) ranges 53 — — — spectra in the visible ranges 53 — — — x-ray spectra 53 — — — — emission 53 — — — — photoelectron 53 — — Seebeck coefficient 51-52 — — specific electrical resistance (resistivity) 49-51, 127-128, 831833, 846, 858 — — superconductivity 51 — — thermal coefficient of resistivity 49-51, 831-832, 846 — — thermoionic emission characteristics 54, 57-58, 831-832, 846 — — — Richardson constant 54, 57-58, 831-832, 846 — — — work function 54, 5758, 831-832, 846 — nuclear physical properties 123-130, 832, 851 — — changes in properties after irradiation exposure 123, 126-128 — — isotopes of metal 123, 130, 832, 851 — — — mass range 123, 130, 832, 851 — — — total number 123, 130, 832, 851 — — parameters of formation and migration of lattice point defects 123-125 — — — in metal sublattice 124125 — — — in non-metal sublattice 124-125

889 — — — interstitial atoms 124125 — — — vacancies 124 — — resonance integral for neutron capture 123, 130, 832, 851 — — thermal neutron cross sections 123-124, 832, 851 — — under bombardment 123, 126, 128-130 — — — by deuterium ions 128130 — — — by electrons 123 — — — by fast neutrons 123, 126 — — — by gamma radiation 123 — — — by helium ions 129 — — — by hydrogen ions 128130 — — — by protons 129 — physico-mechanical properties 58122, 127-128, 831-833, 835, 848-849, 859-869 — — bulk (compression) modulus 101-115, 117-119, 121-122, 833, 867-868 — — compressive strength 88, 95, 97, 832-833, 848, 859-860 — — Coulomb’s (shear) modulus 101-115, 117-119, 121-122, 833, 865-867 — — creep characteristics 94, 9697, 117 — — — activation energy 94 — — — exponent constant 94 — — density 13-15, 33-34, 831, 835 — — ductile-to-brittle transition temperature 94, 97, 130 — — elastic constants 101-115, 117-119, 121-122, 832-833, 848, 861-869 — — flexural (bending) strength 87, 94-97, 117, 832-833, 848-849, 859-860

890 — — fracture toughness (critical stress intensity factor) 89-94, 97 — — hardness characteristics 5866, 70-86, 93, 95, 127-128, 832, 848 — — — in HK scale 61, 63-66, 70-86, 93, 95 — — — in HRA scale 61 — — — in HV scale 58-66, 7082, 84-86, 93, 95, 127-128, 832, 848 — — — in Mohs scale 85 — — — microhardness 58-66, 70-86, 93, 95, 127-128, 832, 848 — — Poisson’s ratio 101-102, 104113, 115, 117-119, 121, 833, 869 — — sound velocities 119-120 — — — average 119-120 — — — longitudinal 119-120 — — — transversal 119-120 — — stiffness coefficients 101-102, 106-113, 121 — — tensile strength 95-97, 122, 130, 832-833, 848-849, 859-860 — — tensile/flexural strengths ratio 95-97, 849 — — thermal shock / stress resistance (thermal strength) 121-122 — — volume compressibility 109, 111, 117 — — Young’s modulus 101-115, 117-119, 121-122, 832-833, 848, 860-865 — structures 11-15, 17-19, 25-34, 123, 126, 831, 835 — — 2D-molecular MXenes 33 — — chemical bonding 11-12, 2627 — — C/Me radii ratio 12 — — crystal system 13, 831, 835 — — crystal type 13, 831, 835 — — densities 13-15, 33-34, 831, 835 — — — bulk density 33-34, 831, 835

Index (Physical Properties) — — — XRD density 13-15, 33, 831, 835 — — homogeneity region 11, 41, 831, 835 — — lattice parameters 13-15, 1719, 28-31, 33, 123, 126-127, 831, 835 — — lattice point defects 27, 33, 44, 123-125, 130, 275, 321, 357, 364, 545, 573 — — metal-carbon phase diagram 11 — — minimal Burger’s vector 27 — — nanostructures 13-15, 17-19, 27, 29-33, 51-52, 57, 59, 74-76, 7880, 86, 95, 102, 106, 110, 113, 130, 132, 134, 136, 149, 154, 159, 182183, 185-188, 190-192, 193, 197, 203-204, 214-215, 218, 225-228, 230, 234, 240, 244, 248, 252, 258, 279, 282, 348, 359, 363, 368, 370, 376, 391, 394-395, 403-404, 409, 411, 427-430, 439, 441, 443, 445, 457, 475, 481, 485, 487-488, 491, 498, 500, 504, 509, 511, 514, 517, 520, 523-524, 532-533, 539, 541542, 560, 565 — — — nanofibers 32, 187 — — — nanoparticles 13, 15, 17, 19, 29-30, 95, 132, 134, 136, 154, 159, 149, 182-183, 185188, 190-191, 193, 197, 203204, 214-215, 218, 225-228, 234, 244, 248, 252, 279, 359, 363, 376, 391, 409, 428-429, 445, 457, 469, 480-481, 485, 487-488, 496, 504 — — — nanorods 13, 17, 30, 32, 240, 411, 428, 469, 480, 487, 496, 511, 532 — — — nanotubes 13, 17, 29, 32, 228, 230, 539 — — — nanowires 31-32, 51, 134, 187, 218, 240, 282, 394, 488

Index (Physical Properties) — — — thin films/coatings 14, 18, 32, 51-52, 57, 59, 74-76, 7880, 86, 102, 106, 110, 113, 130, 159, 185-186, 192, 258, 348, 368, 370, 394-395, 403-404, 427-428, 430, 439, 441, 443, 445, 475, 491, 498, 500, 509, 514, 517, 520, 523-524, 533, 541-542, 560, 565 — — — whiskers 31 — — slip systems 26, 97 — thermal properties 11, 34-49, 831, 833, 837, 839, 841, 843, 857-858 — — boiling point 36, 831, 841, 843 — — character of vaporization 39, 41-44, 831, 843 — — coefficient of linear thermal expansion 46-49, 831, 841 — — melting point 11, 34, 36-37, 831, 841 — — molar enthalpy difference 831, 839 — — molar enthalpy (heat) of atomization from solid state 36-37 — — molar entropy 35, 39, 831, 837 — — molar heat capacity 34-35, 37, 39-41, 831, 837 — — relative thermal expansion 48-49, 831, 841 — — specific enthalpy difference 831, 839 — — specific heat capacity 36, 39, 831, 837 — — standard heat of formation 35-37, 39, 831, 837 — — standard molar entropy 35, 39, 831, 837 — — standard molar heat capacity 35, 39, 831, 837 — — thermal conductivity 44-45, 48-49, 831, 833, 841, 857-858 — — thermodynamic properties 3437, 39, 831, 837, 839, 841

891 Tungsten semicarbide W2±xC — chemical properties and materials design 6, 131, 133, 138, 144, 147, 154, 159-164, 168-172, 174, 176-177, 179, 191-194, 200-202, 205-207, 210-215, 217-220, 222-224, 226, 229-238, 240242, 244, 249, 252-253, 283-287, 301, 318, 344, 349, 352, 359, 363-364, 367, 371-373, 376-379, 383, 393-400, 402, 409-410, 413, 418, 422, 426-427, 429431, 433-434, 436, 438-442, 445-448, 455, 458, 463, 467, 471, 474, 483, 486, 489-493, 496, 500-501, 504-507, 509517, 522-524, 529-530, 532-533, 536, 539-540, 543, 551-557, 569-571, 573, 579-580, 832-833, 856 — — catalytic activity 6, 131, 552556 — — chemical interaction and compatibility 131, 133, 138, 144, 147, 154, 159-164, 168-172, 174, 176-177, 179, 191-194, 200-202, 205-207, 210-215, 217-220, 222226, 229-238, 240-242, 244, 249, 252-253, 283-287, 301, 318, 344, 349, 352, 359, 363-364, 367, 371373, 376-379, 383, 393-400, 402, 409-410, 413, 418, 422, 426-427, 429-431, 433-434, 436, 438-442, 445-448, 455, 458, 463, 467, 471, 474, 483, 486, 489-493, 496, 500501, 504-507, 509-517, 522-524, 529-530, 532-533, 536, 539-540, 543, 551-552, 579-580, 832-833, 856 — — — with elements (solid and liquid metals / non-metals) 131, 133, 138, 144, 147, 154, 159-164, 168-172, 174, 176177, 179, 191-194, 200-202, 205-207, 210-215, 217-220, 222-224, 226, 229-238, 240242, 244, 249, 252-253, 283287, 301, 318, 344, 349, 352, 359, 363-364, 367, 371-373,

892

Index (Physical Properties) 376-379, 383, 393-400, 402, 409-410, 413, 418, 422, 426427, 429-431, 433-434, 436, 438-442, 445-448 — — — with reagents (acids, alkalies and salts) in aqueous solutions 579-580, 832-833, 856 — — — with refractory and other compounds 455, 458, 463, 467, 471, 474, 483, 486, 489493, 496, 500-501, 504-507, 509-517, 522-524, 529-530, 532 — — — with gaseous media 131, 532-533, 536, 539-540, 543, 551-552 — — — — oxidation resistance 131, 551-552 — — diffusion characteristics 569571, 573 — — — self-diffusion characteristics 569-571 — — electrochemical behaviour 556-557 — — quasi-binary systems 160161, 193-194, 287, 349, 359, 372, 394-396, 399, 402, 410, 426-427, 430-431, 433-434, 436, 438-442, 445-446, 448, 455, 463, 467, 471, 483, 486, 489, 492, 501, 504, 506507, 509, 511-517, 523-524, 530 — — quasi-ternary and multicomponent systems 133, 138, 144, 147, 154, 159, 161-164, 168-172, 174, 176-177, 179, 191-193, 200202, 205-207, 210-215, 217-220, 222-226, 229-238, 240-242, 244, 249, 252-253, 283-287, 301, 318, 344, 352, 359, 363-364, 367, 371, 373, 376-379, 383, 393, 397-400, 409-410, 413, 418, 422, 429-430, 445-447, 455, 458, 474, 489-491, 493, 496, 500, 504-506, 509-514, 522-523, 529, 532 — — recommended chemical etching agents 579-580

— electro-magnetic and optical properties 49-56, 58, 127-128, 831-833, 846, 858 — — colour at the common conditions 54 — — Hall coefficient 52 — — integral (total) emittance 54, 58, 831-832, 846 — — molar magnetic susceptibility 52-53 — — normal monochromatic emittance (spectral emissivity) 54-55, 58, 831-832, 846 — — — isosbestic points (Xpoints) 54-55 — — Seebeck coefficient 52 — — specific electrical resistance (resistivity) 49-51, 58, 127-128, 831-832, 846, 858 — — superconductivity 51 — — thermal coefficient of resistivity 49-51, 58, 831-832, 846 — — thermoionic emission characteristics 54, 56, 58, 831-832, 846 — — — Richardson constant 54, 56, 58, 831-832, 846 — — — work function 54, 56, 58, 831-832, 846 — nuclear physical properties 123-124, 126-130, 832, 851 — — changes in properties after irradiation exposure 123, 126-128 — — isotopes of metal 123, 130, 832, 851 — — — mass range 123, 130, 832, 851 — — — total number 123, 130, 832, 851 — — resonance integral for neutron capture 123, 130, 832, 851 — — thermal neutron cross sections 123-124, 832, 851 — — under bombardment 123, 128-130

Index (Physical Properties) — — — by deuterium ions 128129 — — — by fast neutrons 123 — — — by heavy ions 130 — physico-mechanical properties 58, 61-62, 66-69, 81, 83-85, 87-89, 93, 95, 98-99, 106-108, 114-117, 119-122, 127-128, 831-833, 835, 848-849, 859869 — — bulk (compression) modulus 98-99, 106-108, 116-117, 122, 833, 867-868 — — compressive strength 88, 95, 832-833, 848, 859-860 — — Coulomb’s (shear) modulus 98-99, 106-108, 117, 122, 833, 865867 — — density 20-25, 33-34, 831, 835 — — elastic constants 98-99, 106108, 114-117, 121-122, 832-833, 848, 861-869 — — flexural (bending) strength 87, 95, 97, 832-833, 848-849, 859860 — — fracture toughness (critical stress intensity factor) 89, 93, 97 — — hardness characteristics 58, 61-62, 66-69, 81, 83-85, 127-128, 832, 848 — — — in HK scale 85 — — — in HRA scale 85 — — — in HV scale 61-62, 6669, 81, 83-85, 127-128, 832, 848 — — — in Mohs scale 85 — — — microhardness 61-62, 66-69, 81, 83-85, 127-128, 832, 848 — — Poisson’s ratio 98-99, 106108, 116-117, 833, 869 — — sound velocities 119-121 — — — average 119-121 — — — longitudinal 120-121 — — — transversal 120-121

893 — — stiffness coefficients 98-99, 106-108, 121 — — tensile strength 95, 122, 832833, 848-849, 859-860 — — Young’s modulus 98-99, 106108, 114-117, 121-122, 832-833, 848, 860-865 — structures 11-12, 20-27, 29-34, 123, 126, 831, 834-835 — — 2D-molecular MXenes 33 — — chemical bonding 11-12 — — C/Me radii ratio 12 — — crystal system 20-22, 831, 834-835 — — crystal type 20-22, 831, 834835 — — densities 20-25, 33-34, 831, 834-835 — — — bulk density 33-34, 831, 834-835 — — — XRD density 20-25, 33, 831, 834-835 — — homogeneity region 11, 25, 33-34, 83, 85, 116-117, 831, 834835 — — lattice parameters 20-25, 27, 29, 33, 123, 126, 831, 834-835 — — metal-carbon phase diagram 11 — — nanostructures 20, 23, 29-33, 51-52, 56, 67, 159, 161-162, 179, 191-194, 200, 210, 213-214, 218, 222-223, 226, 230, 240, 253, 430, 436, 445-446, 458, 498, 500-501, 504, 510-511, 514, 517, 522-523, 532, 540 — — — nanoparticles 159, 161162, 191, 193-194, 200, 210, 214, 218, 222-223, 226, 230, 253, 445, 458, 501, 504, 523 — — — nanorods 30, 32, 240, 510-511, 532 — — — nanotubes 29, 32, 230 — — — nanowires 31-32, 218, 240

894 — — — thin films/coatings 20, 23, 32, 51-52, 56, 67, 179, 191192, 213-214, 430, 436, 446, 498, 500, 514, 517, 522, 540 — — order-disorder transformation 11-12, 20, 22, 24-25, 123, 498 — — ordered structures 11-12, 2022, 24-25, 32-33 — — slip systems 27 — thermal properties 34, 37-45, 47-49, 831, 833, 837, 839, 841, 843, 857-858 — — boiling point 38, 831, 841, 843 — — character of vaporization 39, 41-44, 831, 843 — — coefficient of linear thermal expansion 47-49, 831, 841 — — melting point 11, 34, 37-38, 831, 841 — — molar enthalpy difference 37, 831, 839 — — molar enthalpy (heat) of atomization from solid state 38 — — molar entropy 37-39, 831, 837 — — molar heat capacity 34, 3741, 831, 837 — — relative thermal expansion 49, 831, 841 — — specific enthalpy difference 831, 839 — — specific heat capacity 37, 831, 837 — — standard heat of formation 37-39, 831, 837 — — standard molar entropy 37-39, 831, 837 — — standard molar heat capacity 37-39, 831, 837 — — thermal conductivity 44-45, 49, 831, 833, 841, 857-858 — — thermodynamic properties 34, 37-39, 831, 837, 839, 841

Index (Physical Properties) U Ultimate compressive strength 88, 95-97, 832-833, 847-849, 859-860 Ultimate tensile strength 95-96, 121, 832833, 847-849, 859-860

V Vaporization rates 41, 44, 831, 842-844 Vapour pressures 39, 41-44, 831, 842-844

Y Young’s moduli 98-119, 121-122, 832833, 847-849, 860-865

Index (Chemical Systems)

A 2Al2O3∙2MgO∙5SiO2 – WC, see WC – 2Al2O3∙2MgO∙5SiO2 3Al2O3∙2SiO2 – WC, see WC – 3Al2O3∙2SiO2 Ag – Be – Cd – Co – Cu – Ni – WC – Zn, see WC – Ag – Be – Cd – Co – Cu – Ni – Zn

Ag – Co – Cu – Mn – Ni – WC – Zn, see WC – Ag – Co – Cu – Mn – Ni – Zn Ag – Co – Cu – Ni – Si – WC – Zn, see WC – Ag – Co – Cu – Ni – Si – Zn Ag – Co – Cu – Ni – WC – Zn, see WC – Ag – Co – Cu – Ni – Zn Ag – Co – Cu – SiC – Ti – WC, see WC – SiC – Ag – Co – Cu – Ti

Ag – BN – Co – Cu – In – Ti – WC, see WC – BN – Ag – Co – Cu – In – Ti

Ag – Co – Cu – WC, see WC – Ag – Co – Cu

Ag – BN – Co – Cu – Ti – WC, see WC – BN – Ag – Co – Cu – Ti

Ag – Co – WC, see WC – Ag – Co

Ag – C – Co – Cr – Cu – Fe – Mn – Mo – Ni – WC – Zn, see WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn Ag – C – Co – Cr – Cu – Fe – Mo – Ti – WC, see WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti

Ag – Cu – Ni – WC, see WC – Ag – Cu – Ni Ag – Cu – WC, see WC – Ag – Cu Ag – Ni – WC, see WC – Ag – Ni Ag – Pb – WC – ZrO2, see WC – ZrO2 – Ag – Pb

Ag – C – Co – Cu – Fe – Mn – WC, see WC – Ag – Co – Cu – (Fe – C – Mn)

Ag – Pb – WC, see WC – Ag – Pb

Ag – C – Co – Cu – Ti – WC, see WC – Ag – C – Co – Cu – Ti

Ag – WC, see WC – Ag

Ag – C – W2C, see W2C – Ag – C Ag – C – WC, see WC – Ag – C Ag – Cd – Co – Cu – Ni – WC – Zn, see WC – Ag – Cd – Co – Cu – Ni – Zn Ag – Cd – Co – Cu – WC – Zn, see WC – Ag – Cd – Co – Cu – Zn Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – WC – Zn, see WC – Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – Zn Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – WC – Zn, see WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti – WC, see WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti Ag – Co – Cu – (Fe – C – Mn) – WC, see WC – Ag – Co – Cu – (Fe – C – Mn)

Ag – WC – Zr, see WC – Ag – Zr Al – (C6H4CH2C6H4OCH2CHOHCH2O)n – Co – WC, see WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – Al – Co Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti – WC, see WC – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti Al – (Fe – C – Cr – Mn – Ni) – Ni – WC, see WC – Al – (Fe – C – Cr – Mn – Ni) – Ni Al – [(CkHl)(CpHq)Si(CH2)]n – Co – SiC – WC, see WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – Al – Co Al – [C6H4(NH)]n – Pb – WC, see WC – [C6H4(NH)]n – Al – Pb Al – Al2O3 – Co – WC, see WC – Al2O3 – Al – Co Al – Al2O3 – Ni – WC – Zn, see WC – Al2O3 – Al – Ni – Zn Al – Al2O3 – WC, see WC – Al2O3 – Al

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 I. L. Shabalin, Ultra-High Temperature Materials IV, https://doi.org/10.1007/978-3-031-07175-1

895

896 Al – B – C – CeO2 – Co – Cr – Fe – Mg – Ni – Si – W – WC – Zn, see WC – CeO2 – Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – WC – Zn, see WC – Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn

Index (Chemical Systems) Al – C – Mg – Si – WC, see WC – Al – C – Mg – Si Al – C – Mg – WC, see WC – Al – C – Mg Al – C – Si – SiC – WC, see WC – SiC – Al – C – Si Al – C – WC, see WC – Al – C

Al – B – Co – Cr – Ni – Si – WC, see WC – Al – B – Co – Cr – Ni – Si

Al – CaF2 – Co – WC, see WC – (BaF2, CaF2) – Al – Co

Al – B – Co – Cr – Ti – V – WC, see WC – Al – B – Co – Cr – Ti – V

Al – Co – Cr – Cu – Fe – Ni – WC, see WC – Al – Co – Cr – Cu – Fe – Ni

Al – B – Cr – Cu – Fe – Ni – Si – WC, see WC – Al – B – Cr – Cu – Fe – Ni – Si

Al – Co – Cr – Fe – Ni – Ti – WC, see WC – Al – Co – Cr – Fe – Ni – Ti

Al – B – Cr – Fe – Ni – WC – Zr, see WC – Al – B – Cr – Fe – Ni – Zr

Al – Co – Cr – Fe – Ni – V – WC – W2C, see WC – W2C – Al – Co – Cr – Fe – Ni – V

Al – B – Cr – Mo – Ni – WC – Zr, see WC – Al – B – Cr – Mo – Ni – Zr Al – B – Fe – WC, see WC – Al – B – Fe Al – B – Ni – WC – Zr, see WC – Al – B – Ni – Zr

Al – Co – Cr – Fe – Ni – WC, see WC – Al – Co – Cr – Fe – Ni Al – Co – Cr – Ni – SiC – WC, see WC – SiC – Al – Co – Cr – Ni

Al – B – Ni – WC, see WC – Al – B – Ni

Al – Co – Cr – Ni – WC, see WC – Al – Co – Cr – Ni

Al – B4C – Cu – Mg – WC, see WC – B4C – Al – Cu – Mg

Al – Co – Cr – WC, see WC – Al – Co – Cr

Al – B4C – Mg – Si – WC, see WC – B4C – Al – Mg – Si

Al – Co – Cr3C2 – WC, see WC – Cr3C2 – Al – Co

Al – BaF2 – Co – WC, see WC – (BaF2, CaF2) – Al – Co

Al – Co – Cu – (Fe – C – Mn) – Ni – WC, see WC – Al – Co – Cu – (Fe – C – Mn) – Ni

