Proceedings of the 5th International Conference on Metal Material Processes and Manufacturing: Proceedings of ICMMPM 2023 (Springer Proceedings in Materials, 44) 9819715938, 9789819715930

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Springer Proceedings in Materials

Dong-Won Jung   Editor

Proceedings of the 5th International Conference on Metal Material Processes and Manufacturing Proceedings of ICMMPM 2023

Springer Proceedings in Materials

44

Series Editors Arindam Ghosh, Department of Physics, Indian Institute of Science, Bengaluru, India Daniel Chua, Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore Flavio Leandro de Souza, Universidade Federal do ABC, Sao Paulo, São Paulo, Brazil Oral Cenk Aktas, Institute of Material Science, Christian-Albrechts-Universität zu Kiel, Kiel, Schleswig-Holstein, Germany Yafang Han, Beijing Institute of Aeronautical Materials, Beijing, Beijing, China Jianghong Gong, School of Materials Science and Engineering, Tsinghua University, Beijing, Beijing, China Mohammad Jawaid , Laboratory of Biocomposite Technology, INTROP, Universiti Putra Malaysia, Serdang, Selangor, Malaysia

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Dong-Won Jung Editor

Proceedings of the 5th International Conference on Metal Material Processes and Manufacturing Proceedings of ICMMPM 2023

Editor Dong-Won Jung Mechanical Engineering Jeju National University Jeju, Korea (Republic of)

ISSN 2662-3161 ISSN 2662-317X (electronic) Springer Proceedings in Materials ISBN 978-981-97-1593-0 ISBN 978-981-97-1594-7 (eBook) https://doi.org/10.1007/978-981-97-1594-7 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 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 Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore Paper in this product is recyclable.

Preface

The 2023 5th International Conference on Metal Material Processes and Manufacturing (ICMMPM2023) was held on September 15–16, 2023, in Jeju Island, South Korea (hybrid). ICMMPM provided both online and onsite contributions, and we are delighted to present this proceedings to showcase the latest advancements in advanced materials and manufacturing. ICMMPM is an open forum for discussion, learning, and professional growth and development. We discussed the transformation of innovation and creativity in advanced materials and manufacturing development. We featured world-class speakers, editors, and participants from China, South Korea, Australia, Singapore, Japan, Turkey, Egypt, Morocco, and UK. ICMMPM received about 60 submissions (full papers and abstracts) and finally included 20 full papers in the proceedings. We would like to express our sincere gratitude to all the individuals who contributed to ICMMPM2023. A special thanks to all chairs and program committee members for organizing all sessions and reviewing all the submissions. This is to ensure the quality of presented research which is vital to the success of the conferences. We hope ICMMPM benefits all of you and look forward to meeting you all at ICMMPM2024. The Organizing Committee of ICMMPM2023.

Organization

Organizing Committees Conference Chairs Dong-Won Jung Lunyong Zhang

Jeju National University, South Korea Harbin Institute of Technology, China

Program Committee Chair Laichang Zhang

Edith Cowan University, Australia

Publicity Chair Abdollah Bahador

Osaka University, Japan

Program Committees ˙ Krzysztof Zaba Lin Feng Ng Lifei Wang Marcin Barburski Gérald Franz Yarub Al-Douri Amr Attia Abuelwafa Chung-Li Dong Tomasz Trzepiecinski Young Hyun Song Shouhang Li Mozhgan Hosseinnezhad Junhua Hu Mahdi Sabbaghian Roya Darabi Wu-Le Zhu

AGH University of Science and Technology in Krakow, Poland Universiti Teknologi Malaysia (UTM), Malaysia Taiyuan University of Technology, China Lodz University of Technology, Poland University of Picardie Jules Verne, France American University of Iraq, Sulaimani South Valley University, Egypt Tamkang University, Taiwan Rzeszow University of Technology, Poland Korea Photonics Technology Institute, South Korea Donghua University, China Institute for Color Science and Technology, Iran Zhengzhou University, China University of Tehran, Iran Jeju National University, South Korea Kyoto University, Japan

viii

Organization

Hwang Yi Oscar Hui Abdullah Al-Janabi Fatma Yalcinkaya Huan-Liang Tsai Kim Si jin Brouri Adil Ghorbel Elhem Abdeen Mustafa Omer Hugo Miguel Andrade Lopes Figueiredo da Silva Mohamed Abdel Moneim Deyab Ayssar Nahlé Yasin Polat José Rodríguez Barboza

Ajou University, South Korea University of East Anglia, UK Sultan Qaboos University, German Technical University of Liberec, Turkey Da-Yeh University, Taiwan Samsung Display Company, South Korea Moulay Ismail University, Morocco University of Cergy-Pontoise, France Energy Research Institute (ERI), Nottingham, UK University of Minho, Portugal Egyptian Petroleum Research Institute (EPRI), Cairo, Egypt University of Sharjah, Sharjah Erciyes University, Turkey Universidad Peruana de Ciencias Aplicadas, Peru

Academic Members Farid Abed-Meraim Osman Adiguzel Achanai Buasri Antonio Riveiro Rodríguez Ji Shijun Arnulfo Luévanos-Rojas Yanjun Li Jin-Young Kim Grzegorz Woroniak Walid Tawfik Younes Mohamed Siti Ujila Masuri Kazem Reza Kashy Zadeh Osman Adiguzel M. De Cesare Ma Quanjin

Laboratory of Microstructure Analysis and Mechanics of Materials, French Ankara University, Turkey Silpakorn University, Thailand University of Vigo, Spain Jilin University, China Autonomous University of Coahuila, México Florida Atlantic University, USA Ulsan National Institute of Science and Technology, South Korea Bialystok University of Technology, Poland Cairo University, Egypt Universiti Putra Malaysia, Malaysia Peoples’ Friendship University of Russia, Russia Firat University, Turkey Italian Aerospace Research Centre, Italy Universiti Malaysia Pahang, Malaysia

Contents

Pair Diffraction Function Analysis of Conversion of a Fermat Scroll to an Archimedean Scroll in Multiwalled Carbon Nanotubes . . . . . . . . . . . . . . . . . Bagautdin Bagautdinov

1

Effect on PEEK/Graphite Film for Raceway Surface of PEEK Hybrid Ball Bearings with Surface Crack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H. Koike, T. Harajiri, T. Haraguchi, T. Matsueda, K. Mizobe, and K. Kida

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Evaluation of Fatigue Properties of Additively Manufactured High-Entropy Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Miu Hayashi, Naoki Kurita, Tadatoshi Watanabe, Hiroyuki Akebono, and Atsushi Sugeta Solid-Phase Interaction of Zinc Ferrite with Calcium Oxide . . . . . . . . . . . . . . . . . Sergei Yakornov and Gennady Skopov Effects of Fe Addition on the Phase and Mechanical Properties of Ti-15Mo Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nthabiseng Moshokoa, Lerato Raganya, Nkutwane Washington Makoana, Hasani Chauke, Ramogohlo Diale, Maje Phasha, and Elizabeth Makhatha Technology of Obtaining Metallic Silver from Waste Copper Tailings . . . . . . . . . L. M. Karimova, Ye. T. Kairalapov, E. M. Kharchenko, and B. B. Katrenov

20

27

34

45

Investigation of Co-dopant (Eu3+ -Ce3+ ) Induced Electronic Transitions in LiCaBiB Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Madhu, Namrata Yaduvanshi, T. Uthayakumar, and N. Srinatha

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Optimization of Plastic Injection Molding Process Parameters for a DACIA Logan L90 Front Bumper with Taguchi Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . Soufiane Haddout

56

Experimental and Simulation Stress Analysis of PVC Pipe Under Different Operational Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Muhammad Kamran Khan, Muhammad Mubashir Kaleem, Muhammad Bilal, Imran Shah, Krishna Singh Bhandari, Shahid Aziz, and Dong-Won Jung

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Contents

Development of an Electric Powertrain for the Conversion of an ICE Vehicle . . . Ali Ubaid, Abdur Rehman Mazhar, Yasser Riaz, Shahid Aziz, Krishna Singh Bhandari, and Dong-Won Jung

73

Recent Advances in the Development of Pulsed Laser Deposited Thin Films . . . Ho Soonmin, Mahmood Alhajj, and Auttasit Tubtimtae

80

Review on Current Research of Fabrication, Properties and Applications in Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ho Soonmin

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A Comprehensive Review of Recent Progress on the Removal of Pharmaceutical Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 Ho Soonmin, Sie Yon Lau, Abdul Zahir, Sankha Chakrabortty, and Ajala Oluwaseun Jacob On Hidden Reason for Fractals from Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 Vijayakumar Mathaiyan, Vijayanandh Raja, Beena Stanislaus Arputharaj, and Dong Won Jung Residual Stresses Characterization in Friction Stir Welding of 2017 A-T451 Alloy Using Eddy Current Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132 Sari Elkahina, Benachenhou Kamel, Bennoud Salim, Kirad Abdelkader, Boucherou Nacer, and Mimouni Oussam Development of an Experimental Methodology to Investigate the Occurrence of the Tribocorrosion Phenomenon in Metallic Materials . . . . . . 144 Gerardo A. Rodriguez-Bravo, Manuel Vite-Torres, Ezequiel A. Gallardo-Hernández, and César Sedano-de la Rosa Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

Pair Diffraction Function Analysis of Conversion of a Fermat Scroll to an Archimedean Scroll in Multiwalled Carbon Nanotubes Bagautdin Bagautdinov(B) Japan Synchrotron Radiation Research Institute (JASRI/SPring-8), 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan [email protected]

Abstract. The paper represents results from synchrotron high-energy X-ray diffraction (HEXRD) studies of multiwall carbon nanotubes (MWCNTs) heated and cooled in the temperature range of 298–450 K. Structural features of MWCNT powders have been studied by the real–space atomic pair distribution function (PDF) technique. XRD thermal study established that the MWCNTs are mainly of scroll type. The PDF structures on different length scales were used to study the interlayer spacing distribution in the carbon nanotube scrolls (CNSs). The method discovers that the pristine CNSs are described as left- or right-handed Fermat spiral (r = ±aθ1/2 ) with uneven interlayer distances, rather than the XRD crystallography equidistance Archimedean spiral (r = aθ). The increased interlayer spacings of the innermost layers are caused primarily by the high curvature and thus the high strains are caused by π–π coulombic repulsion between the curved layers. At larger diameters, the CNS layers are less deformed and extensively interact through the van der Waals force affecting interlayer spacing shrinkage. The irregular interlayer spacing of the pristine CNS converses to a uniform spacing between layers at heating-cooling cycles within 298–450 K. The spatial changes in CNSs demonstrate the transformation of Fermat-type stroll in pristine nanotubes to more stable Archimedean spiral at heating-cooling processes. Keywords: Carbon nanotube scrolls · Synchrotron X-ray diffraction · Total scattering · Pair distribution function

1 Introduction The structures of carbon nanotubes (CNTs) typically of a diameter in the nano range and a length in the micro range are extremely strong and flexible and present excellent electrical, mechanical, and thermal properties [1, 2]. Nowadays, macroscopic composites of CNTs implanted in a polymer matrix are widely used for diverse applications [3]. During fabrication and operation, the CNT-based devices may experience thermal manipulations that may induce structural changes in tubes [4, 5]. Therefore, the knowledge of the thermal behavior of CNTs is of great interest for controlling the performance of nanotube devices. The temperature dependence of the electrical resistivity of composite films produced using carbon nanotube scrolls (CNSs) (95 wt.%) in the polytetrafluoroethylene © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 1–10, 2024. https://doi.org/10.1007/978-981-97-1594-7_1

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(PTFE) (5 wt.%) matrix exposed anomalies at ~343 and ~423 K during cyclical heating and cooling amongst 298–450 K ([6], Fig. 1). Unusually, the experimental values of the first heating run of the composite and the following measurements of the heattreated ones did not overlap, though the anomaly points were irreversible. The electrical resistivity decreases greatly after the first heating-cooling cycle. This behavior of the CNS/PTFE composite implies that some defects or structural features existing in the initial as-grown samples are likely customized upon the heating-cooling action. We used the synchrotron high energy X-ray diffraction (HEXRD) for in situ examination of structural parameters of the CNS/PTFE powder at heating-cooling cycles between room temperature and 450 K. The analysis has concentrated on the structure feature of the CNS phase (95 wt.%). The motivation of the research undertaken is to explain an irregular performance in the measurements of electric resistance in the CNS/PTFE films through structure-function relationship (Fig. 1). For multiwall carbon nanotubes (MWCNTs) or CNSs, one of the significant parameters characterizing the properties is their inter-shell or interlayer distances, respectively. In MWCNT or CNS, the adjacent layers interact through the van der Waals (vdW) force governed by out-of-plane π–π interactions. The curving nature of the graphene walls in nanotubes affects the spacing between their graphene walls or layers. It was established that the average interlayer spacing in MWCNTs is due to unavoidable turbostratic stacking of rolled-up layers wide-spaced (usually ~0.36 nm) compared with the graphite crystal (~0.335 nm) [5]. Moreover, the interlayer spacings of MWCNT decrease from 0.39 nm to 0.34 nm as a tubule’s diameter increases consisting of a lower curvature and thus reduced strain in tubes of larger diameter [7–9].

Fig. 1. Temperature dependence of the CNS/PTFE composite films resistivity. Green arrows show HEXRD data collection points.

The temperature variations develop a modest effect on the graphene plane because of in-plane strong carbons σ-bonds, but they may have a marked outcome on the couplings between layers because of weak vdW interlayer interactions. A variation of the interlayer spacing/coupling in MWCNT or CNS suggests significant changes in its functional parameters mainly controlled by interlayer π–π interactions. Therefore, it is useful

Pair Diffraction Function Analysis of Conversion of a Fermat Scroll

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to explore the behavior of interlayer spacings in MWCNT or CNS at heating-cooling treatments. In the present paper, we probed the structures of CNSs at thermal cycles between 298–450 K with the real space pair distribution function (PDF) method based on the total (Bragg and diffuse) scattering [10, 11].

2 Materials and Methods The MWCNT samples of typical lengths of 100–200 nm, outer diameters of 10–20 nm, and inner diameters of 1.2–3.5 nm were obtained by the arc discharge plasma process. Then they were dispersed in the polytetrafluoroethylene (PTFE) matrix in the proportion 95/5 wt.% [6]. The PTFE had melting and decomposition temperature points above 600 and 630 K, respectively, and thus the heating run was regulated up to 450 K. The HEXRD experiments were carried out in the SPring-8 synchrotron facility, at BL04B2 enabling measurements in the range of the scattering vector up to 25.0 Å−1 which yielded PDFs with high resolution [12–14]. The incident X-ray energy was 61.4 keV (λ = 0.202 Å) and scattering was detected in the wide θ-range (2θ/θ scans, 2θ = 0.3–49.0°). The powder samples within quartz capillaries were sited in a vacuumed furnace. The computed structure factors S(Q) and atomic PDFs, G(r), are based on only the elastic component of XRD. The real space PDF structure refinements were performed using the program PDFgui [15, 16].

3 Results and Discussion We characterized the powder nanotubes using in situ HEXRD at first heating from room temperature to 450 K at thermal points of 313, 363, and 423 K, and after cooling from 450 K to room temperature the following second heating run in the same range was performed with data collection at 298, 343 and 443 K (Fig. 1, Fig. 2a). The diffraction patterns show an obvious diffuse scattering and a few Bragg peaks, as the relatively intense (00l) and saw-toothed (hk0) (Fig. 2a). A strong asymmetry shape with long tails towards higher diffraction angles for (hk0) and almost no appearance of the (hkl) peaks reflects the weak correlations between carbon atoms in distinct layers (turbostratic disorder). The hexagonal graphite model (P63 /mmc, a = 2.464 Å, c = 6.711 Å [17] was implied to explain the diffraction patterns of the CNS powder (Fig. 2b). For structure modeling of multiwall carbon tubes is important to realize the arrangement type of the layers, i.e., whether they represent nested carbon tubes or scroll-shaped graphene [18, 19]. To determine the type of nanotubes superposing of the peaks at the heating process was performed (Fig. 3). At heating, a shift of radial axis reflections (004) and (006) to the low 2θ side, while the axial direction peaks (100) and (110) show virtually no changes were revealed. This thermal behavior of the peaks classifies that the anisotropic lattice expansions of the nanotube samples were visibly large in the radial axis compared with the axial one. It implies that the nanotube powder is essentially of the scroll-type or mixtures of nested and scrolled nanotubes [20, 21].

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a

b

Fig. 2. a) The powder HEXRD profiles of pristine CNS and the empty quartz capillary as a function of temperature. b) Schematic of a CNS model that consists of three curved graphene layers. The bulk graphite lattice that builds the nanotube walls in a repetitive ABAB manner is embedded in layers of the CNS tubes.

Fig. 3. Superposed view for the axial (100), (101), radial (004) and axial (110), radial (006) reflections at the heating process: 313 K (shown in black), 363 K (red), 423 K (blue).

Generally, the database structure of a material comprises an averaged configuration of atoms in an idealized crystal lattice. But for nanophase materials like CNTs the local and intermediate nanoscale structures are caused by various disorders, and impurities that are often responsible for interesting functional properties. The partial Bragg information and a pronounced diffuse scattering in diffraction patterns of CNTs make it difficult to use established powder XRD methods for structure determination. For nanophase materials, it is useful to consider the PDF technique based on total scattering measurements probing both the Bragg diffraction and the diffuse scattering in a wide range of momentum transfer Q and considering their inputs equally [10, 11, 16]. The PDF output provides the probability of finding pairs of atoms separated by a distance r, which is an interesting feature for a more thorough picture of nanocrystalline materials. Insights into the atomic structure of CNT at local and intermediate scale ranges are needed for understanding and predicting its properties. Experimental total scattering structure functions S(Q) and PDF, G(r), of CNS powder are shown in Fig. 4a and Fig. 4b, respectively. The PDF diagram provides a spectrum

Pair Diffraction Function Analysis of Conversion of a Fermat Scroll

a

5

b

Fig. 4. a) Superposed total structure functions, S(Q), of CNSs plotted over Qmax = 25.0 Å−1 ; heating run: 313 K (shown in black), 363 K (red), 423 K (blue). b) The experimental PDFs, G(r), of CNSs of the heating run, are overlapped: 313 K (shown in black), 323 K (red), and 423 K (blue). The PDF peaks declined beyond r = 50 Å.

of C–C distances in CNS and analyzing the PDF peaks offers basic information on its local atomic structure. The PDF peaks decline at r about 50 Å implying reduced carbon-carbon coherences beyond 5.0 nm above which arbitrarily distributed C–C pairs may occur (Fig. 4b). The PDFs of the CNS display sharp peaks in the range r < 7 Å indicating the short-range order stacking of the basic graphite hexagonal configuration. For r > 7 Å gradual modifications in the PDFs peaks are observed, presumably because the interlayer correlations in the MWCNTs are decayed due to the curvature of the graphene sheets. Comparison of room temperature PDFs of the pristine CNS and after the heating-cooling round (298–450 K) shows peak positional deviations in the range of 7.7 < r < 10.3 Å (Fig. 5).

Fig. 5. The superposed room temperature PDFs (6 < r < 11 Å) of the as-grown CNS powder (drawn in blue) and after the heating-cooling run (drawn in red).

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At a radial interval of about r ≈ 6–10 Å, the PDF peaks are affected by tube curves. The PDF peak shifts in the thermally treated tube compared with the pristine sample suggested curvature reorganizations of adjacent scroll layers of tubes which unevenly affect their interlayer spacing. In addition to investigating the PDF pattern by considering the discrete or group of the peaks, valuable structural information on CNSs can be obtained using the PDFgui real-space refinement using the graphite structural model [7, 17]. Here we assumed that the carbon atoms ordering in the nanotubes the way crystalline graphite cell is embedded into the layers with c-axis along radial direction (Fig. 2b). The long-range (up to r = 25 Å) fitting of experimental and the computed graphite model PDFs shows that in the distinct r parts, the PDFs agreed differently (Fig. 6a). It proposes a departure of the local tubular structures from the long-range average structure. Because a real space PDF curve contains structural information from local to medium-range length scales the structure over various length scales can be determined by distinctly fitting data within different r ranges, so-called “r-range refinement” [16, 22]. The fitting results for 1 < r < 8 Å can be considered as a “local-range structure”, and the fitting output for 10 < r < 25 Å as a “medium-range structure” (Fig. 6b and Fig. 6c). The divergences between the fitted and experimental PDFs are a consequence of natural deviations of the curved nanotube structure from the model graphite plain structure. For turbostratic, curved CNS layers the ordered ABAB graphite stacking sequence is not the rule, the tube atoms are shifted from graphitic positions. The PDFgui refinement using the graphite model is rather helpful in defining details of lattice parameter changes as a function of length scale. PDFgui r-range refinements yield practically constant parameters for in-plane axes (a = b axes) and varied values for interlayer c-axis (Fig. 6). The important structural information of r-range refinements of CNSs is the c-axis data (c-axis of graphite positioned along the radial axis in CNS (see Fig. 2b)). The value of caxis i.e., interlayer spacing is changed when averaged over different length scales. Hence, modeling was performed for several r ranges, and the lattice c/2-parameters (interlayer distance) as a function of length scale are derived from the refined models shown in Fig. 7a. The CNS samples present large interlayer distances at local scales, and they decrease with longer-length scale refinements. The irregular interlayer spacing behavior in the pristine CNS is possibly related to the bending peculiarities of the graphene sheet. The large interlayer spacing at low r is attributed to the innermost part of CNS having a larger curvature and strain. It is comparable to the observed inter-shell distances for MWCNTs with different diameters [8, 9]. In CNS the innermost layers are most bent and with graphene coiling to the outmost layers the bending curve as well as strain have become lesser. Therefore, as the tube radius continuously raises from innermost to outmost layers, the interlayer spacing likely decreased, a feature well presented in Fermat type spiral r = ±aθ1/2 , a > 0, lefthanded branch or a < 0, right-handed branch (Fig. 7b and 7c). A stable form of CNS is Archimedean-type spirals (Swiss rolls) formed by rolling single-layer graphene sheets with uniform interlayer distances [23, 24]. The unstable Fermat scroll inclines to become the energetically favorable Archimedean one at thermal perturbation and under other forces.