Al – BN – Co – Ni – WC, see WC – BN – Al – Co – Ni Al – C – Co – Cu – Fe – Mn – Ni – WC, see WC – Al – C – Co – Cu – Fe – Mn – Ni Al – C – Co – Cu – Fe – Mn – Ni – WC, see WC – Al – Co – Cu – (Fe – C – Mn) – Ni Al – C – Co – Fe – Mn – Ni – Si – Ti – WC, see WC – Co – (Fe – C – Mn – Si) – (Ni – C – Al – Ti) Al – C – Cr – Fe – Mn – Ni – Si – Ti – WC, see WC – Al – C – Cr – Fe – Mn – Ni – Si – Ti and WC – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti Al – C – Cr – Fe – Mn – Ni – WC, see WC – Al – C – Cr – Fe – Mn – Ni and WC – Al – (Fe – C – Cr – Mn – Ni) – Ni Al – C – Cu – Ni – Si – WC, see WC – Al – C – Cu – Ni – Si

Al – Co – Cu – Mg – WC – Zn, see WC – Al – Co – Cu – Mg – Zn Al – Co – Cu – WC, see WC – Al – Co – Cu Al – Co – Ni – WC, see WC – Al – Co – Ni Al – Co – VC – WC, see WC – VC – Al – Co Al – Co – WC – Zn, see WC – Al – Co – Zn Al – Co – WC, see WC – Al – Co Al – Cr – Fe – Mo – Nb – Ni – Ti – WC – W2C, see WC – W2C – Al – Cr – Fe – Mo – Nb – Ni – Ti Al – Cr – Fe – WC, see WC – Al – Cr – Fe Al – Cr – Mo – Ni – WC, see WC – Al – Cr – Mo – Ni Al – Cu – Fe – WC, see WC – Al – Cu – Fe

Index (Chemical Systems)

897

Al – Cu – Mg – Mn – WC, see WC – Al – Cu – Mg – Mn

Al – Mg – WC – Zn, see WC – Al – Mg – Zn

Al – Cu – Mg – Si – WC, see WC – Al – Cu – Mg – Si

Al – Mo – Mo2C – Ni – TiC – TiN – WC, see WC – Mo2C – TiC – TiN – Al – Mo – Ni

Al – Cu – Mg – WC – Zn, see WC – Al – Cu – Mg – Zn

Al – Nb – WC, see WC – Al – Nb

Al – Cu – Mg – WC, see WC – Al – Cu – Mg

Al – Ni – WC –W2C, see WC –W2C – Al – Ni

Al – Cu – Mn – Si – WC, see WC – Al – Cu – Mn – Si

Al – Ni – WC, see WC – Al – Ni

Al – Cu – Nb – Ni – Ti – WC, see WC – Al – Cu – Nb – Ni – Ti Al – Cu – Nb – Ni – WC – Zr, see WC – Al – Cu – Nb – Ni – Zr Al – Cu – Ni – WC – Zr, see WC – Al – Cu – Ni – Zr

Al – Pb – PbO2 – WC, see WC – PbO2 – Al – Pb Al – Pb – WC – ZrO2, see WC – ZrO2–x – Al – Pb Al – Si – SiC – WC, see WC – SiC – Al – Si Al – Si – WC, see WC – Al – Si

Al – Cu – Si – WC, see WC – Al – Cu – Si

Al – Ti – V – WC, see WC – Al – Ti – V

Al – Cu – WC, see WC – Al – Cu

Al – WC – W2C, see WC – W2C – Al

Al – Fe – FeAl – Fe3Al – WC, see WC – FeAl – Fe3Al – Al – Fe

Al – WC, WC – Al

Al – Fe – Mn – WC, see WC – Al – Fe – Mn Al – Fe – Mo – WC, see WC – Al – Fe – Mo Al – Fe – Nb – WC, see WC – Al – Fe – Nb

Al2O3 – B – Cr – Fe – Ni – Si – WC, see WC – Al2O3 – B – Cr – Fe – Ni – Si Al2O3 – C – Cr – Ni – WC, see WC – Al2O3 – C – Cr – Ni Al2O3 – C – Cr3C2 – TiC – VC – WC, see WC – Al2O3 – Cr3C2 – TiC – VC – C

Al – Fe – Ni – WC, see WC – Al – Fe – Ni

Al2O3 – C – TiO2 – WC, see WC – Al2O3 – TiO2 – C

Al – Fe – Ta – WC, see WC – Al – Fe – Ta

Al2O3 – C – WC, see WC – Al2O3 – C

Al – Fe – Ti – WC, see WC – Al – Fe – Ti

Al2O3 – CaF2 – Ni – P – TiC1–x – WC, see WC – Al2O3 – CaF2 – TiC1–x – Ni – P

Al – Fe – TiC – TiN – WC, see WC – TiC – TiN – Al – Fe Al – Fe – V – WC, see WC – Al – Fe – V

Al2O3 – CaF2 – TiC – WC, see WC – Al2O3 – CaF2 – TiC

Al – Fe – WC – Y2O3, see WC – Y2O3 – Al – Fe

Al2O3 – CaO – SiC – WC – Y2O3, see WC – Al2O3 – CaO – SiC – Y2O3

Al – Fe – WC – Zr, see WC – Al – Fe – Zr Al – Fe – WC, see WC – Al – Fe

Al2O3 – CaO – WC – ZrO2, see WC – Al2O3 – CaO – ZrO2

Al – Mg – Mn – Si – WC, see WC – Al – Mg – Mn – Si

Al2O3 – CeO2 – MgO – WC, see WC – Al2O3 – CeO2 – MgO

Al – Mg – MoS2 – WC – Zn, see WC – MoS2 – Al – Mg – Zn

Al2O3 – CeO2 – WC, see WC – Al2O3 – CeO2

Al – Mg – Si – SiC – WC, see WC – SiC – Al – Mg – Si

Al2O3 – Co – Ni – TiC – WC, see WC – Al2O3 – TiC – Co – Ni

Al – Mg – Si – Ti – WC, see WC – Al – Mg – Si – Ti

Al2O3 – Co – TiC – WC, see WC – Al2O3 – TiC – Co

Al – Mg – Si – WC, see WC – Al – Mg – Si

Al2O3 – Co – WC – Y2O3 – ZrO2, see WC – Al2O3 – Y2O3 – ZrO2 – Co

898

Index (Chemical Systems)

Al2O3 – Co – WC, see WC – Al2O3 – Co

Al4C3 – Co – WC, see WC – Al4C3 – Co

Al2O3 – Cr – Cu – WC, see WC – Al2O3 – Cr – Cu

Al4C3 – Fe – Ni – WC, see WC – Al4C3 – Fe – Ni

Al2O3 – Cr – Ni – WC, see WC – Al2O3 – Cr – Ni

Al4C3 – NbC – WC, see WC – Al4C3 – NbC

Al2O3 – Cr3C2 – Ni – WC, see WC – Al2O3 – Cr3C2 – Ni

Al4C3 – Ni – WC, see WC – Al4C3 – Ni

Al2O3 – Cr3C2 – Si3N4 – WC – Y2O3, see WC – Al2O3 – Cr3C2 – Si3N4 – Y2O3

AlB2 – AlN – BN – TiC – WC, see WC – AlB2 – AlN – BN – TiC

Al2O3 – Cr3C2 – TiC – VC – WC, see WC – Al2O3 – Cr3C2 – TiC – VC

AlN – [(CkHl)(CpHq)Si(CH2)]n – Co – SiC – WC1±x, see WC – AlN – [(CkHl)(CpHq)Si(CH2)]n – SiC – Co

Al2O3 – Cr3C2 – WC, see WC – Al2O3 – Cr3C2 Al2O3 – Cu – WC, see WC – Al2O3 – Cu Al2O3 – MgO – WC – ZrO2, see WC – Al2O3 – MgO – ZrO2 Al2O3 – MgO – WC, see WC – Al2O3 – MgO

Al4C3 – WC, see WC – Al4C3

AlN – Al2O3 – Si3N4 – WC – Y2O3, see WC – AlN – Al2O3 – Si3N4 – Y2O3 AlN – B – [(CkHl)(CpHq)Si(CH2)]n – Co – SiC – WC, see WC – AlN – [(CkHl)(CpHq)Si(CH2)]n – SiC – B – Co AlN – Co – WC, see WC – AlN – Co

Al2O3 – Mo2C – WC, see WC – Al2O3 – Mo2C

AlN – Cr3C2 – Mo2C – TiN – WC, see WC – AlN – Cr3C2 – Mo2C – TiN

Al2O3 – Ni – TiC – WC, see WC – Al2O3 – TiC – Ni

AlN – CrN – WC, see WC – AlN – CrN

Al2O3 – Ni – WC, see WC – Al2O3 – Ni

AlN – Mo – Ni – TiC – TiN – WC, see WC – AlN – TiC – TiN – Mo – Ni

Al2O3 – Si3N4 – W2C – Y2O3, see W2C – Al2O3 – Si3N4 – Y2O3

AlN – Si3N4 – WC – Y2O3, see WC – AlN – Si3N4 – Y2O3

Al2O3 – Si3N4 – WC – Y2O3, see WC – Al2O3 – Si3N4 – Y2O3

AlN – TiN – WC, see WC – AlN – TiN

Al2O3 – SiC – TiC – WC, see WC – Al2O3 – SiC – TiC

As – WC, see WC – As

Al2O3 – TiC – W – WC – W2C, see WC – W2C – Al2O3 – TiC – W Al2O3 – TiC – WC, see WC – Al2O3 – TiC Al2O3 – TiO2 – WC, see WC – Al2O3 – TiO2

AlN – WC, see WC – AlN Au – C – Pd – Pt – WC, see WC – Au – C – Pd – Pt Au – C – Pd – WC, see WC – Au – C – Pd Au – Cu – Pt – SiC – Si3N4 – Ti – WC, see WC – SiC – Si3N4 – Au – Cu – Pt – Ti

Al2O3 – VC – WC, see WC – Al2O3 – VC

Au – Pd – Pt – WC, see WC – Au – Pd – Pt

Al2O3 – W – WC, see WC – Al2O3 – W

Au – Pd – WC, see WC – Au – Pd

Al2O3 – W2C, see W2C – Al2O3

Au – Pt – Sn – W2C, see W2C – Au – Pt – Sn

Al2O3 – WC – W2C, see WC – W2C – Al2O3

Au – Sn – WC, see WC – Au – Sn

Al2O3 – WC – Y2O3 – ZrO2, see WC – Al2O3 – Y2O3 – ZrO2

Au – WC, see WC – Au

Al2O3 – WC – Y2O3, see WC – Al2O3 – Y2O3

B

Al2O3 – WC – ZrO2, see WC – Al2O3 – ZrO2

B – [(CkHl)(CpHq)Si(CH2)]n – Co – SiC – WC, see WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – B – Co

Al2O3 – WC, see WC – Al2O3

Index (Chemical Systems)

899

B – C – Co – Cr – Cr3C2 – Cu – Fe – Ni – Si – WC – Zn, see WC – Cr3C2 – B – Co – Cr – Cu – (Fe – C) – Ni – Si – Zn

B – C – Ni – Si – WC – W2C, see WC – W2C – B – C – Ni – Si

B – C – Co – Cr – Fe – Mn – Ni – Si – W – WC – W2C, see WC – W2C – B – C – Co – Cr – Fe – Mn – Ni – Si – W

B – C – WC, see WC – B – C

B – C – Co – Cr – Fe – Mn – Ni – Si – W – WC – W2C, see WC – W2C – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W B – C – Co – Cr – Fe – Mo – WC, see WC – B – C – Co – Cr – Fe – Mo B – C – Co – Cr – Fe – Ni – Si – WC, see WC – B – C – Co – Cr – Fe – Ni – Si

B – C – W2C, see W2C – B – C B – CaF2 – Cr – Fe – Ni – Si – WC, see WC – CaF2 – B – Cr – Fe – Ni – Si B – CeO2 – Co – Cr – Fe – Ni – Si – WC, see WC – CeO2 – B – Co – Cr – Fe – Ni – Si B – Co – Cr – (Fe – C – Mn) – Ni – Si – W – WC – W2C, see WC – W2C – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W

B – C – Co – Cr – Ni – Si – W – W2C, see W2C – B – C – Co – Cr – Ni – Si – W

B – Co – Cr – Cr3C2 – Cu – (Fe – C) – Ni – Si – WC – Zn, see WC – Cr3C2 – B – Co – Cr – Cu – (Fe – C) – Ni – Si – Zn

B – C – Cr – Cu – Fe – Mo – Ni – Si – WC, see WC – B – C – Cr – Cu – Fe – Mo – Ni – Si

B – Co – Cr – Fe – Ni – Si – WC, see WC – B – Co – Cr – Fe – Ni – Si

B – C – Cr – Fe – Mn – Mo – Si – W – WC, see WC – B – C – Cr – Fe – Mn – Mo – Si – W B – C – Cr – Fe – Mn – Ni – Si – WC – W2C, see WC – W2C – B – C – Cr – Fe – Mn – Ni – Si

B – Co – Cr – Fe – WC, see WC – B – Co – Cr – Fe B – Co – Cr – Ni – Si – WC – W2C, see WC – W2C – B – Co – Cr – Ni – Si B – Co – Cr – Ni – Si – WC, see WC – B – Co – Cr – Ni – Si

B – C – Cr – Fe – Mn – Ni – Si – WC, see WC – B – C – Cr – Fe – Mn – Ni – Si

B – Co – Cu – Ni – WC, see WC – B – Co – Cu – Ni

B – C – Cr – Fe – Mn – Ni – Si – WC, see WC – B – Cr – Fe – (Fe – C – Mn – Si) – Ni – Si

B – Co – Fe – Mo – Ni – WC, see WC – B – Co – Fe – Mo – Ni

B – C – Cr – Fe – Ni – Si – W – WC – W2C, see WC – W2C – B – C – Cr – Fe – Ni – Si – W B – C – Cr – Fe – Ni – Si – W – WC, see WC – B – C – Cr – Fe – Ni – Si – W B – C – Cr – Fe – Ni – Si – W2C, see W2C – B – C – Cr – Fe – Ni – Si

B – Co – Fe – Si – WC, see WC – B – Co – Fe – Si B – Co – Ni – TiB2 – WC, see WC – TiB2 – B – Co – Ni B – Co – WC, see WC – B – Co B – Cr – Cr3C2 – Fe – Ni – Si – WC, see WC – Cr3C2 – B – Cr – Fe – Ni – Si

B – C – Cr – Fe – Ni – Si – WC – W2C, see WC – W2C – B – C – Cr – Fe – Ni – Si

B – Cr – Fe – (Fe – C – Mn – Si) – Ni – Si – WC, see WC – B – Cr – Fe – (Fe – C – Mn – Si) – Ni – Si

B – C – Cr – Fe – Ni – Si – WC, see WC – B – C – Cr – Fe – Ni – Si

B – Cr – Fe – Mo – Ni – Si – WC, see WC – B – Cr – Fe – Mo – Ni – Si

B – C – Cr – Ni – Si – WC – W2C, see WC – W2C – B – C – Cr – Ni – Si

B – Cr – Fe – Mo – Si – WC, see WC – B – Cr – Fe – Mo – Si

B – C – Fe – Ni – Si – W – WC – W2C, see WC – W2C – B – C – Fe – Ni – Si – W

B – Cr – Fe – Ni – Si – WC, see WC – B – Cr – Fe – Ni – Si

B – C – Fe – Ni – Si – WC – W2C, see WC – W2C – B – C – Fe – Ni – Si

B – Cr – Fe – Ni – WC, see WC – B – Cr – Fe – Ni

B – C – Mo – WC, see WC – B – C – Mo

B – Cr – Fe – WC, see WC – B – Cr – Fe

900

Index (Chemical Systems)

B – Cr – Mo – Ni3Al – WC – Zr, see WC – Ni3Al – B – Cr – Mo – Zr

B4C – Co – SiC – WC, see WC – B4C – SiC – Co

B – Cr – Ni – Si – Ti – WC, see WC – B – Cr – Ni – Si – Ti

B4C – Co – TiB2 – WC, see WC – B4C – TiB2 – Co

B – Cr – Ni – Si – WC – W2C, see WC – W2C – B – Cr – Ni – Si

B4C – Co – WC – Y2O3, see WC – B4C – Y2O3 – Co

B – Cr – Ni – Si – WC, see WC – B – Cr – Ni – Si

B4C – Co – WC, see WC – B4C – Co

B – Cr – Ni – W – WC, see WC – B – Cr – Ni – W B – Cr – Ni3Al – WC – Zr, see WC – Ni3Al – B – Cr – Zr

B4C – Ni – Si – WC, see WC – B4C – Ni – Si B4C – SiC – WC – ZrB2, see WC – B4C – SiC – ZrB2 B4C – SiC – WC, see WC – B4C – SiC

B – Cu – Fe – Ni – Si – WC, see WC – B – Cu – Fe – Ni – Si

B4C – TiC – WC, see WC – B4C – TiC

B – Fe – Ni – Si – WC, see WC – B – Fe – Ni – Si

B4C – WC – ZrB2, see WC – B4C – ZrB2

B4C – W – WC, see WC – B4C – W

B – Fe3Al – WC, see WC – Fe3Al – B

B4C – WC, see WC – B4C

B – FeAl – WC, see WC – FeAl – B

BaCl2 – NaCl – WC, see WC – BaCl2 – NaCl

B – Mo – Ni – Si – WC, see WC – B – Mo – Ni – Si B – Ni – NiAl – WC, see WC – NiAl – B – Ni

BaF2 – CaF2 – Co – Cu – WC, see WC – BaF2 – CaF2 – Co – Cu Bi – WC, see WC – Bi

B – Ni – Si – WC – W2C, see WC – W2C – B – Ni – Si

BN – C – Cu – Ni – WC, see WC – BN – C – Cu – Ni

B – Ni – Si – WC, see WC – B – Ni – Si

BN – Co – Cr3C2 – WC, see WC – BN – Cr3C2 – Co

B – Ni – WC, see WC – B – Ni B – Ni3Al – WC – Zr, see WC – Ni3Al – B – Zr B – Ni3Al – WC, see WC – Ni3Al – B B – Pt – Si – W2C, see W2C – B – Pt – Si

BN – Co – Ni – Ni2P – WC, see WC – BN – NiPx (Ni3P, Ni2–xP) – Co – Ni BN – Co – Ni – Ni3P – WC, see WC – BN – NiPx (Ni3P, Ni2–xP) – Co – Ni

B – W2C, see W2C – B

BN – Co – WC – Y2O3 – ZrO2, see WC – BN – Y2O3 – ZrO2 – Co

B – WC, see WC – B

BN – Co – WC, see WC – BN – Co

B2O3 – W2C, see W2C – B2O3 B2O3 – WC, see WC – B2O3

BN – Cr – Cu – WC, see WC – BN – Cr – Cu

B4C – BN – Cr – Cu – WC, see WC – B4C – BN – Cr – Cu

BN – Cu – Sn – Ti – WC, see WC – BN – Cu – Sn – Ti

B4C – C – (C6H4COC6H4O)n – WC, see WC – B4C – (C6H4COC6H4O)n – C

BN – Ni – VC – WC, see WC – BN – VC – Ni

B4C – C – Cr – Cr7C3 – Cr23C6 – Fe – Ni – WC – W2C, see WC – W2C – B4C – Cr7C3 – Cr23C6 – C – Cr – Fe – Ni

BN – Si3N4 – WC – Y2O3, see WC – BN – Si3N4 – Y2O3

B4C – C – Fe – Mn – Mo – Ni – WC – Zr, see WC – B4C – (Fe – C – Mn) – Mo – Ni – Zr

Br2 – WC, see WC – Br2

B4C – C – WC, see WC – B4C – C

BN – WC, see WC – BN

C (C2F4)n – WC, see WC – (C2F4)n

Index (Chemical Systems) (C2H4)n – WC, see WC – (C2H4)n (C6H4CH2C6H4OCH2CHOHCH2O)n – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt) – WC, see WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt) (C6H4CH2C6H4OCH2CHOHCH2O)n – SiO2 – WC, see WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – SiO2 (C6H4CH2C6H4OCH2CHOHCH2O)n – WC, see WC – (C6H4CH2C6H4OCH2CHOHCH2O)n

901 [C6H4 C2(NH)]n – WC, see WC – [C6H4 C2(NH)]n [C6H7O2(OH)3]n – WC, see WC – [C6H7O2(OH)3]n [CH2C(CH3)COO(CH3)]n – [(C6H5)CHCH2]m – WC, see WC – [CH2C(CH3)COO(CH3)]n – [(C6H5)CHCH2]m 3CaO∙Al2O3 – 4CaO∙Al2O3∙Fe2O3 – 2CaO∙SiO2 – 3CaO∙SiO2 – WC, see WC – 3CaO∙Al2O3 – 4CaO∙Al2O3∙Fe2O3 – 2CaO∙SiO2 – 3CaO∙SiO2 C – (C2F4)n – WC, see WC – (C2F4)n – C

(C6H4COC6H4O)n – WC, see WC – (C6H4COC6H4O)n

C – (C6H4COC6H4O)n – WC, see WC – (C6H4COC6H4O)n – C

(C8H6O2)n – Co – Fe – Ge – WC, see WC – (C8H6O2)n – Co – Fe – Ge

C – (Fe – C – Cr – Mn – Nb) – WC, see WC – C – (Fe – C – Cr – Mn – Nb)

(CF2CF2)n(CF2CFCF3)m – Mo – Ni – WC, see WC – (CF2CF2)n(CF2CFCF3)m – Mo – Ni

C – [C6H3(CN)2OC6H4C(CH3)2C6H4OC6H3 (CN)2]n – WC, see WC – [C6H3(CN)2OC6H4C(CH3)2C6H4OC6H3 (CN)2]n – C

[(C2H4)n–(CH2CHOCOCH3)m] – WC, see WC – [(C2H4)n–(CH2CHOCOCH3)m] [(C6H10O5)7(OH)(CH2)4O2CHOH (C6H10O5)7(OH)O2]n – WC, see WC – [(C6H10O5)7(OH)(CH2)4O2CHOH (C6H10O5)7(OH)O2]n [(C6H3)(CN)2O(C6H4)C(CH3)2(C6H4)O (C6H4)(CN)2]n – WC, see WC – [(C6H3)(CN)2O(C6H4)C(CH3)2(C6H4)O (C6H4)(CN)2]n

C – Co – Cr – Cr3C2 – Mn – Si – W – WC, see WC – Cr3C2 – C – Co – Cr – Mn – Si – W C – Co – Cr – Cr7C3 – Fe – Mn – WC, see WC – Cr7C3 – C – Co – Cr – Fe – Mn C – Co – Cr – Cu – Fe – La2O3 –Mn – Ni – Si – WC, see WC – La2O3 – Co – Cu – (Fe – C – Cr – Mn – Ni – Si)

[(C6H4O)2CO(C6H4)]n – WC, see WC – [(C6H4O)2CO(C6H4)]n

C – Co – Cr – Cu – Fe – Mn – Ni – WC – Zn, see WC – Co – Cu – (Fe – C – Cr – Mn) – Ni – Zn

[(CkHl)(CpHq)Si(CH2)]n – Co – SiC – WC, see WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – Co

C – Co – Cr – Cu – Fe – Mo – V – W – WC, see WC – Cu – (Fe – C – Co – Cr – Mo – V – W)

[(CkHl)ON(CpHq)O]n – Co – WC, see WC – [(CkHl)ON(CpHq)O]n – Co

C – Co – Cr – Cu – Fe – N – Nb – Ni – Ta – Ti – WC, see WC – C – Co – Cr – Cu – Fe – N – Nb – Ni – Ta – Ti

[C(CH3)COOH]n – WC, see WC – [C(CH3)COOH]n [C4H2(NH)]n – WC, see WC – [C4H2(NH)]n [C6H4(NH)]n – CeO2 – WC, see WC – [C6H4(NH)]n – CeO2 [C6H4(NH)]n – Pb – WC, see WC – [C6H4(NH)]n – Pb [C6H4(NH)]n – WC, see WC – [C6H4(NH)]n

C – Co – Cr – Cu – Fe – Ni – Si – WC – Zn, see WC – Co – Cu – (Fe – C – Cr – Si) – Ni – Zn C – Co – Cr – Fe – Mn – Mo – Nb – Ni – Si – WC, see WC – Co – (Fe – C – Cr – Mn – Mo – Ni – Si) – (Fe – C – Mn – Nb – Ni) C – Co – Cr – Fe – Mn – Ni – Ti – WC, see WC – Co – (Fe – C – Cr – Mn) – Ni – Ti

902

Index (Chemical Systems)

C – Co – Cr – Fe – Mn – Ni – WC, see WC – Co – (Fe – C – Cr – Mn) – Ni

C – Co – Fe – Mn – Nb – Ni – WC, see WC – Co – (Fe – C – Mn – Nb – Ni)

C – Co – Cr – Fe – Mn – Si – WC, see WC – Co – (Fe – C – Cr – Mn – Si)

C – Co – Fe – Mn – Si – WC, see WC – Co – (Fe – C – Mn – Si)

C – Co – Cr – Fe – Mn – WC – W2C, see WC – W2C – Co – (Fe – C – Cr – Mn)

C – Co – Fe – Mo – Ni – WC, see WC – (Fe – C – Co – Mo – Ni)

C – Co – Cr – Fe – Mo – Ni – V – W – WC, see WC – Co – (Fe – C – Cr – Mo – Ni – V – W)

C – Co – Fe – N – WC, see WC – C – Co – Fe – N

C – Co – Cr – Fe – Mo – Si – V – WC, see WC – Co – (Fe – C – Cr – Mo – Si – V)

C – Co – Fe – WC, see WC – Co – (Fe – C) C – Co – N – WC, see WC – C – Co – N

C – Co – Cr – Fe – Mo – V – W – WC, see WC – Co – (Fe – C – Cr – Mo – V – W)

C – Co – NbN – WC, see WC – NbN – C – Co

C – Co – Cr – Fe – Mo – V – WC, see WC – Co – (Fe – C – Cr – Mo – V) and WC – (Fe – C – Co – Cr – Mo – V)

C – Co – Ni – TiC – WC, see WC – TiC – C – Co – Ni

C – Co – Cr – Fe – WC, see WC – Co – (Fe – C – Cr) C – Co – Cr – Mn – Mo – Ni – Si – WC, see WC – Co – (Co – C – Cr – Mn – Mo – Ni – Si) C – Co – Cr – WC – W2C, see WC – W2C – C – Co – Cr C – Co – Cr3C2 – TiC – TiN – Mo – Ni – WC, see WC – Cr3C2 – TiC – TiN – C – Co – Mo – Ni C – Co – Cr7C3 – TiC – WC, see WC – Cr7C3 – TiC – C – Co C – Co – CrB2 – W2B5 – WC, see WC – CrB2 – W2B5 – C – Co C – Co – CrB2 – WC, see WC – CrB2 – C – Co

C – Co – Pd – WC, see WC – C – Co – Pd C – Co – TiC – WC, see WC – TiC – C – Co C – Co – W2B5 – WC, see WC – W2B5 – C – Co C – Co – W2C, see W2C – C – Co C – Co – WC – W2C, see WC – W2C – C – Co C – Co – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – C – Co C – Co – WC, see WC – C – Co C – Co3O4 – Fe2O3 – NiO – WC, see WC – Co3O4 – Fe2O3 – NiO – C C – Co3O4 – N – WC, see WC – Co3O4 – C –N

C – Co – Cu – Fe – Mn – WC, see WC – Co – Cu – (Fe – C – Mn)

C – Cr – Cr3C2 – Fe – Mn – Mo – Ni – Si – WC, see WC – Cr3C2 – (Fe – C – Cr – Mn – Ni – Si) – Mo

C – Co – Cu – Fe – Ni – WC, see WC – C – Co – Cu – Fe – Ni

C – Cr – Cr3C2 – Fe – Ni – WC, see WC – Cr3C2 – (Fe – C – Cr – Ni)

C – Co – Cu – Fe – Sn – WC, see WC – C – Co – Cu – Fe – Sn

C – Cr – Cu – Fe – Ni – WC, see WC – Cu – (Fe – C – Cr – Ni)

C – Co – Cu – Fe – WC, see WC – Co – Cu – (Fe – C)

C – Cr – Fe – La – Ni – Si – WC, see WC – C – Cr – Fe – La – Ni – Si

C – Co – Cu – TiC – WC, see WC – TiC – C – Co – Cu C – Co – Fe – FeNi – Mn – Si – WC, see WC – FeNi – Co – (Fe – C – Mn – Si)

C – Cr – Fe – Mn – Mo – Ni – Si – WC, see WC – (Fe – C – Cr – Mn – Mo – Ni – Si) and WC – (Fe – C – Cr – Mn – Mo – Ni – Si) – Ni – Si

C – Co – Fe – Mn – Nb – Ni – Si – WC – Y, see WC – Co – (Fe – C – Mn – Si) – (Ni – C – Fe – Nb – Y)

C – Cr – Fe – Mn – Nb – WC, see WC – C – (Fe – C – Cr – Mn – Nb) and WC – (Fe – C – Cr – Mn – Nb)

Index (Chemical Systems)

903

C – Cr – Fe – Mn – Ni – Si – WC – W2C, see WC – W2C – (Fe – C – Cr – Mn – Ni – Si)

C – Cu – Mn – Ni – Pb – Sn – WC – Zn, see WC – C – Cu – Mn – Ni – Pb – Sn – Zn

C – Cr – Fe – Mn – Ni – Si – WC, see WC – (Fe – C – Cr – Mn – Ni – Si)

C – Cu – Pt – WC, see WC – C – Cu – Pt

C – Cr – Fe – Mn – Ni – WC, see WC – (Fe – C – Cr – Mn – Ni)

C – Cu2O – WC, see WC – Cu2O – C

C – Cr – Fe – Mn – W – WC, see WC – (Fe – C – Cr – Mn – W) C – Cr – Fe – Mo – Nb – Ti – V – WC, see WC – (Fe – C – Cr – Mo – Nb – Ti – V) C – Cr – Fe – Mo – Ni – WC, see WC – (Fe – C – Cr – Mo – Ni) C – Cr – Fe – Mo – Si – V – WC, see WC – (Fe – C – Cr – Mo – Si – V) C – Cr – Fe – Mo – V – WC – W2C, see WC – W2C – (Fe – C – Cr – Mo – V) C – Cr – Fe – Ni – Si – WC – W2C, see WC – W2C – C – Cr – Fe – Ni – Si

C – Cu – WC, see WC – C – Cu C – Fe – La2O3 – WC, see WC – La2O3 – C – Fe C – Fe – Mn – Si – W – WC, see WC – (Fe – C – Mn – Si) – W C – Fe – Mn – Si – WC – W2C, see WC – W2C – (Fe – C – Mn – Si) C – Fe – Mn – Si – WC, see WC – (Fe – C – Mn – Si) C – Fe – Mn – WC, see WC – (Fe – C – Mn) C – Fe – N – WC, see WC – C – Fe – N C – Fe – Ni – WC, see WC – (Fe – C – Ni)

C – Cr – Fe – Ni – Si – WC, see WC – C – Cr – Fe – Ni – Si

C – Fe – Pd – WC, see WC – C – Fe – Pd

C – Cr – Fe – Ni – WC, see WC – C – Cr – Fe – Ni and WC – (Fe – C – Cr – Ni) and WC – (Fe – C – Cr) – Ni

C – Fe – SiC – WC, see WC – SiC – C – Fe

C – Cr – Fe – V – W – WC, see WC – (Fe – C – Cr – V – W)

C – Fe – W2C, see W2C – C – Fe and W2C – (Fe – C)

C – Cr – Fe – W – WC, see WC – (Fe – C – Cr) – W

C – Fe – WC, see WC – C – Fe and WC – (Fe – C)

C – Cr – Fe – WC, see WC – Cr – (Fe – C) and WC – (Fe – C – Cr)

C – Fe2N – FeWO4 – WC, see WC – Fe2N – FeWO4 – C

C – Cr – Fe –Mn – Ni – Si – Ti – WC – W2C, see WC – W2C – (Fe – C – Cr – Mn – Ni – Si – Ti)

C – Fe2O3 – NiO – WC, see WC – Fe2O3 – NiO – C

C – Cr – W2C, see W2C – C – Cr C – Cr – WC, see WC – C – Cr C – Cr3C2 – Fe – Mn – WC, see WC – Cr3C2 – (Fe – C – Mn) C – Cr3C2 – Ni – WC, see WC – Cr3C2 – C – Ni C – Cr3C2 – Y2O3 – ZrO2 – Ni – WC, see WC – Cr3C2 – Y2O3 – ZrO2 – C – Ni C – CrN – WC, see WC – CrN – C C – CrSi2 – WC, see WC – CrSi2 – C C – Cu – Fe – Mo – Ni – WC, see WC – C – Cu – Fe – Mo – Ni

C – Fe – Si – WC, see WC – (Fe – C – Si)

C – Fe – Ti – WC, see WC – (Fe – C) – Ti

C – Fe2O3 – WC, see WC – Fe2O3 – C C – Fe3C – WC, see WC – Fe3C – C C – FePt – FeS – N – WC, see WC – FePt – FeS – C – N C – H – O – WC – W2C, see WC – W2C – C–H–O C – H – WC – W2C, see WC – W2C – C – H C – H – WC, see WC – C – H C – Hf – W2C, see W2C – C – Hf C – Hf – WC, see WC – C – Hf C – Ir – W2C, see W2C – C – Ir C – Ir – WC, see WC – C – Ir C – Mg – WC, see WC – C – Mg

904 C – Mn – Rh – W – WC – W2C, see WC – W2C – C – Mn – Rh – W C – Mn – WC, see WC – C – Mn C – Mo – W2C, see W2C – C – Mo

Index (Chemical Systems) C – Ni – WC, see WC – C – Ni C – Ni2P –WC, see WC – NiPx (Ni3P, Ni2P) – C

C – Mo – WC, see WC – C – Mo

C – Ni3P – WC, see WC – NiPx (Ni3P, Ni2P) – C

C – Mo2C – N – WC, see WC – Mo2C – C –N

C – NiO – SiC – WC, see WC – NiO – SiC –C

C – Mo2C – Pd – WC, see WC – Mo2C – C – Pd

C – Os – W2C, see W2C – C – Os

C – Mo2C – Pt – WC, see WC – Mo2C – C – Pt

C – Pd – Pt – WC, see WC – C – Pd – Pt

C – Mo2C – SiC – WC, see WC – Mo2C – SiC – C C – Mo2C – WC – W2C, see WC – W2C – Mo2C – C C – Mo2C – WC, see WC – Mo2C – C C – MoC – WC, see WC – MoC – C C – MoS2 – WC, see WC – MoS2 – C

C – Os – WC, see WC – C – Os C – Pd – W – WC – W2C, see WC – W2C – C – Pd – W C – Pd – WC, see WC – C – Pd C – Pt – Rh – WC, see WC – C – Pt – Rh C – Pt – Ru – WC, see WC – C – Pt – Ru C – Pt – Sn – WC, see WC – C – Pt – Sn C – Pt – TiC – WC, see WC – TiC – C – Pt

C – N – Ni – WC, see WC – C – N – Ni

C – Pt – TiO2 – WC, see WC – TiO2 – C – Pt

C – N – P – W – W2C, see W2C – C – N – P–W

C – Pt – W2C, see W2C – C – Pt

C – N – P – W2C, see W2C – C – N – P

C – Pt – WC – W2C, see WC – W2C – C – Pt

C – N – Pt – WC – W24O68, see WC – W24O68 – C – N – Pt

C – Pt – WC, see WC – C – Pt

C – N – W2C – WN, see W2C – WN – C – N

C – Pu – W2C, see W2C – C – Pu

C – Pu – U – WC, see WC – C – Pu – U

C – N – W2C – WP, see W2C – WP – C – N

C – Pu – WC, see WC – C – Pu

C – N – W2C, see W2C – C – N

C – Re – WC, see WC – C – Re

C – N – WC – W2C, see WC – W2C – C – N

C – Rh – W2C, see W2C – C – Rh

C – N – WC, see WC – C – N

C – Ru – W2C, see W2C – C – Ru

C – Nb – W2C, see W2C – C – Nb

C – Ru – WC, see WC – C – Ru

C – Nb – WC, see WC – C – Nb

C – Sc – W2C, see W2C – C – Sc

C – Ni – P – WC, see WC – C – Ni – P

C – Sc – WC, see WC – C – Sc

C – Ni – Pt – WC, see WC – C – Ni – Pt

C – Si – W2C, see W2C – C – Si

C – Ni – Si – WC, see WC – C – Ni – Si

C – Si – WC, see WC – C – Si

C – Ni – Ti – WC, see WC – C – Ni – Ti

C – SiC – WC, see WC – SiC – C

C – Ni – W2C, see W2C – C – Ni

C – Sn – WC, see WC – C – Sn

C – Ni – WC – W2C, see WC – W2C – C – Ni

C – Ta – W2C, see W2C – C – Ta

C – Ni – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – C – Ni

C – Tc – W2C, see W2C – C – Tc

C – Ni – WC – ZrO2, see WC – ZrO2 – C – Ni

C – Re – W2C, see W2C – C – Re

C – Rh – WC, see WC – C – Rh

C – Ta – WC, see WC – C – Ta C – Tc – WC, see WC – C – Tc C – Th – W2C, see W2C – C – Th

Index (Chemical Systems)

905

C – Th – WC, see WC – C – Th

C6H6 – WC, see WC – C6H6

C – Ti – W2C, see W2C – C – Ti

CaF2 – Co – WC, see WC – CaF2 – Co

C – Ti – WC, see WC – C – Ti

CaO – WC – ZrO2, see WC – CaO – ZrO2

C – TiC – WC – ZrC, see WC – TiC – ZrC –C

CaO – WC, see WC – CaO

C – TiC – WC, see WC – TiC – C

CdS – TiO2 – WC, see WC – CdS – TiO2

C – U – W2C, see W2C – C – U

CdS – WC, see WC – CdS

C – U – WC, see WC – C – U

Ce – Co – Mo2C – Ni – TaC – TiC – TiN – WC, see WC – Mo2C – TaC – TiC – TiN – Ce – Co – Ni

C – V – W2C, see W2C – C – V C – V – WC, see WC – C – V C – VC – WC – ZrC, see WC – VC – ZrC –C

Cd – WC, see WC – Cd

Ce – Co – WC, see WC – Ce – Co

C – W – W2C, see W2C – C – W

Ce – Co – WC, see WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y)

C – W – WC – W2C, see WC – W2C – C – W

Ce – Cu – Fe – Si – WC, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si

C – W – WC – WN, see WC – WN – C – W

Ce – Fe – Ni – WC, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

C – W – WC, see WC – C – W

Ce – Ni – WC, see WC – Ce – Ni and WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

C – W2C – Zr, see W2C – C – Zr C – W2C, see W2C – C

CeB6 – Co – WC, see WC – CeB6 – Co

C – WC – W2C – WN, see WC – W2C – WN – C

CeO2 – Co – MgSiN2 – Si3N4 – WC – Y2O3, see WC – CeO2 – MgSiN2 – Si3N4 – Y2O3 – Co

C – WC – W2C, see WC – W2C – C

CeO2 – Co – WC, see WC – CeO2 – Co

C – WC – WN, see WC – WN – C

CeO2 – Cr3C2 – Ni – WC, see WC – CeO2 – Cr3C2 – Ni

C – WC – WS2, see WC – WS2 – C C – WC – Zr, see WC – C – Zr C – WC – ZrB2, see WC – ZrB2 – C C – WC, see WC – C C12H22O11 – Co3O4 – Fe2O3 – NiO – WC, see WC – C12H22O11 – Co3O4 – Fe2O3 – NiO C12H22O11 – Fe2O3 – NiO – WC, see WC – C12H22O11 – Fe2O3 – NiO C12H22O11 – Fe2O3 – WC, see WC – C12H22O11 – Fe2O3 C2H4 – WC, see WC – C2H4 C2H6 – W2C, see W2C – C2H6 C2H6 – WC, see WC – C2H6 C35H28N2O7 – WC, see WC – C35H28N2O7 C3N4 – Ni – W2C, see W2C – C3N4 – Ni C3N4 – P – WC, see WC – C3N4 – P C3N4 – W2C, see W2C – C3N4 C3N4 – WC, see WC – C3N4

CeO2 – Fe – Ni – WC, see WC – CeO2 – Fe – Ni CeO2 – MgO – Ni – WC, see WC – CeO2 – MgO – Ni CeO2 – MgSiN2 – Si3N4 – WC – Y2O3, see WC – CeO2 – MgSiN2 – Si3N4 – Y2O3 CeO2 – Ni – WC, see WC – CeO2 – Ni CeO2 – Pb – WC – ZrO2, see WC – CeO2 – ZrO2 – Pb CeO2 – WC – Y2O3 – ZrO2, see WC – CeO2 – Y2O3 – ZrO2 CH3OH/CH3OD – WC, see WC – CH3OH/CH3OD CH4 – H2 – WC, see WC – CH4 – H2 CH4 – W2C, see W2C – CH4 CH4 – WC, see WC – CH4 Cl2 – W2C, see W2C – Cl2 Cl2 – WC, see WC – Cl2

906

Index (Chemical Systems)

CnH2n+2 (n = 20÷40) – WC, see WC – CnH2n+2 (n = 20÷40)

Co – Cr – W – WC, see WC – Co – Cr – W

Co – (SiO2 – B2O3 – Na2O – K2O) – WC, see WC – (SiO2 – B2O3 – Na2O – K2O) – Co

Co – Cr – WC, see WC – Co – Cr

Co – (SiO2 – PbO – K2O – Na2O) – WC, see WC – (SiO2 – PbO – K2O – Na2O) – Co Co – CeO2 – WC, see WC – LnOy (La2O3, CeO2, Y2O3) – Co Co – CoPy – WC, see WC – CoPy – Co Co – Cr – Cr3C2 – Fe – Ni – WC, see WC – Cr3C2 – Co – Cr – Fe – Ni Co – Cr – Cr3C2 – Mo – Ni – WC, see WC – Cr3C2 – Co – Cr – Mo – Ni Co – Cr – Cr3C2 – Ni – WC, see WC – Cr3C2 – Co – Cr – Ni Co – Cr – Cr3C2 – WC, see WC – Cr3C2 – Co – Cr Co – Cr – Cu – Fe – Nb – Ni – Ta – Ti – WC, see WC – Co – Cr – Cu – Fe – Nb – Ni – Ta – Ti Co – Cr – Cu – Fe – Ni – WC, see WC – Co – Cr – Cu – Fe – Ni Co – Cr – Fe – Mn – Ni – WC, see WC – Co – Cr – Fe – Mn – Ni Co – Cr – Fe – Mo – Nb – Ni – WC, see WC – Co – Cr – Fe – Mo – Nb – Ni Co – Cr – Fe – Mo – Ni – WC, see WC – Co – Cr – Fe – Mo – Ni Co – Cr – Fe – Nb – Ni – Ta – Ti – WC, see WC – Co – Cr – Fe – Nb – Ni – Ta – Ti Co – Cr – Fe – Ni – WC, see WC – Co – Cr – Fe – Ni Co – Cr – Fe – Si – Ti – WC, see WC – Co – Cr – Fe – Si – Ti Co – Cr – Mo – Ni – WC, see WC – Co – Cr – Mo – Ni Co – Cr – Ni – TiC – WC, see WC – TiC – Co – Cr – Ni Co – Cr – Ni – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – Co – Cr – Ni Co – Cr – Ni – WC, see WC – Co – Cr – Ni Co – Cr – Ta – WC, see WC – Co – Cr – Ta