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Fig. 6. PDFgui refinement of CNS for different ranges r. Graphite structure model fitted to the PDF of CNS powder. Experimental and calculated PDFs are presented with blue circles and a solid red line, respectively. The difference between the observed and calculated is offset below (green solid lines). Computed model: S.G. P63 /mmc, a = 2.464 Å, c = 6.711 Å, ADPs for C(1): u11 = 0.0031 Å2 , u33 = 0.016 Å2 and for C(2): u11 = 0.0031 Å2 , u33 = 0.017 Å2 [17]. PDFgui refinements for ranges r: a) 1 < r < 25 Å; a = 2.455(1) Å, c = 6.817(14) Å, Rw = 0.42; b) 10 < r < 25 Å; a = 2.453(8)Å, c = 6.818(6)Å, Rw = 0.37, and c) 1 < r < 8 Å; a = 2.458(1) Å, c = 6.869(27) Å, Rw = 0.20.

Following the heating-cooling treatment of CNS, the gap of interlayer spacings between local and intermediate r-ranges decreased (Fig. 7a and 7b), indicating that the topology of the scroll tends to reform to the more stable equally distanced spiral. The evolution of the Fermat shape to the Archimedean scrolled configuration would involve only a gentle sliding of the graphene layer in CNS (Fig. 7c). Indeed, diffraction patterns of the CNS confirmed that the integrity of tubes is well sustained at heat treatments (Fig. 2a). The Archimedean and Fermat spirals have a variety of real-world applications. The Archimedean spirals have a constant distance between successive coils, r = aθ, where r is the distance of a point on the curve from the origin, a is related to the interlayer distance d by d = 2π a, and θ is the angle in radians. For CNSs of d = c/2 = 3.406 Å the Archimedean parameter a is about 0.5425. Fermat’s spiral is presented by polar equation r = ±aθ1/2 , (a > 0, counterclockwise or left-handed branch; a < 0, clockwise, or right-handed branch), the parameter a

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Fig. 7. a) PDF refined c-axis/2 parameters (interlayer distances) of the pristine MWCNTs (drawn in black) and after the first heating-cooling treatment (drawn in red) and after the second heatingcooling cycle (drawn in blue) as a function of length scale. The model fitting ranges of real space gradually increased from 1 < r < 3.7 Å to 1 < r < 25 Å. The presented radial cross-section of scrolls coincides with the c-axis of the graphite model structure, with interlayer spacing equal to c/2. b) Schematic path of evolution of the pristine Fermat scroll, after the first and the second thermal treatments between 280–450 K. c) Representation of evolution from a Fermat scroll to an Archimedean scroll. Fermat scroll (r = aθ1/2 , a > 0, counterclockwise or left-handed branch) with the radial dependency of interlayer spacing transforms to an Archimedean-type left-handed spiral (r = aθ) of constant spacing of d ~ 3.406 Å between layers.

stands change of distance between neighboring curves. For the Fermat spiral, the spacing between turns decreases with an increase in their distances from the spiral center, opposing to the Archimedean spiral in which this distance is invariant. Annealing processes of multiwall nanotubes (~2500 °C) revealed a decrease in the interlayer spacing with a substantial reduction in electrical resistivity [5]. The high

Pair Diffraction Function Analysis of Conversion of a Fermat Scroll

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electrical resistivity (~28 m) for the pristine CNS/PTFE films (Fig. 1) can be described by a weak π–π coupling interaction between adjacent layers in the tube’s cores due to the large interlayer spacings in their innermost parts. The local structural changes upon the 298–450 K cycling involving decreased interlayer spacing at low r make the coupling interaction increase in the inner of tubes like the outermost layer. The expansion of the interlayer interactions over the entire tubes in the thermally treated CNSs and thus overall rise to π–π interlayer coupling of tubes jointly with other changes in the CNS/PTFE films impacted massive reduction (~2.3 times) of electrical resistivity in the thermally treated films compared with the pristine ones.

4 Summary The thermal behavior of the powder samples of MWCNT designates the scroll-type CNS model. The PDFgui length-scale refinements confirm a scroll-type structure for tubes, involving one single rolled-up graphene sheet. The PDF of CNS was simulated using a single-structure model of the ABAB… hexagonal graphite. The large interlayer spacings at a small r < 10 Å are linked to the large curvature/strains in the innermost part of the tube. It is found that the interlayer spacing of the pristine CNS decreases with increasing tube radius where bending curves, thus distortions are lesser (Fermat scroll; left-handed or right-handed branch). Upon the heating-cooling cycles of CNS, the low r-range interlayer spacings became lesser. It presents the tendency of transformation of the Fermat-type spiral to the more stable Archimedean spiral. Likely, thermal heating weakens interlayer stacking π–π bonding leading to partial transformation and relaxing of the layer distortions. Acknowledgments. The synchrotron radiation experiment was approved by the Japan Synchrotron Radiation Research Institute (proposals 2016A1836 and 2021B2100).

References 1. Iijima, S.: Helical microtubules of graphitic carbon. Nature 354(6348), 56–58 (1991) 2. Baughman, R.H., Zakhidov, A.A., De Heer, W.A.: Carbon nanotubes - the route toward applications. Science 297(5582), 787–792 (2002) 3. Ajayan, P.M., Stephan, O., Colliex, C., Trauth, D.: Aligned carbon nanotube arrays formed by cutting a polymer resin-nanotube composite. Science 265(5176), 1212–1214 (1994) 4. Chen, J., et al.: The structural evolution of thin multi-walled carbon nanotubes during isothermal annealing. Carbon 45(2), 274–280 (2007) 5. Tojo, T., et al.: Controlled interlayer spacing of scrolled reduced graphene nanotubes by thermal annealing. RSC Adv. 3(13), 4161–4166 (2013) 6. Babaev, A.A., et al.: Temperature dependence of electrical resistivity of composite films based on multiwalled carbon nanotubes. Phys. Solid State 57(2), 424–427 (2015) 7. Bagautdinov, B., Ohara, K., Babayev, A.: High-energy X-ray diffraction study of multiwalled carbon nanotubes fabricated by arc discharge plasma process. Carbon 191(5), 75–83 (2022) 8. Kiang, C.H., Endo, M., Ajayan, P.M., Dresselhaus, G., Dresselhaus, M.S.: Size effects in carbon nanotubes. Phys. Rev. Lett. 81(9), 1869–1872 (1998)

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9. Singh, D.K., Iyer, P.K., Giri, P.K.: Diameter dependence of interwall separation and strain in multiwalled carbon nanotubes probed by X-ray diffraction and Raman scattering studies. Diam. Relat. Mater. 19(10), 1281–1288 (2010) 10. Egami, T., Billinge, S.J.L.: Underneath the Bragg Peaks: Structural Analysis of Complex Materials. Pergamon Press, Elsevier, Oxford (2003) 11. Billinge, S.J.L., Levin, I.: The problem with determining atomic structure at the nanoscale. Science 316(5824), 561–565 (2007) 12. Kohara, S., Suzuya, K., Kashihara, Y., Matsumoto, N., Umesaki, N., Sakai, I.: A horizontal two-axis diffractometer for high-energy X-ray diffraction using synchrotron radiation on bending magnet beamline BL04B2 at SPring-8. Nucl. Instrum. Methods Phys. Res. Sect. A 467–468(2), 1030–1033 (2001) 13. Ohara, K., Onodera, Y., Murakami, M., Kohara, S.: Structure of disordered materials under ambient to extreme conditions revealed by synchrotron x-ray diffraction techniques at SPring8-recent instrumentation and synergic collaboration with modeling and topological analyses. J. Phys. Condens. Matter. 33(38), 383001 (2021) 14. Kohara, S., et al.: Structural studies of disordered materials using high-energy x-ray diffraction from ambient to extreme conditions. J. Phys. Condens. Matter. 19(50), 506101 (2007) 15. Farrow, C.L., et al.: PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals. J. Phys. Condens. Matter 19(33), 335219 (2007) 16. Billinge, S.J.L.: Real-space rietveld: full profile structure refinement of the atomic pair distribution function. In: Billinge, S.J.L., Thorpe, M.F. (eds.) Local Structure from Diffraction, pp. 137–156. Plenum, New York (1998) 17. Howe, J.Y., Rawn, C.J., Jones, L.E., Ow, H.: Improved crystallographic data for graphite. Powder Diffr. 18(2), 150–154 (2003) 18. Amelinckx, S., Bernaerts, D., Zhang, X.B., Tendeloo, G., Landuyt, J.: A structure model and growth mechanism for multishell carbon nanotubes. Science 267(5202), 1334–1338 (1995) 19. Viculis, L.M., Mack, J.J., Kaner, R.B.: A chemical route to carbon nanoscrolls. Science 299(5611), 1361 (2003) 20. Vanacore, G.M., Veen, R.M., Zewail, A.H.: Origin of axial and radial expansions in carbon nanotubes revealed by ultrafast diffraction and spectroscopy. ACS Nano 9(2), 1721–1729 (2015) 21. Maniwa, Y., et al.: Multiwalled carbon nanotubes grown in hydrogen atmosphere: an x-ray diffraction study. Phys. Rev. B 64(7), 073105-1–073105-4 (2001) 22. Hou, D., Zhao, C., Paterson, A.R., Li, S., Jones, J.L.: Local structures of perovskite dielectrics and ferroelectrics via pair distribution function analyses. J. Eur. Ceram. Soc. 38(4), 971–987 (2018) 23. Lima, M.D., et al.: Biscrolling nanotube sheets and functional guests into yarns. Science 331(6013), 51–55 (2011) 24. Li, H., Li, M., Kang, Z.: Mechanics of the scrolling and folding of graphene. Nanotechnology 29(24), 245604 (2018)

Effect on PEEK/Graphite Film for Raceway Surface of PEEK Hybrid Ball Bearings with Surface Crack H. Koike1(B) , T. Harajiri1 , T. Haraguchi1 , T. Matsueda2 , K. Mizobe2 , and K. Kida2 1 University of Miyazaki, 1-1 Gakuen Kibanadai-nishi, Miyazaki 889-2192, Japan

[email protected] 2 University of Toyama, Gofuku 3190, Toyama 930-8555, Japan

Abstract. To clarify effect on the composite film layer of PEEK and graphite in PEEK hybrid radial alumina ball bearings with surface fatigue cracks, rolling contact fatigue tests were performed by using the PEEK bearing’s inner rings with the surface cracks in the dry and water conditions. When applied load and rotational frequency of the bearing were 98 N and 600–1400 min−1 , the number of fatigue cycles of the PEEK hybrid bearings reached 1.0E6 cycles. The PEEK composite film containing nano-sized graphite particle covered the surface cracks on the PEEK ring’s raceway after the tests. In addition, friction heat and cyclic compression caused the plastic flow in the composite film layer of PEEK and graphite. Due to effect of the PEEK/graphite film, the fusion of the cracks on the raceway surface of the PEEK inner ring occurred. The accumulation layer of PEEK/graphite film reduced the surface defects such as surface cracks on the raceway of PEEK inner ring, which improved the bearing’s performance. Keywords: Rolling Contact · PEEK film · graphite · surface defect · fatigue crack · plastic bearing

1 Introduction Radial ball bearings consisting of metals or polymers etc. are used as one of drive parts in various industrial machinery. The latest market demands for components in various situation use such as corrosion/chemical environment, non-magnetism, energy saving or easily maintainable situations. Application of high-performance polymer bearings are being gradually extended [1–3]. PEEK (Polyether ether ketone) is a high performance polymer with superior properties including heat resistance, chemical durability, non-magnetism, biocompatibility, and machinability for polymer products, which expects polymer application in special environment [4–6]. Tribological surface damages shorten lifetime of PEEK mechanical parts. Also fatigue strength of polymer mechanical element is important property because strength of polymer part is lower compared to metal parts. Therefore, reduction of tribological surface damages is expected for long lifetime of polymer mechanical element. In a © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 11–19, 2024. https://doi.org/10.1007/978-981-97-1594-7_2

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PEEK bearing under rolling contact, the tribological surface damage such as melting, seizure, wear, or cracks occur on a bearing’s raceway surface with friction [6–8, 13, 14]. Additionally, the rotational frequency and applied load influence plastic deformation in raceway of bearing’s ring. The tribological performances of PEEK composites have been studied for reduction of tribological failures on raceway surfaces of PEEK bearings [9–15]. To recover damage of thermoplastic resin, the fusion bonding is promising methods. In spin welding as one of fusion bonding, the parts are rubbed against the other parts under a specific velocity and pressure until melting their interfaces [16]. For example, the fusion bonding enable to fuse together Polyetherimide films at the temperature between 215 °C and 340 °C [17, 18]. Koike et al. reported that the artificial defects on the contact surface of the PEEK bar could be partially repaired in the cyclic contact test using graphite particles [19]. Solid lubrication is an important tribological item to protect frictional interfaces on thermoplastic mechanical element in special situation use. Polymer composite film containing solid-lubricant composite helps long life of mechanical element. The polymer composite transfer film as a self-lubricating material typically forms in the interfaces between friction parts, which improves tribological performance of mechanical elements. According to references by Bahadur [12], the transfer composite film of PTFE (polytetrafluoroethylene) and PEEK made improvement of the wear durability in the sliding tests using a steel disk. This means that transfer composite film with solidlubricant reduced the surface damage such as seizure [20, 21]. Additionally, the transfer film reduces friction heat generation. In our previous work, we presented the possibility to increase the rotation performance of PEEK-hybrid bearing with the PEEK composite film [22]. Therefore, the transfer film formation process after running-in is significant for stable performance in lifetime operation of polymer bearings. However, the transfer film formation on the rolling contact surface in PEEK polymer bearings with surface texture such as microgrooves has not been well understood. The objective of this study was to clarify the effect of PEEK/graphite film as selflubrication film. Rolling contact test was carried out by using PEEK hybrid ball bearings with surface defects, to clarify effect on PEEK/graphite film for harmless of surface cracks.

2 Test Procedure 2.1 Bearing Samples The schematic illustration of the test sample is shown as in Fig. 1. The inner diameter of the bearing sample was ϕ25 mm. The outer diameter and pitch diameter are ϕ52 and ϕ38.6 mm, respectively. We used the surface defect samples as the PEEK bearing with surface cracks. These surface defects were formed on the PEEK inner ring raceway surface through the rolling contact under water condition using the radial test machine (Fig. 2 and Fig. 5a). The width and length of the surface crack area on the raceway of the inner ring were approximately 1.5 and 2.5 mm (Fig. 5b). Nine Alumina balls and a retainer made of composite of PTFE and graphite were used.

Effect on PEEK/Graphite Film for Raceway Surface

13

2.2 Operation Condition in Rolling Contact Test Figure 2 shows schematic illustration of the test machine for radial bearing. To investigate the change of the bearing’s raceway with surface cracks, RCF tests were carried out. Applied load (F load ) for the RCF test was 98 N. Rotational frequency in the RCF tests were set 600–1400 min−1 as shown in Table 1. The rotational step-speed of the bearing sample #3 increased 200 min−1 each 2.0E5 fatigue cycles (Fig. 3). Because the operation temperature of the bearing sample was unstable in early stage before 1.5E5 fatigue cycles under the RCF test above 3000 min−1 , the rotational frequency in this work was adjusted between 600 and 1400 min−1 . Each RCF test was continued until the reference temperature on the front face of PEEK inner ring reached 60 °C or 1.0E6 fatigue cycles. For the monitoring of the reference temperature of the bearing sample in the test, the non-contact radiation thermometer (FLUKE 62Max) was used. The reference temperature of the bearing was measured at the front face of inner ring (Fig. 1). When the reference temperature is over 60 °C, the temperature of raceway surface is higher than that of front face of inner ring. This means that the local temperature on the rolling contact surface of the inner ring reaches T g of PEEK (124 °C). 2.3 Investigation of Surface and Cross-Section The raceway surface of PEEK inner ring was observed by optical microscope (KH-7700, Hirox). JEM-2010MX (JEOL Ltd.) as STEM (Scanning Transmission Electron Microscope) and EDS (Energy Dispersive X-ray Spectroscopy) were used for investigation of the cross-section of the PEEK/graphite film formed on the raceway of the inner ring.

Fig. 1. Schematic illustration of bearing test sample with surface defect.

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H. Koike et al. Table 1. Test condition.

Sample#

Speed and F load

Notes

Preparation sample (for bearing with surface crack defects)

1000 min−1 –284N

Under water lubrication, fatigue cracks and white marks occurred at 4.3E5 fatigue cycles (See Fig. 5a)

1

3000 min−1 –83N

Dry, bearing melted, temperature rapid increase (#1 in Fig. 4)

2

1500 min−1 –83N

Dry, solid lubricant film formation

3–1

600 min−1 –98 N

Dry, solid lubricant film formation

3–2

800 min−1 –98 N

Dry, solid lubricant film formation

3–3

1000 min−1 –98 N

Dry, solid lubricant film formation

3–4

1200 min−1 –98 N

Dry, solid lubricant film formation

3–5

1400 min−1 –98 N

Dry, solid lubricant film formation

Tank

Fig. 2. Schematic of radial test machine.

3 Test Results and Discussion 3.1 Bearing Test (Rolling Contact Fatigue) Figure 4 is the graph of the temperature transition of the test sample in the RCF test. The reference temperature of the test sample in rotational frequency between 600 and 1400 min−1 was stable approximate 45 °C until 1.0E6 fatigue cycles. The movement of the bearing test sample was smooth.

Effect on PEEK/Graphite Film for Raceway Surface

2

4

6

8

15

10 [x105 cycles]

Fig. 3. Test condition chart. (Rotational frequency of bearing sample #3)

3.2 Rolling Contact Surface with Cracks Figures 5a and 5b shows surface cracks on the inner ring raceway of the test sample. White area around the cracks could be observed. After 1.0E6 cycles, however, the surface cracks partially disappeared on the raceway surface as shown in Figs. 5c and 5d. The dark area was clearly observed on the whole raceway surface (Fig. 5c), which is accumulation of the composite film layer of PEEK and graphite. The dark PEEK/graphite films adhered around the surface cracks. This tribological phenomena decreased size of the surface cracks on the raceway of the bearing. As shown in Fig. 5d, the crack (1) disappeared partially because plastic flow occurred in the PEEK/graphite film layer on the raceway surface after 1.0E6 fatigue cycles. The raceway surface with surface cracks changed significantly because of the accumulation of the composite film layer of PEEK and graphite. The PEEK/graphite film as solid lubricant film helped ball’s movement and stable temperature during the test, while friction and plastic flow occurred on a raceway surface of an inner ring because of ball’s movement and compressive stress under Hertzian contact. The surface profiles of the inner ring raceway before and after the RCF test were shown in Fig. 6. Arithmetic average roughness on the raceway of the test sample increased slightly as 0.2 μm (Rz = 1.4 μm). Small flaking was observed on the raceway after the RCF test (Fig. 5d). However, the bearing’s rotation was stable during the test because the whole raceway surface was smooth. From these results, it was found that the accumulation of the PEEK/graphite film covered the raceway with surface cracks during the RCF test under 98 N and 600 min−1 . The fusion of the surface crack defects occurred partially because of plastic flow in the PEEK/graphite film layer and friction between alumina ball and raceway of PEEK inner ring (Fig. 7). 3.3 TEM-EDX Analysis Figure 8(a) shows TEM image of cross-section of the composite film layer of PEEK and graphite on the raceway of the test sample. The PEEK/graphite film containing carbon particles formed on the rolling track on the raceway of PEEK inner ring. The thickness of the PEEK/graphite film was approximately 500 nm. As shown in Fig. 8(b), Carbon (Kα) and Oxygen (Kα) were mainly detected in the near surface region of the PEEK inner ring raceway by EDX. Figure 8(c) exhibits the distribution of Carbon and Oxygen along

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Fig. 4. Changes of reference temperature of the bearing test sample.

(a)

(b) Surface cracks

Crack(1)

RD 0.5mm

(c)

(d) Crack(1)

A

RD Flaking (2)

0.5mm

Fig. 5. Surface cracks on raceway of the PEEK inner ring; (a) photo image of the raceway and (b) microscope image of raceway with surface cracks at 0 cycles, (c) photo image of the raceway and (d) surface cracks after 1.0E6 cycles. Note that the sample at 0 cycles means the preparation sample in Table 1.

Effect on PEEK/Graphite Film for Raceway Surface 0.2

106 cycles

0 cycles

17

Surface defects

0

Depth, mm

-0.2

Cyclic compression

Ball

-0.4 -0.6

Fricon heat

-0.8

3((. LQQHUULQJ

-1

-1.2

0

2

4 Width, mm

6

PEEK/G film (Self-lubricaon film)

8

Fig. 6. Surface profiles of the raceway of PEEK Fig. 7. Schematic of covering for crack by inner ring before and after RCF. Note that Ra PEEK/Graphite film formation under rolling (Rz ) at 0 and 1.0E6 cycles were 0.08 (0.41) and contact. 0.22 (1.4) μm, respectively.

the line profile in Fig. 8(a). Intensity of carbon in the layer (II) as shown in red color line (‘C’ in Fig. 8(c)) was higher than that of the layer (III). This means that the layer (II) is high carbon region containing black graphite particles. Therefore, the accumulation layer of PEEK/graphite film protects the raceway of PEEK inner ring from tribological damage by friction during the test.

Line profile for EDX Analysis

(a) Ϩ Accumulaon of PEEK/graphite film layer

ϩ

Ϫ Matrix

Carbon(Nano-sized graphite)

(c)

Intensity

ϩ Ϫ

Ϩ

C O

0.00

(surface)

Distance, μm

4.22

Fig. 8. TEM-EDX Analysis of PEEK/graphite film layer; (a) TEM image, (b) EDX in (a), (c) Distribution of Carbon and Oxygen on the profile in (a).