Co – Cr2N – WC, see WC – Cr2N – Co Co – Cr3C2 – Cr2N – VC –WC, see WC – Cr3C2 – Cr2N – VC – Co Co – Cr3C2 – Cr7C3 – WC, see WC – Cr3C2 – Cr7C3 – Co Co – Cr3C2 – Fe – Mo2C – Ni – WC, see WC – Cr3C2 – Mo2C – Co – Fe – Ni Co – Cr3C2 – Fe – Ni – WC, see WC – Cr3C2 – Co – Fe – Ni Co – Cr3C2 – La2O3 – VC – WC, see WC – Cr3C2 – La2O3 – VC – Co Co – Cr3C2 – La2O3 – WC, see WC – Cr3C2 – La2O3 – Co Co – Cr3C2 – Mo2C – WC, see WC – Cr3C2 – Mo2C – Co Co – Cr3C2 – Mo2C –Ni – TaC – TiC – TiN– WC, see WC – Cr3C2 – Mo2C – TaC – TiC – TiN – Co – Ni Co – Cr3C2 – Ni – TiAl3 – WC, see WC – Cr3C2 – TiAl3 – Co – Ni Co – Cr3C2 – Ni – WC, see WC – Cr3C2 – Co – Ni Co – Cr3C2 – TiB2 – TiC – TiN – WC, see WC – Cr3C2 – TiB2 – TiC – TiN – Co Co – Cr3C2 – TiB2 – VC – WC, see WC – Cr3C2 – TiB2 – VC – Co Co – Cr3C2 – TiB2 – WC, see WC – Cr3C2 – TiB2 – Co Co – Cr3C2 – TiC – VC – WC, see WC – Cr3C2 – TiC – VC – Co Co – Cr3C2 – TiC – WC, see WC – Cr3C2 – TiC – Co Co – Cr3C2 – TiN – WC, see WC – Cr3C2 – TiN – Co Co – Cr3C2 – VC – WC, see WC – Cr3C2 – VC – Co Co – Cr3C2 – W – WC, see WC – Cr3C2 – Co – W Co – Cr3C2 – WC – Y2O3, see WC – Cr3C2 – Y2O3 – Co Co – Cr3C2 – WC, see WC – Cr3C2 – Co Co – CrB2 – WC, see WC – CrB2 – Co Co – CrSi2 – WC, see WC – CrSi2 – Co

Index (Chemical Systems)

907

Co – Cu – Fe – Ni – WC, see WC – Co – Cu – Fe – Ni

Co – Ga – Mn – Ni – WC, see WC – Co – Ga – Mn – Ni

Co – Cu – Fe – WC, see WC – Co – Cu – Fe

Co – Ga – WC, see WC – Co – Ga

Co – Cu – La2O3 – WC, see WC – La2O3 – Co – Cu Co – Cu – Mn – Ni – Sn – WC – Zn, see WC – Co – Cu – Mn – Ni – Sn – Zn Co – Cu – Mn – Ni – WC – Zn, see WC – Co – Cu – Mn – Ni – Zn Co – Cu – Mn – Ni – WC, see WC – Co – Cu – Mn – Ni

Co – HfC – Mo2C – TaC – TiC – TiN – WC, see WC – HfC – Mo2C – TaC – TiC – TiN – Co Co – In – WC, see WC – Co – In Co – La – WC, see WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y) Co – La2O3 – VC – WC, see WC – La2O3 – VC – Co Co – La2O3 – WC, see WC – La2O3 – Co

Co – Cu – Mn – WC – Zn, see WC – Co – Cu – Mn – Zn

Co – La2O3 – WC, see WC – LnOy (La2O3, CeO2, Y2O3) – Co

Co – Cu – Mn – WC, see WC – Co – Cu – Mn

Co – Mn – Ni – WC, see WC – Co – Mn – Ni

Co – Cu – MoS2 – WC, see WC – MoS2 – Co – Cu

Co – Mn – WC, see WC – Co – Mn

Co – Cu – Ni – Si – WC – Zn, see WC – Co – Cu – Ni – Si – Zn

Co – Mo – NbC – Ni – TaC – TiC – TiN – VC − WC, see WC – NbC – TaC – TiC – TiN – VC − Co – Mo – Ni

Co – Cu – Ni – Si – WC, see WC – Co – Cu – Ni – Si

Co – Mo – Ni – PbO – WC, see WC – PbO – Co – Mo – Ni

Co – Cu – Ni – WC – Zn, see WC – Co – Cu – Ni – Zn

Co – Mo – Ni – TiC – TiN – WC, see WC – TiC – TiN – Co – Mo – Ni

Co – Cu – Ni – WC, see WC – Co – Cu – Ni

Co – Mo – Ni – WC, see WC – Co – Mo – Ni

Co – Cu – WC – Zn, see WC – Co – Cu – Zn

Co – Mo – WC, see WC – Co – Mo

Co – Cu – WC, see WC – Co – Cu Co – Dy – WC, see WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y) Co – Fe – Mo – Ni – WC, see WC – Co – Fe – Mo – Ni Co – Fe – Ni – TiC – TiN – WC, see WC – TiC – TiN – Co – Fe – Ni Co – Fe – Ni – TiC – W – WC, see WC – TiC – Co – Fe – Ni – W

Co – Mo2C – NbC – Ni – TiC – TiN – WC, see WC – Mo2C – NbC – TiC – TiN – Co – Ni Co – Mo2C – Ni – Si3N4 – TiC – TiN – WC, see WC – Mo2C – Si3N4 – TiC – TiN – Co – Ni Co – Mo2C – Ni – TaC – TiC – TiN – VC – WC, see WC – Mo2C – TaC – TiC – TiN – VC – Co – Ni

Co – Fe – Ni – VC – WC, see WC – VC – Co – Fe – Ni

Co – Mo2C – Ni – TaC – TiC – TiN – WC, see WC – Mo2C – TaC – TiC – TiN – Co – Ni

Co – Fe – Ni – WC, see WC – Co – Fe – Ni

Co – Mo2C – Ni – TaC – TiC – WC, see WC – Mo2C – TaC – TiC – Co – Ni

Co – Fe – Si – WC, see WC – Co – Fe – Si

Co – Mo2C – Ni – TiC – TiN – VC – WC, see WC – Mo2C – TiC – TiN – VC – Co – Ni

Co – Fe – TiAl – TiB2 – WC – Y2O3 – ZrO2, see WC – TiAl – TiB2 – Y2O3 – ZrO2 – Co – Fe Co – Fe – WC, see WC – Co – Fe

Co – Mo2C – Ni – TiC – TiN – WC, see WC – Mo2C – TiC – TiN – Co – Ni

908

Index (Chemical Systems)

Co – Mo2C – Ni – TiC – WC, see WC – Mo2C – TiC – Co – Ni

Co – P – WC, see WC – CoPy – Co

Co – Mo2C – Ni – TiN – WC, see WC – Mo2C – TiN – Co – Ni

Co – Pr – WC, see WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y)

Co – Mo2C – Ni – WC, see WC – Mo2C – Co – Ni

Co – Re – VC – VN – WC, see WC – VC – VN – Co – Re

Co – Mo2C – TiC – TiN – WC, see WC – Mo2C – TiC – TiN – Co

Co – Re – WC, see WC – Co – Re

Co – Mo2C – TiN – WC, see WC – Mo2C – TiN – Co Co – Mo2C – WC, see WC – Mo2C – Co Co – MoC – TiC – WC, see WC – MoC – TiC – Co

Co – Pd – WC, see WC – Co – Pd

Co – Ru – VC – WC, see WC – VC – Co – Ru Co – Ru – WC, see WC – Co – Ru Co – S – WC, see WC – Co – S Co – Se – WC, see WC – Co – Se

Co – MoS2 – WC, see WC – MoS2 – Co

Co – Si – WC, see WC – Co – Si

Co – N – WC, see WC – Co – N

Co – SiC – Ti – WC, see WC – SiC – Co – Ti

Co – Nb – Ta – Ti – WC, see WC – Co – Nb – Ta – Ti

Co – SiC – WC, see WC – SiC – Co

Co – Nb – WC, see WC – Co – Nb

Co – Sn – WC, see WC – Co – Sn

Co – NbC – TaC – TiC – TiN – WC, see WC – NbC – TaC – TiC – TiN – Co

Co – Ta – WC, see WC – Co – Ta

Co – NbC – TaC – TiC – WC, see WC – NbC – TaC – TiC – Co Co – NbC – TaC – WC, see WC – NbC – TaC – Co Co – NbC – VC – WC, see WC – NbC – VC – Co Co – NbC – WC, see WC – NbC – Co Co – Nd – WC, see WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y) Co – Ni – Ni2P – WC, see WC – NiPx (Ni3P, Ni2P) – Co – Ni Co – Ni – Ni3P – WC, see WC – NiPx (Ni3P, Ni2P) – Co – Ni Co – Ni – Re – WC, see WC – Co – Ni – Re

Co – TaC – TiC – WC, see WC – TaC – TiC – Co Co – TaC – WC, see WC – TaC – Co Co – Ti – WC, see WC – Co – Ti Co – Ti3SiC2 – WC, see WC – Ti3SiC2 – Co Co – TiB2 – TiC – WC, see WC – TiB2 – TiC – Co Co – TiB2 – WC, see WC – TiB2 – Co Co – TiC – TiN – VC – VN – WC, see WC – TiC – TiN – VC – VN – Co Co – TiC – TiN – WC, see WC – TiC – TiN – Co Co – TiC – VC – WC – ZrC, see WC – TiC – VC – ZrC – Co Co – TiC – W2C, see W2C – TiC – Co

Co – Ni – SiC – WC, see WC – SiC – Co – Ni

Co – TiC – WC – ZrC, see WC – TiC – ZrC – Co

Co – Ni – TaC – TiC – TiN – WC, see WC – TaC – TiC – TiN – Co – Ni

Co – TiC – WC, see WC – TiC – Co

Co – Ni – TiC – TiN – WC, see WC – TiC – TiN – Co – Ni

Co – V – WC, see WC – Co – V

Co – Ni – TiC – WC, see WC – TiC – Co – Ni Co – Ni – WC, see WC – Co – Ni Co – NiAl – WC, see WC – NiAl – Co Co – Os – WC, see WC – Co – Os

Co – TiN – WC, see WC – TiN – Co Co – VC – VN – WC, see WC – VC – VN – Co Co – VC – WC – ZrC, see WC – VC – ZrC – Co Co – VC – WC, see WC – VC – Co

Index (Chemical Systems)

909

Co – W – WC – W2C, see WC – W2C – Co –W

Cr – Fe – Mo – WC, see WC – Cr – Fe – Mo

Co – W – WC, see WC – Co – W

Cr – Fe – Nb – WC, see WC – Cr – Fe – Nb

Co – W2C, see W2C – Co Co – WB – WC, see WC – WB – Co Co – WC – W2C, see WC – W2C – Co Co – WC – WN, see WC – WN – Co Co – WC – Y, see WC – Co – Y and WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y)

Cr – Fe – Ni – TiC – WC, see WC – TiC – Cr – Fe – Ni Cr – Fe – Ni – WC, see WC – Cr – Fe – Ni Cr – Fe – Si – WC, see WC – Cr – Fe – Si Cr – Fe – Ta – WC, see WC – Cr – Fe – Ta

Co – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – Co

Cr – Fe – Ti – WC, see WC – Cr – Fe – Ti

Co – WC – Y2O3, see WC – Y2O3 – Co

Cr – Fe – WC, see WC – Cr – Fe

Co – WC – Zn, see WC – Co – Zn

Cr – Fe – Zr – WC, see WC – Cr – Fe – Zr

Co – WC – ZrO2, see WC – ZrO2 – Co

Cr – Fe3Al – WC, see WC – Fe3Al – Cr

Co – WC, see WC – Co CO – WC, see WC – CO

Cr – Mn – Ni – WC, see WC – Cr – Mn – Ni

Co – Y2O3 – WC, see WC – LnOy (La2O3, CeO2, Y2O3) – Co

Cr – Mo – Ni – WC, see WC – Cr – Mo – Ni

Co(OH)2 – WC, see WC – Co(OH)2

Cr – Mo – V – WC, see WC – Cr – Mo – V

CO2 – WC, see WC – CO2 Co3O4 – Fe2O3 – NiO – WC, see WC – Co3O4 – Fe2O3 – NiO Co3O4 – WC, see WC – Co3O4 CoF3 – WC, see WC – CoF3 CoO – WC, see WC – CoO Cr – Cr3C2 – Ni – TiC – TiN –WC, see WC – Cr3C2 – TiC – TiN – Cr – Ni

Cr – Fe – V – WC, see WC – Cr – Fe – V

Cr – NbC – Ni – TiC – VC – WC, see WC – NbC – TiC – VC – Cr – Ni Cr – Ni – W – WC, see WC – Cr – Ni – W Cr – Ni – WC – WS2, see WC – WS2 – Cr – Ni Cr – Ni – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – Cr – Ni Cr – Ni – WC, see WC – Cr – Ni

Cr – Cr3C2 – Ni – WC, see WC – Cr3C2 – Cr – Ni

Cr – W2C, see W2C – Cr

Cr – Cu – Fe – WC, see WC – Cr – Cu – Fe

Cr23C6 – WC, see WC – Cr23C6

Cr – Cu – WC – ZrO2, see WC – ZrO2 – Cr – Cu

Cr – WC, see WC – Cr Cr2O3 – WC, see WC – Cr2O3

Cr – Cu – WC, see WC – Cr – Cu

Cr3C – Fe3C – Mn3C – W2C, see W2C – Cr3C – Fe3C – Mn3C

Cr – Fe – Mn – Mo – Ni – Ti – WC, see WC – Cr – Fe – Mn – Mo – Ni – Ti

Cr3C2 – Cr7C3 – Ni – WC – W2C, see WC – W2C – Cr3C2 – Cr7C3 – Ni

Cr – Fe – Mn – Mo – Ni – WC, see WC – Cr – Fe – Mn – Mo – Ni

Cr3C2 – Cr7C3 – WC, see WC – Cr3C2 – Cr7C3

Cr – Fe – Mn – WC, see WC – Cr – Fe – Mn

Cr3C2 – Fe – Mo2C – Ni – WC, see WC – Cr3C2 – Mo2C – Fe – Ni

Cr – Fe – Mo – Nb – Ni – Ti – WC – W2C, see WC – W2C – Cr – Fe – Mo – Nb – Ni – Ti

Cr3C2 – Fe – Ni – WC, see WC – Cr3C2 – Fe – Ni

Cr – Fe – Mo – Ni – WC, see WC – Cr – Fe – Mo – Ni

Cr3C2 – FeAl – WC, see WC – Cr3C2 – FeAl

Cr3C2 – Fe – WC, see WC – Cr3C2 – Fe

910 Cr3C2 – HfC – Mo2C – TiC – TiN – WC, see WC – Cr3C2 – HfC – Mo2C – TiC – TiN Cr3C2 – MgO – TiN – WC, see WC – Cr3C2 – MgO – TiN Cr3C2 – MgO – VC – WC, see WC – Cr3C2 – MgO – VC Cr3C2 – MgO – WC, see WC – Cr3C2 – MgO Cr3C2 – Mo – Ni – SiC – TiC – TiN – WC, see WC – Cr3C2 – SiC – TiC – TiN – Mo – Ni

Index (Chemical Systems) Cr3C2 – WC (γ, δ), see WC (γ, δ) – Cr3C2 Cr7C3 – WC, see WC – Cr7C3 CrB2 – WC, see WC – CrB2 CrN – WC, see WC – CrN Cs – WC, see WC – Cs Cu – Dy – Fe – Si – WC, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si Cu – Fe – La – Si – WC, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si Cu – Fe – Mn – WC, see WC – Cu – Fe – Mn

Cr3C2 – Mo – Ni – TaC – TiC – WC, see WC – Cr3C2 – TaC – TiC – Mo – Ni

Cu – Fe – Mo – WC, see WC – Cu – Fe – Mo

Cr3C2 – Mo – Ni – TiC – TiN – VC – WC, see WC – Cr3C2 – TiC – TiN – VC – Mo – Ni

Cu – Fe – Nb – WC, see WC – Cu – Fe – Nb

Cr3C2 – Mo – Ni – TiC – TiN – WC, see WC – Cr3C2 – TiC – TiN – Mo – Ni Cr3C2 – Mo2C – Ni – TiC – WC, see WC – Cr3C2 – Mo2C – TiC – Ni Cr3C2 – Mo2C – SiC – WC, see WC – Cr3C2 – Mo2C – SiC Cr3C2 – Mo2C – VC – WC, see WC – Cr3C2 – Mo2C – VC Cr3C2 – Mo2C – WC, see WC – Cr3C2 – Mo2C Cr3C2 – Ni – TiC – TiN – WC, see WC – Cr3C2 – TiC – TiN – Ni Cr3C2 – Ni – TiC – WC, see WC – Cr3C2 – TiC – Ni

Cu – Fe – Nd – Si – WC, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si Cu – Fe – Ni – WC, see WC – Cu – Fe – Ni Cu – Fe – Pr – Si – WC, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si Cu – Fe – Si – WC – Y, see WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si Cu – Fe – Ta – WC, see WC – Cu – Fe – Ta Cu – Fe – Ti – WC, see WC – Cu – Fe – Ti Cu – Fe – V – WC, see WC – Cu – Fe – V Cu – Fe – WC – Zr, see WC – Cu – Fe – Zr Cu – Fe – WC, see WC – Cu – Fe

Cr3C2 – Ni – WC – ZrO2, see WC – Cr3C2 – ZrO2 – Ni

Cu – Hf – WC, see WC – Cu – Hf

Cr3C2 – Ni – WC, see WC – Cr3C2 – Ni

Cu – In – Mn – Ni – WC – Zn, see WC – Cu – In – Mn – Ni – Zn

Cr3C2 – Pt – TiC – WC, see WC – Cr3C2 – TiC – Pt Cr3C2 – Si3N4 – VC – WC – Y2O3, see WC – Cr3C2 – Si3N4 – VC – Y2O3 Cr3C2 – SiC – VC – WC, see WC – Cr3C2 – SiC – VC Cr3C2 – SiC – WC, see WC – Cr3C2 – SiC Cr3C2 – TiB2 – TiC – TiN – WC, see WC – Cr3C2 – TiB2 – TiC – TiN Cr3C2 – TiC – WC, see WC – Cr3C2 – TiC Cr3C2 – W2C, see W2C – Cr3C2 Cr3C2 – WC – Y2O3 – ZrO2, see WC – Cr3C2 – Y2O3 – ZrO2

Cu – Mn – Ni – P – WC, see WC – Cu – Mn – Ni – P Cu – Mn – Ni – Pb – Sn – WC – Zn, see WC – Cu – Mn – Ni – Pb – Sn – Zn Cu – Mn – Ni – Si – WC, see WC – Cu – Mn – Ni – Si Cu – Mn – Ni – Ti – V – WC – Zr, see WC – Cu – Mn – Ni – Ti – V – Zr Cu – Mn – Ni – WC – Zn, see WC – Cu – Mn – Ni – Zn Cu – Mn – Ni – WC, see WC – Cu – Mn – Ni Cu – Mn – WC, see WC – Cu – Mn

Index (Chemical Systems)

911

Cu – Mo – WC – Zr, see WC – Cu – Mo – Zr

F

Cu – Mo – WC, see WC – Cu – Mo

F2 – WC, see WC – F2

Cu – Mo2C – WC – Zr, see WC – Mo2C – Cu – Zr

Fe – Fe3C – W – WC, see WC – Fe3C – Fe –W

Cu – MoS2 – WC, see WC – MoS2 – Cu

Fe – FeAl2 –WC, see WC – FeAl2 – Fe

Cu – Ni – Si – Sn – Ti – WC – Zr, see WC – Cu – Ni – Si – Sn – Ti – Zr

Fe – La – Ni – WC, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

Cu – Ni – Sn – Ti – WC, see WC – Cu – Ni – Sn – Ti

Fe – La – WC, see WC – Fe – La

Cu – Ni – Sn – WC – W2C, see WC – W2C – Cu – Ni – Sn Cu – Ni – W – WC – W2C, see WC – W2C – Cu – Ni – W Cu – Ni – W – WC, see WC – Cu – Ni – W Cu – Ni – WC, see WC – Cu – Ni Cu – P – Sn – WC, see WC – Cu – P – Sn Cu – Pd – Si – WC, see WC – Cu – Pd – Si Cu – Si – WC, see WC – Cu – Si

F2 – W2C, see W2C – F2

Fe – Mn – Mo – WC, see WC – Fe – Mn – Mo Fe – Mn – Nb – WC, see WC – Fe – Mn – Nb Fe – Mn – Ni – WC, see WC – Fe – Mn – Ni Fe – Mn – Ta – WC, see WC – Fe – Mn – Ta Fe – Mn – Ti – WC, see WC – Fe – Mn – Ti

Cu – SiO2 – W2C, see W2C – SiO2 – Cu

Fe – Mn – V – WC, see WC – Fe – Mn – V

Cu – SiO2 – WC – WN, see WC – SiO2 – WN – Cu

Fe – Mn – WC – Zr, see WC – Fe – Mn – Zr

Cu – SiO2 – WC, see WC – SiO2 – Cu

Fe – Mn – WC, see WC – Fe – Mn

Cu – Ti – WC – Zr, see WC – Cu – Ti – Zr

Fe – Mo – Nb – WC, see WC – Fe – Mo – Nb

Cu – W – WC, see WC – Cu – W Cu – W2C, see W2C – Cu Cu – WC – W2C, see WC – W2C – Cu Cu – WC – WN, see WC – WN – Cu Cu – WC – Zn, see WC – Cu – Zn Cu – WC – Zr, see WC – Cu – Zr Cu – WC, see WC – Cu Cu3N – TiN – WC, see WC – Cu3N – TiN Cu51Zr14 – Mo2C – WC, see WC – (Cu51Zr14, CuZr2) – Mo2C CuZr2 – Mo2C – WC, see WC – (Cu51Zr14, CuZr2) – Mo2C CuZr2 – WC, see WC – CuZr2

Fe – Mo – Ni – WC, see WC – Fe – Mo – Ni Fe – Mo – Ta – WC, see WC – Fe – Mo – Ta Fe – Mo – Ti – WC, see WC – Fe – Mo – Ti Fe – Mo – V – WC, see WC – Fe – Mo – V Fe – Mo – WC – Zr, see WC – Fe – Mo – Zr Fe – Mo – WC, see WC – Fe – Mo Fe – Mo2C – Ni – WC, see WC – Mo2C – Fe – Ni Fe – Mo2C – W2C, see W2C – Mo2C – Fe

D Dy – Fe – Ni – WC, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni Dy – Ni – WC, see WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

Fe – N – WC, see WC – Fe – N Fe – Nb – Ni – WC, see WC – Fe – Nb – Ni Fe – Nb – Ta – WC, see WC – Fe – Nb – Ta

912

Index (Chemical Systems)

Fe – Nb – Ti – WC, see WC – Fe – Nb – Ti

Fe3Al – WC, see WC – Fe3Al

Fe – Nb – V – WC, see WC – Fe – Nb – V

Fe3O4 – WC, see WC – Fe3O4

Fe – Nb – WC – Zr, see WC – Fe – Nb – Zr

Fe5Si3 – WC, see WC – Fe5Si3

Fe – Nb – WC, see WC – Fe – Nb Fe – Nd – Ni – WC, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni Fe – Ni – Pr– WC, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni Fe – Ni – Si – WC, see WC – Fe – Ni – Si

Fe3C – WC, see WC – Fe3C

FeAl – Fe2B – WC, see WC – FeAl – Fe2B FeAl – WC – Y2O3, see WC – FeAl – Y2O3 FeAl – WC, see WC – FeAl FeAl3 – WC, see WC – FeAl3 FexN – WC, see WC – FexN

Fe – Ni – Ta – WC, see WC – Fe – Ni – Ta Fe – Ni – Ti – WC, see WC – Fe – Ni – Ti

G

Fe – Ni – V – WC, see WC – Fe – Ni – V

Ga – WC, see WC – Ga

Fe – Ni – W – W2B – WC, see WC – (W2B, WB) – Fe – Ni – W

Ge – WC, see WC – Ge

Fe – Ni – W – WB – WC, see WC – (W2B, WB) – Fe – Ni – W

H

Fe – Ni – WC – Y, see WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

H(OCH2CH2)nOH – La2O3 – WC, see WC – H(OCH2CH2)nOH – La2O3 H2 – H2O – WC, see WC – H2 – H2O

Fe – Ni – WC – Zr, see WC – Fe – Ni – Zr

H2/D2 – W2C, see W2C – H2/D2

Fe – Ni – WC, see WC – Fe – Ni

H2/D2 – WC, see WC – H2/D2

Fe – Ru – WC, see WC – Fe – Ru

H2CO – WC, see WC – H2CO

Fe – Si – WC, see WC – Fe – Si

H2O – O2 – WC, see WC – H2O – O2

Fe – Ta – Ti – WC, see WC – Fe – Ta – Ti

H2O – WC, see WC – H2O

Fe – Ta – V – WC, see WC – Fe – Ta – V

H2S – WC, see WC – H2S

Fe – Ta – WC – Zr, see WC – Fe – Ta – Zr

HCN – WC, see WC – HCN

Fe – Ta – WC, see WC – Fe – Ta

Hf – W2C, see W2C – Hf

Fe – Ti – V – WC, see WC – Fe – Ti – V

Hf – WC, see WC – Hf

Fe – Ti – WC – Zr, see WC – Fe – Ti – Zr Fe – Ti – WC, see WC – Fe – Ti

HfB2 – HfO2 – WC, see WC – HfB2 – HfO2

Fe – TiB2 – WC, see WC – TiB2 – Fe

HfB2 – SiC – WC, see WC – HfB2 – SiC

Fe – TiC – WC, see WC – TiC – Fe

HfB2 – WC, see WC – HfB2

Fe – V – WC – Zr, see WC – Fe – V – Zr

HfC – Mo2C – Ni – TaC – TiC – TiN – WC, see WC – HfC – Mo2C – TaC – TiC – TiN – Ni

Fe – V – WC, see WC – Fe – V Fe – VC – WC, see WC – VC – Fe Fe – W2C, see W2C – Fe

HfC – NbC – WC, see WC – HfC – NbC

Fe – WC – W2C, see WC – W2C – Fe

HfC – Ni – TiC – TiN – WC, see WC – HfC – TiC – TiN – Ni

Fe – WC – Y2O3, see WC – Y2O3 – Fe

HfC – Ni – WC, see WC – HfC – Ni

Fe – WC – Zr, see WC – Fe – Zr

HfC – TaC – WC, see WC – HfC – TaC

Fe – WC, see WC – Fe

HfC – TiC – WC, see WC – HfC – TiC

Fe(OH)3 – WC, see WC – Fe(OH)3

HfC – VC – WC, see WC – HfC – VC

Fe2O3 – WC, see WC – Fe2O3

HfC – W2C, see W2C – HfC

Index (Chemical Systems)

913

HfC – WC (γ, δ), see WC (γ, δ) – HfC

Mn – Ni – WC, see WC – Mn – Ni

HfC – ZrC – WC, see WC – HfC – ZrC HfO2 – WC, see WC – HfO2

Mn – Rh – W – WC – W2C, see WC – W2C – Mn – Rh – W

Hg – WC, see WC – Hg

Mn – V – WC, see WC – Mn – V Mn – W2C, see W2C – Mn

I

Mn – WC, see WC – Mn

I2 – WC, see WC – I2

Mn(OH)2 – WC, see WC – Mn(OH)2

In – WC, see WC – In

Mn15C4 – WC, see WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

Ir – W2C, see W2C – Ir Ir – WC, see WC – Ir

Mn23C6 – WC, see WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

K

Mn3C – WC, see WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

K – Na – WC, see WC – K – Na KCl – LiCl – WC, see WC – KCl – LiCl

Mn5C2 – WC, see WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

KCl – NaCl – Na2WO4 – WC, see WC – KCl – NaCl – Na2WO4

Mn7C3 – WC, see WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6)

KCl – NaCl – WC, see WC – KCl – NaCl

MnO2 – PbO2 – WC – ZrO2, see WC – MnO2 – PbO2 – ZrO2

KNO3 – NaNO3 – WC, see WC – KNO3 – NaNO3 KOH – NaOH – WC, see WC – KOH – NaOH L La – Ni – WC, see WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni La – WC, see WC – La La2O3 – MgO – WC, see WC – La2O3 – MgO La2O3 – Ni – WC, see WC – La2O3 – Ni La2O3 – WC, see WC – La2O3

MnO2 – WC, see WC – MnO2 MnS – WC, see WC – MnS Mo – Mo2C – Ni – SiC – TiC – TiN – WC, see WC – Mo2C – SiC – TiC – TiN – Mo – Ni Mo – Ni – TaC – TiC – TiN – WC – ZrC, see WC – TaC – TiC – TiN – ZrC – Mo – Ni Mo – Ni – TaC – TiC – WC, see WC – TaC – TiC – Mo – Ni Mo – Ni – TiB2 – TiC – TiN – WC, see WC – TiB2 – TiC – TiN – Mo – Ni

LaAlO3 – WC, see WC – LaAlO3

Mo – Ni – TiB2 – TiC – WC, see WC – TiB2 – TiC – Mo – Ni

LaB6 – Ni3Al – WC, see WC – LaB6 – Ni3Al

Mo – Ni – TiB2 – WC, see WC – TiB2 – Mo – Ni

LaB6 – WC, see WC – LaB6

Mo – Ni – TiC – TiN – VC – WC, see WC – TiC – TiN – VC – Mo – Ni

LiV3O8 – WC, see WC – LiV3O8 M Mg – WC, see WC – Mg MgO – Ni – WC, see WC – MgO – Ni MgO – Pd – WC – ZrO2, see WC – MgO – ZrO2 – Pd

Mo – Ni – TiC – TiN – WC, see WC – TiC – TiN – Mo – Ni Mo – Ni – TiC – WC, see WC – TiC – Mo – Ni Mo – Ni – W – WC, see WC – Mo – Ni – W

MgO – W2C, see W2C – MgO

Mo – Ni – WC – W2C, see WC – W2C – Mo – Ni

MgO – WC, see WC – MgO

Mo – Ni – WC, see WC – Mo – Ni

914

Index (Chemical Systems)

Mo – Ni3Al – TiC – TiN – WC, see WC – Ni3Al – TiC – TiN – Mo

Na2SO4 – WC, see WC – Na2SO4

Mo – Ni3Al – TiC – WC, see WC – Ni3Al – TiC – Mo

Nb – W2C, see W2C – Nb

Mo – W – W2C, see W2C – Mo – W

NaOH – WC, see WC – NaOH Nb – WC, see WC – Nb

Mo – W2C, see W2C – Mo

Nb2C – Ta2C – W2C, see W2C – Nb2C – Ta2C

Mo – WC – W2C, see WC – W2C – Mo

Nb2C – W2C, see W2C – Nb2C

Mo – WC, see WC – Mo

Nb2O5 – WC, see WC – Nb2O5

Mo2C – Ni – TaC – TiC – TiN – WC, see WC – Mo2C – TaC – TiC – TiN – Ni

NbC – NbN – WC, see WC – NbC – NbN

Mo2C – Ni – TiC – TiN – VC – WC, see WC – Mo2C – TiC – TiN – VC – Ni Mo2C – Ni – TiC – TiN – WC, see WC – Mo2C – TiC – TiN – Ni

NbC – Ni – TiC – TiN – WC, see WC – NbC – TiC – TiN – Ni NbC – TaC – WC, see WC – NbC – TaC NbC – TiC – WC, see WC – NbC – TiC

Mo2C – Ni – TiC – WC, see WC – Mo2C – TiC – Ni

NbC – UC – WC, see WC – NbC – UC

Mo2C – Ni – WC, see WC – Mo2C – Ni

NbC – W2C, see W2C – NbC

Mo2C – SiC – WC, see WC – Mo2C – SiC

NbC – WC – ZrC, see WC – NbC – ZrC

Mo2C – TiC – TiN – VC – WC, see WC – Mo2C – TiC – TiN – VC

NbC – WC (γ, δ), see WC (γ, δ) – NbC

Mo2C – W2C, see W2C – Mo2C

NbC – VC – WC, see WC – NbC – VC

Nd – Ni – WC, see WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

Mo2C – WC – W2C, see WC – W2C – Mo2C

Nd2Fe14B – WC, see WC – Nd2Fe14B

Mo2C – WC, see WC – Mo2C

Ni – Ni2P – W – WC, see WC – NiPx (Ni3P, Ni2P) – Ni – W

MoB – MoC – WB – WC, see WC – MoB – MoC – WB MoC – MoN – WC – WN, see WC – MoC – MoN – WN

NH3 – WC, see WC – NH3

Ni – Ni2P – WC, see WC – NiPx (Ni3P, Ni2P) – Ni

MoC – SiO2 – WC, see WC – MoC – SiO2

Ni – Ni3P – W – WC, see WC – NiPx (Ni3P, Ni2P) – Ni – W

MoC – TiC – TiN – WC, see WC – MoC – TiC – TiN

Ni – Ni3P – WC – W2C, see WC – W2C – Ni3P – Ni

MoC (α, γ, η) – WC (γ, δ), see WC (γ, δ) – MoC (α, γ, η)

Ni – Ni3P – WC, see WC – NiPx (Ni3P, Ni2P) – Ni

MoC (α, η) – W2C, see W2C – MoC (α, η) MoS2 – Ni – WC, see WC – MoS2 – Ni

Ni – NiAl – NiB – WC, see WC – NiAl – NiB – Ni

MoS2 – WC, see WC – MoS2

Ni – P – WC, see WC – Ni – P Ni – Pb – Pt – WC, see WC – Ni – Pb – Pt

N

Ni – Pd – WC, see WC – Ni – Pd

(Na,Ca)(Al,Mg)6(Si4O10)3(OH)6⸱nH2O – WC – W2C, see WC – W2C – (Na,Ca)(Al,Mg)6(Si4O10)3(OH)6⸱nH2O

Ni – Pr – WC, see WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

N2 – W2C, see W2C – N2

Ni – Re – WC, see WC – Ni – Re

N2 – WC, see WC – N2

Ni – Si – Ti – WC, see WC – Ni – Si – Ti

Na2S2O8 – WC – Y2O3 – ZrO2, see WC – Na2S2O8 – Y2O3 – ZrO2

Ni – Si – WC, see WC – Ni – Si

Ni – Pt – WC, see WC – Ni – Pt

Ni – SiC – WC, see WC – SiC – Ni

Index (Chemical Systems)

915

Ni – Sn – WC, see WC – Ni – Sn

NO – WC, see WC – NO

Ni – TaC – TiC – TiN – WC, see WC – TaC – TiC – TiN – Ni

Np – WC, see WC – Np

Ni – Ti – WC, see WC – Ni – Ti

O

Ni – TiB2 – TiC – WC, see WC – TiB2 – TiC – Ni

O2 – W2C, see W2C – O2

Ni – TiB2 – WC, see WC – TiB2 – Ni Ni – TiC – TiN – WC – ZrC, see WC – TiC – TiN – ZrC – Ni Ni – TiC – TiN – WC, see WC – TiC – TiN – Ni

O2 – WC, see WC – O2 Os – W2C, see W2C – Os Os – WC, see WC – Os P

Ni – TiC – VC – WC, see WC – TiC – VC – Ni

Pb – WC – ZrO2, see WC – ZrO2 – Pb

Ni – TiC – WC, see WC – TiC – Ni

PbO2 – WC, see WC – PbO2

Ni – TiH2 – WC, see WC – TiH2 – Ni

Pd – W2C, see W2C – Pd

Ni – V – WC, see WC – Ni – V

Pd – WC, see WC – Pd

Ni – VC – WC, see WC – VC – Ni

Pd3Au – WC, see WC – Pd3Au

Ni – W – WC – Y2O3, see WC – Y2O3 – Ni –W

Pt – Ru – TiC – WC, see WC – TiC – Pt – Ru

Ni – W – WC, see WC – Ni – W Ni – W2C, see W2C – Ni

Pt – Ru – W – WC – WO2 – WO3, see WC – WO2 – WO3 – Pt – Ru – W

Ni – WC – W2C, see WC – W2C – Ni

Pt – Ru – WC, see WC – Pt – Ru

Ni – WC – WS2, see WC – WS2 – Ni

Pt – TiC –WC, see WC – TiC – Pt

Ni – WC – Y, see WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni

Pt – TiO2 – WC, see WC – TiO2 – Pt

Ni – WC – Y2O3 – ZrO2, see WC – Y2O3 – ZrO2 – Ni

Pb – WC, see WC – Pb

Pt – W – WC – W2C, see WC – W2C – Pt –W Pt – W2C, see W2C – Pt

Ni – WC – Zn, see WC – Ni – Zn

Pt – WC – W2C, see WC – W2C – Pt

Ni – WC – ZrC, see WC – ZrC – Ni

Pt – WC – WO3, see WC – WO3 – Pt

Ni – WC – ZrO2, see WC – ZrO2 – Ni

Pt – WC, see WC – Pt

Ni – WC, see WC – Ni

Pu – Re – U – WC, see WC – Pu – Re – U

Ni(OH)2 – WC, see WC – Ni(OH)2

Pu – U – WC, see WC – Pu – U

Ni2P – WC, see WC – NiPx (Ni3P, Ni2P)

Pu – W2C, see W2C – Pu

Ni3Al – TiC – WC, see WC – Ni3Al – TiC

Pu – WC, see WC – Pu

Ni3Al – WC – W2C, see WC – W2C – Ni3Al

PuC – UC – WC, see WC – PuC – UC

Ni3Al – WC, see WC – Ni3Al

PuC – WC, see WC – PuC PuC2 – WC, see WC – PuC2

Ni3P – WC, see WC – NiPx (Ni3P, Ni2P) NiAl – Ni3Al – WC, see WC – NiAl – Ni3Al NiAl – WC, see WC – NiAl NiAl3 – TiC – WC, see WC – NiAl3 – TiC NiAl3 – WC, see WC – NiAl3 NiO – WC, see WC – NiO

R Re – W2C, see W2C – Re Re – WC, see WC – Re Rh – W2C, see W2C – Rh Rh – WC, see WC – Rh

916

Index (Chemical Systems)

Ru – W2C, see W2C – Ru

T

Ru – WC, see WC – Ru

Ta – W2C, see W2C – Ta Ta – WC, see WC – Ta

S

Ta2C – V2C – W2C, see W2C – Ta2C – V2C

(SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt) – WC, see WC – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt)

Ta2C – W2C, see W2C – Ta2C

(SiO2 – MeI2O – B2O3 – MeIIO) – WC, see WC – (SiO2 – MeI2O – B2O3 – MeIIO)

Ta2C – WC, see WC – Ta2C Ta2O5 – WC, see WC – Ta2O5 TaC – TiC – WC, see WC – TaC – TiC

2SiO2∙Al2O3∙Na2O∙xH2O – WC – W2C, see WC – W2C – 2SiO2∙Al2O3∙Na2O∙xH2O

TaC – VC – WC, see WC – TaC – VC

2SiO2∙Al2O3∙Na2O∙xH2O – WC, see WC – 2SiO2∙Al2O3∙Na2O∙xH2O

TaC – WC – ZrC, see WC – TaC – ZrC

S – WC, see WC – S

Tc – W2C, see W2C – Tc

Sb – WC, see WC – Sb

Tc – WC, see WC – Tc

Sc – W2C, see W2C – Sc

Th – W2C, see W2C – Th

Sc – WC, see WC – Sc

Th – WC, see WC – Th

ScC – WC (γ, δ), see WC (γ, δ) – ScC

ThC – W2C, see W2C – ThC

Se – WC, see WC – Se

ThC – WC, see WC – ThC

Si – SiC – WC – ZrB2, see WC – SiC – ZrB2 – Si

ThC2 – WC, see WC – ThC2

Si – SiC – WC, see WC – SiC – Si

TaC – W2C, see W2C – TaC TaC – WC (γ, δ), see WC (γ, δ) – TaC

ThO2 – W2C, see W2C – ThO2

Si – W2C, see W2C – Si

Ti – TiB2 – WC – WN, see WC – TiB2 – WN – Ti

Si – WC, see WC – Si

Ti – TiB2 – WC, see WC – TiB2 – Ti

Si3N4 – W2C, see W2C – Si3N4

Ti – W2C, see W2C – Ti

Si3N4 – WC, see WC – Si3N4

Ti – WC, see WC – Ti

SiC – TiC – WC, see WC – SiC – TiC

Ti2O3 – WC, see WC – Ti2O3

SiC – VC – WC, see WC – SiC – VC

TiAl – TiB2 – WC, see WC – TiAl – TiB2

SiC – W – W2C, see W2C – SiC – W

TiAl – WC, see WC – TiAl

SiC – W2C, see W2C – SiC

TiAl3 – WC, see WC – TiAl3

SiC – WC – W2C, see WC – W2C – SiC SiC – WC – WSi2, see WC – SiC – WSi2

TiB2 – TiC – TiN – WC, see WC – TiB2 – TiC – TiN

SiC – WC – ZrB2, see WC – SiC – ZrB2

TiB2 – WC, see WC – TiB2

SiC – WC – ZrC, see WC – SiC – ZrC

TiC – TiN – WC, see WC – TiC – TiN

SiC – WC, see WC – SiC SiO – WC, see WC – SiO

TiC – TiNi – Ti2Ni – WC, see WC – TiC – TiNi – Ti2Ni

SiO2 – W2C, see W2C – SiO2

TiC – VC – WC, see WC – TiC – VC

SiO2 – WC – W2C, see WC – W2C – SiO2

TiC – W – W2C, see W2C – TiC – W

SiO2 – WC, see WC – SiO2

TiC – W2C, see W2C – TiC

Sn – WC, see WC – Sn

TiC – WC – W2C, see WC – W2C – TiC

SnO2 – WC – W2C, see WC – W2C – SnO2

TiC – WC – Y2O3 – ZrO2, see WC – TiC – Y2O3 – ZrO2 TiC – WC – ZrC, see WC – TiC – ZrC

Index (Chemical Systems)

917

TiC – WC (γ, δ), see WC (γ, δ) – TiC

W – WC – W2C, see WC – W2C – W

TiN – WC, see WC – TiN

W – WC – WN, see WC – WN – W

TiNi – WC, see WC – TiNi

W – WC, see WC – W

TiO2 – TinO2n–1 (n = 4÷6) – WC – W2C, see WC – W2C – TiO2 – TinO2n–1 (n = 4÷6)