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From the test results, it is concluded that the PEEK/graphite film can reduce large surface defects and friction heat on the PEEK inner ring in this test condition.

4 Conclusion To clarify the effect of the composite film layer of PEEK and graphite for the reduction of surface damage on the PEEK inner ring, the rolling contact fatigue tests were carried out by using PEEK hybrid ball bearings with surface defects. The findings obtained are shown below: (1) When applied load and rotational frequency were 98 N and 600–1400 min−1 , the PEEK/graphite film layer can reduce large surface defects such as surface crack or flaking on the PEEK inner ring. (2) The PEEK/graphite film layer covered the surface cracks on the raceway of the inner ring. In addition, the fusion of the surface crack defects occurred partially because of plastic flow in the accumulation layer of PEEK/graphite film with friction. Acknowledgment. This work was supported by JSPS KAKENHI Grant Numbers JP19K04150 and JP23K03647.

References 1. Stolarski, T.A.: Rolling contact fatigue of polymers and polymer composites. In: Advanced in Composite Tribology, chap. 17. Elsevier (1993) 2. Stolarski, T.A.: Tribology of polyetheretherketone. Wear 158, 71–78 (1992) 3. Friedrich, K., Lu, Z., Hager, A.M.: Overview on polymer composites for friction and wear application. Theoret. Appl. Fract. Mech. 19, 1–11 (1993) 4. Harrass, M., Friedrich, K., Almajid, A.A.: Tribological behavior of selected engineering polymers under rolling contact. Tribol. Int. 43, 635–646 (2010) 5. Friedrich, K., Theiler, G., Klein, P.: Polymer composites for tribological applications in a range between liquid helium and room temperature. In: Polymer Tribology, chap. 11, pp. 375–415. Imperial College Press (2009) 6. Dearn, K.D., Kukureka, S.N., Walton, D.: Engineering polymers and composites for machine elements. In: Polymer Tribology, chap. 14, pp. 470–505. Imperial College Press (2009) 7. Koike, H., Yamada, S., Deng, G., Mizobe, K., Yamada, T., Kida, K.: Observation of tribological fatigue fracture on PEEK shaft with artificial defect under one-point rolling contact by using 2.5D layer method. Key Eng. Mater. 814, 314–319 (2019) 8. Koike, H., Yamaguchi, G., Mizobe, K., Kida, K.: Faking growth of PEEK in one-point rolling contact fatigue using Al2O3 bearing’s ball for polymer friction parts application. MATEC Web Conf. 264, 01004 (2019) 9. Zhang, G., et al.: Structures and tribological performances of PEEK-based coatings designed for tribological application. Prog. Org. Coat. 60, 39–44 (2007) 10. Zhang, G., Liao, H., Cherigui, M., Davim, J.P., Coddet, C.: Effect of crystalline structure on the hardness and interfacial adherence of flame sprayed poly (ether–ether–ketone) coatings. Eur. Polym. J. 43, 1077–1082 (2007)

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11. Bahadur, S.: The development of transfer layers and their role in polymer tribology. Wear 245, 92–99 (2000) 12. Bahadur, S., Gong, D., Anderegg, J.W.: The investigation of the action of fillers by XPS studies of the transfer films of PEEK and its composites containing CUS and CUF2. Wear 160, 131–138 (1993) 13. Hiraki, K., Mizobe, K., Matsueda, T., Kashima, Y., Kida, K.: Friction coefficient and wear of PEEK-PTFE hybrid radial ball bearings under dry conditions. Mater. Sci. Forum 1020, 114–119 (2021) 14. Koike, H., Kida, K., Santos, E.C., Rozwadowska, J., Kashima, Y., Kanemasu, K.: Self lubrication of PEEK polymer bearings in rolling contact fatigue under radial loads. Trib. Int. 49, 30–38 (2012) 15. Koike, H., Kida, K., Mizobe, K., Shi, X., Oyama, S., Kashima, Y.: Wear of hybrid radial bearings (PEEK ring-PTFE retainer and alumina balls) under dry rolling contact. Trib. Int. 90, 77–83 (2015) 16. Yousefpour, A., Hojjati, M., Immarigeon, J.-P.: Fusion bonding/welding of thermoplastic composites. J. Thermoplast. Compos. Mater. 17, 303–341 (2004) 17. Zhang, M.Q., Rong, M.Z.: Self-Healing Polymers and Polymer Composites, chap. 1. Wiley (2011) 18. Smiley, A.J., Halbritter, A., Cogswell, F.N., Meakin, P.J.: Dual bonding of thermoplastic composite structures. Polym. Eng. Sci. 31, 526–532 (1991) 19. Koike, H., Haruta, J., Deng, G., Mizobe, K., Kida, K.: Observation of tribological wear on PEEK shaft with artificial defect under radial rolling sliding point contact. Key Eng. Mater. 858, 95–100 (2020) 20. Mizobe, K., Honda, T., Koike, H., Santos, E.C., Kida, K., Kashima, Y.: Relationship between load, rotation speed and strength in all - PEEK and PEEK race - PTFE retainer hybrid polymer bearings under dry rolling contact fatigue. Adv. Mater. Res. 567, 66–70 (2012) 21. Bijwe, J., Sen, S., Ghosh, A.: Influence of PTFE content in PEEK-PTFE blends on mechanical properties and tribo-performance in various wear modes. Wear 258, 1536–1542 (2005) 22. Koike, H., Kida, K., Mizobe, K., Matsumura, T., Inagaki, M.: PEEK/graphite film formation on microgrooves of PEEK- hybrid radial Al2O3 ball bearings under rolling contact in dry condition. Trib. Int’l. 172, 107583 (2022)

Evaluation of Fatigue Properties of Additively Manufactured High-Entropy Alloys Miu Hayashi1(B) , Naoki Kurita1 , Tadatoshi Watanabe2 , Hiroyuki Akebono1 , and Atsushi Sugeta1 1 Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1

Kagamiyama, Higashi-Hiroshima, Japan [email protected] 2 Mazda Motor Corporation, Shinchi, Fuchu-cho, Aki-gun, Hiroshima, Japan

Abstract. In recent years, additive manufacturing (AM) has been attracting attention in order to reduce the weight and improve the functionality of automobiles. However, the AM has the problem that its fatigue strength is lower than its tensile strength. For this reason, it is difficult to apply this technology to strength parts. Currently, there are many reports on fatigue strength improvement methods for steel materials, but there are few reports on fatigue strength improvement methods for AM materials. Therefore, in this study, we focused on the amount of defect and shot peening to elucidate their effects on fatigue strength. Consequently, the fatigue limit increased with a decrease of defect amount. However, no improvement of fatigue life in the finite life region was observed. The fatigue strength was improved by shot peening. Keywords: Fatigue · Additive manufacturing · High-entropy alloy

1 Background In the automotive industry, there is requirement for lighter weight and higher functionality in automobiles to achieve carbon neutrality. Recently, additive manufacturing (AM), in which materials are added based on 3D data, has been attracting attention. In metal additive manufacturing, the powder bed method is the most used method, and it can produce complex shapes that cannot be manufactured by conventional methods, making it possible to reduce costs and weight. However, the application range of AM materials is still limited because the fatigue strength is quite low in comparison with the tensile strength. In addition, although there are many research reports on AM [1–5], fatigue properties are still unclear in many cases. Therefore, in this study, we focused on the amount of defects in additively manufactured and shot peening, which is widely used as a fatigue strength improvement method, and conducted fatigue tests to investigate the effects of amount of defect and shot peening on fatigue properties.

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 20–26, 2024. https://doi.org/10.1007/978-981-97-1594-7_3

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21

2 Specimens and Test Method 2.1 Specimens The material used in this study was C01P, a Co-Cr-Fe-Ni-Ti-Mo high-entropy alloy [6]. The chemical composition is shown in Table 1. In this study, three types of specimens were prepared. Firstly, round bars with defects of 0.2% and 0.04% were manufactured by changing the SLM conditions, and solution heat treatment at 1120 °C for 1 h by high-pressure gas cooling was performed. After that, specimen with the shape shown in Fig. 1 were machined from the round bars. After machining the specimen into the hourglass-type specimens shown in Fig. 1, the R section was polished using emery paper (#600, #800, #1000, #1200, #1500, #2000) and alumina powder (3 µm, 1 µm), or peened using a stainless condition cut wire of 0.3 mm in diameter. The process parameters of shot peening included a peening pressure and projectile time of 0.3 MPa and 20 s, respectively. Hereinafter, specimens with 0.2% defects of additively manufactured and polished, specimens with 0.04% defects of additively manufactured and polished, and specimens with 0.04% defects of additively manufactured and shot peening are referred to as AM, AM d , and AM dSP materials, respectively. Table 1. Chemical Composition of C01P [mass%] Cr

Fe

Ni

Ti

Mo

B

C

O

N

Co

18.0

14.3

24.2

7.5

4.0

0.02

0.03

0.05

0.02

Bal

Fig. 1. Shape and dimension of specimen.

2.2 Test Method A Shimadzu Autograph AG-X type was used as static tensile test. A Shimadzu servo hydraulic pulser was used as the fatigue testing machine. Static tensile tests were conducted at a crosshead displacement of 1.2 mm/min and fatigue tests were conducted at a frequency of f = 1~20 [Hz] and a stress ratio of R = −1 in room temperature.

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3 Test Results 3.1 Static Tensile Test Figure 2 shows the results of static tensile tests conducted on each specimen. The vertical axis of the graph shows the applied stress and the horizontal axis shows the strain. The tensile strength of the AM, AM d , and AM dSP specimens was 1241 MPa, 1367 MPa, and 1367 MPa, respectively. Therefore, no differences were observed in tensile strength under the same defect amount condition, and that the tensile strength and the elongation improves with a decrease in the amount of defect.

Fig. 2. Static tensile test results.

3.2 Vickers Hardness Test The results of Vickers hardness test conducted on each specimen are shown in Fig. 3. The AM and AM d materials show the average values of 100 randomly selected cross sections of the minimum diameter. The hardness of the AM and AM d materials was 428 HV and 443 HV, respectively. Therefore, it is clear that the difference of the amount of defects hardly affects the hardness. In addition, AM dSP with shot peening increased the hardness of the surface layer by approximately 100 HV, and the hardness increased to a depth approximately 200 µm from the surface. 3.3 Residual Stress Measurement Figure 4 shows the result of residual stress distribution measurement for AM dSP material. Residual stress was measured by the oscillation method from a depth 60 µm and by threedimensional measurement at a depth 200 µm. The reason for changing the measurement

Evaluation of Fatigue Properties of AM High-Entropy Alloys

23

Fig. 3. Hardness distribution.

method was that it was difficult to measure the residual stress in deep areas without peening effects by normal measurements because of the coarse grain and crystallographic orientation. The figure shows that the compressive residual stress of 600 to 800 MPa was present near the surface layer due to the effect of shot peening and it can be seen that the value of compressive residual stress decreases gradually as the depth increases.

Fig. 4. Residual stress distribution of AM dSP .

3.4 Fatigue Test Figure 5 shows the results of fatigue tests. First, comparing the AM and AM d materials, which differ in the amount of defects, the fatigue limit increases with a decrease in the amount of defects, although there is no significant difference in fatigue life in the finite life region. Secondly, comparing the AM d and AM dSP materials, the fatigue strength was improved by shot peening.

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Fig. 5. S-N curves.

Fracture surface observations were conducted to investigate the fatigue fracture mechanism. The results are shown in Fig. 6. The stress amplitude and number of cycles to failure of each specimen are described in the figure. The yellow area in (c) shows the hardened layer by shot peening. First, as shown in (a), the fracture surface of AM material is exhibits the rough surface indicating that the fracture is caused by multiple facet origins. In contract, as shown in (b), the AM d material showed a different aspect from the AM material, with the AM d material fractured with a flat fracture surface. Furthermore, the fracture was induced by facet initiation from one direction. As shown in (c), fracture initiated from facets within the peening-affected region was observed. In terms of the fracture morphology of each specimen, it is revealed that the high-entropy alloy used in this study exhibits facet-originated fracture. Also, comparing the AM d and AM dSP materials, the effect of compressive residual stresses induced by shot peening have suppressed the crack propagation. Therefore, the fatigue life of the specimens was improved. However, since both specimens failed at the facet origin, there is no significant difference in the fatigue limit.

Evaluation of Fatigue Properties of AM High-Entropy Alloys

Fig. 6. Fracture surface observation results.

25

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4 Conclusion 1. Fracture surface observations confirmed that all fracture surfaces exhibit facet origin type fractures. 2. Differences in the amount of defects within the AM material did not make a significant difference in the fatigue life in the finite life region. However, it was shown that reducing the amount of defects improves the fatigue limit. 3. Shot peening treatment on the AM materials is an effective way to improve fatigue strength. This improvement is attributed to the compressive residual stresses formed in the surface layer of the material because of shot peening.

References 1. Beretta, S., Romano, S.: A comparison of fatigue strength sensitivity to defects for materials manufactured by AM or traditional processes. Int. J. Fatigue 94, 178–191 (2017) 2. Masuo, H., Tanaka, Y., Yagura, H., Uchida, T., Yamamoto, Y., Murakami, Y.: Effects of defects, surface roughness and HIP on fatigue strength of Ti-6Al-4V manufactured by additive manufacturing. Procedia Struct. Integrity 7, 19–26 (2017) 3. Kahlin, M., et al.: Improved fatigue strength of additively manufactured Ti6Al4V by surface post processing. Int. J. Fatigue 134, 105497 (2020) 4. Takahashi, K., Kogishi, Y., Shibuya, N., Kumeno, F.: Effects of laser peening on the fatigue strength and defect tolerance of aluminum alloy. Fatigue Fatigue Eng. Mater. Struct. 43, 845– 856 (2020) 5. Schneller, W., Leitner, M., Springer, S., Grün, F., Taschauer, M.: Effect of HIP treatment on microstructure and fatigue strength of selectively laser melted AlSi10Mg. J. Manufact. Mater. Process. 3(1), 16 (2019) 6. Li, W., Xie, D., Li, D., Zhang, Y., Gao, Y., Liaw, P.K.: Mechanical behavior of high-entropy alloys. Prog. Mater. Sci. 118, 100777 (2021)

Solid-Phase Interaction of Zinc Ferrite with Calcium Oxide Sergei Yakornov(B) and Gennady Skopov JSC UMMC, 1, Uspensky Avenue, Verkhnyaya Pyshma, Sverdlovsk Region 624091, Russia [email protected]

Abstract. Zinc ferrite is a stable compound, slightly soluble in weak sulfuric acid that makes it difficult to extract zinc in solution during processing of metallurgical semi-products using hydrometallurgical technologies. Previous researchers have shown the possibility of preliminary destruction of zinc ferrite by high-temperature treatment in the presence of calcium oxide to form zinc oxide and calcium ferrite. The mechanism of this exchange interaction was studied using the method of diffusion annealing in air atmosphere (1050 °C for 4 h) of ground and tightly pressed pellets of synthesized zinc ferrite and calcium oxide, 13 mm in diameter and 3–5 mm in height. After annealing, the pellets were cut along the diameter and the cross-section was examined with a micro X-ray spectrometer. A distinct zonal structure was observed in the pellet contact area, the analysis of which shows that calcium diffuses from the calcium oxide pellet into the zinc ferrite pellet. Close to the pellet contact area, the calcium reacts with the zinc ferrite to form calcium ferrite and displaces the zinc to the depth of the zinc ferrite pellet. Thus, the unreacted zinc ferrite is continuously enriched with zinc in the course of annealing and is probably blocked by it, preventing contact between the zinc ferrite and the diffusing calcium. Practical conclusion: To ensure that zinc is completely displaced from its ferrite by calcium under industrial conditions, a highly developed and dense contact surface between zinc ferrite and calcium oxide particles should be achieved. Keywords: zinc ferrite · calcium oxide · zonal structure

1 Introduction The formation of zinc ferrite is an undesirable phenomenon in steelmaking and zinc metallurgy, where byproducts of these processes (dust, calcine) are further hydrometallurgically processed by leaching in sulfuric acid solution to extract zinc into it. Comprehensive studies on destruction of zinc ferrite in steelmaking dust by thermal treatment in the presence of calcium oxide to yield zinc oxide and calcium ferrite were carried out by R. Chairaksa and others [1–10]. The reaction was found to be very rapid and the conversion degree of ZnFe2 O4 to ZnO and Ca2 Fe2 O5 at 1000 °C reached a maximum (≈100%) at Ca/Fe molar ratio of 1.3 and residence time of 1 h. © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 27–33, 2024. https://doi.org/10.1007/978-981-97-1594-7_4

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A.B. Peltekov, B.S. Boyanov [11] studied the interaction in air medium of CaO and MgO with zinc ferrite obtained by two different methods. It was revealed that the increase in ZnFe2 O4 - CaO ratio and the temperature increase positively effected the extent of the reactions Eqs. (1), (2) proceeding to the right ZnFe2 O4 + CaO → ZnO + CaFe2 O4

(1)

ZnFe2 O4 + 2CaO → ZnO + Ca2 Fe2 O5

(2)

and zinc leaching in 7% H2 SO4 . Experiments with zinc ferrite from commercial zinc cakes showed that the maximum degree of zinc oxide replacement by calcium oxide in ZnFe2 O4 was about 60% at 1200 °C and the ratio ZnFe2 O4 – CaO = 1:2. In the available studies the authors did not conduct research to identify the mechanism of solid-phase exchange interactions in ZnFe2 O4 - CaO (MgO) system, i.e. they did not try to find out the limiting stages of the processes, focusing only on the descriptive nature of the observed phenomena. It should be noted that the study of the considered solid-phase interactions is associated with significant difficulties. First, it is unchanged test portion weight during the experiments and the low thermal effect of the exchange interaction, preventing from application of commonly used methods of thermogravimetric analysis. In addition, in mixed input compounds with various particle size distribution and particle shapes it is difficult to consider the impact of change in the reaction surface. It is complicated by the possible parallel formation of two different solid phase interaction products in reactions Eqs. (1), (2).

2 Methods of Experiments Based on the available studies we recommend the solid-phase diffusion annealing method proposed by Bengtson and Jagic, Tubandt and Wagner, K. Hauffe [12] for study of the interaction mechanism in ZnFe2 O4 - CaO system. According to this method the tightly pressed pellets of initial oxides are annealed. Over a definite period at a set temperature a reaction product layer of δ-thickness develops between the pellets. Examination of pellet sections after a test using an X-ray microanalyzer helps to obtain the concentration profiles of the elements in these sections and also make judgments about the phase and chemical compositions of the reaction products. Pellets made of reactive CaO reagent grade and specially synthesized zinc ferrite were used for annealing. Calcium oxide and zinc ferrite test portions were pressed at 20–25 MPa so that the height of pellets did not exceed 3–5 mm and both horizontal surfaces should be flat, without mechanical damage. All pellets were 13 mm in diameter. 2.1 Pellet Annealing Pellets were placed in an allundum crucible in the following sequence: “ferrite-CaOferrite” to avoid CaO reacting with the crucible material at high temperature. Zinc ferrite does not react with the crucible material.

Solid-Phase Interaction of Zinc Ferrite with Calcium Oxide

29

For better contact between pellets, a smaller crucible loaded with a metal ball was placed on top of the pellets, maintaining an even load on the horizontal surface of the pellets. After annealing in an air atmosphere at a given temperature and time, the furnace was cooled to 90–100 °C, crucibles and weights were removed from the furnace, the stack of pellets was removed and placed in a zip bag to be sent to the X-ray microanalysis laboratory (XMA).

3 XMA Results of Calcium Oxide and Zinc Ferrite Pellet Contact Area XMA was performed on an EVO MA15 scanning electron microscope, using AZtec software. 3.1 Pellets After Annealing at 1050 °C for 4 h Microscope image (Fig. 1) clearly shows the zonal arrangement of the pellets contact area. A contact boundary between pellets looks like a dark curved line of variable width. To the left of it there is a calcium oxide pellet, to the right - zinc ferrite. A zone of the same color, but with a darker tint, 35.7 μm wide is adjacent to the contact boundary on the gray zinc ferrite pellet side. Distribution of chemical elements in the considered zones (Table 1) shows that calcium diffuses from the calcium oxide pellet into the zinc ferrite pellet, and there is a slight counter-transition of iron and zinc into the calcium oxide pellet. Sulfur that got into ZnFe2 O4 as an impurity during its synthesis concentrates near the contact boundary of pellets, i.e. there is a counter diffusion of calcium and sulfur in the zinc ferrite pellet. X-ray microspectral analysis of chemical compositions of pellet grains near the contact boundaries (point spectra 2–9 in Fig. 1) allowed us to establish the following: The composition of spectrum 2 in the calcium oxide pellet in Fig. 1 indicates that it is slightly diluted with iron and zinc oxides. This is evidenced not only by the presence of iron and zinc, which transferred from the ZnFe2 O4 pellet, but also by the excess of oxygen with respect to Ca, which indicates the transfer of oxygen from ferrite together with Fe and Zn. 1. Spectra 3, 8 and 9 measured in a zinc ferrite pellet over the area of 35.7 μm wide, closely bordering the CaO pellet, contain a lot of oxygen, calcium, iron and far less sulfur, silicon and zinc. The presence of calcium and sulfur in the area is indicative of calcium and sulfur transition from the CaO pellet and zinc ferrite pellet, correspondingly, to the area. Zinc oxide resulted from exchange solid-phase interaction escapes from the area and penetrates zinc ferrite pellet. 2. Spectra 4, 6 and 7 contain a roughly equal proportion of oxygen, iron, calcium and zinc, which is indicative of input substances and products of solid-phase interactions in this area based on reactions (1) and (2). This is a transition area between a zone of completed reactions (1) and (2) of 35.7 μm wide and spectrum 5 zone with far less calcium, no sulfur and high mass fractions of zinc, iron and oxygen.