W2B – W2C, see W2C – W2B

TiO2 – WC – W2C – ZrO2, see WC – W2C – TiO2 – ZrO2

W2B5 – WC, see WC – W2B5

TiO2 – WC – W2C, see WC – W2C – TiO2 TiO2 – WC, see WC – TiO2 Tl – WC, see WC – Tl WC – TiC – TiN – Y2O3 – ZrO2, see WC – TiC – TiN – Y2O3 – ZrO2

W2B – WC, see WC – W2B W2C – (Fe – C), 373 W2C – Ag – C, 133 W2C – Al2O3, 455 W2C – Al2O3 – Si3N4 – Y2O3, 458 W2C – Au – Pt – Sn, 159 W2C – B, 160-161

U

W2C – B – C, 161-162

U – W2C, see W2C – U

W2C – B – C – Co – Cr – Ni – Si – W, 163

U – WC, see WC – U

W2C – B – C – Cr – Fe – Ni – Si, 170

UC – WC – ZrC, see WC – UC – ZrC

W2C – B – Pt – Si, 179

UC – WC, see WC – UC

W2C – B2O3, 463

UC2 – W2C, see W2C – UC2

W2C – C, 193-194

UC2 – WC, see WC – UC2

W2C – C – Co, 200-201 W2C – C – Cr, 205

V

W2C – C – Fe, 210-211

V – W2C, see W2C – V

W2C – C – Hf, 214

V – WC, see WC – V

W2C – C – Ir, 214-215

V2C – W2C, see W2C – V2C

W2C – C – Mo, 217

V2O3 – WC, see WC – V2O3

W2C – C – N, 218

V2O5 – WC, see WC – V2O5

W2C – C – N – P, 218

VC – W2C, see W2C – VC

W2C – C – N – P – W, 218

VC – WC – W2C – W2B, see WC – W2C – VC – (W2B, WB)

W2C – C – Nb, 219-220

VC – WC – W2C – WB, see WC – W2C – VC – (W2B, WB)

W2C – C – Os, 224-225

VC – WC – W2C, see WC – W2C – VC

W2C – C – Pu, 231

VC – WC – Y2O3 – ZrO2, see WC – VC – Y2O3 – ZrO2

W2C – C – Re, 231-232

VC – WC – ZrC, see WC – VC – ZrC VC – WC (γ, δ), see WC (γ, δ) – VC VO – WC, see WC – VO W W – W2B – W2C, see W2C – W2B – W W – W2C – ZrC, see W2C – ZrC – W W – W2C, see W2C – W

W2C – C – Ni, 223-224 W2C – C – Pt, 230

W2C – C – Rh, 232 W2C – C – Ru, 233 W2C – C – Sc, 233 W2C – C – Si, 234 W2C – C – Ta, 235 W2C – C – Tc, 235 W2C – C – Th, 236 W2C – C – Ti, 236-237

918

Index (Chemical Systems)

W2C – C – U, 237-238

W2C – Sc, 434

W2C – C – V, 238

W2C – Si, 436

W2C – C – W, 240-241

W2C – Si3N4, 504

W2C – C – Zr, 242

W2C – SiC, 501

W2C – C2H6, 533

W2C – SiC – W, 447

W2C – C3N4, 467

W2C – SiO2, 504

W2C – C3N4 – Ni, 413

W2C – SiO2 – Cu, 367

W2C – CH4, 532

W2C – Ta, 438

W2C – Cl2, 536

W2C – Ta2C, 506

W2C – Co, 287

W2C – Ta2C – V2C, 506

W2C – Cr, 349

W2C – TaC, 506

W2C – Cr3C – Fe3C – Mn3C, 474

W2C – Tc, 438

W2C – Cr3C2, 471

W2C – Th, 439

W2C – Cu, 359

W2C – ThC, 507

W2C – F2, 536

W2C – ThO2, 507

W2C – Fe, 372

W2C – Ti, 440-441

W2C – H2/D2, 539-540

W2C – TiC, 509

W2C – Hf, 394

W2C – TiC – Co, 344

W2C – HfC, 483

W2C – TiC – W, 447

W2C – Ir, 395

W2C – U, 441

W2C – MgO, 486

W2C – UC2, 511

W2C – Mn, 396

W2C – V, 442

W2C – Mo, 399

W2C – V2C, 512

W2C – Mo – W, 400

W2C – VC, 512

W2C – Mo2C, 489

W2C – W, 445-446

W2C – Mo2C – Fe, 393

W2C – W2B, 514

W2C – MoC (α, η), 490

W2C – W2B – W, 447

W2C – N2, 543

W2C – WB, 513

W2C – Nb, 402

W2C – WB – W2B, 514

W2C – Nb2C, 492

W2C – WN – C – N, 252

W2C – Nb2C – Ta2C, 493

W2C – WO3, 523

W2C – NbC, 492

W2C – WP – C – N, 253

W2C – Ni, 410

W2C – WS2, 524

W2C – O2, 551-552

W2C – Zr, 448

W2C – Os, 426

W2C – ZrC, 530

W2C – Pd, 427

W2C – ZrC – W, 447

W2C – Pt, 430

WB – W2B – W2C, see W2C – WB – W2B

W2C – Pu, 431

WB – W2B – WC, see WC – WB – W2B

W2C – Re, 433

WB – W2C, see W2C – WB

W2C – Rh, 433

WB – WC – W2C, see WC – W2C – WB

W2C – Ru, 434

WB – WC, see WC – WB

Index (Chemical Systems)

919

WC – (BaF2, CaF2) – Al – Co, 156

WC – (Fe – C), 372-373

WC – (C2F4)n, 463

WC – (Fe – C) – Ti, 390

WC – (C2F4)n – C, 244 WC – (C2H4)n, 464

WC – (Mn7C3, Mn5C2, Mn3C, Mn15C4, Mn23C6), 486

WC – (C6H4CH2C6H4OCH2CHOHCH2O)n, 464

WC – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt), 505

WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – (SiO2 – Al2O3 – CaO – Fe2O3 – MgO) (basalt), 465

WC – (SiO2 – B2O3 – Na2O – K2O) – Co, 343

WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – Al – Co, 156

WC – (SiO2 – PbO – K2O – Na2O) – Co, 343

WC – (C6H4CH2C6H4OCH2CHOHCH2O)n – SiO2, 465

WC – (W2B, WB) – Fe – Ni – W, 393

WC – (C6H4COC6H4O)n, 465

WC – [(C6H10O5)7(OH)(CH2)4O2CHOH (C6H10O5)7(OH)O2]n, 466

WC – (C6H4COC6H4O)n – C, 245 WC – (C8H6O2)n – Co – Fe – Ge, 325

WC – (SiO2 – MeI2O – B2O3 – MeIIO), 505

WC – [(C2H4)n–(CH2CHOCOCH3)m], 464

WC – (CF2CF2)n(CF2CFCF3)m – Mo – Ni, 400

WC – [(C6H3)(CN)2O(C6H4)C(CH3)2(C6H4)O (C6H4)(CN)2]n, 464

WC – (Cu51Zr14, CuZr2) – Mo2C, 476

WC – [(C6H4O)2CO(C6H4)]n, 465

WC – (Fe – C – Co – Cr – Mo – V), 373

WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – Al – Co, 157

WC – (Fe – C – Co – Mo – Ni), 374 WC – (Fe – C – Cr – Mn – Mo – Ni – Si), 375 WC – (Fe – C – Cr – Mn – Mo – Ni – Si) – Ni – Si, 389 WC – (Fe – C – Cr – Mn – Nb), 375 WC – (Fe – C – Cr – Mn – Ni – Si), 376 WC – (Fe – C – Cr – Mn – Ni), 376 WC – (Fe – C – Cr – Mn – W), 377 WC – (Fe – C – Cr – Mo – Nb – Ti – V), 377

WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – B – Co, 179 WC – [(CkHl)(CpHq)Si(CH2)]n – SiC – Co, 325 WC – [(CkHl)ON(CpHq)O]n – Co, 325 WC – [C(CH3)COOH]n, 463 WC – [C4H2(NH)]n, 464 WC – [C6H3(CN)2OC6H4C(CH3)2C6H4OC6H3 (CN)2]n – C, 244-245 WC – [C6H4(NH)]n, 465

WC – (Fe – C – Cr – Mo – Ni), 377-378

WC – [C6H4(NH)]n – Al – Pb, 156

WC – (Fe – C – Cr – Mo – Si – V), 378

WC – [C6H4(NH)]n – CeO2, 465

WC – (Fe – C – Cr – Ni), 379-381

WC – [C6H4(NH)]n – Pb, 426

WC – (Fe – C – Cr – V – W), 381

WC – [C6H4C2(NH)]n, 465

WC – (Fe – C – Cr), 374

WC – [C6H7O2(OH)3]n, 465

WC – (Fe – C – Cr) – Ni, 389 WC – (Fe – C – Cr) – W, 390

WC – [CH2 C(CH3)COO(CH3)]n – [(C6H5)CHCH2]m, 463

WC – (Fe – C – Mn – Si), 382

WC – 2Al2O3∙2MgO∙5SiO2, 460

WC – (Fe – C – Mn – Si) – W, 391

WC – 2SiO2∙Al2O3∙Na2O∙xH2O, 505

WC – (Fe – C – Mn), 381-382

WC – 3Al2O3∙2SiO2, 460

WC – (Fe – C – Ni), 383

WC – 3CaO∙Al2O3 – 4CaO∙Al2O3∙Fe2O3 – 2CaO∙SiO2 – 3CaO∙SiO2, 467

WC – (Fe – C – Si), 383

WC – Ag, 132

920

Index (Chemical Systems)

WC – Ag – Be – Cd – Co – Cu – Ni – Zn, 132

WC – Al – B – Fe, 140

WC – Ag – C, 132

WC – Al – B – Ni – Zr, 140

WC – Ag – C – Co – Cr – Cu – Fe – Mn – Mo – Ni – Zn, see WC – Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – Zn and WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn

WC – Al – C, 140

WC – Ag – C – Co – Cr – Cu – Fe – Mo – Ti, see WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti

WC – Al – C – Co – Fe – Mn – Ni – Si – Ti, see WC – Co – (Fe – C – Mn – Si) – (Ni – C – Al – Ti)

WC – Ag – C – Co – Cu – Fe – Mn, see WC – Ag – Co – Cu – (Fe – C – Mn)

WC – Al – C – Cr – Fe – Mn – Ni, see WC – Al – (Fe – C – Cr – Mn – Ni) – Ni

WC – Ag – C – Co – Cu – Ti, 133 WC – Ag – Cd – Co – Cu – Ni – Zn, 133

WC – Al – C – Cr – Fe – Mn – Ni – Si – Ti, see WC – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti

WC – Ag – Cd – Co – Cu – Zn, 133

WC – Al – C – Cu – Ni – Si, 141

WC – Ag – Co, 133

WC – Al – C – Mg, 141

WC – Ag – Co – Cu, 133

WC – Al – C – Mg – Si, 141

WC – Ag – Co – Cu – (Fe – C – Cr – Mn – Mo) – Mn – Ni – Zn, 133

WC – Al – Co, 141-142

WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Mn – Ni – Zn, 134 WC – Ag – Co – Cu – (Fe – C – Cr – Mo) – Ti, 134

WC – Al – B – Ni, 140

WC – Al – C – Co – Cu – Fe – Mn – Ni, see WC – Al – Co – Cu – (Fe – C – Mn) Ni

WC – Al – Co – Cr – Cu – Fe – Ni, 143144 WC – Al – Co – Cr – Fe – Ni, 144 WC – Al – Co – Cr – Fe – Ni – Ti, 144

WC – Ag – Co – Cu – (Fe – C – Mn), 134

WC – Al – Co – Cr – Ni, 145

WC – Ag – Co – Cu – Mn – Ni – Zn, 134

WC – Al – Co – Cr, see WC – Cr3C2 – Al – Co

WC – Ag – Co – Cu – Ni – Si – Zn, 134 WC – Ag – Co – Cu – Ni – Zn, 134

WC – Al – Co – Cu, 145

WC – Ag – Cu, 134

WC – Al – Co – Cu – (Fe – C – Mn) – Ni, 145

WC – Ag – Cu – Ni, 134

WC – Al – Co – Cu – Mg – Zn, 145

WC – Ag – Ni, 135

WC – Al – Co – Ni, 145-146

WC – Ag – Pb, 135

WC – Al – Co – Zn, 146

WC – Ag – Zr, 135

WC – Al – Cr – Fe, 146-147

WC – Al, 136-138

WC – Al – Cr – Mo – Ni, 147

WC – Al – (Fe – C – Cr – Mn – Ni – Si) – Ni – Si – Ti, 151

WC – Al – Cu, 147

WC – Al – (Fe – C – Cr – Mn – Ni) – Ni, 151

WC – Al – Cu – Mg, 148

WC – Al – Cu – Fe, 148

WC – Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn, 138-139

WC – Al – Cu – Mg – Mn, 148

WC – Al – B – Co – Cr – Ni – Si, 139

WC – Al – Cu – Mg – Zn, 148

WC – Al – B – Co – Cr – Ti – V, 139

WC – Al – Cu – Mn – Si, 148

WC – Al – B – Cr – Cu – Fe – Ni – Si, 139

WC – Al – Cu – Nb – Ni – Ti, 149

WC – Al – B – Cr – Fe – Ni – Zr, 139

WC – Al – Cu – Nb – Ni – Zr, 149

WC – Al – B – Cr – Mo – Ni – Zr, 140

WC – Al – Cu – Ni – Zr, 149

WC – Al – Cu – Mg – Si, 148

Index (Chemical Systems)

921

WC – Al – Cu – Si, 149

WC – Al2O3 – MgO – ZrO2, 457

WC – Al – Fe, 149-150

WC – Al2O3 – Mo2C, 457

WC – Al – Fe – Mn, 150

WC – Al2O3 – Ni, 413

WC – Al – Fe – Mo, 150

WC – Al2O3 – Si3N4 – Y2O3, 457-458

WC – Al – Fe – Nb, 150

WC – Al2O3 – SiC – TiC, 457

WC – Al – Fe – Ni, 150

WC – Al2O3 – TiC, 458

WC – Al – Fe – Ta, 151

WC – Al2O3 – TiC – Co, 321

WC – Al – Fe – Ti, 151

WC – Al2O3 – TiC – Co – Ni, 321

WC – Al – Fe – V, 151

WC – Al2O3 – TiC – Ni, 413

WC – Al – Fe – Zr, 151

WC – Al2O3 – TiO2, 459

WC – Al – Mg – Mn – Si, 151

WC – Al2O3 – TiO2 – C, 243

WC – Al – Mg – Si, 151-152

WC – Al2O3 – VC, 459

WC – Al – Mg – Si – Ti, 152

WC – Al2O3 – W, 446

WC – Al – Mg – Zn, 152

WC – Al2O3 – Y2O3, 459

WC – Al – Nb, 152

WC – Al2O3 – Y2O3 – ZrO2, 459-460

WC – Al – Ni, 153-154

WC – Al2O3 – Y2O3 – ZrO2 – Co, 321

WC – Al – Si, 154

WC – Al2O3 – ZrO2, 460

WC – Al – Ti – V, 154-155

WC – Al4C3, 449

WC – Al2O3, 451-455

WC – Al4C3 – Co, 319

WC – Al2O3 – Al, 155

WC – Al4C3 – Fe – Ni, 391

WC – Al2O3 – Al – Co, 155

WC – Al4C3 – NbC, 449

WC – Al2O3 – Al – Ni – Zn, 155

WC – Al4C3 – Ni, 412-413

WC – Al2O3 – B – Cr – Fe – Ni – Si, 179

WC – AlB2 – AlN – BN – TiC, 449

WC – Al2O3 – C, 243

WC – AlN, 450

WC – Al2O3 – C – Cr – Ni, 243

WC – AlN – [(CkHl)(CpHq)Si(CH2)]n – SiC – B – Co, 179

WC – Al2O3 – CaF2 – TiC, 455 WC – Al2O3 – CaF2 – TiC – Ni – P, 413 WC – Al2O3 – CaO – SiC – Y2O3, 455 WC – Al2O3 – CaO – ZrO2, 455 WC – Al2O3 – CeO2, 456 WC – Al2O3 – CeO2 – MgO, 456 WC – Al2O3 – Co, 320-321 WC – Al2O3 – Cr – Cu, 355 WC – Al2O3 – Cr – Ni, 356 WC – Al2O3 – Cr3C2, 456 WC – Al2O3 – Cr3C2 – Ni, 413 WC – Al2O3 – Cr3C2 – Si3N4 – Y2O3, 457 WC – Al2O3 – Cr3C2 – TiC – VC, 457 WC – Al2O3 – Cr3C2 – TiC – VC – C, 243 WC – Al2O3 – Cu, 366 WC – Al2O3 – MgO, 457

WC – AlN – [(CkHl)(CpHq)Si(CH2)]n – SiC – Co, 319 WC – AlN – Al2O3 – Si3N4 – Y2O3, 450 WC – AlN – Co, 319 WC – AlN – Cr3C2 – Mo2C – TiN, 450 WC – AlN – CrN, 451 WC – AlN – Si3N4 – Y2O3, 451 WC – AlN – TiC – TiN – Mo – Ni, 400 WC – AlN – TiN, 451 WC – As, 159 WC – Au, 159 WC – Au – C – Pd, 159 WC – Au – C – Pd – Pt, 159 WC – Au – Pd, 159 WC – Au – Pd – Pt, 159 WC – Au – Sn, 159

922

Index (Chemical Systems)

WC – B, 160

WC – B4C – C, 243-244

WC – B – C, 161

WC – B4C – C – Fe – Mn – Mo – Ni – Zr, see WC – B4C – (Fe – C – Mn) – Mo – Ni – Zr

WC – B – C – Co – Cr – Fe – Mo, 162 WC – B – C – Co – Cr – Fe – Ni – Si, 163 WC – B – C – Cr – Cu – Fe – Mo – Ni – Si, 163

WC – B4C – Co, 321-322 WC – B4C – Ni – Si, 413

WC – B – C – Cr – Fe – Mn – Mo – Si – W, 163

WC – B4C – SiC, 461

WC – B – C – Cr – Fe – Mn – Ni – Si, 164

WC – B4C – SiC – ZrB2, 462

WC – B – C – Cr – Fe – Ni – Si, 164-168

WC – B4C – TiB2 – Co, 322

WC – B – C – Cr – Fe – Ni – Si – W, 170

WC – B4C – TiC, 462

WC – B – C – Mo, 171

WC – B4C – W, 446

WC – B – Co, 172-173

WC – B4C – Y2O3 – Co, 322

WC – B – Co – Cr – Fe, 173

WC – B4C – ZrB2, 462

WC – B – Co – Cr – Fe – Ni – Si, 173

WC – BaCl2 – NaCl, 463

WC – B – Co – Cr – Ni – Si, 174 WC – B – Co – Cu – Ni, 174

WC – BaF2 – Al – Co, see WC – (BaF2, CaF2) – Al – Co

WC – B – Co – Fe – Mo – Ni, 174

WC – BaF2 – CaF2 – Co – Cu, 324

WC – B – Co – Fe – Si, 174

WC – Bi, 182

WC – B – Cr – Fe, 174

WC – BN, 462-463

WC – B – Cr – Fe – (Fe – C – Mn – Si) – Ni – Si, 175

WC – BN – Ag – Co – Cu – In – Ti, 135

WC – B – Cr – Fe – Mo – Ni – Si, 175

WC – BN – Al – Co – Ni, 156

WC – B – Cr – Fe – Mo – Si, 175

WC – BN – C – Cu – Ni, 244

WC – B – Cr – Fe – Ni, 175

WC – BN – Co, 322-324

WC – B – Cr – Fe – Ni – Si, 175-176

WC – BN – Cr – Cu, 356

WC – B – Cr – Ni – Si, 176

WC – BN – Cr3C2 – Co, 324

WC – B – Cr – Ni – Si – Ti, 177

WC – BN – Cu – Sn – Ti, 366

WC – B – Cr – Ni – W, 177 WC – B – Cu – Fe – Ni – Si, 177

WC – BN – NiPx (Ni3P, Ni2–xP) – Co – Ni, 324

WC – B – Fe – Ni – Si, 178

WC – BN – Si3N4 – Y2O3, 463

WC – B – Mo – Ni – Si, 178

WC – BN – VC – Ni, 413

WC – B – Ni, 178

WC – BN – Y2O3 – ZrO2 – Co, 324

WC – B – Ni – Si, 178-179

WC – Br2, 532

WC – B2O3, 463

WC – C, 182-191

WC – B4C, 461

WC – C – (Fe – C – Cr – Mn – Nb), 212

WC – B4C – (C6H4COC6H4O)n – C, 244

WC – C – Co, 194-200

WC – B4C – (Fe – C – Mn) – Mo – Ni – Zr, 391

WC – C – Co – Cr – Cu – Fe – Mn – Ni – Zn, see WC – Co – Cu – (Fe – C – Cr – Mn) – Ni – Zn

WC – B4C – Al – Cu – Mg, 156 WC – B4C – Al – Mg – Si, 156 WC – B4C – BN – Cr – Cu, 356

WC – B4C – SiC – Co, 322

WC – BN – Ag – Co – Cu – Ti, 135

WC – C – Co – Cr – Cu – Fe – Mo – V – W, see WC – Cu – (Fe – C – Co – Cr – Mo – V – W)

Index (Chemical Systems)

923

WC – C – Co – Cr – Cu – Fe – N – Nb – Ni – Ta – Ti, 201

WC – C – Co – Fe, see WC – Co – (Fe – C)

WC – C – Co – Cr – Cu – Fe – Ni – Si – Zn, see WC – Co – Cu – (Fe – C – Cr – Si) – Ni – Zn

WC – C – Co – N, 203-204

WC – C – Co – Cr – Fe, see WC – Co – (Fe – C – Cr) WC – C – Co – Cr – Fe – Mn – Mo – Nb – Ni – Si, see WC – Co – (Fe – C – Cr – Mn – Mo – Ni – Si) – (Fe – C – Mn – Nb – Ni) WC – C – Co – Cr – Fe – Mn – Ni – Ti, see WC – Co – (Fe – C – Cr – Mn) – Ni – Ti WC – C – Co – Cr – Fe – Mn – Ni, see WC – Co – (Fe – C – Cr – Mn) – Ni WC – C – Co – Cr – Fe – Mn – Si, see WC – Co – (Fe – C – Cr – Mn – Si) WC – C – Co – Cr – Fe – Mo – Ni – V – W, see WC – Co – (Fe – C – Cr – Mo – Ni – V – W) WC – C – Co – Cr – Fe – Mo – Si – V, 202 WC – C – Co – Cr – Fe – Mo – V – W, see WC – Co – (Fe – C – Cr – Mo – V – W) WC – C – Co – Cr – Fe – Mo – V, see WC – (Fe – C – Co – Cr – Mo – V) and WC – Co – (Fe – C – Cr – Mo – V)

WC – C – Co – Pd, 204 WC – C – Cr, 204-205 WC – C – Cr – Cu – Fe – Ni, see WC – Cu – (Fe – C – Cr – Ni) WC – C – Cr – Fe – La – Ni – Si, 206 WC – C – Cr – Fe – Mn – Mo – Ni – Si, see WC – (Fe – C – Cr – Mn – Mo – Ni – Si) and WC – (Fe – C – Cr – Mn – Mo – Ni – Si) – Ni – Si WC – C – Cr – Fe – Mn – Nb, see WC – C – (Fe – C – Cr – Mn – Nb) and WC – (Fe – C – Cr – Mn – Nb) WC – C – Cr – Fe – Mn – Ni – Si, see WC – (Fe – C – Cr – Mn – Ni – Si) WC – C – Cr – Fe – Mn – Ni, see WC – (Fe – C – Cr – Mn – Ni) WC – C – Cr – Fe – Mn – W, see WC – (Fe – C – Cr – Mn – W) WC – C – Cr – Fe – Mo – Nb – Ti – V, see WC – (Fe – C – Cr – Mo – Nb – Ti – V) WC – C – Cr – Fe – Mo – Ni, see WC – (Fe – C – Cr – Mo – Ni)

WC – C – Co – Cr – Fe, see WC – Co – (Fe – C – Cr)

WC – C – Cr – Fe – Mo – Si – V, see WC – (Fe – C – Cr – Mo – Si – V)

WC – C – Co – Cr – Mn – Mo – Ni – Si, see WC – Co – (Co – C – Cr – Mn – Mo – Ni – Si)

WC – C – Cr – Fe – Ni – Si, 207

WC – C – Co – Cu – Fe – Mn, see WC – Co – Cu – (Fe – C – Mn) WC – C – Co – Cu – Fe – Ni, 203 WC – C – Co – Cu – Fe – Sn, 203 WC – C – Co – Cu – Fe, see WC – Co – Cu – (Fe – C)

WC – C – Cr – Fe – Ni, 207 WC – C – Cr – Fe – V – W, see WC – (Fe – C – Cr – V – W) WC – C – Cr – Fe – W, see WC – (Fe – C – Cr) – W WC – C – Cr – Fe, see WC – Cr – (Fe – C) and WC – (Fe – C – Cr) WC – C – Cu, 208

WC – C – Co – Fe – Mn – Nb – Ni – Si – Y, see WC – Co – (Fe – C – Mn – Si) – (Ni – C – Fe – Nb – Y)

WC – C – Cu – Fe – Mo – Ni, 208

WC – C – Co – Fe – Mn – Nb – Ni, see WC – Co – (Fe – C – Mn – Nb – Ni)

WC – C – Cu – Pt, 208

WC – C – Co – Fe – Mn – Si, see WC – Co – (Fe – C – Mn – Si) WC – C – Co – Fe – Mo – Ni, see WC – (Fe – C – Co – Mo – Ni) WC – C – Co – Fe – N, 203

WC – C – Cu – Mn – Ni – Pb – Sn – Zn, 208 WC – C – Fe – Mn – Si – W, see WC – (Fe – C – Mn – Si) – W WC – C – Fe – Mn – Si, see WC – (Fe – C – Mn – Si) WC – C – Fe – Mn, see WC – (Fe – C – Mn)

924

Index (Chemical Systems)

WC – C – Fe – N, 212

WC – C – W, 238-240

WC – C – Fe – Ni, see WC – (Fe – C – Ni)

WC – C – Zr, 241-242

WC – C – Fe – Pd, 212 WC – C – Fe – Si, see WC – (Fe – C – Si)

WC – C12H22O11 – Co3O4 – Fe2O3 – NiO, 466

WC – C – Fe – Ti, see WC – (Fe – C) – Ti

WC – C12H22O11 – Fe2O3, 466

WC – C – Fe, 208-210

WC – C12H22O11 – Fe2O3 – NiO, 466

WC – C – H, 212-213

WC – C2H4, 533

WC – C – Hf, 214

WC – C2H6, 533

WC – C – Ir, 214

WC – C35H28N2O7, 467

WC – C – Mg, 215

WC – C3N4, 467

WC – C – Mn, 215

WC – C3N4 – P, 426

WC – C – Mo, 215-216

WC – C6H6, 533

WC – C – N, 218

WC – CaF2 – Al – Co, see WC – (BaF2, CaF2) – Al – Co

WC – C – N – Ni, 218 WC – C – Nb, 218-219

WC – CaF2 – B – Cr – Fe – Ni – Si, 179180

WC – C – Ni, 220-222

WC – CaF2 – Co, 325

WC – C – Ni – P, 224

WC – CaO, 467

WC – C – Ni – Pt, 224

WC – CaO – ZrO2, 467-468

WC – C – Ni – Si, 224

WC – Cd, 254

WC – C – Ni – Ti, 224

WC – CdS, 468

WC – C – Os, 224

WC – CdS – TiO2, 468

WC – C – Pd, 225-226

WC – Ce – Co, 254

WC – C – Pd – Pt, 226

WC – Ce – Ni, see WC – CeO2 – Ni

WC – C – Pt, 226-229

WC – CeB6 – Co, 325

WC – C – Pt – Rh, 230

WC – CeO2 – Al – B – C – Co – Cr – Fe – Mg – Ni – Si – W – Zn, 157

WC – C – Pt – Ru, 230 WC – C – Pt – Sn, 230 WC – C – Pu, 231

WC – CeO2 – B – Co – Cr – Fe – Ni – Si, 180

WC – C – Pu – U, 231

WC – CeO2 – Co, 326

WC – C – Re, 231

WC – CeO2 – Cr3C2 – Ni, 414

WC – C – Rh, 232

WC – CeO2 – Fe – Ni, 391

WC – C – Ru, 232

WC – CeO2 – MgO – Ni, 414

WC – C – Sc, 233

WC – CeO2 – MgSiN2 – Si3N4 – Y2O3, 468

WC – C – Si, 233

WC – CeO2 – MgSiN2 – Si3N4 – Y2O3 – Co, 326

WC – C – Sn, 234 WC – C – Ta, 234 WC – C – Tc, 235 WC – C – Th, 236 WC – C – Ti, 236 WC – C – U, 237 WC – C – V, 238

WC – CeO2 – Ni, 413-414 WC – CeO2 – Y2O3 – ZrO2, 468 WC – CeO2 – ZrO2 – Pb, 426 WC – CH3OH/CH3OD, 533 WC – CH4, 532 WC – CH4 – H2, 533 WC – Cl2, 535-536

Index (Chemical Systems) WC – CnH2n+2 (n = 20÷40), 466

925

WC – Co, 254-283

WC – Co – Cu – (Fe – C – Cr – Si) – Ni – Zn, 298

WC – CO, 533-534

WC – Co – Cu – (Fe – C – Mn), 298

WC – Co – (Co – C – Cr – Mn – Mo – Ni – Si), 287

WC – Co – Cu – (Fe – C), 297

WC – Co – (Fe – C – Cr – Mn – Mo – Ni – Si) – (Fe – C – Mn – Nb – Ni), 301

WC – Co – Cu – Fe – Ni, 298

WC – Co – (Fe – C – Cr – Mn – Si), 301

WC – Co – Cu – Mn – Ni, 299

WC – Co – (Fe – C – Cr – Mn) – Ni, 306

WC – Co – Cu – Mn – Ni – Sn – Zn, 299

WC – Co – (Fe – C – Cr – Mn) – Ni – Ti, 306

WC – Co – Cu – Mn – Ni – Zn, 299

WC – Co – (Fe – C – Cr – Mo – Ni – V – W), 301

WC – Co – Cu – Ni, 299

WC – Co – Cu – Fe, 297 WC – Co – Cu – Mn, 298-299

WC – Co – Cu – Mn – Zn, 299

WC – Co – (Fe – C – Cr – Mo – Si – V), 301-302

WC – Co – Cu – Ni – Si, 299

WC – Co – (Fe – C – Cr – Mo – V – W), 302

WC – Co – Cu – Ni – Zn, 300

WC – Co – (Fe – C – Cr – Mo – V), 302

WC – Co – Fe, 300

WC – Co – (Fe – C – Cr), 300

WC – Co – Fe – Mo – Ni, 303

WC – Co – (Fe – C – Mn – Nb – Ni), 302

WC – Co – Fe – Ni, 303-306

WC – Co – (Fe – C – Mn – Si), 302-303

WC – Co – Fe – Si, 307

WC – Co – (Fe – C – Mn – Si) – (Ni – C – Al – Ti), 307

WC – Co – Ga, 307

WC – Co – (Fe – C – Mn – Si) – (Ni – C – Fe – Nb – Y), 307

WC – Co – In, 307

WC – Co – (Fe – C), 300

WC – Co – Ln (La, Ce, Nd, Dy, Pr, Y), 307-308

WC – Co – Cr, 287-292 WC – Co – Cr – Cu – Fe – Nb – Ni – Ta – Ti, 292 WC – Co – Cr – Cu – Fe – Ni, 292 WC – Co – Cr – Fe – Mn – Ni, 293 WC – Co – Cr – Fe – Mo – Nb – Ni, 293 WC – Co – Cr – Fe – Mo – Ni, 293-294 WC – Co – Cr – Fe – Nb – Ni – Ta – Ti, 294

WC – Co – Cu – Ni – Si – Zn, 300 WC – Co – Cu – Zn, 300

WC – Co – Ga – Mn – Ni, 307

WC – Co – Mn, 308-309 WC – Co – Mn – Ni, 309 WC – Co – Mo, 309 WC – Co – Mo – Ni, 309 WC – Co – N, 310 WC – Co – Nb, 310 WC – Co – Nb – Ta – Ti, 310 WC – Co – Ni, 310-313

WC – Co – Cr – Fe – Ni, 294

WC – Co – Ni – Re, 313

WC – Co – Cr – Fe – Si – Ti, 294

WC – Co – Os, 313

WC – Co – Cr – Mo – Ni, 294

WC – Co – P, see WC – CoPy – Co

WC – Co – Cr – Ni, 295

WC – Co – Pd, 313

WC – Co – Cr – Ta, 295

WC – Co – Re, 313-314

WC – Co – Cr – W, 295

WC – Co – Ru, 314-315

WC – Co – Cu, 296-297

WC – Co – S, 315

WC – Co – Cu – (Fe – C – Cr – Mn) – Ni – Zn, 298

WC – Co – Se, 315 WC – Co – Si, 315

926 WC – Co – Sn, 315

Index (Chemical Systems)

WC – Co – Ta, 315-316

WC – Cr3C2 – (Fe – C – Cr – Mn – Ni – Si) – Mo, 392

WC – Co – Ti, 316-317

WC – Cr3C2 – (Fe – C – Cr – Ni), 392

WC – Co – V, 317

WC – Cr3C2 – (Fe – C – Mn), 392

WC – Co – W, 317

WC – Cr3C2 – Al – Co, 157

WC – Co – Y, 318

WC – Cr3C2 – B – C – Co – Cr – Cu – Fe – Ni – Si – Zn, see WC – Cr3C2 – B – Co – Cr – Cu – (Fe – C) – Ni – Si – Zn

WC – Co – Zn, 318-319 WC – Co(OH)2, 469 WC – CO2, 534-535

WC – Cr3C2 – B – Co – Cr – Cu – (Fe – C) – Ni – Si – Zn, 180

WC – Co3O4, 468

WC – Cr3C2 – B – Cr – Fe – Ni – Si, 180

WC – Co3O4 – C – N, 245

WC – Cr3C2 – C – Co – Cr – Mn – Si – W, 245

WC – Co3O4 – Fe2O3 – NiO, 469 WC – Co3O4 – Fe2O3 – NiO – C, 245 WC – CoF3, 468 WC – CoO, 469 WC – CoPy – Co, 326 WC – Cr, 348-349

WC – Cr3C2 – C – Cr – Fe – Mn – Mo – Ni – Si, see WC – Cr3C2 – (Fe – C – Cr – Mn – Ni – Si) – Mo WC – Cr3C2 – C – Cr – Fe – Ni, see WC – Cr3C2 – (Fe – C – Cr – Ni)

WC – Cr – Cu, 349

WC – Cr3C2 – C – Fe – Mn, see WC – Cr3C2 – (Fe – C – Mn)

WC – Cr – Cu – Fe, 350

WC – Cr3C2 – C – Ni, 246

WC – Cr – Fe, 350-351

WC – Cr3C2 – Co, 327-332

WC – Cr – Fe – Mn, 351

WC – Cr3C2 – Co – Cr, 332

WC – Cr – Fe – Mn – Mo – Ni, 351

WC – Cr3C2 – Co – Cr – Fe – Ni, 332

WC – Cr – Fe – Mn – Mo – Ni – Ti, 351

WC – Cr3C2 – Co – Cr – Mo – Ni, 332

WC – Cr – Fe – Mo, 352

WC – Cr3C2 – Co – Cr – Ni, 333

WC – Cr – Fe – Mo – Ni, 352

WC – Cr3C2 – Co – Fe – Ni, 334

WC – Cr – Fe – Nb, 352

WC – Cr3C2 – Co – Ni, 334

WC – Cr – Fe – Ni, 352-353

WC – Cr3C2 – Co – W, 334

WC – Cr – Fe – Si, 353

WC – Cr3C2 – Cr – Ni, 356

WC – Cr – Fe – Ta, 353

WC – Cr3C2 – Cr2N – VC – Co, 334

WC – Cr – Fe – Ti, 353

WC – Cr3C2 – Cr7C3, 472

WC – Cr – Fe – V, 353

WC – Cr3C2 – Cr7C3 – Co, 334

WC – Cr – Fe – Zr, 354

WC – Cr3C2 – Fe, 391-392

WC – Cr – Mn – Ni, 354

WC – Cr3C2 – Fe – Ni, 392

WC – Cr – Mo – Ni, 354

WC – Cr3C2 – FeAl, 472

WC – Cr – Mo – V, 354 WC – Cr – Ni, 354-355

WC – Cr3C2 – HfC – Mo2C – TiC – TiN, 472

WC – Cr – Ni – W, 355

WC – Cr3C2 – La2O3 – Co, 335

WC – Cr23C6, 474-475

WC – Cr3C2 – La2O3 – VC – Co, 335

WC – Cr2N – Co, 337

WC – Cr3C2 – MgO, 472

WC – Cr2O3, 475

WC – Cr3C2 – MgO – TiN, 472

WC (γ, δ) – Cr3C2, 469-471

WC – Cr3C2 – MgO – VC, 472 WC – Cr3C2 – Mo2C, 472

Index (Chemical Systems)

927

WC – Cr3C2 – Mo2C – Co, 335

WC – CrB2 – C – Co, 245

WC – Cr3C2 – Mo2C – Co – Fe – Ni, 335336

WC – CrB2 – Co, 327

WC – Cr3C2 – Mo2C – Fe – Ni, 392

WC – CrN, 475

WC – Cr3C2 – Mo2C – SiC, 473

WC – CrN – C, 246

WC – Cr3C2 – Mo2C – TaC – TiC – TiN – Co – Ni, 336

WC – CrSi2 – C – Co, 247

WC – Cr3C2 – Mo2C – TiC – Ni, 418 WC – Cr3C2 – Mo2C – VC, 473 WC – Cr3C2 – Ni, 414-418

WC – CrB2 – W2B5 – C – Co, 245

WC – CrSi2 – Co, 337 WC – Cs, 357 WC – Cu, 357-359

WC – Cr3C2 – Si3N4 – VC – Y2O3, 473

WC – Cu – (Fe – C – Co – Cr – Mo – V – W), 360

WC – Cr3C2 – SiC, 473

WC – Cu – (Fe – C – Cr – Ni), 360

WC – Cr3C2 – SiC – TiC – TiN – Mo – Ni, 400

WC – Cu – Fe, 360

WC – Cr3C2 – SiC – VC, 473

WC – Cu – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Si, 361

WC – Cr3C2 – TaC – TiC – Mo – Ni, 400

WC – Cu – Fe – Mn, 361

WC – Cr3C2 – TiAl3 – Co – Ni, 336

WC – Cu – Fe – Mo, 361

WC – Cr3C2 – TiB2 – Co, 336

WC – Cu – Fe – Nb, 361

WC – Cr3C2 – TiB2 – TiC – TiN, 474

WC – Cu – Fe – Ni, 361

WC – Cr3C2 – TiB2 – TiC – TiN – Co, 336

WC – Cu – Fe – Ta, 361

WC – Cr3C2 – TiB2 – VC – Co, 336

WC – Cu – Fe – Ti, 361

WC – Cr3C2 – TiC, 474

WC – Cu – Fe – V, 361

WC – Cr3C2 – TiC – Co, 336

WC – Cu – Fe – Zr, 361

WC – Cr3C2 – TiC – Ni, 419

WC – Cu – Hf, 361

WC – Cr3C2 – TiC – Pt, 430

WC – Cu – In – Mn – Ni – Zn, 362

WC – Cr3C2 – TiC – TiN – C – Co – Mo – Ni, 246

WC – Cu – Mn, 362

WC – Cr3C2 – TiC – TiN – Cr – Ni, 356 WC – Cr3C2 – TiC – TiN – Mo – Ni, 400 WC – Cr3C2 – TiC – TiN – Ni, 419 WC – Cr3C2 – TiC – TiN – VC – Mo – Ni, 400

WC – Cu – Mn – Ni, 362 WC – Cu – Mn – Ni – P, 362 WC – Cu – Mn – Ni – Pb – Sn – Zn, 362 WC – Cu – Mn – Ni – Si, 362 WC – Cu – Mn – Ni – Ti – V – Zr, 362

WC – Cr3C2 – TiC – VC – Co, 336

WC – Cu – Mn – Ni – Zn, 363

WC – Cr3C2 – TiN – Co, 336

WC – Cu – Mo, 363

WC – Cr3C2 – VC – Co, 337

WC – Cu – Mo – Zr, 363

WC – Cr3C2 – Y2O3 – Co, 337

WC – Cu – Ni, 363

WC – Cr3C2 – Y2O3 – ZrO2, 474

WC – Cu – Ni – Si – Sn – Ti – Zr, 363

WC – Cr3C2 – Y2O3 – ZrO2 – C – Ni, 246

WC – Cu – Ni – Sn – Ti, 363

WC – Cr3C2 – ZrO2 – Ni, 419

WC – Cu – Ni – W, 364

WC – Cr7C3, 474

WC – Cu – P – Sn, 364

WC – Cr7C3 – C – Co – Cr – Fe – Mn, 246

WC – Cu – Pd – Si, 364

WC – Cr7C3 – TiC – C – Co, 246

WC – Cu – Si, 364

WC – CrB2, 469

WC – Cu – Ti – Zr, 365

928

Index (Chemical Systems)

WC – Cu – W, 365

WC – Fe – Ta – Ti, 390

WC – Cu – Zn, 365

WC – Fe – Ta – V, 390

WC – Cu – Zr, 365-366

WC – Fe – Ta – Zr, 390

WC – Cu2O – C, 247

WC – Fe – Ti, 390

WC – Cu3N – TiN, 475

WC – Fe – Ti – V, 390

WC – CuZr2, 475-476

WC – Fe – Ti – Zr, 390

WC – F2, 536

WC – Fe – V, 390

WC – Fe, 367-371

WC – Fe – V – Zr, 390

WC – Fe – La, 383

WC – Fe – Zr, 391

WC – Fe – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni, 383

WC – Fe(OH)3, 480

WC – Fe – Mn, 383-384

WC – Fe2O3, 480

WC – Fe – Mn – Mo, 384

WC – Fe2O3 – C, 248

WC – Fe – Mn – Nb, 384

WC – Fe2O3 – NiO – C, 248

WC – Fe – Mn – Ni, 384

WC – Fe3Al, 479-480

WC – Fe – Mn – Ta, 384

WC – Fe3Al – B, 181

WC – Fe – Mn – Ti, 384

WC – Fe3Al – Cr, 356

WC – Fe – Mn – V, 385

WC – Fe3C, 480

WC – Fe – Mn – Zr, 385

WC – Fe3C – C, 247

WC – Fe – Mo, 385

WC – Fe3C – Fe – W, 393

WC – Fe – Mo – Nb, 385

WC – Fe3O4, 480

WC – Fe – Mo – Ni, 385

WC – Fe5Si3, 480

WC – Fe – Mo – Ta, 385

WC – FeAl, 476-479

WC – Fe – Mo – Ti, 385

WC – FeAl – B, 181

WC – Fe – Mo – V, 385

WC – FeAl – Fe2B, 479

WC – Fe – Mo – Zr, 385

WC – FeAl – Fe3Al – Al – Fe, 157

WC – Fe – N, 385

WC – FeAl – Y2O3, 479

WC – Fe – Nb, 385

WC – FeAl2 – Fe, 392-393

WC – Fe – Nb – Ni, 385

WC – FeAl3, 476

WC – Fe – Nb – Ta, 385 WC – Fe – Nb – Ti, 385

WC – FeNi – C – Co – Fe – Mn – Si, see WC – FeNi – Co – (Fe – C – Mn – Si)