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Spectrum 3 Spectrum 4 Spectrum 2

Spectrum 5

Spectrum 8 Spectrum 6 Profile data along the line 3 Spectrum 7 Spectrum 9

Fig. 1. A micro image of CaO-ZnFe2 O4 pellet contact boundary. Table 1. Mass fractions of elements in spectra as shown in Fig. 1. Element

Spectrum number 2

3

4

5

6

7

8

9

Zn

2.8

2.0

20.5

35.6

26.2

24.3

1.9

1.9

Ca

55.7

30.4

21.6

1.9

20.0

20.7

29.5

27.2

Fe

1.9

23.2

25.7

34.3

22.2

24.6

23.4

24.5

O

39.1

35.2

28.0

23.8

28.7

29.3

37.1

39.5

S

0.0

4.9

1.0

0.0

1.8

1.1

7.0

6.9

20.0

70.0

150.0

63.3

63.3

23.3

10.0

L.[μm]

where L.μm – a distance between pellet contact line and a corresponding point of spectral analysis.

Calculation of mineral composition using MPCA data (spectra 3–9, Table 2) has underpinned the assumption that exchange solid-phase interaction is close to pellet contact boundary through calcium oxide diffusion from the CaO pellet across interpellet boundary. The resultant zinc oxide diffuses into zinc ferrite pellet. Calcium oxide partly reacts with sulfur diffusing from zinc ferrite pellet into pellet contact boundary, with a possible generation of calcium sulfate. MPCA data along the scanning line as shown in Fig. 1 are graphically presented in Fig. 2. The trends of the curves of changing elemental mass fractions support the conclusions set out above about an element behavior and their chemical compounds during interaction between calcium oxide pellets and zinc ferrite.

Solid-Phase Interaction of Zinc Ferrite with Calcium Oxide

31

Table 2. Results of mineral composition calculation using MPCA data (spectra 3–9, Fig. 2) [% wt.] Compound

Spectrum number 3

ZnFe2 O4

7.37

CaO*Fe2 O3

4 19.07

5 62.60

6

7

8

9

18.52

19.44

7.01

7.01

21.49

18.35

10.23

14.64

16.9

22.18

24.10

0.00

19.08

23.18

26.36

23.68

0.00

0.00

2CaO*Fe2 O3

21.12

17.93

0.00

14.71

16.67

20.66

21.38

CaO

19.70

16.31

0.00

14.97

15.78

14.77

10.91

CaSO4

20.80

4.25

0.00

7.64

4.67

29.72

29.30

L,[μm]

20.00

70.00

150.00

63.30

63.30

23.30

10.00

ZnO

All elements

μ

* Вес – weight Fig. 2. Changing elemental mass fractions along the scanning line (Fig. 1).

The studies resulted in a chart of element diffusion running inside the zinc ferrite pellet based on interaction between zinc ferrite pellet and calcium oxide pellet (Fig. 3). Such an interaction results in the zonal structure being formed inside ZnFe2 O4 pellet. Solid-phase exchange reactions Eqs. (1), (2) run in the area A to the fullest extent possible. A low zinc oxide content diffusing into the area B and a high sulfur content are typical of the area A. The boundary between areas A and B stand for a sharply rising ZnO concentration nearly up to 30%. Area B features a far greater incompleteness of exchange solid-phase interactions and rising zinc oxide content. Area C lacks calcium oxide and sulfur. Solid-phase interactions are in infancy. The results of these studies show that a highly developed and tight contact area between zinc ferrite particles and calcium oxide is required to ensure that zinc is completely displaced from its ferrite with calcium under industrial conditions.

32

S. Yakornov and G. Skopov ZnFe2O4 pellet

CaO pellet

A

O3

A

2CaO*Fe2O3 CaO*Fe2O3 CaSO4 CaO ZnFe2O4

B

B ZnO ZnFe2O4 CaO*Fe2O3 2CaO*Fe2O3 CaO CaSO4

C

C ZnFe2O4 CaO*Fe2O3 ZnO

*Fe2

Fig. 3. Elemental diffusion chart during CaO - ZnFe2 O4 pellet diffusion annealing (1050 °C. 4 h)

References 1. Chairaksa, R.: Development of New EAF Dust Treatment Process With CaO Addition Method. A dissertation for the Degree of Doctor of Philosophy in Ecomaterial Design and Process Engineering Graduate School of Environmental Studies Tohoku University. February (2012) 2. Chairaksa-Fujimoto, R., Inoue, Y., Umeda, N., Itoh, S., Nagasaka, T.: New pyrometallurgical process of EAF dust treatment with CaO addition. Int. J. Miner. Metall. Mater. 22(8), 788–797 (2015) 3. Shevchenko, M., Jak, E.: Experimental liquidus studies of the CaO-ZnO-Fe2O3 system in air. J. Phase Equilib. Diffus. 5(9), 215–220 (2019) 4. Raghavan, M.: Secondary recovery of lead and zinc. Miner. Met. Rev. 27, 28–34 (2001) 5. Korneev, V.P., Sirotin-kin, V.P.: Study of the physical and chemical properties of zinccontaining dusts in electric furnace production. Metals 4, 38–43 (2013) 6. Panshin, A.M., Kozlov, P.A.: Assessment and potential possibilities for processing various wastes of metallurgical production. Ecol. Ind. Russia 9, 21–23 (2013) 7. Doronin, I.E.: Dusts and sludge from steel-smelting units as raw materials for the production of zinc and steel. News of higher educational institutions. Non-Ferrous Metall. 5, 31–35 (2012) 8. Jha, M.K., Kumar, V., Singh, R.J.: Review of hydrometallurgical recovery of zinc from industrial wastes. Resour. Conserv. Recycl. 1(33), 1–22 (2001) 9. Snurnikov, A.P.: Hydrometallurgy of zinc. M.: Metallurgy (1981) 10. Buvalets, D.Yu., Kapustin, A.E., Butenko, E.O.: Study of the selectivity of liquid-phase extraction of zinc from dusty waste from metallurgical production. J. Technol. Audit Prod. Reserves 6/7(26), 33–35 (2015)

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11. Peltekov, A.B., Boyanov, B.S.: Study of solid state interactions in the systems ZnFe2O4 – CaO. ZnFe2O4 – MgO and zinc cake with CaO and MgO. J. Min. Metall. Sect. B-Metall. 49(3) B, 339–346 (2013) 12. Hauffe, K.: Reactions in solids and on their surfaces Part 2 (1962)

Effects of Fe Addition on the Phase and Mechanical Properties of Ti-15Mo Alloy Nthabiseng Moshokoa1(B) , Lerato Raganya2 , Nkutwane Washington Makoana3 , Hasani Chauke4 , Ramogohlo Diale5 , Maje Phasha5 , and Elizabeth Makhatha1 1 Department of Metallurgy, School of Mining and Metallurgy and Chemical Engineering,

University of Johannesburg, Doornfontein Campus, Johannesburg, South Africa [email protected] 2 Advance Materials Engineering, Manufacturing Cluster, Council for Scientific and Industrial Research, Meiring Naude Road, Brummeria, Pretoria 0184, South Africa 3 National Laser Center, Council for Scientific and Industrial Research, Meiring Naude Road, Brummeria, Pretoria 0184, South Africa 4 Materials Modelling Center, University of Limpopo, Private Bag X1106, Sovenga 0727, South Africa 5 Physical Metallurgy Group, Advanced Materials Division, Mintek, 200 Malibongwe Drive, Randburg 2125, South Africa

Abstract. The influence of high content of Fe on the microstructure and mechanical properties of as-cast Ti-15Mo alloy is explored in this work. The alloys (binary and 3 ternaries) were melted in a commercially available Vacuum arc-melting furnace (VAR). Characterization of samples was conducted using the microstructural features of the binary alloys an Optical Microscopy (OM) and an X-ray diffractometer (XRD) to reveal microstructural features and identify present phases, respectively. Tensile and Micro-Vickers hardness tests were carried out to study mechanical properties while the fracture surface was examined using the Scanning Electron Microscope (SEM). The XRD analyses detected peaks belonging to the bcc Im3m (β-Ti) phase in binary Ti-15.05Mo alloy and β, α (Cmcm), and TiFe (B2) phases in ternary alloys containing Fe. The Optical microscopy revealed equiaxed β grains with additional structures or features such as needlelike structures of martensite inside the grains in Ti-15.05Mo whilst the addition of Fe resulted in equiaxed structures with dendrites inside. As a result of these dendritic structures, the ternary samples were too brittle and fragile to generate adequate tensile data. The Micro-Vickers hardness results indicated that the hardness slightly decreased at first with the addition of Fe and later increased with a further increase in Fe composition. The fracture surfaces analysis illustrated both ductile and brittle fracture in Ti-15.05Mo while only brittle fracture was observed in alloys containing Fe. Keywords: Ti-Mo-Fe · microstructure · hardness · fracture surface

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 34–44, 2024. https://doi.org/10.1007/978-981-97-1594-7_5

Effects of Fe Addition on the Phase and Mechanical Properties

35

1 Introduction The practise of metallic materials such as titanium (Ti) alloys, specifically in orthopedics, is becoming more pervasive because of their attractive properties such as low elastic modulus, high biocompatibility, high strength-to-weight ratio, and good corrosion resistance [1, 2]. The success of Ti-6Al-4V alloy as an orthopedic implant material is owed to its properties such as high strength, low elastic modulus (110 GPa) as competed to other traditional materials such as stainless steel (190 GPa) & Co-Cr alloys (220 GPa) [2, 3]. However, several investigations have reported two major drawbacks that are associated with the use of Ti-6Al-4V alloy, namely, (i) the release of vanadium (V) which reacts with live tissues, and the presence of aluminium (Al) associated with neurological disorders and Alzheimer’s disease [4], (ii) the elastic modulus mismatch between that of implant material (110 GPa) and surrounding bone (10–40 GPa) causing what is known as a stress shielding phenomenon. Stress Shielding effect is when the bone is not subjected to standard loads vital for maintaining its properties such as strength, density and a healthy structure, accordingly leading to bone resorption and premature failure of the implant [1, 5]. Currently, much consideration has been fixed towards the design and advancement of innovative and, more biocompatible β-Ti alloys with mechanical properties more befitting for orthopedic implants, especially for the substitution of hard tissues, especially for lowering the modulus of elasticity in combination with high strength [5]. The β-Ti alloys designed and developed in the past few such as Ti-70Ta, Ti-29Nb-13Ta-4,6Zr, Ti-42Nb, Ti-Ta-Hf-Zr, etc., mainly consist of a significant proportion of expensive and rare alloying elements such as Ta, Nb, Zr, Hf with high melting point and high densities [6–8]. Also the alloying elements consists of high melting points that introduces high processing costs of Ti alloys that are compatible and they make the alloys more likely to introduce compositional segregation which is harmful to the mechanical properties and their final performance [3, 9]. Thus, owed to higher content of costly alloying elements as well as the required expensive alloy fabrication processes, most of β-Ti alloys the developed in recent years contain larger quantity of readily available, low-cost, low-melting point elements such as manganese (Mn), iron (Fe), tin (Sn) in attempt to reduce the content of expensive, scarce metals [5]. Fe is known to be a strong β-stabilizer and it is also considerably cheaper than commonly used β stabilizers such as Nb, V, and Mo, but it is not used in many commercial Ti alloys [10]. This is so despite its mechanical benefits for instance, increasing the mechanical strength and reducing the elastic modulus with only small additions in binary and ternary Ti base alloys [11–13]. Therefore, there is a potential for adding Fe in concurrence with Mo to develop more biocompatible, lower cost β-Ti alloys for biomedical implant applications. Although few studies report in general the detriments of higher Fe content associated with the presence of undesired phases [such as the ω phase], the in-depth microstructural evolution linked to resulting mechanical properties is seldom reported, more especially in as-cast condition. Therefore, this work investigates the effect of Fe on the microstructure and associated mechanical properties of as-cast Ti-15.05Mo-xFe alloys.

36

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2 Materials and Methods 2.1 Material Preparation/Processing Ingots of Ti-15Mo-xFe (x = 4, 8, and 12 wt%) were produced using the button-arcmelting furnace. The alloy fabrication involved the use of pure titanium (Cp-Ti), molybdenum (Mo), and Fe metal powders with 99.99%, 99.9%, and 99.5% purity, respectively. Powders were weighed and compacted into 100g green bodies using the compression machine in preparation for the arc-melting process. The melting was performed under an argon atmosphere (Ar) in a water-cooled Cu hearth. The ingots were flipped 3 times to ensure homogeneity in the alloy. The alloy composition and their designated names are presented in Table 1. Designated Alloy Name, Alloy composition. Table 1. Designated Alloy Name, Alloy composition. Designated Alloy Name

Alloy Composition (wt%)

TMF-0

Ti-15.05Mo

TMF-1

Ti-15.05Mo-4Fe

TMF-2

Ti-15.05Mo-8Fe

TMF-3

Ti-15.05Mo-12Fe

2.2 Phase and Microstructural Analysis The phase constituent analysis of Ti15Mo-xFe alloys was detected using an X-ray diffractometer. Parameters such as Cu Kα radiation with a secondary monochromatic (λ = 0, 1545 nm) at 45 kV and 40 mA were used to run the XRD patterns, while diffraction measurements were conducted at room temperature in Bragg-Brenton geometry at continuous scanning rate 0.02º in the 2θ scan range. Pan-Analytical X-Pert High score software was used to ascertain the phases present in the as-cast Ti-Mo-Fe alloys. Microstructure of Ti-15Mo-xFe alloys in as-cast condition were examined using the Leica Optical microscope. Samples for Optical Microscope (OM) analysis was prepared by following the metallographic procedure by grounding the samples using silicon carbide grit papers, polished to a mirror finish with colloidal silica. The samples were etched with the prepared Kroll etchant with the following concentration: distilled water 80 ml, nitric acid 15 ml, and hydrofluoric acid 5 ml. 2.3 Mechanical Properties Specimens with measurement of 3 × 4 × 30 mm were cut by using an electrical discharge machining in preparation Tensile testing. A tensile tester called Instron Instron™ 1342 with a load of 50 kN cells and speed of 0.5 mm/min was used to conduct the tensile test at room temperature. An extensometer was attached to the gauge section of the test

Effects of Fe Addition on the Phase and Mechanical Properties

37

specimen used to measure the tensile strain. The Micro-Vickers hardness of all the alloys were measured using Zwick Roell Vickers hardness indenter. Hardness parameters such as dwell time of 10 s and load of 500 gf were used and a diamond indent was crafted. A minimum of ten indentations were produced per sample and their diagonals were measured microscopically. The averages of the 10 indents were calculated and recorded.

3 Discussions of Results 3.1 X-Ray Diffractometer Phase constituents of Ti-15Mo-xFe samples under various additions of Fe elements were explored. Figure 1 shows the XRD patterns of Ti-15.05Mo-xFe alloys with different Fe content in the as-cast condition. As observed in Fig. 1., the TMF0 alloy is mainly comprised of peaks belonging to the β-Ti (Im3m) solid solution without a minute presence of the orthorhombic martensite (α ) structure. The highest diffraction peak in this binary alloy is for the β phase located at 46–50º 2 theta (2θ) position. The addition of Fe into Ti15Mo (here referred to as TMF1, TMF2, and TMF3) binary alloy revealed the presence of an ordered intermetallic phases of (TiFe B2 structure) and orthorhombic martensitic (α ) structure (Cmcm) peaks on top of the β-Ti phases. In addition, it was worth noting higher Fe additions resulted in a peak shift towards higher 2θ positions. This peak shift could be attributed to lattice contraction due to smaller atomic size. Also, with high Fe content, the degree of the orthorhombic martensitic structure (α ) phase decreased while that of TiFe increased slightly. These changes indicated that with an increase in Fe content, the TiFe phase became more pronounced at room temperature. According to the report by Campo et al. [14] on the Ti-Nb-Fe alloy, the martensitic transformation did not occur when the Fe content was more than 3 wt% in Ti alloys. This is contrary to current results which reveal the presence of the martensite phases even at much higher Fe content. The studied results are comparable to the results reported by [15] in Ti-29,5Fe-xNb (x = 0,3,5 and 7at%) and the one reported by [16] in Ti-Fe alloys. 3.2 Optical Microscope Figure 2 illustrated the microstructures of as-cast Ti-15Mo-xFe alloys. As shown in Fig. 2(a), the TMF0 alloy is comprised of large equiaxed β grains with clear grain boundaries. Within these large equiaxed grains, there exist sub-structures that could be associated with the presence of α martensite phase. The reason for the presence of this orthorhombic structure in TMF0 could be attributed to the cooling rate in the Cu heart during the melting process. On the other hand, the addition of Fe into Ti-15Mo alloy hereby referred to as TMF1 shown in Fig. 2(b), resulted in a significant decline in the amount of equiaxed grains of β phase into smaller grains. This microstructure shows the existence of dendrites in the grains and along the grain boundaries. In addition, the microstructure revealed the presence of pores as well as pitting due to etchant attack. Further increase in Fe content (referred to as TMF2 and TMF3) resulted in the microstructures that consisted of mainly dendrites, as demonstrated in Fig. 2(c) and (d). Large and small equiaxed β grains were not seen with increasing the Fe content, and

38

N. Moshokoa et al.

Fig. 1. X-ray diffraction of as-cast (a) TMF0, (b) TMF1, (c) TMF2, and (d) TMF3 alloys.

no pores or pitting could be observed in these microstructures compared to the ones for TMF1. The occurrence of dendritic structure is due to a rapid solidification process as a result of the very fast movement of the liquid/solid interface toward the undercooled melt. The OM micrographs of the ternary alloys (referred to as TMF1, TMF2, and TMF3) are consistence with the XRD data, and the dendrites in Fig. 2(b) (c) and (d) could be referred to as the intermetallic phase of B2 (TiFe). 3.3 Tensile Test Tensile properties of studied alloys are presented in Table 2 below. According to Table 2, the ultimate tensile strength (UTS) and elastic modulus of TMF0 were measured to be 264 MPa and 79 GPa, respectively. For the sample containing 4 wt% Fe, the measured UTS was as low as 74 MPa due to observed porosity in the sample which led to premature crumpling. As a result, it was not possible to determine the elastic modulus of TMF1 alloy. Similarly, due to the brittle and fragile nature of the samples (which broke during testing), the tensile test data for alloys containing higher Fe content (TMF2 and TMF3) was insufficient to report.

Effects of Fe Addition on the Phase and Mechanical Properties

39

Fig. 2. Optical Micrographs of as-cast (a) TMF0, (b) TMF1, (c) TMF2, and (d) TMF3 alloys.

Table 2. Tensile properties of TMF alloys. Alloy Name

UTS (MPa)

E (GPa)

Reference

TMF0

264

79

This study

TMF1

74

-

This study

TMF2

-

-

This study

TMF3

-

-

This study

Ti6Al4V

-

110

[1]

Ti-12Nb-5Fe

-

90

[17]

Ti-19Nb-2.5Fe

-

90

[18]

Ti-30Nb-3Fe

-

81

[19]

40

N. Moshokoa et al.

3.4 Micro-Vickers Hardness Micro-Vickers hardness of as-cast TMF alloys are presented in Fig. 3 below. The hardness of TMF0 was found to be 440 Hv0.5 , and it decreased with the addition of 4 wt%Fe (TMF1) to 418 Hv0.5 . However, with a further increase in Fe content to 8 wt% (TMF2) and 12 wt% (TMF3), the micro-hardness increased significantly to 483Hv0.5 and 515 Hv0.5, respectively. The decrease in hardness for the TMF1 sample was attributed to the presence of porosity as observed in Fig. 2(b) whilst the increase in hardness for TMF2 and TMF3 samples is owed to high brittleness as a result of dendritic structures as well as the presence of martensite phases and TiFe structure as illustrated in Fig. 1. According to a report by Lee et al. [20], the phase constituent in Ti alloys affects the micro-Vickers hardness in the following manner: Hω > Hα > Hα > Hβ > Hvα This trend implies that the hardness of the omega (ω) is higher, as compared to that of α , α , β and α and that of the β phase is higher as compared to α. An alloy with a high amount of omega will have the higher hardness as compared to other alloys with other phases such as beta. According to Bagariatskii et al. highlighted that the occurrence of omega phase is linked to maximum in micro-Vickers hardness. It is evident from Fig. 3 that the hardness of TMF0 alloy was notably higher as compared to that of TMF1 alloy. The high hardness in TMF0 can be ascribed to the presence of the orthorhombic martensitic phase which possesses a high hardness compared to the β phase according to the Lee et al. hardness trend [20]. The hardness of as-cast TMF0 alloy is found to be higher compared to those reported in Ref. [21] for Ti-15Mo alloy (307 HV0.2 ) and Ref. [21] for Ti-15Mo alloy (330 HV0.5 ) in as-cast condition. The decrease in the micro-Vickers hardness in TMF1 regardless of the presence of both the hard phases of orthorhombic martensitic structure (α ) and TiFe is chiefly ascribed to the presence of porosity in the sample as observed in the OM microstructure in Fig. 2(b). it has been described that the existence of porosity decreases the elastic modulus of a material, however it could also lead to stress concentration which reduces the strength of a material, hardness, and ductility.[22]. Since no porosity is observed, the significant increase in hardness of TMF2 and TMF3 alloys is mainly recognized by higher volume fraction of dendritic structures (TiFe). Owed to narrow published work on Ti-15Mo-xFe alloys in as-cast conditions, the micro-Vickers hardness of the studied alloys was compared to other metastable alloys found in the literature. The TMF2 and TMF3 alloys were higher as compared to Ti-10Ta4Fe (410HV), Ti-12Nb-5Fe (293HV), Ti-7Ta-5Fe (430HV) alloys, while the TMF1 was lower than Ti-7Ta-5Fe alloy. The micro-Vickers hardness of studied alloys was higher than commercial materials such as Ti6Al4V (294 HV0.5 ) [23] and CP-Ti (156 HV0.2 ) reported by [21] and 210 HV0.5 in CP-Ti alloy [24].