WC – Fe – Nb – V, 385

WC – FeNi – Co – (Fe – C – Mn – Si), 337

WC – Fe – Nb – Zr, 385

WC – FePt – FeS – C – N, 248

WC – Fe – Ni, 386-388

WC – FexN, 480

WC – Fe – Ni – Si, 389

WC – Ga, 394

WC – Fe – Ni – Ta, 389

WC – Ge, 394

WC – Fe – Ni – Ti, 389

WC – H(OCH2CH2)nOH – La2O3, 481

WC – Fe – Ni – V, 389

WC – H2 – H2O, 540

WC – Fe – Ni – Zr, 389

WC – H2/D2, 536-539

WC – Fe – Ru, 389-390

WC – H2CO, 541

WC – Fe – Si, 390

WC – H2O, 541

WC – Fe – Ta, 390

WC – H2O – O2, 541

WC – Fe2N – FeWO4 – C, 247

Index (Chemical Systems)

929

WC – H2S, 541

WC – LaB6, 484

WC – HCN, 540

WC – LaB6 – Ni3Al, 484

WC – Hf, 394

WC – LiV3 O8, 485

WC – HfB2, 481

WC – Ln (La, Ce, Nd, Dy, Pr, Y) – Ni, 396

WC – HfB2 – HfO2, 481 WC – HfB2 – SiC, 481-483

WC – LnOy (La2O3, CeO2, Y2O3) – Co, 338

WC (γ, δ) – HfC, 483

WC – Mg, 396

WC – HfC – Mo2C – TaC – TiC – TiN – Co, 337

WC – MgO, 485-486

WC – HfC – Mo2C – TaC – TiC – TiN – Ni, 419

WC – MgO – ZrO2 – Pd, 428

WC – HfC – NbC, 483

WC – Mn – Ni, 396

WC – HfC – Ni, 419

WC – Mn – V, 397

WC – HfC – TaC, 483

WC – Mn(OH)2, 487

WC – HfC – TiC, 483

WC – MnO2, 486

WC – HfC – TiC – TiN – Ni, 419

WC – MnO2 – PbO2 – ZrO2, 486

WC – HfC – VC, 483

WC – MnS, 487

WC – HfC – ZrC, 483

WC – Mo, 397-398

WC – HfO2, 483

WC – Mo – Ni, 399

WC – Hg, 394

WC – Mo – Ni – W, 399

WC – I2, 541

WC – Mo2C, 488-489

WC – In, 395

WC – Mo2C – C, 248-249

WC – Ir, 395

WC – Mo2C – C – N, 249

WC – K – Na, 395

WC – Mo2C – C – Pd, 249

WC – KCl – LiCl, 483

WC – Mo2C – C – Pt, 249

WC – KCl – NaCl, 483

WC – Mo2C – Co, 338-339

WC – KCl – NaCl – Na2WO4, 484

WC – Mo2C – Co – Ni, 339

WC – KNO3 – NaNO3, 484

WC – Mo2C – Cu – Zr, 366

WC – KOH – NaOH, 484

WC – Mo2C – Fe – Ni, 393

WC – La, 395

WC – Mo2C – NbC – TiC – TiN – Co – Ni, 339

WC – La2O3, 484-485

WC – MgO – Ni, 419 WC – Mn, 396

WC – La2O3 – C – Co – Cr – Cu – Fe – Mn – Ni – Si, see WC – La2O3 – Co – Cu – (Fe – C – Cr – Mn – Ni – Si)

WC – Mo2C – Ni, 420

WC – La2O3 – C – Fe, 248

WC – Mo2C – SiC, 489-490

WC – La2O3 – Co, 337

WC – Mo2C – SiC – C, 250

WC – La2O3 – Co – Cu, 338

WC – Mo2C – SiC – TiC – TiN – Mo – Ni, 400

WC – La2O3 – Co – Cu – (Fe – C – Cr – Mn – Ni – Si), 338 WC – La2O3 – MgO, 485 WC – La2O3 – Ni, 419 WC – La2O3 – VC – Co, 338 WC – LaAlO3, 484

WC – Mo2C – Si3N4 – TiC – TiN – Co – Ni, 340

WC – Mo2C – TaC – TiC – Co – Ni, 340 WC – Mo2C – TaC – TiC – TiN – Ce – Co – Ni, 254 WC – Mo2C – TaC – TiC – TiN – Co – Ni, 340

930

Index (Chemical Systems)

WC – Mo2C – TaC – TiC – TiN – Ni, 420

WC – NbC – TaC – TiC – Co, 341

WC – Mo2C – TaC – TiC – TiN – VC – Co – Ni, 340

WC – NbC – TaC – TiC – TiN – Co, 341

WC – Mo2C – TiC – Co – Ni, 340

WC – NbC – TaC – TiC – TiN – VC − Co – Mo – Ni, 341

WC – Mo2C – TiC – Ni, 420

WC – NbC – TiC, 492

WC – Mo2C – TiC – TiN – Al – Mo – Ni, 157

WC – NbC – TiC – TiN – Ni, 421

WC – Mo2C – TiC – TiN – Co, 340

WC – NbC – UC, 492

WC – Mo2C – TiC – TiN – Co – Ni, 340

WC – NbC – VC, 493

WC – Mo2C – TiC – TiN – Ni, 420

WC – NbC – VC – Co, 341

WC – Mo2C – TiC – TiN – VC, 490

WC – NbC – ZrC, 493

WC – Mo2C – TiC – TiN – VC – Co – Ni, 340

WC – NbN – C – Co, 250

WC – Mo2C – TiC – TiN – VC – Ni, 420 WC – Mo2C – TiN – Co, 340 WC – Mo2C – TiN – Co – Ni, 340 WC – MoB – MoC – WB, 487 WC (γ, δ) – MoC (α, γ, η), 487-488, 490491

WC – NbC – TiC – VC – Cr – Ni, 357

WC – Nd2Fe14B, 493 WC – NH3, 543 WC – Ni, 403-409 WC – Ni – P, 410 WC – Ni – Pb – Pt, 410 WC – Ni – Pd, 410

WC – MoC – C, 248

WC – Ni – Pt, 410-411

WC – MoC – MoN – WN, 488

WC – Ni – Re, 411

WC – MoC – SiO2, 488

WC – Ni – Si, 411

WC – MoC – TiC – Co, 338

WC – Ni – Si – Ti, 411

WC – MoC – TiC – TiN, 491

WC – Ni – Sn, 411

WC – MoS2, 491

WC – Ni – Ti, 411

WC – MoS2 – Al – Mg – Zn, 158

WC – Ni – V, 411

WC – MoS2 – C, 250

WC – Ni – W, 411-412

WC – MoS2 – Co, 341

WC – Ni – Zn, 412

WC – MoS2 – Co – Cu, 341

WC – Ni(OH)2, 496

WC – MoS2 – Cu, 367

WC – Ni3Al, 494-496

WC – MoS2 – Ni, 420-421

WC – Ni3Al – B, 181

WC – N2, 541-542

WC – Ni3Al – B – Cr – Mo – Zr, 181

WC – Na2S2O8 – Y2O3 – ZrO2, 492

WC – Ni3Al – B – Cr – Zr, 182

WC – Na2SO4, 492

WC – Ni3Al – B – Zr, 182

WC – NaOH, 491

WC – Ni3Al – TiC, 496

WC – Nb, 402

WC – Ni3Al – TiC – Mo, 401

WC – Nb2O5, 493

WC – Ni3Al – TiC – TiN – Mo, 401

WC (γ, δ) – NbC, 492

WC – NiAl, 493-494

WC – NbC – Co, 341

WC – NiAl – B – Ni, 181

WC – NbC – NbN, 492

WC – NiAl – Co, 342

WC – NbC – TaC, 492

WC – NiAl – Ni3Al, 494

WC – NbC – TaC – Co, 341

WC – NiAl – NiB – Ni, 421 WC – NiAl3, 493

Index (Chemical Systems)

931

WC – NiAl3 – TiC, 493

WC – SiC – Al – Si, 158

WC – NiO, 496

WC – SiC – C, 251

WC – NiO – SiC – C, 250-251

WC – SiC – C – Fe, 251

WC – NiPx (Ni3P, Ni2P), 496-497

WC – SiC – Co, 342

WC – NiPx (Ni3P, Ni2P) – C, 251

WC – SiC – Co – Ni, 342

WC – NiPx (Ni3P, Ni2P) – Co – Ni, 342

WC – SiC – Co – Ti, 342

WC – NiPx (Ni3P, Ni2P) – Ni, 421-422

WC – SiC – Ni, 422

WC – NiPx (Ni3P, Ni2P) – Ni – W, 422

WC – SiC – Si, 436

WC – NO, 543 WC – Np, 425

WC – SiC – Si3N4 – Au – Cu – Pt – Ti, 159

WC – O2, 543-551

WC – SiC – TiC, 501

WC – Os, 426

WC – SiC – VC, 501

WC – Pb, 426

WC – SiC – WSi2, 501

WC – PbO – Co – Mo – Ni, 342

WC – SiC – ZrB2, 501

WC – PbO2, 497

WC – SiC – ZrB2 – Si, 437

WC – PbO2 – Al – Pb, 158

WC – SiC – ZrC, 503

WC – Pd, 427

WC – SiO, 552

WC – Pd3Au, 497

WC – SiO2, 504

WC – Pt, 428-429

WC – SiO2 – Cu, 367

WC – Pt – Ru, 430

WC – SiO2 – WN – Cu, 367

WC – Pu, 431

WC – Sn, 437

WC – Pu – Re – U, 431

WC – Ta, 437-438

WC – Pu – U, 432

WC – Ta2C, 506

WC – PuC, 497

WC – Ta2O5, 507

WC – PuC – UC, 497

WC (γ, δ) – TaC, 506

WC – PuC2, 497

WC – TaC – Co, 343

WC – Re, 432-433

WC – TaC – TiC, 506

WC – Rh, 433

WC – TaC – TiC – Co, 343

WC – Ru, 433-434

WC – TaC – TiC – Mo – Ni, 401

WC – S, 434

WC – TaC – TiC – TiN – Co – Ni, 343

WC – Sb, 434

WC – TaC – TiC – TiN – Ni, 422

WC – Sc, 434

WC – TaC – TiC – TiN – ZrC – Mo – Ni, 401

WC (γ, δ) – ScC, 497-498 WC – Se, 434 WC – Si, 434-436 WC – Si3N4, 503-504 WC – SiC, 498-500 WC – SiC – Ag – Co – Cu – Ti, 135 WC – SiC – Al – C – Si, 158 WC – SiC – Al – Co – Cr – Ni, 158 WC – SiC – Al – Mg – Si, 158

WC – TaC – VC, 506 WC – TaC – ZrC, 506 WC – Tc, 438 WC – Th, 438 WC – ThC, 507 WC – ThC2, 507 WC – Ti, 439-440 WC – Ti2O3, 511 WC – Ti3SiC2 – Co, 345

932

Index (Chemical Systems)

WC – TiAl, 508

WC – TiC – TiN – Ni, 423

WC – TiAl – TiB2, 508

WC – TiC – TiN – VC – Mo – Ni, 401

WC – TiAl – TiB2 – Y2O3 – ZrO2 – Co – Fe, 343

WC – TiC – TiN – VC – VN – Co, 345

WC – TiAl3, 508

WC – TiC – TiN – ZrC – Ni, 423

WC – TiB2, 508

WC – TiC – TiNi – Ti2Ni, 509

WC – TiB2 – B – Co – Ni, 182

WC – TiC – VC, 509

WC – TiB2 – Co, 343-344

WC – TiC – VC – Ni, 423

WC – TiB2 – Fe, 393

WC – TiC – VC – ZrC – Co, 345

WC – TiB2 – Mo – Ni, 401

WC – TiC – Y2O3 – ZrO2, 509

WC – TiB2 – Ni, 423

WC – TiC – ZrC, 509

WC – TiB2 – Ti, 441

WC – TiC – ZrC – C, 251

WC – TiB2 – TiC – Co, 344

WC – TiC – ZrC – Co, 345

WC – TiB2 – TiC – Mo – Ni, 401

WC – TiH2 – Ni, 424

WC – TiB2 – TiC – Ni, 423

WC – TiN, 509

WC – TiB2 – TiC – TiN, 508

WC – TiN – Co, 345

WC – TiB2 – TiC – TiN – Mo – Ni, 401

WC – TiNi, 510

WC – TiB2 – WN – Ti, 441

WC – TiO2, 510

WC (γ, δ) – TiC, 509

WC – TiO2 – C – Pt, 252

WC – TiC – (Co – C), 344

WC – TiO2 – Pt, 431

WC – TiC – C, 251

WC – Tl, 441

WC – TiC – C – Co, 251

WC – U, 441

WC – TiC – C – Co – Cu, 251

WC – UC, 511

WC – TiC – C – Co – Ni, 251

WC – UC – ZrC, 512

WC – TiC – C – Pt, 251

WC – UC2, 511

WC – TiC – Co, 344

WC – V, 442

WC – TiC – Co – Cr – Ni, 344

WC – V2O3, 512-513

WC – TiC – Co – Fe – Ni – W, 344

WC – V2O5, 512

WC – TiC – Co – Ni, 344

WC (γ, δ) – VC, 512

WC – TiC – Cr – Fe – Ni, 357

WC – VC – Al – Co, 158

WC – TiC – Fe, 393

WC – VC – Co, 345

WC – TiC – Mo – Ni, 401

WC – VC – Co – Fe – Ni, 345

WC – TiC – Ni, 423

WC – VC – Co – Ru, 345

WC – TiC – Pt, 431

WC – VC – Fe, 393

WC – TiC – Pt – Ru, 431

WC – VC – Ni, 424

WC – TiC – TiN, 509

WC – VC – VN – Co, 345

WC – TiC – TiN – Al – Fe, 158

WC – VC – VN – Co – Re, 345

WC – TiC – TiN – Co, 344

WC – VC – Y2O3 – ZrO2, 512

WC – TiC – TiN – Co – Fe – Ni, 344

WC – VC – ZrC, 512

WC – TiC – TiN – Co – Mo – Ni, 344

WC – VC – ZrC – C, 252

WC – TiC – TiN – Co – Ni, 344

WC – VC – ZrC – Co, 345

WC – TiC – TiN – Mo – Ni, 401

WC – TiC – TiN – Y2O3 – ZrO2, 509

Index (Chemical Systems)

933

WC – VO, 513

WC – W2C – B – Ni – Si, 179

WC – W, 443-445 WC – W24O68 – C – N – Pt, 253

WC – W2C – B4C – Cr7C3 – Cr23C6 – C – Cr – Fe – Ni, 244

WC – W2B, 513

WC – W2C – C, 191-193

WC – W2B5, 513

WC – W2C – C – Co, 200

WC – W2B5 – C – Co, 252

WC – W2C – C – Co – Cr, 201

WC – W2C, 514-517

WC – W2C – C – Co – Cr – Fe – Mn, see WC – W2C – Co – (Fe – C – Cr – Mn)

WC – W2C – (Fe – C – Cr – Mn – Ni – Si – Ti), 377 WC – W2C – (Fe – C – Cr – Mn – Ni – Si), 376-377 WC – W2C – (Fe – C – Cr – Mo – V), 378379 WC – W2C – (Fe – C – Mn – Si), 383

WC – W2C – C – Cr – Fe – Mn – Ni – Si, see WC – W2C – (Fe – C – Cr – Mn – Ni – Si) WC – W2C – C – Cr – Fe – Mo – V, see WC – W2C – (Fe – C – Cr – Mo – V) WC – W2C – C – Cr – Fe – Ni – Si, 207

WC – W2C – (Na,Ca)(Al,Mg)6(Si4O10)3(OH)6⸱nH2O, 491

WC – W2C – C – Cr – Fe –Mn – Ni – Si – Ti, see WC – W2C – (Fe – C – Cr – Mn – Ni – Si – Ti)

WC – W2C – 2SiO2∙Al2O3∙Na2O∙xH2O, 505

WC – W2C – C – Fe – Mn – Si, see WC – W2C – (Fe – C – Mn – Si)

WC – W2C – Al, 138

WC – W2C – C – H, 213-214

WC – W2C – Al – Co – Cr – Fe – Ni – V, 144

WC – W2C – C – H – O, 214

WC – W2C – Al – Cr – Fe – Mo – Nb – Ni – Ti, 147

WC – W2C – C – N, 218

WC – W2C – C – Mn – Rh – W, 215

WC – W2C – Al – Ni, see WC – W2C – Ni3Al

WC – W2C – C – Ni, 222-223

WC – W2C – Al2O3, 455

WC – W2C – C – Pt, 229-230

WC – W2C – Al2O3 – TiC – W, 446

WC – W2C – C – W, 240

WC – W2C – B – C – Co – Cr – Fe – Mn – Ni – Si – W, see WC – W2C – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W

WC – W2C – Co, 283-287

WC – W2C – B – C – Cr – Fe – Mn – Ni – Si, 164

WC – W2C – Co – W, 318

WC – W2C – B – C – Cr – Fe – Ni – Si, 168-170 WC – W2C – B – C – Cr – Fe – Ni – Si – W, 170

WC – W2C – C – Pd – W, 226

WC – W2C – Co – (Fe – C – Cr – Mn), 301 WC – W2C – Cr – Fe – Mo – Nb – Ni – Ti, 352 WC – W2C – Cr3C2 – Cr7C3 – Ni, 418 WC – W2C – Cu, 359

WC – W2C – B – C – Cr – Ni – Si, 171

WC – W2C – Cu – Ni – Sn, 363

WC – W2C – B – C – Fe – Ni – Si, 171

WC – W2C – Cu – Ni – W, 364

WC – W2C – B – C – Fe – Ni – Si – W, 171

WC – W2C – Fe, 371

WC – W2C – B – C – Ni – Si, 171-172

WC – W2C – Mo, 398-399

WC – W2C – B – Co – Cr – (Fe – C – Mn) – Ni – Si – W, 174

WC – W2C – Mo – Ni, 399

WC – W2C – B – Co – Cr – Ni – Si, 174

WC – W2C – Mo2C – C, 249

WC – W2C – B – Cr – Ni – Si, 176-177

WC – W2C – Ni, 409-410

WC – W2C – Mn – Rh – W, 397

WC – W2C – Mo2C, 489

934

Index (Chemical Systems)

WC – W2C – Ni – P, see WC – W2C – Ni3P – Ni

WC – WS2 – Ni, 424

WC – W2C – Ni3Al, 496

WC – WSi2 – W5Si3, 524

WC – W2C – Ni3P – Ni, 422

WC – Y, 447

WC – W2C – Pt, 429-430

WC – Y2O3, 524

WC – W2C – Pt – W, 430

WC – Y2O3 – Al – Fe, 158

WC – W2C – SiC, 500

WC – Y2O3 – Co, 346-347

WC – W2C – SiO2, 504

WC – Y2O3 – Fe, 393-394

WC – W2C – SnO2, 506

WC – Y2O3 – Ni – W, 424

WC – W2C – TiC, 509

WC – Y2O3 – ZrO2, 524-529

WC – W2C – TiO2, 510

WC – Y2O3 – ZrO2 – C – Co, 253

WC – W2C – TiO2 – TinO2n–1 (n = 4÷6), 510

WC – Y2O3 – ZrO2 – C – Ni, 253

WC – W2C – TiO2 – ZrO2, 511 WC – W2C – VC, 512 WC – W2C – VC – (W2B, WB), 512 WC – W2C – W, 445 WC – W2C – WB, 513 WC – W2C – WN – C, 252 WC – W2C – WO3, 522-523 WC – W2C – Y2O3 – ZrO2, 529 WC – W2C – ZrO2, 532 WC – WB, 513 WC – WB – Co, 345-346 WC – WB – W2B, 513 WC – WCoB, 517 WC – WN, 517-521 WC – WN – C, 252 WC – WN – C – W, 252 WC – WN – Co, 346 WC – WN – Cu, 367 WC – WN – W, 447 WC (γ, δ) – WN – WO3, 521 WC – WN – WO3 – WO2, 521 WC – WO2, 523 WC – WO2 – WO3 – Pt – Ru – W, 431 WC – WO3, 522 WC – WO3 – Pt, 431 WC – WO3 – WS2, 523 WC – WS2, 524 WC – WS2 – C, 253 WC – WS2 – Cr – Ni, 357

WC – WSe2, 524

WC – Y2O3 – ZrO2 – Co, 347 WC – Y2O3 – ZrO2 – Co – Cr – Ni, 347 WC – Y2O3 – ZrO2 – Cr – Ni, 357 WC – Y2O3 – ZrO2 – Ni, 424-425 WC – Zn, 447-448 WC – Zr, 448 WC – ZrB2, 529 WC – ZrB2 – C, 254 WC – ZrB2 – ZrO2, 529-530 WC (γ, δ) – ZrC, 530 WC – ZrC – Ni, 425 WC – ZrN, 530 WC – ZrO2, 530-532 WC – ZrO2 – Ag – Pb, 136 WC – ZrO2 – Al – Pb, 158 WC – ZrO2 – C – Ni, 254 WC – ZrO2 – Co, 347-348 WC – ZrO2 – Cr – Cu, 357 WC – ZrO2 – Ni, 425 WC – ZrO2 – Pb, 426