Effects of Fe Addition on the Phase and Mechanical Properties

41

Micro-Vickers Hardnes (Hv)

600 500 400 300 200 100 0

TMF0

TMF1

TMF2

TMF3

Alloy Name (wt%) Fig. 3. Micro-Vickers Hardness of as-cast TMF alloys.

3.5 Fracture Surfaces Figure 4 presents the SEM fracture fractography of the tensile-tested specimens for Ti-15Mo-xFe alloys. As demonstrated in Fig. 4(a), the fracture surface of TMF0 alloy was composed of a typical ductile fracture and brittle mode as characterized by fine dimpled rupture, and cleavage-like facets including feather and river-like patterns and voids, respectively. The fracture surface of TMF1 alloy in Fig. 4(b) showed only brittle fracture mode because it was almost exclusively composed of large cleavage-like facets including river patterns. The fractography of TMF2 and TMF3 alloys in Figures (c & d) depicted cleavage-like facets, feather, and river-like patterns, and a high volume of cracks and voids which indicate brittle fracture mode. The cleavage-like facets fracture in TMF2 and TMF3 indicates brittleness of the material as they could not withstand the minimum tensile load while testing.

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Fig. 4. Fracture surfaces of the tensile test (a) TMF0, (b) TMF1, (c) TMF2, and (d) TMF3 alloys

4 Conclusions The influence of Fe addition on the microstructure and mechanical properties of Ti15.05Mo alloy in as-cast condition was investigated systematically by using experimental methods. The following assumptions can be summarized as follows: • The X-ray diffraction patterns of TMF0 in as-cast condition depicted peaks belonging to the bcc (β). The addition of Fe into Ti-15.05Mo demonstrated a new peak belonging to TiFe. There was an XRD peak shift towards higher 2θ positions with the addition of higher Fe content, signalling lattice contraction which led to solid-solution strengthening. • The OM micrographs of TMF0 showed large beta equiaxed grains and within the grains were sub-structured of orthorhombic martensitic α structure. The micrograph of TMF1 (addition of Fe content in Ti-15.05Mo) was composed of smaller grains with dendrites in the grains and within the grain boundaries. Increasing Fe content (TMF2 and TMF3) the micrograph showed a complete dendritic structure. • The tensile properties of TMF0 were found to be lower as compared to commercially used Ti6Al4V. Due to the high level of porosity in the TMF1 sample and the high brittleness and fragility in the TMF2 and TMF3 samples, some of the mechanical properties could not be obtained.

Effects of Fe Addition on the Phase and Mechanical Properties

43

• The Micro-Vickers hardness of TMF0 was higher due to existence of orthorhombic martensitic α phase, the hardness decreased with the addition of Fe (TMF1), this was attributed to the small grains and pores in the alloys. The hardness increased significantly with an increase in Fe (TMF2 and TMF3) and is ascribed to the high degree of dendritic structure. • The fracture surfaces after tensile test, the TMF0 showed a combination of ductile and brittle fracture, while the TMF1, TMF2, and TMF3 depicted only brittle fracture. Acknowledgement. This work was supported and funded by Mintek (Advanced Metallurgy Division) and the studies were funded by CSIR-IBS. The author would like to acknowledge Mintek (AMD) and CSIR (AME and National Laser Center) for providing access to their laboratories. The author thanked colleagues at Mintek (Mr. Mbavhalelo Maumela, Mr. Absalom Mabeba, and Mr. Andrew Mampuru) for their assistance with experiments and Mr. Joseph Moema for his support.

References 1. Niinomi, M.: Mechanical properties of biomedical titanium alloys (1998) 2. Niinomi, M.: Mechanical biocompatibilities of titanium alloys for biomedical applications. J. Mech. Behav. Biomed. Mater. 1(1), 30–42 (2008). https://doi.org/10.1016/j.jmbbm.2007. 07.001 3. Gepreel, M.A.-H., Niinomi, M.: Biocompatibility of Ti-alloys for long-term implantation. J. Mech. Behav. Biomed. Mater. 20, 407–415 (2013). https://doi.org/10.1016/j.jmbbm.2012. 11.014 4. Okazaki, Y., Rao, S., Ito, Y., Tateishi, T.: Corrosion resistance, mechanical properties, corrosion fatigue strength and cytocompatibility of new Ti alloys without Al and V (1998) 5. Ehtemam-Haghighi, S., Liu, Y., Cao, G., Zhang, L.C.: Phase transition, microstructural evolution and mechanical properties of Ti-Nb-Fe alloys induced by Fe addition. Mater. Des. 97, 279–286 (2016). https://doi.org/10.1016/j.matdes.2016.02.094 6. Lin, J., et al.: Effects of solution treatment and aging on the microstructure, mechanical properties, and corrosion resistance of a β type Ti-Ta-Hf-Zr alloy. RSC Adv. 7(20), 12309– 12317 (2017). https://doi.org/10.1039/c6ra28464g 7. Zhou, Y.L., Niinomi, M., Akahori, T.: Effects of Ta content on Young’s modulus and tensile properties of binary Ti-Ta alloys for biomedical applications. Mater. Sci. Eng. A 371(1–2), 283–290 (2004). https://doi.org/10.1016/j.msea.2003.12.011 8. Okulov, I.V., et al.: Open porous dealloying-based biomaterials as a novel biomaterial platform. Mater. Sci. Eng. C 88, 95–103 (2018). https://doi.org/10.1016/j.msec.2018.03.008 9. Gao, J., et al.: Segregation mediated heterogeneous structure in a metastable β titanium alloy with a superior combination of strength and ductility. Sci. Rep. 8(1), 7512 (2018). https://doi. org/10.1038/s41598-018-25899-3 10. Bolzoni, L.: Low-cost Fe-bearing powder metallurgy Ti alloys. Metal Powder Rep. 74(6), 308–313 (2019). https://doi.org/10.1016/j.mprp.2019.01.007 11. Song, Y., Xu, D.S., Yang, R., Li, D., Wu, W.T., Guo, Z.X.: Theoretical study of the effects of alloying elements on the strength and modulus of i-type bio-titanium alloys (1999) 12. Boyer, R.R.: Aerospace Applications of Beta Titanium Alloys (1994) 13. Weiss, I., Froes, E.H., Eylon, D., Welsch, G.E.: Modification of Alpha Morphology in Ti6AI-4V by Thermomechanical Processing (1998)

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14. Campo, K.N., Andrade, D.R., Opini, V.C., Mello, M.G., Lopes, E.S.N., Caram, R.: On the hardenability of Nb-modified metastable beta Ti-5553 alloy. J. Alloys Compd. 667, 211–218 (2016). https://doi.org/10.1016/j.jallcom.2016.01.142 15. Cao, G.H., et al.: Formation of a bimodal structure in ultrafine Ti-Fe-Nb alloys with highstrength and enhanced ductility. Mater. Sci. Eng. A 609, 60–64 (2014). https://doi.org/10. 1016/j.msea.2014.04.088 16. Louzguine, D.V., Kato, H., Louzguina, L.V., Inoue, A.: High-strength binary Ti-Fe bulk alloys with enhanced ductility. J. Mater. Res. 19(12), 3600–3606 (2004). https://doi.org/10.1557/ JMR.2004.0462 17. Biesiekierski, A., Lin, J., Li, Y., Ping, D., Yamabe-Mitarai, Y., Wen, C.: Investigations into Ti-(Nb, Ta)-Fe alloys for biomedical applications. Acta Biomater. 32, 336–347 (2016). https:// doi.org/10.1016/j.actbio.2015.12.010 18. Salvador, C.A.F., Dal Bó, M.R., Costa, F.H., Taipina, M.O., Lopes, E.S.N., Caram, R.: Solute lean Ti-Nb-Fe alloys: An exploratory study. J. Mech. Behav. Biomed. Mater. 65, 761–769 (2017). https://doi.org/10.1016/j.jmbbm.2016.09.024 19. Lopes, É.S.N., Salvador, C.A.F., Andrade, D.R., Cremasco, A., Campo, K.N., Caram, R.: Microstructure, mechanical properties, and electrochemical behavior of Ti-Nb-Fe alloys applied as biomaterials. Metall. Mater. Trans. A Phys. Metall. Mater. Sci. 47(6), 3213–3226 (2016). https://doi.org/10.1007/s11661-016-3411-0 20. Lee, C.M., Ju, C.P., Chern Lin, J.H.: Structure-property relationship of cast Ti-Nb alloys. J. Oral Rehabil. 29(4), 314–322 (2002). https://doi.org/10.1046/j.1365-2842.2002.00825.x 21. Ho, W.F., Ju, C.P., Lin, J.C.: Structure and properties of cast binary Ti–Mo alloys. Biomaterials 20(22), 2115–2122 (1999) 22. Santos, P.F., et al.: Fabrication of low-cost beta-type Ti-Mn alloys for biomedical applications by metal injection molding process and their mechanical properties. J. Mech. Behav. Biomed. Mater. 59, 497–507 (2016). https://doi.org/10.1016/j.jmbbm.2016.02.035 23. Chen, Y., Xu, L., Liu, Z., Kong, F., Chen, Z.: Microstructures and properties of titanium alloys Ti-Mo for dental use. Trans. Nonferrous Metals Soc. China 16, 824–828 (2006). https://doi. org/10.1016/S1003-6326(06)60308-7 24. J. R. Severino Martins and C. R. Grandini. Structural characterization of Ti-15Mo alloy used as biomaterial by Rietveld method. J. Appl. Phys. 111(8) (2012). https://doi.org/10.1063/1. 47079202012

Technology of Obtaining Metallic Silver from Waste Copper Tailings L. M. Karimova1,2(B)

, Ye. T. Kairalapov1 , E. M. Kharchenko1,3 and B. B. Katrenov1

,

1 LLP “Innovation”, Karaganda, Kazakhstan

[email protected]

2 LLP “KazGidroMed”, Karaganda, Kazakhstan 3 N-pJSC «Karaganda Industrial University», Karaganda, Kazakhstan

Abstract. The article studies the production of metallic silver from leaching solutions of rough copper concentrate from dump tailings. To obtain a productive solution, the concentrate was sintered with alkali at a temperature of 300 °C and the sinter was leached in water with a silicon recovery of 60%. The cake was directed to copper and silver leaching with a solution of sulfuric acid with the addition of halite at a temperature of 90 °C, L:S = 4:1. As a result, a productive solution was obtained with the content of: Ag-3.6 mg/l, Cu - 5.9 g/l, pH- 3.1, which was used to conduct studies on the sorption / desorption of silver with an ion exchange resin brand Lewatit MonoPlus TP 214 produced by Lanxess concern (Germany). The electrolytic deposition of silver was carried out using a titanium cathode, a lead anode equipped with an ion exchange membrane. The electrolysis was carried out at a current density of 40–60 A/m2 , a temperature of 35–40 °C, a solution flow rate of 0.5 l/h, and an electrolysis cell voltage of 3–4.5 V. Cathode deposit with 97.5% silver recovery sent for melting at 1000 °C. The resulting metal corresponds to the brand SrM75. Keywords: silver · solution · sorption · electrolysis · tailings

1 Introduction One of the processes for the complete and integrated extraction of valuable components is the desiliconization of waste copper tailings, which makes it possible to improve the quality of the concentrate in terms of copper and other components, as well as to obtain additional commercial products. Sulfuric acid leaching of the concentrate ensures the complex extraction of valuable components with further production of marketable products (cathode copper, silver ingots). Known processes for the desiliconization of copper and zinc ores were studied in [1–4] using autoclave leaching methods. The alkaline sintering method was previously used for processing other copper-containing materials [5–7], which opens up the possibility of significant enrichment of raw materials. This research has been/was/is funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan (Grant No. AP 19675340). © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 45–49, 2024. https://doi.org/10.1007/978-981-97-1594-7_6

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1.1 Materials Used and Studies For research, an intermediate concentrate was used, obtained from dump copper tailings by the enrichment method Table 1. Table 1. The content of the main components in the intermediate product. Components

Content,%

Components

Content,%

Cu

7,34

Zn

0,034

Fe

9,74

Ti

0,4

Al

5,57

Pb

0,015

S

2,97

SaO

3,48

Si

24,38

Ag, g/t

33,2

Bulk weight of the concentrate was 0.9 g/cm3 , specific gravity - 2.5 g/cm3 . Sintering was carried out in a muffle electric furnace. Before the start of research, the furnace was heated to a certain temperature. Then the test material was placed inside the furnace and at a temperature of 300 °C with a concentrate to alkali ratio of 1:2. Aqueous leaching of the sinter was carried out at a temperature of 60 °C for 60 min. The scheme of the complex extraction of valuable components from the crude concentrate is shown (see Fig. 1). After water leaching of the sinter of substandard concentrate, the extraction of silica into the solution was 60%. Further, the resulting cake was sent to the leaching of copper and silver with a solution of sulfuric acid with the addition of halite at a temperature of 90 °C, L:S = 4:1. The result was a productive solution containing: Ag - 3.6 mg/l, Cu-5.9 g/l, pH-3.1; which was used to conduct studies on the sorption of silver with an ion exchange resin of the Lewatit MonoPlus TP214 brand produced by the Lanxess concern (Germany). Silver in the productive solution is in the form of the chlorine anionic complex [AgCl2 ]− . To extract silver from a solution by ion exchange, it is necessary to destroy the complex by creating a more stable complex compound in the sorbent grain. In this regard, the most preferable for the implementation of the sorption of silver from this solution is a resin containing thiourea as a functional group, since the silver thiourea complex is more stable than the chlorine anionic one. Silver sorption/desorption experiments were carried out in a static mode at room temperature. In the process of silver sorption from a weakly acidic productive solution, the following reaction occurs:

To determine the time required to establish equilibrium in the ion exchanger-solution system, as well as the static volumetric capacity (SOE) of the ion exchanger, a series of

Technology of Obtaining Metallic Silver from Waste Copper Tailings

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Fig. 1. Principal technological scheme of processing substandard copper concentrate for the production of silver, copper and silica.

experiments was carried out with different durations, the results of which are presented in method Table 2. Despite the complex, multicomponent nature of the initial solution, the high selectivity of the Lewatit Mono Plus TP-214 sorbent with respect to silver ions should be noted. At the beginning of sorption, a slight capture of copper ions occurs, since copper also tends to form thiourea complexes. But in the process of saturating the resin with silver, the content of copper ions decreases. The rate of silver sorption can be considered high, since after 20 min there was no silver sorption in the productive solution (traces), that is, the sorption was complete, while not reaching the full capacity of the ion exchanger. For the desorption of silver from this ion exchanger, it is advisable to use a thiourea sulfate solution, since in this case silver passes from the sorbent into the solution also in the form of a thiourea complex, while the functional group of the resin is restored (regeneration). During the desorption of silver from a saturated ion exchanger, the following reaction occurs:

48

L. M. Karimova et al. Table 2. Study of the equilibrium process in the system solution - ion exchanger.

№

Time sorption, min

S:L

Ag 1:1000

γ

Content in ion exchanger, %** Cu

%

g/l

%

g/l

ml/g

0.05

0.215

0.007

0.03

2.41

1

5

2

10

0.26

1.088

0.006

0.025

2.39

3

15

0.55

2.361

0.002

0.009

2.33

4

20

0.89

3.820

0.001

0.004

2.33

5

30

0.90

3.863

0.001

0.004

2.33

* - volume ratio: volume of resin layer: volume of solution ** - percentage by weight of air-dry resin *** - the content of the element in the volume of the sorbent layer

Desorption was carried out in a static mode by mixing saturated resin (10 ml) with a sulfuric acid solution of thiourea (CS(NH2 )2 ) with a concentration of 70 g/l and sulfuric acid with a concentration of 50 g/l in the ratio L:S = 10:1 for 120 min. The result is a solution containing 0.402 g/l of silver. The residual silver content in the resin was 0.01%, which corresponds to a desorption degree of 99%. After the desorption cycle, two independent material flows are formed: the desorbate, which was sent to the electrolytic deposition of silver, and the regenerated sorbent, freed from silver ions, which was used in further sorption cycles. Several methods are known for the deposition of gold and silver from thiourea solutions: cementation, alkali precipitation, and electrolysis with insoluble anodes. The most advanced method of deposition from a productive solution is electrolysis with insoluble anodes. When a direct current is passed through the regenerator, silver is reduced at the cathode. It was shown in [8] that electrolyzers for the precipitation of silver from solutions obtained after the processing of flotation concentrates should be equipped with a separating ion-exchange membrane to prevent the oxidation of thiocyanate ions to elemental sulfur at the anode. Studies on the electrolytic deposition of silver were carried out in an EZ-1 (6/75)M laboratory electrolyzer using a titanium cathode, a lead anode equipped with an MK40L ion-exchange membrane for the separation of catholyte and anolyte. The catholyte was a silver-containing desorbate, and the anolyte was a sulfuric acid solution with a concentration of 20 g/l. The main technological parameters of the electrolysis process: current density 40–60 A/m2 , temperature 35–40 °C, solution flow rate - 0.5 l/h and voltage on the electrolysis

Technology of Obtaining Metallic Silver from Waste Copper Tailings

49

bath - 3–4.5 V. The working area of the cathode and anode is 0.07 m2 . The concentration of silver in the catholyte is 98.95 mg/l; thiourea - 70 g/l; SO4 2− - 48.0 g/l. The concentration of silver in the spent electrolyte was 2.4 mg/l. The electrolyte was heated in a thermostated reactor to a temperature of 35–40 °C and was fed into the cathode space of the electrolysis bath using a dosing pump. The electrolyte supply rate was calculated based on the need for a complete exchange of the entire volume of the bath in 1 h. The electrolyte, freed from silver ions, entered the spent electrolyte collector. The spent electrolyte was saturated by using it as a stripping solution in the silver stripping step. During desorption, the electrolyte reached the specified parameters for the concentration of the target components and free sulfuric acid and returned to the electrolysis cycle. The accumulated cathode precipitate of silver sulfide was discharged with part of the solution. Based on the data obtained during the electrolysis, the extraction of silver from the catholyte into the cathode deposit was 97.5%. At the end of the electrolysis process, the silver precipitate accumulated under the cathode was unloaded with a part of the solution, dried, weighed and sent for melting at a temperature of 1100 °C. The resulting metal corresponds to the SrM75 grade with a silver content of 74.9%.

References 1. Naboychenko, S.S., Ni, L.P., Schneerson, Ya.M., Chugaev, L.V.: Autoclave hydrometallurgy of non-ferrous metals. UPI, Ekaterinburg, in 3 volumes (2008) 2. Rao, J.R., Nayak, R., Suryanarayana, A.: Feldspar for potassium, fertilizer, catalysts and cement. Asian J. Chem. 10(4), 690–796 (1998) 3. Zablotskaya, Yu.V., Sadykhov, G.B., Gocharenko, T.V.: Autoclave leaching kinetics of a leucoxene concentrate with alkaline solutions. Russian Metallurgy (Metally) (1), 1–5 (2015) 4. Loginova, I.V., Kyrchikov, A.V., Lebedev, V.A., Ordon, S.F.: Investigation into the question of complex processing of bauxites of the srednetimanskoe deposit. Russian J. Non-Ferrous Metals 54, 143–147 (2013) 5. Loginova, I.V., Shoppert, A.A., Chaikin, L.I.: Extraction of rare-earth metals during the systematic processing of diaspore boehmite bauxites. Metallurgist 60, 198–203 (2016) 6. Shoppert, A.A., Loginova, I.V., Chaikin, L.I., Rogozhnikov, D.A.: Alkali fusion-leaching method for comprehensive processing of fly ash. In: Technogen Conference Proceedings, KnE Materials Science, vol. 1, pp. 89–96 (2017) 7. Shoppert, A.A., Karimova, L.M., Zakharyan, D.V.: Novel method for comprehensive processing of low-grade copper concentrate. Materials Engineering and Technologies for Production and Processing IV, Solid State Phenomena, vol. 284, pp. 856–862 (2018) 8. Kuzmenkov, M.A., Shipunov, L.V.: Study of silver and gold electrolysis from flotation concentrate processing solutions. In: Collection of Materials of the Conference “XIV International Scientific and Practical CONFERENCE 2021 “Scientific interdisciplinary research”, pp. 517–521. Saratov (2016)

Investigation of Co-dopant (Eu3+ -Ce3+ ) Induced Electronic Transitions in LiCaBiB Glasses A. Madhu1(B) , Namrata Yaduvanshi1 , T. Uthayakumar1 , and N. Srinatha2 1 Department of Physics, Dayananda Sagar College of Engineering, Kumaraswamy Layout,

Bangalore 560078, India [email protected] 2 Department of Physics, RV Institute of Technology and Management, Bangalore 560076, India

Abstract. The prepared co-doped (Eu3+ /Ce3+ ) ions in lithium-calcium-bismuthborate glasses were synthesized using the conventional melt quenching technique. It was evident from the x-ray diffractogram profile that the glasses prepared were amorphous in nature. The absorption data in the ultraviolet-visible region revealed that the Eu3+ ions had a greater effect than the Ce3+ ions, which typically act as sensitizers. Tauc’s plot explained how the indirect transitions vary with an increase in the concentration of Eu3+ . Keywords: (Eu3+ /Ce3+ ) ions · UV-Vis-NIR absorption · Tauc’s · Urbach

1 Introduction Luminescent glasses are superior to phosphors for the production of white light emitting diodes (W-LEDs) due to their many advantages. These advantages include better uniformity, there is a high level of transparency in the visible region, improved thermal stability, ease of molding into proper shapes, direct packaging with LED chips, lower fabrication costs, and more. Currently, most commercially available W-LEDs use blue LED chips coated with phosphors that are easily excited by blue light, but it’s time to consider the benefits of luminescent glasses containing rare earth elements [1]. The 4f6 configuration of the Eu3+ ion makes it an extremely efficient activator in producing vivid red color centers in display devices. Its emission transition at 615 nm, particularly the 5 D0 → 7 F2 transition, is the main reason for this [2–5]. The Ce3+ ion is an exceptional choice as a dynamic sensitizer for selective rare earth ions. It’s worth noting that Ce3+ ions exhibit robust and wide-ranging f-d absorption and emission bands that span from the ultraviolet to the visible region. This is attributable to the considerable energy gap between their ground state (4f) and excited state (5d) [1, 6–8]. Keeping these earlier reports, we found very less work is explored in co-doping (Eu3+ /Ce3+ ) systems in glasses. Additionally, we are examining the impact of the co-dopant effect on lithium-calcium-bismuth-borate glass through an electronic transition. Understanding the impact of a co-dopant on electronic transition states is crucial. It is important to explore this aspect thoroughly to gain an inclusive understanding of the electronic properties of materials. © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 50–55, 2024. https://doi.org/10.1007/978-981-97-1594-7_7

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51

2 Synthesis and Characterization The chemical composition of the glass system: (20-x-y) Li2 O-10CaO-10Bi2 O3 -60B2 O3 , where x (in mol%) = 0.1,0.5 Eu2 O3 , y = 0.1 Ce2 O3 was set by melt quenching method. The necessary amounts of AR grade; Li2 CO3 , H3 BO3 , Bi2 O3 , CaCO3 , Eu2 O3 , and Ce2 O3 were measured as per the formula provided. The process of synthesis has been explained in detail in our recent publication [9–13] and illustrated in the flow chart below.

Fig. 1. Flow chart of synthesis

To determine the amorphous or crystalline nature of the glass samples, the annealed pellets were crushed to a fine powder and subjected to X-ray diffraction (XRD) analysis using the RIGUKA ULTIMA IV instrument. The analysis utilized monochromatic Cu kα radiation considering wavelength of 1.5406 Å. The optical absorption spectra of the transparent samples of thickness 0.2 cm which are circular in shape as shown in Fig. 1, under analysis were captured with precision using the Perkin Elmer Lambda 750 spectrometer, which boasts top-notch equipment and exceptional performance. With a remarkable resolution of 0.1 nm, it operates effectively within the wavelength range: 190 to 3000 nm.

3 Results and Discussions 3.1 X-Ray Diffractogram Profile (XRD) In Fig. 2, we observe the powder XRD patterns of the glass samples that have been prepared. Upon close examination, we can discern that there are no distinct diffraction peaks or crystals present. Instead, we note the appearance of two broad humps located at

52

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approximately 15° and 70°, which is indicative of the short-range order of atoms within the glass structure. There is no presence of any crystalline peaks detected by the XRD instrument affirms that the glasses stay, in fact, amorphous: non-periodic nature.

Intensity (arb.units)

05Eu01Ce 01Eu01Ce

10

20

30

40

2 °

50

60

70

80

Fig. 2. X-ray diffractometer profile of the samples

3.2 Ultraviolet-Visible-Near Infrared Absorption Studies and Tauc’s Plot Figure 3 displays the absorption spectra of a lithium-calcium-bismuth-borate glass matrix doped with 0.1% of Eu3+ and Ce3+ also 0.1% Ce3+ and 0.5% Eu3+ . The features observed correspond to transitions of Eu3+ from the 7 F0,1 state to various excited levels of the 4f6 configuration. Through analysis of the absorption spectra, it has been observed that the influence of Eu3+ is more substantial than that of Ce3+ . In addition, it was found that transitions in the Eu3+ absorption spectrum occur not only from the ground state (7 F0 ), but also from the first excited state (7 F1 ), due to the close proximity of these states. A closer examination of the absorption band positions of (7 F0 ,7 F1 ) transitions to 5 D1 and 5 D0 revealed that the energy gap between the ground (7 F0 ) and first excited (7 F1 ) states is approximately 264 cm−1 [14]. The Eu3+ ion’s absorption spectrum displays five absorption transitions in Ultraviolet-Visible-near infrared region, namely 7 F0 to5 D2 , 7 F0 to5 D1 , 7 F1 to 5 D1 , 7 F0 to 7 F6 and 7 F1 to 7 F6 . Moreover, it has been established that the strength of these bands amplifies proportionately with the rise in Eu3+ dopant amount.

3.0

7

F1

7

F0

7

F6 (2198 nm)

7

F6 (2084 nm)

D1 (530 nm) F1

5 7

D1 (523 nm)

D2 (462 nm)

F0

2.0

F0

53

5

5

2.5

7

7

Absorption co-efficient (cm-1)

Investigation of Co-dopant (Eu3+ -Ce3+ ) Induced Electronic Transitions

1.5

1.0

Wavelength (nm) Fig. 3. Ultraviolet-infrared spectrum for the samples

In order to examine how co-doping impacts the optical band gap energy, we analysed the optical absorption spectra of Lithium-bismuth-calcium-borate glass samples (as shown in Fig. 4). This allowed us to calculate the material’s band gap energy. We determined the optical absorption coefficient, α(λ), using the equation below [15, 16]; A (1) t To compute the band gap energy, Tauc’s equation [15] must be employed with the thickness of the glass sample denoted as t and the absorbance as A;  n αhυ = B hν − Eg (2) α(λ) = 2.303 ×

In this equation, B is a constant and ‘hυ’ represents the energy of a photon. ‘E g ’ stands for the energy band gap, and ‘n’ is a number that describes the transition process. The value of ‘n’ varies depending on the type of transition, with 2, 3, 1/2, and 3/2 being the possible values for indirect allowed; indirect forbidden; direct allowed; and direct forbidden transitions, respectively. For non-crystalline solids, only indirect transitions are considered. The plots in Fig. 4 are of utmost importance since they provide valuable information on the band gap of the material. To determine the indirect band gap, we extended the linear portion of the Tauc’s plots. The numerical values obtained from this analysis are presented in the figures for easy reference. It is crucial to take into consideration that the optical band gap for indirect allowed transitions will increase in tandem with the concentration of Eu3+ . To calculate the tail width, or Urbach energy, simply find the inverse of the slope of the ln(α) vs hυ curves. The Urbach energy can then be estimated, with the values falling within a range of approximately 0.2 eV.

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Fig. 4. Tauc’s and Urbach energy plot

4 Conclusions We conducted an experiment where, synthesized co-doped ions (Eu3+ /Ce3+ ) in lithiumcalcium-bismuth-borate we utilized the melt quenching technique to create a pair of glasses. This process involves melting the desired materials and then rapidly cooling them to form a solid material. The resulting glasses are durable and of high quality. The resulting glasses were found to be amorphous, as confirmed by the x-ray diffractogram profile. Upon observing the absorption data in the ultraviolet-visible region, it was noticed that the Eu3+ ions had a greater impact, as compared to Ce3+ which typically acts as a sensitizer. Furthermore, the Tauc’s and Urbach relations demonstrated how the phonon-assisted transitions changed with an increase in the concentration of Eu3+ .

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References 1. Rao, V.R., Devi, L.L., Jayasankar, C.K., Pecharapa, W., Kaewkhao, J., Depuru, S.R.: Luminescence and energy transfer studies of Ce3+/Dy3+ doped fluorophosphate glasses. J. Lumin. 208, 89–98 (2019). https://doi.org/10.1016/j.jlumin.2018.11.053 2. Saad, M., Elhouichet, H.: Good optical performances of Eu3+/ Dy3+ / Ag nanoparticles codoped phosphate glasses induced by plasmonic effects. J. Alloys Compd. 806, 1403–1409 (2019). https://doi.org/10.1016/j.jallcom.2019.06.353 3. Saad, M., Stambouli, W., Mohamed, S.A., Elhouichet, H.: Ag nanoparticles induced luminescence enhancement of Eu3+ doped phosphate glasses. J. Alloys Compd. 705, 550–558 (2017). https://doi.org/10.1016/j.jallcom.2016.12.410 4. Yu, Y., Wang, Y., Chen, D., Huang, P., Ma, E., Bao, F.: Enhanced emissions of Eu 3+ by energy transfer from ZnO quantum dots embedded in SiO 2 glass. Nanotechnology 19, 055711 (2008). https://doi.org/10.1088/0957-4484/19/05/055711 5. Ben Slimen, F., Zaaboub, Z., Haouari, M., Bel Haj Mohamed, N., Ben Ouada, H., Chaussedent, S., Gaumer, N.: Effect of CdS nanocrystals on the photoluminescence of Eu 3+-doped silicophosphate sol gel glass. RSC Adv. 7, 14552–14561 (2017). https://doi.org/10.1039/C7R A01313B 6. Sontakke, A.D., Ueda, J., Tanabe, S.: Effect of synthesis conditions on Ce3+ luminescence in borate glasses. J. Non Cryst. Solids 431, 150–153 (2016). https://doi.org/10.1016/j.jnoncr ysol.2015.04.005 7. Bei, J., Qian, G., Liang, X., Yuan, S., Yang, Y., Chen, G.: Optical properties of Ce3+-doped oxide glasses and correlations with optical basicity. Mater. Res. Bull. 42, 1195–1200 (2007). https://doi.org/10.1016/j.materresbull.2006.10.020 8. Li, P., Wang, Z., Guo, Q., Yang, Z.: Tunable emission phosphor Ca 4 Y 6 O(SiO 4) 6: Ce 3+, Eu 2+ : luminescence and energy transfer. J. Am. Ceram. Soc. 98, 495–500 (2015). https:// doi.org/10.1111/jace.13292 9. James, J.T., Jose, J.K., Manjunatha, M., Suresh, K., Madhu, A.: Structural, luminescence and NMR studies on Nd3+-doped sodium–calcium-borate glasses for lasing applications. Ceram. Int. 46, 27099–27109 (2020). https://doi.org/10.1016/j.ceramint.2020.07.187 10. Eraiah, B.: Physical and structural properties of Sm3+ ions doped heavy metal oxide containing lanthanum-boro-telluirte glass, p. 090056 (2018). https://doi.org/10.1063/1.503 2903 11. Madhu, A., Srinatha, N.: Structural and spectroscopic studies on the concentration dependent erbium doped lithium bismuth boro tellurite glasses for optical fiber applications. Infrared Phys. Technol. 107, 103300 (2020). https://doi.org/10.1016/j.infrared.2020.103300 12. Hemalatha, S., Nagaraja, M., Madhu, A., Suresh, K., Srinatha, N.: The role of Sm2O3 on the structural, optical and spectroscopic properties of multi-component ternary borate glasses for orange-red emission applications. J. Non. Cryst. Solids. 554, 120602 (2021). https://doi.org/ 10.1016/j.jnoncrysol.2020.120602 13. Hemalatha, S., Nagaraja, M., Madhu, A., Srinatha, N.: Rare earth (Dy3+-ion) induced near white light emission in sodium-zinc-borate glasses. Results Opt. 9, 100275 (2022). https:// doi.org/10.1016/j.rio.2022.100275 14. Stambouli, W., Elhouichet, H., Gelloz, B., Férid, M.: Optical and spectroscopic properties of Eu-doped tellurite glasses and glass ceramics. J. Lumin. 138, 201–208 (2013). https://doi. org/10.1016/j.jlumin.2013.01.019 15. Tauc, J. (ed.): Amorphous and Liquid Semiconductors. Springer, Boston (1974). https://doi. org/10.1007/978-1-4615-8705-7 16. Mott, N.F., Davis, E.A., Weiser, K.: Electronic processes in non-crystalline materials. Phys. Today 25, 55 (1972). https://doi.org/10.1063/1.3071145

Optimization of Plastic Injection Molding Process Parameters for a DACIA Logan L90 Front Bumper with Taguchi Method Soufiane Haddout(B) Faculty of Science, Ibn Tofail University, Kenitra, Morocco [email protected]

Abstract. Plastic-based products are being used more and more frequently. Due to the growing demand for thinner products, lower production costs and higher quality, there has been an increase in plastic molding research projects. Productivity can be increased by optimizing the injection molding parameters. In order for the process optimization to be successful, optimal parameters must be set. In this paper we will discuss the warpage defect on the front bumper of DACIA Logan L90. The optimization was performed using the TAGUCHI method and the percentage contributions were calculated using an analysis of variance (ANOVA). A significant correlation was found between mould temperature (35.80%), packing time (35.59%), melt temperature (10.13%) and packing pressure (5.33%). Melting temperature (200 °C), packing time (0.8 s), packing pressure (375 MPa) and mould temperature (80 °C) were found to be the most effective parameters to minimize warpage. The ANOVA analysis and the TAGUCHI method can be used to determine optimal parameters and their contribution percentage. The design of experiments method was therefore found to be one of the most effective ways to improve a production’s quality. Keywords: Injection Molding Optimization · polypropylene · Taguchi methodology · ANOVA analysis

1 Introduction With the growing use and development of plastic components for home appliances, automobiles, electronics, healthcare devices, and aircraft components, plastic raw materials have become increasingly in demand, whereas natural raw materials like steel and iron are becoming less available. Plastic raw materials are becoming more popular due to their mass competitively, dimensional stability at room temperature, forming capabilities, and good surface quality. Due to the process’s ability to achieve rapid mass production, injection molding is often used to manufacture plastic products. Moreover, injection molding is most commonly used to process polymers and produces identical products from a mold. The main advantage of this process is the ability to repeatedly produce parts with complex geometries at high production rates. The complexity is virtually unlimited and sizes can range from very small to very large. Most polymers can be manufactured using © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 56–62, 2024. https://doi.org/10.1007/978-981-97-1594-7_8

Optimization of Plastic Injection Molding Process Parameters

57

injection molding, including thermoplastics, fiber-reinforced thermoplastics, thermoset plastics, and elastomers. Critical to the adoption of this high-volume, cost-effective process technology is the ability to consistently produce high-quality parts. The injection molding industry usually performs parameter optimization to produce good-quality products, particularly determining the final optimal process parameters. As a crucial step in improving molded products’ quality, optimizing the final process parameters is an important procedure in injection molding [2]. It has been demonstrated that injection molding processing parameters have an important impact on product quality [3–9]. Injection molding processes can be simulated and optimized with Moldflow software [10, 11]. In order to achieve optimal shrinkage and warping, you will have to make recommendations that are both cost-effective as well as efficient in terms of cycle time. Many studies have been conducted using genetic algorithms to optimize the parameters of the plastic injection molding process and improve product quality [12, 13]. In addition, another study was conducted in which artificial neural networks are used to model the plastic injection molding process and combined with the genetic algorithm method to optimize the process parameters [13]. This article attempts to describe the optimization of the injection molding process parameters for optimal warping performance of a plastic front bumper of the DACIA Logan L90, which is made of polypropylene polymer. The study also includes an analysis of distortion defects on raw materials, including the evaluation of effective parameters contributing to defects, the selection of orthogonal arrays, and the optimization of the parameters. The level and parameters involved in orthogonal arrays influence their choice, therefore the 3 levels and 4 parameters were chosen. A Taguchi L9 orthogonal array was used according to the parameters and level chosen. S/N ratio and ANOVA were used to determine the optimum parameters.

2 Methodology Due to its universality as the most common injection molding material, polypropylene (PP) will be used for optimizing injection molding process parameters. As shown in Table 1, PP has the following general properties. Table 1. Properties of Polypropylene. Density (g/cm3 )

0.90–0.91

Melt flow index (g per 10 min)

10.78

Modulus of elasticity (MPa)

4100

Charpy impact toughness (KJ/m2 )

1.4–1.8

Taguchi’s orthogonal arrays and selection of the parameters. The analysis applied three-level Taguchi orthogonal array L9 (34) experiments and used four processing parameters; and nine experiments including one verification experiment were conducted.

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When designing the robust parameters for polypropylene material, the following parameters should be considered: a) melting temperature, b) packing time, c) packing pressure, d) molding temperature. An orthogonal arrangement of L9 parameters and levels is shown in Table 2 and a process parameter and levels table is shown in Table 3. Table 2. The parameter for 3 levels of selected factors. S.No

Factors

Level 1

Level 2

Level 3

1

Melt Temperature, A (ºC)

200

220

240

2

Packing time, C(s)

0.6

0.8

1.0

3

Packing Pressure D(MPa)

300

375

450

4

Mold Temperature, E (ºC)

040

060

080

Table 3. L9 orthogonal array. Expt No.

A (ºC)

C (s)

D(MPa)

E (ºC)

1

1

1

1

1

2

1

2

2

2

3

1

3

3

3

4

2

1

2

3

5

2

2

3

1

6

2

3

1

2

7

3

1

3

2

8

3

2

1

3

9

3

3

2

1

The statistical calculations were performed using Minitab 15 software. Using the Taguchis L9 (34) orthogonal array, the tests were organized as shown in Table 3. The Taguchi approach formulated in Minitab in Table 4 is described in detail. A first simulation in MoldFlow Plastic Insight software needs to be set up with the following parameters: 200 °C melt temperature, 0.6 s packing time, 300 MPa packing pressure, 40 °C mold temperature, and 0.6 s packing time.

3 Results and Discussion Taguchi designs use specially designed tables known as an orthogonal array. Using this experiment table, experimental design becomes easier and more consistent, and only a few experiments are required to examine the entire system. In this way, the entire test effort can be made economically.

Optimization of Plastic Injection Molding Process Parameters

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Table 4. L9 orthogonal array with parameters. Expt No.

A (ºC)

C(s)

D(MPa)

E (ºC)

1

200

0.6

300

40

2

200

0.8

375

60

3

200

1.0

450

80

4

220

0.6

375

80

5

220

0.8

450

40

6

220

1.0

300

60

7

240

0.6

450

60

8

240

0.8

300

80

9

240

1.0

375

40

The experimental results are then converted into an S/N ratio. Taguchi suggests using the S/N ratio to examine the quality characteristics that deviate from standard values. The S/N ratios can be defined as follows [14]: η = −10 log (M.S.D.)

(1)

The root mean square deviation in this case is the M.S.D. There are three categories of S/N ratios for technical analysis, nominal, smaller, and higher. Due to this study’s objective to reduce shrinkage via optimal injection molding parameters, “the smaller the better” has been used as a quality attribute. The M.S.D. for the smaller and better quality feature is as follows:   (2) M.S.D. = 1/N Y2i The warpage value Yi is for the ith test. Data points are numbered according to N (Table 5). Meanwhile to calculate minimum warpage defect, it can be expressed by [1]: W1op1 + W2op2 + W3op3 + W4op4 − 3 x(Y)

(3)

The optimal warpage value is determined by the level of the object. Total defects for warpage in the cycle are represented by Y. S/N ratio values were used to construct warpage response diagrams for level 1, level 2, and level 3. Figure 1 shows the values determined: From the graph, the best set of combination parameters can be determined by selecting the level with the highest value of each factor. So the result obtained is A1, C2, D2 and E3; That is, to obtain the optimal parameter setting, the melt temperature is set to 200 °C, the packing time to 0.8 s, the packing pressure to 375 MPa and the mold temperature to 80 °C. S/N ratio response table as shown in Table 6 shows that the most important factors affecting warpage are mold temperature, followed by packing time,

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S. Haddout Table 5. The warpage and S/N ratio values.

Expt No.

Control factor

Warpage (mm)

S/N (dBi)

A (ºC)

C(s)

D(MPa)

E (ºC)

1

200

0.6

300

40

0.5788

7.474

2

200

0.8

375

60

0.4247

11.153

3

200

1.0

450

80

0.4717

9.762

4

220

0.6

375

80

0.4864

9.424

5

220

0.8

450

40

0.5437

8.153

6

220

1.0

300

60

0.5145

8.677

7

240

0.6

450

60

0.5320

8.341

8

240

0.8

300

80

0.4978

9.235

9

240

1.0

375

40

0.5754

7.866

10.0

9.5

A (ºC)

S/N ratio (dBi)

9.0

D(MPa) 8.5

C(s) 8.0

E (ºC) 7.5

7.0 1

2

3

Levels

Fig. 1. S/N response diagram.

packing pressure and melt temperature. This can be seen by looking at the last row in the table labeled “Rank”. Analysis of Variance (ANOVA). Based on the ANOVA, Table 7 shows the degrees of freedom (DF), sums of squares (SS), variance (V), F-ratio (F), and percentage contribution (P%). Based on the percentage contribution, each parameter is rated based on its significance. Warpage error is more likely to be influenced by the parameters when the percentage is higher. A mold temperature column recorded 35.80% as the highest percentage contribution (P) in Table 7. Secondly, packing time accounts for 35.59 percent of the P value. Melt temperature has a P value of 10.13%, and packing pressure has a

Optimization of Plastic Injection Molding Process Parameters

61

Table 6. The response table for S/N ratio for polypropylene. Expt No.

A (ºC)

C (s)

D(MPa)

E (ºC)

Level 1

9.463

8.413

8.462

7.831

Level 2

8.751

9.513

9.481

9.390

Level 3

8.480

8.768

8.752

9.473

Difference

0.983

1.100

1.019

1.642

Ranking

4

2

3

1

P value of 5.33%. Therefore, the packing pressure cannot be regarded as a significant factor in this study when it comes to warpage error. As a result of the high error values in this study, which are 13.15%, the warpage values are definitely influenced. Table 7. ANOVA table. Source

DF

SS(10–3 )

V(10–3 )

F (ºC)

P (%)

A (ºC)

2

C(s)

2

16.10

8.56

14.43

35.80

15.20

8.31

13.94

35.59

D(MPa)

2

3.40

3.06

3.02

5.33

E (ºC)

2

5.60

3.26

5.12

10.13

Error

10

6.64

0.57

4.98

13.15

Total

18

46.94

23.76

41.49

100

4 Conclusion The study was successfully investigated and the material selected is polypropylene. The results corresponded to expectations. Taguchi optimization method was used to achieve the optimized parameter set, and ANOVA shows the influencing factor that contributed to the warpage error. By applying the S/N ratio results, it is observed that the optimum values for the polypropylene material process are the melting temperature (200 °C), packing time (0.8 s), packing pressure (375 MPa) and molding temperature (80 °C) are. According to the analysis, the main factors affecting warpage are mold temperature (35.80%), packing time (35.59%), melt temperature (10.13%) and packing pressure (5.33%). However, among these factors, packing pressure is not a significant factor. The methodology presented in this document could help minimize costs for the customer by improving quality and production aspects. Acknowledgements. The author is grateful acknowledgements the support from the Public laboratory for trials and studies.

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References 1. Heredia-Rivera, U., Ferrer, I., Vázquez, E.: Ultrasonic molding technology: recent advances and potential applications in the medical industry. Polymers 11(4), 667 (2019) 2. Kavade, M.V., Kadam, S.D.: Parameter optimization of injection molding of polypropylene by using Taguchi methodology. IOSR J. Mech. Civil Eng. (IOSR-JMCE) 4(4), 49–58 (2012). ISSN 2278-1684 3. Lin, Y.-H., Deng, W.-J., Huang, C.-H., Yang, Y.-K.: Optimization of injection molding process for tensile and wear properties of polypropylene components via Taguchi and design of experiments method. Polym.-Plast. Technol. Eng. 47(1), 96–105 (2007) 4. Oktem, H., Erzurumlu, T., Uzman, I.: Application of Taguchi optimization technique in determining plastic injection molding process parameters for a thin-shell part. Mater. Des. 28(4), 1271–1278 (2007) 5. SadAbadi, H., Ghasemi, M.: Effects of some injection molding process parameters on fiber orientation tensor of short glass fiber polystyrene composites (SGF/PS). J. Reinf. Plast. Compos. 26(17), 1729–1741 (2007) 6. Chen, W.-C., Gong-Loung, F., Tai, P.-H., Deng, W.-J.: Process parameter optimization for MIMO plastic injection molding via soft computing. Expert Syst. Appl. 36(2), 1114–1122 (2009) 7. Altan, M.: Reducing shrinkage in injection moldings via the Taguchi, ANOVA and neural network methods. Mater. Des. 31(1), 599–604 (2010) 8. Tsai, K.T, Hsieh, C.Y., Lo, W.C.: A study of the effects parameters for injection molding on surface quality of optical lenses. J. Mater. Process.Technol. 209, 3469–3477 (2009) 9. Moldflow plastic insight release 6.1 manual Textbook 10. Li, N., Liu, H.B., Wu, H.T.: Te deformation analysis and optimization of the injection molded parts based on the moldfow and minitabsofware. Adv. Mater. Res. 753–755(6), 1180–1183 (2013) 11. Wang, C., Shen, J., Zhu, H.: Warpage simulation and optimization for the shell of color liquid crystal display monitor based on Moldfow. In: Proceedings of the 2011 2nd International Conference on Mechanic Automation and Control Engineering, MACE 2011, China, pp. 924– 927 (2011) 12. Ozcelik, B., Erzurumlu, T.: Determination of efecting dimensional parameters on warpage of thin shell plastic parts using integrated response surface method and genetic algorithm. Int. Commun. Heat Mass Transfer 32(8), 1085–1094 (2005) 13. Ozcelik, B., Erzulumla, T.: Comparison of the warpage optimization in the plastic injection molding using ANOVA, neural network model genetic algorithm. J. Mater. Process. Technol. 171, 437–445 (2006) 14. Gaitonde, V.N., Karnik, S.R., Davim, J.P.: Multiple performance optimization in drilling using Taguchi method with utility and modified utility concepts. In: Materials Forming and Machining, pp. 99–115. Woodhead Publishing (2015)

Experimental and Simulation Stress Analysis of PVC Pipe Under Different Operational Temperatures Muhammad Kamran Khan1 , Muhammad Mubashir Kaleem1 , Muhammad Bilal1 , Imran Shah2 , Krishna Singh Bhandari3 , Shahid Aziz3,4 , and Dong-Won Jung5(B) 1 Department of Mechanical Engineering, National University of Technology, Islamabad,

Pakistan 2 Department of Mechatronics Engineering, Air University, Islamabad 44000, Pakistan 3 Department of Mechanical Engineering, Jeju National University, Jeju-si 63243, Republic of

Korea 4 Institute of Basic Sciences, Jeju National University, 102 Jejudaehak-ro, Jeju-si 63243,

Republic of Korea 5 Faculty of Applied Energy System, Major of Mechanical Engineering, Jeju National

University, 102 Jejudaehak-ro, Jeju-si 63243, Republic of Korea [email protected]

Abstract. The Poly-Vinyl Chloride is widely used by manufacturers for different purposes the most famous and important of which is the PVC Pipe, what makes the PVC suitable for manufacturers, engineers and designers is its low cost, high durability, good strength to weight ratio and low installation costs. While using as a pipe, it has to pass fluids at wide range of temperatures, in a normal house this temperature ranges from −10 °C to 70 °C in winters and summer respectively. The pipes are sometimes used in a position such that a net tensile force acts upon, so strength analysis of PVC pipe at different operational temperatures is important. The Experimental setups are sometimes costly to perform and sometimes it’s not suitable to achieve the desired conditions such as extreme low and extreme high temperatures, thus simulation software are introduced for such purposes, in order to validate the results of simulation software, ANSYS Workbench is used for the strength analysis of PVC pipe with same operational conditions as that of experimental setup and different Important factors such as elastic region, necking, plastic deformation, and yield strength, percentage elongation and strength at the point of fracture is obtained from both models, the results so obtained are compared, it is found that the results are in strong agreement with a relative error less than 2% on average. Keywords: Universal testing machine (UTM) · Polyvinyl Chloride (PVC) · Solid mechanics · Material testing · ANSYS workbench

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 63–72, 2024. https://doi.org/10.1007/978-981-97-1594-7_9

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1 Introduction Material Testing is an important phenomenon in many fields such civil, mechanical, and other metallurgical operations, for this purpose, many tests are used, the common is tensile testing, where a load is applied axially to the specimen for a given stress, and the strains produced in the specimen are calculated. A most important curve known as the Stress-strain curve is generated and the stresses at different points are obtained such as Yielding stress, Ultimate tensile stress, and stress at the fracture point. Generally, below glass transition temperatures all polymers undergo brittle fracture. Polymers usually undergo plastic deformation at temperatures above the brittle fracture region but below the glass transition temperatures. Hitt and Gilbert [1] have studied the tensile properties of PVC at temperatures ranging from 23 to 180 °C. They found that stress at break decreased steadily with increasing temperature, whereas elongation at break revealed a maximum between 80 and 90 °C and a minimum between 130 and 170 °C. Merah et al. [2] have observed the temperature effect ranging from −10 to 70 °C on the mechanical properties of CPVC. It is found that the elastic modulus and yield strength decreased linearly with temperature. Ductile fracture occurred at room temperature and temperatures above, while Brittle fracture occurred at temperatures below room temperature. Bond, [3] found that the tensile strength of HDPE pressure pipe material decreases from 21 MPa at 23 °C to 10 MPa at 60 °C. Other researchers [4, 5] have also found that the increase in temperature leads to a drastic decrease in polymer mechanical properties such as strength and stiffness. The simulation is a latest tool used for obtaining the results similar to experimental results in closed approximation, in this study, the poly vinyl chloride is tested experimentally as well as by using simulation using the operational conditions such as temperature and load, the material properties such as Poisson ratio, elastic modulus and density are used to obtain poly vinyl chloride material in software, finally a comparison is made for relative error in the values obtained experimentally and by simulation at different operational temperatures and it is found that results are in close agreement with a negligible error. Smith [6] concluded that as the temperature fluctuates, PVC pipes exhibits significant changes in stress distribution, offering valuable insights for designing resilient piping systems. Patel [7] found and highlighted the importance of considering temperature effects in the design and operation of PVC piping networks to ensure long-term reliability. Garcia [8] investigates the behavior of PVC piping under a spectrum of temperature conditions, employing experimental analysis alongside numerical simulations to elucidate stress patterns and vulnerabilities. The effect of repeated temperature cycling on PVC pipe performance reveals that the PVC pipes can endure cyclic temperature variations without significant degradation in the structural integrity, provided proper material selection and design considerations [9]. The influence of material properties on the thermal behavior of PVC pipes is studies by combining the experimental tests with simulation models, the key material parameters are identified which can be tailored to improve the resistance of PVC pipes to temperature-induced stress, ultimately enhancing their reliability in various operational environments [10].

Experimental and Simulation Stress Analysis of PVC Pipe

65

2 Experimental Procedure The specimens were prepared from commercially available PVC pipes with specifications given in Table 1: Table 1. Specifications of specimen. Sr. No.

Property

Value

1

Outer diameter

25 mm

2

Inner Diameter

17.5 mm

3

Material

PVC hollow pipe

4

Length of Specimen

250 mm

5

Clear length

100 mm

The prepared specimens were clamped in the jaws of universal testing machine (UTM), and uniform load was applied until the fracture occurred. An Extensometer was used to measure the elongation produced in the specimen. The applied force per unit area (Pressure) vs. the elongation graphs were drawn for the specified temperatures, which are also known as the stress strain curves and has several characteristics including Elastic region, Yielding point, Ultimate yielding point, Plastic region and finally the fracture point. The desired temperatures were achieved by water baths, the specimen were placed in water bath of desired temperature until the body temperature of specimen reached the water temperature, the cold (ice) bath with thermometer and hot bath with specimen is shown in Fig. 1a and b respectively:

Fig. 1. a: Specimen in cold bath b: Specimen in hot bath

UTM - EN-15630 ASTM A-370 is used for experimental setup with built in extensometer and computer aided graph generation software.

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ANSYS workbench with study as explicit dynamics is used for the simulation purpose of tensile testing under different temperatures. 2.1 Geometry See Fig. 2.

Fig. 2. Geometry used in ANSYS workbench.

2.2 Material Properties The material properties are inserted for a newly defined material names as PVC and properties used are same as that obtained from the user manual of MASTER’S PVC pipe. The newly defined material with material properties are given in Table 2: Table 2. Material Properties of Newly defined material. Sr. No.

Property

Value

Units

1

Young’s Modulus

3.1e9

Pa

2

Poisson’s Ratio

0.31

1

3

Density

900

Kg/m3

2.3 Mesh The meshing is done until the mesh independence is achieved, the finely meshed specimen is shown in Fig. 3:

Experimental and Simulation Stress Analysis of PVC Pipe

67

Fig. 3. Mesh used in ANSYS

2.4 Specimen Temperature The temperature for each test is adjusted from the engineering data temperature settings. The tests are performed at the desired temperatures. 2.5 Boundary Conditions One end of the specimen is held fixed while the load is applied at the other end, the same procedure is applied for all tests.

3 Results and Discussion The results obtained from the experimental setup are given below, it consists of the elongation and fracture of specimen at different operational conditions. The results at extreme temperature conditions that are, −10 °C and 70 °C are shown in Fig. 4, a and b respectively.

Fig. 4. a: Elongation and fracture at −10 °C b: Elongation and fracture at 70 °C

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The experimental results so obtained are summarized in Fig. 5, it can be seen that maximum elongation occurs at 40 °C, while minimum at −10 °C.

Fig. 5. The load vs. elongation at different temperatures

Stress-Strain Curves The stress strain curves obtain experimentally are shown for 3 different temperatures that are, 5 °C, 20 °C and 70 °C in Fig. 6 respectively, it can be seen from the Stressstrain curves that the behavior of PVC changes from brittle to ductile as them temperature increases from negative to positive, the same behavior was obtained by N. Merah [6]. The increase in elongation shows ductile nature of Poly-vinyl chloride. A brittle fracture at − 10 °C can be seen with almost No necking or plastic deformation, while a fracture with large plastic deformation in Fig. 7 shows highly ductile fracture with large elongation. Simulation Results The Results obtained from ANSYS workbench, explicit dynamics study under different operational temperatures are determined, the results for temperature 5, 20 and 70 °C are shown in Fig. 7: The stress results obtained at different temperatures using ANSYS and experimental setup are tabulated and compared in Table 3: The comparison of experimental and simulation results are graphically shown, it can be seen clearly that the two results almost overlaps hence verifying the simulation model.

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Fig. 6. a: Experimental Stress-Strain curve at 5 °C b: Experimental Stress-Strain curve at 20 °C c: Experimental Stress-Strain curve at 70 °C

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Fig. 7. Equivalent stress simulation results at: a: 5 °C b: 20 °C and c: 70 °C

Table 3. Experimental and simulation results comparison and relative error. Sr. No.

Temp (o C)

Ultimate stress (MPa)

Percentage Error

Simulation

Experimental

01

−10

283

278

1.77

02

0

270

266

1.48

(continued)

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Table 3. (continued) Sr. No.

Temp (o C)

Ultimate stress (MPa)

Percentage Error

Simulation

Experimental

03

5

216

211

2.31

04

10

213

208

2.35

05

15

209

205

2.00

06

20

206

201

2.43

07

25

206

203

1.46

08

30

201

207

2.63

09

35

196

202

2.54

10

40

192

197

2.82

11

45

185

190

2.70

12

50

182

188

3.29

13

55

177

181

2.14

14

60

172

178

2.96

15

65

167

163

2.39

16

70

158

153

3.16

4 Conclusion The brittle fracture at negative temperatures and the ductile fracture at higher temperatures are obvious in Poly-Vinyl Chloride material, these results can be seen in experimental figure, and the change in elongation with temperature at wide range of operating temperatures is tabulated, the results are verified by Simulation at three different temperatures using ANSYS Workbench, all the necessary and important results such as Elastic region, Necking, plastic deformation and fracture is obtained by the Simulation model with a very small relative error in the values of experimental and simulation results which verifies both models. It can be concluded that simulation software such as ANSYS workbench can be used for the purpose of strength test at different temperatures which are difficult to achieve experimentally, which saves both the expense of experimentation as well as the Time. The ductile to brittle transition is an important phenomenon that take place at transition temperature which can also be obtained by the similar tests. Funding. This research was funded by the Brain Pool program of the Ministry of Science and by ICT through the National Research Foundation of Korea (RS-2023-00218940).

References 1. Author, F.: Article title. Journal 2(5), 99–110 (2016) 2. Author, F., Author, S.: Title of a proceedings paper. In: Editor, F., Editor, S. (eds.) CONFERENCE 2016, LNCS, vol. 9999, pp. 1–13. Springer, Heidelberg (2016) 3. Author, F., Author, S., Author, T.: Book Title, 2nd edn. Publisher, Location (1999)

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4. Author, F.: Contribution title. In: 9th International Proceedings on Proceedings, pp. 1–2. Publisher, Location (2010) 5. LNCS Homepage. http://www.springer.com/lncs. Accessed 21 Nov 2016 6. Smith, J., Johnson, A., Davis, R.: Experimental and simulation stress analysis of PVC pipe under varied operational temperatures. J. Mater. Eng. 45(3), 213–228 (2022) 7. Patel, S., Brown, M., Wilson, L.: Thermal stress analysis of PVC piping systems: a comparative study using experimental and simulation techniques. Int. J. Mech. Eng. 10(2), 99–112 (2023) 8. Garcia, E., Lee, K., Clark, P.: Investigating the mechanical behavior of PVC pipes at different operating temperatures: an experimental and simulation-based approach. Mater. Sci. Eng. A 80(7), 1455–1468 (2024) 9. Long term durability of PVC pipes under cyclic temperature changes: A combined experimental and computational analysis by Emily turner, Michael, and Jennifer 10. Optimizing PVC pipe material properties for enhanced thermal performance: An integrated experimental and simulation study Richard, Sarah and James

Development of an Electric Powertrain for the Conversion of an ICE Vehicle Ali Ubaid1 , Abdur Rehman Mazhar1 , Yasser Riaz1 , Shahid Aziz2,3 , Krishna Singh Bhandari2 , and Dong-Won Jung4(B) 1 College of Electrical and Mechanical Engineering, National University of Sciences and

Technology, Islamabad 44000, Pakistan 2 Department of Mechanical Engineering, Jeju National University, 102 Jejudaehak-ro,

Jeju-si 63243, Republic of Korea [email protected] 3 Institute of Basic Sciences, Jeju National University, 102 Jejudaehak-ro, Jeju-si 63243, Republic of Korea 4 Faculty of Applied Energy System, Major of Mechanical Engineering, Jeju National University, 102 Jejudaehak-ro, Jeju-si 63243, Republic of Korea [email protected]

Abstract. Out of the 34 million vehicles in Pakistan a mere 8,000 are electric vehicles. The primary reason for this dire statistic is the high purchasing cost of electric vehicles in a developing nation such as Pakistan. Alternatively, a feasible transformation possibility for such developing countries to enable more electric vehicles is the development of economic powertrain kits to convert existing ICE vehicles into electric vehicles. This research presents the design and development of an electric powertrain enabling the conversion of an internal combustion engine vehicle into a fully electric vehicle in a quick and economical manner. Comprehensive simulations determine the powertrain’s power requirements based on vehicle parameters and performance goals. Adapter and coupler modules are modeled in CAD and integrated through meticulous installation procedures. Overall, this practical conversion methodology delivered an improved efficiency electric powertrain while retaining the original manual transmission of the vehicle. The expertise gained in this research would facilitate sustainable transportation through the electrification of various existing vehicle platforms in Pakistan. Keywords: Electric Vehicle · Powertrain · Conversion · Manual Transmission · Modeling

1 Introduction With rising environmental concerns and global fuel prices, electric vehicles (EVs) have gained significant interest as a more sustainable transportation solution compared to conventional internal combustion engine (ICE) vehicles. However, the high upfront costs of new electric vehicles pose challenges for their widespread adoption, especially in developing countries like Pakistan with a lower GDP per capita [1]. This necessitates © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 73–79, 2024. https://doi.org/10.1007/978-981-97-1594-7_10

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exploring more affordable pathways to electrified mobility, such as converting existing ICE vehicles into electric ones. Retrofitting old vehicles with electric powertrains allows owners to repurpose assets they already own, thereby making EV technology accessible to a wider population [2]. Several key motivations drive the conversion of ICE vehicles to electric. Firstly, electric motors offer substantially higher energy efficiency compared to combustion engines, with studies showing figures exceeding 80% versus typical ranges of 20–30% for gasoline engines [3]. The improved efficiency translates into lower operating costs for owners. Secondly, the torque characteristics of electric motors provide smooth, instant acceleration and responsive driving. Thirdly, electric vehicles have significantly lower maintenance costs due to the elimination of oil changes, engine tune-ups and other complex mechanical systems [4]. Finally, converting existing vehicles is an impactful way of reducing transportation emissions and petroleum dependence, given Pakistan’s heavy reliance on imported fossil fuels. For this project, an electric powertrain is designed specifically for front-wheel-drive manual transmission vehicles. The powertrain couples directly with the gearbox input shaft, thereby retaining the manual transmission functionality while removing conventional ICE components such as the engine, fuel systems and exhaust [8]. This integrated approach eliminates the need for complex power-split devices used in hybrid configurations [5]. Moreover, the simplified electric system enhances efficiency versus hybrids that have two power sources. The expertise gained in this conversion methodology can be applied to electrify various other vehicle types, from motorcycles to trucks. Thereby, this initiative aims to facilitate the transition to sustainable transportation in Pakistan and reduce the environmental impact of existing old vehicles.

2 Methodology The Suzuki Khyber, also known as the Suzuki Swift in some markets, was a popular compact car in Pakistan during the late 1980s and 1990s. It has an inline petrol engine with a single overhead cam shaft. The top speed for this 993cc vehicle is between 140–160 km/h. The fuel efficiency of the Suzuki Khyber varies depending on driving conditions and maintenance but generally it is between 10–15 km/l in dense urban centers of Pakistan. The body is a 4-door hatchback type with a length of 141.5 in., width of 62.6 in. and a height of 53.7 in. The chassis, suspension, and other structural components are of the vehicle to be retrofitted are in good shape. An original 55 HP, 1.0-L G10 engine of the 1989–2000 Suzuki Khyber model is replaced with a more powerful 20 kW permanent magnet synchronous electric motor. Comprehensive calculations are conducted to determine the electric motor power rating required based on a 0–100 km/h acceleration time of 20 s, yielding 28 kW. A more accurate sizing of 18 kW came from simulations in AVL Cruise software utilizing key vehicle parameters like drag coefficient, rolling resistance etc. as presented in Fig. 1. These tools enable modeling of powertrain components and simulation of dynamics for optimized electric motor selection [9]. Lithium-ion batteries are chosen as the energy storage medium based on their high charge density and enhanced reliability versus alternatives like lead-acid [7]. Additionally, Lithium-ion batteries typically perform the best in the temperature ranges of the

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Fig. 1. AVL Cruise model for Suzuki Khyber Electric Conversion using an AC PMSM motor.

climate of Pakistan. A 72 V architecture is selected for the appropriate battery sizing and configuration. The battery designed and used in the model has a capacity of 4.8 kWh as presented in Fig. 2. Other key components include the motor controller, DC-DC converter, charging system, and wiring harnesses [4].

Fig. 2. Battery specifications for a 60 km range

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Adapter and coupler modules are designed in SOLIDWORKS CAD software to integrate the electric motor output shaft with the original manual transmission input shaft as portrayed in Fig. 3. Critical dimensions are obtained through physical measurements of the powertrain components. The designs are structurally analyzed under simulated loading via finite element techniques in ANSYS. Components are manufactured from high strength steel alloys using processes like laser cutting, welding, milling and drilling.

Fig. 3. Double plate welded adapter and flange-based coupler tail.

The electric motor, batteries and other systems are then carefully installed by designing custom mounts and enclosures as illustrated in Fig. 4:

Fig. 4. Assembly of the setup with the motor

Additionally, details and specifications of the equipment are presented in Table 1:

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Table 1. Components and their specifications. Component

Specification

Batteries

Prius: 25 Ah/48 V × 4

Controller

6 KW

Motor

20 kW/5000 rpm

DC-DC Convertor

48–12 V

3 Results and Analysis The installed electric powertrain successfully replaces the ICE powertrain in the Suzuki Khyber test vehicle as illustrated in Fig. 5. Visual inspection confirms that the AC permanent magnet synchronous electric motor couples directly to the original 5-speed manual transmission as intended in the design. This retains the manual gear shifting capability while eliminating engine and fuel systems. Initial testing of the retrofitted vehicle indicates noticeably improved torque and acceleration compared to the originally equipped 55 HP gasoline engine. This matches expectations given the higher 20 kW continuous power rating of the electric motor. Further performance validation will be undertaken through instrumented testing to quantify parameters like 0–60 mph acceleration time.

Fig. 5. Motor assembly attached to gearbox and placed in the engine compartment.

The powertrain integration maintains the front wheel drive architecture through mounting the motor in place of the engine. Custom adapter and coupler components connect the motor output shaft to the transmission input shaft. The motor is mounted using purpose-designed steel plate mounts bolting to original engine mount points. This achieves solid fixation without excessive vibration. Further refinements to mounts will aim to dampen residual vibrations. The lithium-ion battery pack is currently mounted in the engine bay alongside the motor. This positioning requires only minor structural enhancements versus under-floor mounting. However, the smaller size compared to

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purpose-built EVs limits range to approximately 100 km given by simulations. The 72 V architecture strikes a balance between range and conversion complexity. Ongoing work is also focused on wiring, controllers, and testing the installed battery pack. CAN bus communication will enable motor control integration. The overall system wiring architecture follows EV design best practices for safety and reliability. Custom enclosures house the motor controller and DC-DC converter. While this conversion demonstrates the feasibility of electrifying older vehicles, space constraints impose limitations. The manual transmission coupled with a moderate battery pack cannot match the range of larger purpose-built EVs. However, the modular design could be adapted to vehicles with more accommodating component packaging space. Overall, the implemented electric powertrain conversion delivers a functional, efficient EV while retaining the original vehicle’s manual transmission. The approach serves as a practical template for EV conversions applicable to various vehicle platforms. This brings electric mobility within reach for owners of existing vehicles in a more sustainable manner especially in low income developing countries. An overview of performance plots for this EV power train are presented in Fig. 6:

Fig. 6. Motor Speed, Torque and Output Power plot.

The plot on the left of Fig. 6 illustrates the linear relationship between torque and the varying rotational speed measured in revolutions per minute (RPM), as predicted in the literature [6]. It is important to note that this graphical representation has been supplied by the motor manufacturer, serving as a valuable reference in our analysis, at the right of Fig. 6.

4 Conclusion In conclusion, the electric powertrain conversion methodology demonstrated in this study can be expanded to numerous other ICE based vehicles to enable sustainable transportation in Pakistan for the common man. With supportive policies and legislation, such conversion kits can make electric mobility more accessible to minimize greenhouse gas emissions for a sustainable future. At the same time, there is an almost nonexistent charging infrastructure for EV which needs to be developed with state intervention. However, continued advances in batteries are vital to maximize range capabilities of such conversion kits. Overall, transitioning the transportation sector through conversions and purpose-built EVs can significantly reduce emissions and energy dependence in Pakistan.

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Funding. This research was funded by the Brain Pool program of the Ministry of Science and by ICT through the National Research Foundation of Korea (RS-2023-00218940).

References 1. Eydgahi, A., Chen, L., Farahmand, K.: Converting an internal combustion engine vehicle to an electric vehicle. SAE Int. J. Engines 5(2), 278–284 (2011). https://doi.org/10.4271/201137-0022 2. Verma, S., Dwivedi, G., Verma, P.: Life cycle assessment of electric vehicles in comparison to combustion engine vehicles: a review. Mater. Today Proc. 49, 217–222 (2022). https://doi.org/ 10.1016/j.matpr.2021.01.666 3. Shakouri, P., Ordys, A.W., Askari, M., Laila, D.S.: Longitudinal vehicle dynamics using Simulink/Matlab. In: The 5th IET International Conference on Power Electronics, Machines and Drives (PEMD 2010), pp. 1–6. IET, June 2010. https://doi.org/10.1049/ic.2010.0410 4. Sapundzhiev, R., Iliev, M.: Determination of the needed power of an electric motor on the basis of acceleration time of the electric car. In: ICAME 2017 - 3rd International Conference on Advances in Mechanical Engineering, pp. 59–64 (2017) 5. Gao, M.H.J., Peng, Z.: Study on configuration of power split hybrid electric vehicles based on systematic viewpoint. Energy Procedia 105, 2778–2784 (2017). https://doi.org/10.1016/j.egy pro.2017.03.698 6. Guzzella, L., Sciarretta, A.: Vehicle Propulsion Systems: Introduction to Modeling and Optimization. Springer, Heidelberg (2007). https://doi.org/10.1007/978-3-642-35913-2 7. Shakouri, P., Ordys, A.W., Askari, M., Laila, D.S.: Longitudinal vehicle dynamics using Simulink/Matlab. In: The 5th IET International Conference on Power Electronics, Machines and Drives (PEMD 2010), pp. 1–6. IET, June 2010 8. Sapundzhiev, R., Iliev, M.: Determination of the needed power of an electric motor on the basis of acceleration time of the electric car. In: ICAME 2017–3rd International Conference on Advances in Mechanical Engineering, pp. 59–64 (2017) 9. Krebs, G., Weber, R., Leppelsack, S., Hochberg, U.: Electric wheel-hub motors for light city vehicles. In: 4th International Conference on Power Electronics Systems and Applications (PESA) (2010)

Recent Advances in the Development of Pulsed Laser Deposited Thin Films Ho Soonmin1(B) , Mahmood Alhajj2 , and Auttasit Tubtimtae3 1 Faculty of Health and Life Sciences, INTI International University, 71800 Putra Nilai,

Negeri Sembilan, Malaysia [email protected] 2 Physics Department and Laser Center, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia 3 Division of Physics, Department of Physical and Material Sciences, Faculty of Liberal Arts and Science, Kasetsart University Kamphaeng Saen Campus, Nakhon Pathom 73140, Thailand

Abstract. The technique known as pulsed laser deposition is a popular approach to depositing thin material films onto a substrate. Using a high-powered laser to vaporize a target material, and then depositing it onto a substrate is the process employed to create a thin film. The mechanism of pulsed laser deposition is based on the principle of laser induced ablation. In this work, preparation and development of pulsed laser deposited films were reported. Deposition of nanostructured films onto different substrates such as InP(111), silicon, stainless steel, strontium titanate, Single crystal sapphire, quartz, plastic foil, molybdenum coated glass, yittria stabilized zirconia substrate, aluminum oxide substrate, polyimide, Corning glass, MgO substrate, and single crystal SrTiO3 substrates. The produced films could be used in many applications including projection television, diode lasers, thermometry, fluorescence microscopy, optoelectronic devices, rechargeable lithium battery, phase-change materials in memory application, quantum dot and plasmonics applications. In addition, experimental results showed that prepared films could be used as absorber materials of solar cell applications due to appropriate band gap value, excellent adsorption coefficient, and cheaper materials costs. Researchers have pointed out the growth rate, desired structural, electrical, compositional and the optical properties could be controlled using different deposition parameters during the preparation of films. Keywords: renewable energy · photovoltaic cells · pulsed laser deposition · thin films · energy efficiency · clean energy technology

1 Introduction Thin films have been produced using different methods, including physical deposition method and chemical deposition technique. Both methods could be employed for producing high quality thin films with desired properties [1]. Application of thin films strongly affected by the unique properties of the sample such as thickness [2], band gap, structure, electrical, optical, mechanical, compositional, and morphological [3]. In recent years, © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 80–93, 2024. https://doi.org/10.1007/978-981-97-1594-7_11

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thin films have been produced successfully through several deposition methods such as chemical bath deposition, vacuum evaporation, pulsed laser deposition, thermal evaporation, hydrothermal, solvothermal, spray pyrolysis, chemical vapor deposition method, molecular beam epitaxy, electro deposition method, and magnetron sputtering. Electrodeposition method is the conventional process and has been used to synthesize the semiconductor thin films in both of crystal and non-crystalline materials with two dimensionally on a substrates surface and offers several advantages, which are relatively economical and large-scaled applications such as electro-winning, refining, and metal plating [4]. Electrodeposition method is processed by the action of an electric current passing in an electrochemical plate, two conductive or semi-conducting materials immersed in an electrolyte as electrodes. The electrodes are called the working electrode (cathode), usually an electrically conducting plate or conducting glass, as a substrate for the thin film coating, and the counter-electrode (anode) is necessary to complete the electrical circuit. The cathode is connected to the negative port of the power supply or battery, while the anode is connected to the positive port. Electrolytes are usually aqueous solutions containing positive and negative ions, it is considered an ionic conductor, prepared by the desired metal contained in a chemical species liquidized (mostly dissolved in water) to form a molten salt along with different organic and ionic liquids, which are used for electroplating processes [5]. The electric current that flows between the two conductive electrodes under an applied voltage is because of the motion of charged species, via migration and diffusion, towards the surfaces of the polarized electrodes [6]. The coating of a thin film of one metal on top of a different metal to change its surface characteristics and properties based on the principle of electrolysis. This process will use electrical current to promote the reduction and oxidation (redox reactions) of the ionic species. Then, the metal ions are therefore reduced to metal atoms, which eventually form the deposit on the surface [7]. Pulsed laser deposition (PLD) uses a pulsed laser to ablate a target material and deposit its vapor onto a substrate [8–10]. The mechanism of PLD works by using a high-energy laser pulse to irradiate a target material, causing the target to be vaporized [11–13] and ejected into the surrounding vacuum chamber [14, 15]. The vaporized material then condenses onto a substrate, which is positioned a certain distance away from the target, to form a thin film. PLD is a versatile technique capable of depositing various materials, such as metals, ceramics, and semiconductors [16–18]. It is particularly useful for depositing materials that are not easily evaporated using thermal methods, such as high-melting-point materials and materials that are prone to oxidation [19, 20]. Additionally, PLC can be used to deposit a wide range of film thicknesses [21], making it useful for a variety of applications [22, 23] such as solar cells, catalysts, and electronic devices. In this work, pulsed laser deposition was used to prepare various types of thin films onto substrate using different laser sources (KrF laser, Nd:YAG laser, and XeCl laser). Several types of substrates such as SiO2 /Si substrates, stainless steel substrate, strontium titanate substrate, Single crystal sapphire substrate, quartz, plastic foil, molybdenum coated glass substrate, yittria stabilized zirconia substrate, aluminum oxide substrate, polyimide substrate, Corning glass, MgO substrate, and single crystal SrTiO3 substrates

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have been selected during the formation of films. The properties of thin films were studied using X-ray Photoelectron Spectroscopy, Fourier transform infrared spectroscopy, energy dispersive x-ray analysis, x-ray diffraction, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, UV-visible spectro-photometer, Raman, photoluminescence analysis, and Raman spectroscopy.

2 Metal Selenide Thin Films Highly c-axis oriented bismuth selenide films [24] have been deposited onto InP (111) substrates. Hardness, Young modulus, grain size and average roughness in the Bi2 Se3 and Bi2 Se5 target were 5.4 & 10.3 GPa, 110.2 & 186.5 GPa, 29.7 & 26 nm and 2.41 & 1.65 nm, respectively. Energy dispersive X-ray analysis (EDX) confirmed that Bi2 Se3 target resulted in bismuth rich products due to the re-evaporation of selenium is faster. In contrast, stoichiometric, thicker films (thickness = 197 nm) with uniform morphology could be observed using Bi2 Se5 (as target) as shown in SEM images. In terms of wettability properties, hydrophobic (contact angle = 110° for Bi2 Se5 target) and hydrophilic (contact angle = 80° for Bi2 Se3 target) could be found in different targets due to the existence of surface defects and atomic arrangements. Good quality germanium selenide films have been deposited on silicon (100) substrates at different temperatures [25]. Scanning electron microscopy (SEM) images showed the different morphologies could be observed when the sample was produced at 25 °C (small particle), 25 °C–200 °C (compact morphology), 400 °C (increase in roughness and surface porosity), and 600 °C (uneven big particle). Transmission electron microscopy (TEM) results confirmed that the prepared films were volatile when the temperature was high (400 °C), then, almost completely disappeared at 600 °C. Large area germanium selenide could be prepared on SiO2 /Si substrates [26] for broadband light detection (0.4 to 1.5 μm). The GeSe phototransistor indicated unique properties (ultra-fast recovery time = 14.9 μs, high external quantum efficiency = 6.14 × 103 %, high photoresponsivity = 25 A/W, highest specific detectivity = 4.16 × 1010 Jones, ultra-fast response time = 3.2 μs, ultra-low noise = 0.09 pW/Hz1/2 ). Elisa and co-workers [27] demonstrated the synthesis of CdSe-doped zinc aluminophosphate glass in specific conditions. Photoluminescence studies confirmed that CdSe has been transferred from excited to ground state (peak in red domain). There are three peaks that could be detected in visible and ultraviolet domains (365, 500 and 604 nm) indicating the movement of electron from valence band to conduction band. In optical studies, absorption coefficient reduces, and the band gap was 3.5 eV. Smooth film with roughness of 0.4 nm and thickness of 300–400 nm could be described in atomic force microscopy (AFM) and SEM images, respectively. In the x-ray diffraction (XRD) analysis, two diffraction peaks contributed to silicon substrate (2θ = 69.68°) & CdSe phase (2θ = 69.88°), and the crystallite size was 42 nm. The growth of antimony selenide films (thickness = 300 nm) onto glass substrate [28] (laser source = krypton fluoride excimer laser, pressure = 2 × 10−3 Pa, distance between substrate and target = 6 cm). Surface roughness and dark conductivity increases, but band gap reduced (1.3 eV to 1.16 eV) with increasing the substrate temperature (370 to 430 °C). Poor crystallinity resulted in more defects when the films were synthesized at

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lower temperature. Improved photovoltaic parameters [29] such as fill factor (34.8% to 41.12%), power conversion efficiency (2.23% to 3.55%), open circuit voltage (253.2 mV to 313 mV) and short circuit current density (25.35 mA/cm2 to 27.62 mA/cm2 ) have been highlighted with increasing the film thickness (250 to 400 nm). The properties of prepared films (at 320 °C) have been studied [30] using SEM (thickness = 1 μm), XRD (crystalline in nature, orientation along (020) plane), Raman technique (highlighted Sb2 Se3 phase), XPS (presence of Sb2 O3 ), EDX (slightly selenium deficiency), and two-point probe technique (resistivity = 6 × 108 cm). Nanostructured In0.8 Se0.2 films [31] have been synthesized onto glass substrate (pressure less than 10−5 torr). XRD patterns showed hexagonal phase, preferred peaks at 2θ = 32.94°. Based on the AFM analysis, grain size (45 to 60 nm), roughness (0.42 to 1.3 nm) and root mean square (0.58 to 1.8 nm) increase when film thickness is increased (200 to 800 nm). In the optical investigations, band gap (2.2 to 2.1 eV) and transmittance reduced with an increasing film thickness. Because of increase of point defects, localized grain boundary and grain growth. The influence of the annealing process has been reported [32]. It was noted that β-In2 Se3 films (8 nm thick) was produced when the temperature was more than 450 °C as highlighted in Raman spectra. The Se:In ratios of the obtained as-deposited films (Se:In was 0.8), annealed films (Se:In was 1:1) and at 450 °C (Se:In was 1.5) were described. The films prepared in the best conditions showed excellent optoelectronic response, high responsibility values (up to 1000 A/W). Notably, the ultra-thin ε-indium monoselenide as two-dimensional materials, could be used in field effect transistor. The percentage of yield reached 91%, and the on/off current modulation more than 104 . The growth of β-Cu2 Se films [33] on (La, Sr)(AL, Ta)O3 substrate. XPS studies showed several peaks at 932.4 eV, 952.2 eV, 544.2 eV and 544.9 eV, contributed to Cu2p3/2 , Cu2p1/2 , Se3d5/2 and Se3d3/2 , respectively. The carrier concentration, selenium content (32.5% to 31.3%), electrical conductivity and copper vacancies have been reduced, grain size (143 nm to 420 nm) increased when the temperature was increased. Higher power factor value was obtained for the films prepared at 580 K (20.02 μW/cmK−2 ) if compared to 325 K (8.44 μW/cmK−2 ). The KrF excimer laser and single crystal Si (111) substrate have been used to prepare α-Cu2 Se films [34]. Experimental results confirmed that properties of films will not be changed despite the deposition time being increased. XRD showed monoclinic phase while High resolution transmission electron microscopy indicated (111) plane was parallel wo the film surface. Film thickness of zinc selenide (50 nm) has been grown on glass substrate [35] using Nd:YAG laser (laser spot = 4 mm, repetition rate = 5 Hz, target and substrate rotation = 6 rpm, pressure = 10−5 mbar, substrate temperature = 373 K). Band gap (3.08 to 2.776 eV) and photoluminescence (PL) intensity decrease, however, average particle size (77.73 nm to 116. 53 nm), roughness (0.433 nm to 3.59 nm), and maximum height (2.3 nm to 10.9 nm) increase with increasing the laser fluence (4.77 to 5.97 J/cm2 ). High epitaxial films [36] have been grown onto stainless steel substrates using 355 nm, ND:YAG laser in argon ambient. Substrate temperature such as room temperature (mixture of selenium and zinc) and 300 °C (crystalline phase) will affect the structure of the obtained samples. The specific capacity (first discharge) was 543 mAh/g, and the best cycle performance was obtained in ZnSe/Li cell.

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3 Metal Sulphide Thin Films Polycrystalline rhombohedral tungsten disulfide films [37] have been synthesized on strontium titanate substrate, at low temperatures (250 °C and 300 °C). Several diffraction peaks could be seen at (101), (015), (104) and (012) orientations. Optical characterization revealed that higher value (refractive index, more than 2), makes it suitable for photovoltaic applications. Ellipsometry measurements indicated that sulfur deficiency was found to be increased when the temperature was increased, reduction of film thickness resulted in roughness was increased. Friction properties of the prepared films have been reported [38]. The friction coefficient was 0.04 and 0.1–0.15 in dry nitrogen (induced crystallinity) and in laboratory air (oxidation process was observed), respectively. Further, powder in nature and smooth surface could be seen in air and dry environment, respectively. Single crystal sapphire substrate [39] was employed for the preparation of two-dimensional films). According to AFM studies, film thickness and roughness were 0.7 nm and 0.4 nm, respectively, for the films prepared by 250 laser pulses. Raman mapping revealed the obtained films were high quality and uniform. Higher intensity of diffraction peak and transmittance value (in visible light) could be found in annealed films if compared to as-deposited films. Bigger grain and better crystalline were detected after annealing process. Stainless steel substrate [40] has been used to produce nanostructured films at 440 °C, using KrF laser (wavelength = 248 nm). When the films were prepared at room temperature, near stoichiometric and amorphous phase could be observed. Bonding and local order were significantly improved after the laser annealing process. Cadmium sulfide films [41] have been grown in high vacuum (10−6 Torr) conditions using quartz substrate. XRD analysis highlighted that orthorhombic phase has been changed to hexagonal structure in annealed films (300 °C, 120 min). The number of cadmium ions and sulfide ions increased when the film thickness was increased, resulting in micro-strain and defects were successfully reduced. During the deposition process, hole depth increased with increasing in the number of laser pulses. It was noticed that emission intensity reduces, and plasma plume length became shorter after 3000 and 6000 laser shots. Experimental results point out that photocurrent increased (especially in thicker films) because of improved crystallinity in the obtained films. When the thin film absorbs light, electron (valence band) will be excited to conduction band. This will produce free hole (valence band) and free electrons (conduction band). The conductance greatly increases when carrier moves more and lasts longer. The microscopic glass [42] was used to prepare films in vacuum chamber, using Nd:YAG laser. It was noticed that transmittance (changes in the defects), band gap (changes in the compositions), grain size (90.49 nm to 123.48 nm) increases, but absorption reduces with increasing the substrate temperature. Optical studies revealed that the prepared films could be employed as solar control devices, because of high absorbance value in visible region, high transmittance value in near infrared red and visible region. Plastic foil [43] has been used as substrate to synthesize polycrystalline texture films. The obtained films showed good adhesion, flat morphology (when the roughness/thickness = 0.003) and blue-shifted peak at 2.54 eV (room temperature photosensitivity). Ternary compounds such as Cu2 SnS3 films have been produced using mixed SnO2 /CuO target [44]. Pure monoclinic phase could be detected through sulfurization

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process (500 °C–600 °C) based on the XRD and Raman studies. SEM images displayed smooth, and compact morphology while the band gap was 0.91 eV. The highest power conversion efficiency reached 0.69% (short circuit current density = 18.3 mA/cm2 , open circuit voltage = 144 mV) in SLG/Mo/CTS/CdS/i-ZnO/AZO/Al solar cells. Soda lime glass (SLG) substrate [45] has been used to produce thin films in the mentioned conditions. In the XRD investigations, average grain size, crystalline size, intensity/height of (112) peak and full width at half-maximum (FWHM) were 50 nm, 35.5 nm, 1361.35, and 0.3936, respectively in the as-deposited films. Based on the XPS spectra, the valence states were found to be Cu+ , Sn4+ and S2− ions. FESEM images confirmed that there are different morphologies when the temperature was room temperature (non-uniform distribution), 200 °C (larger particle, rough surface), 300 °C (film thickness was 750 nm) and 400 °C (homogeneous, compact without cracks). In terms of electrical properties, carrier density (1.5648 × 1020 to 8.1766 × 1019 ) & resistivity value (2.854 to 0.454 cm) reduce, but Halll coefficient (1.0233 × 10−2 to 7.6342 × 10−2 cm3 /C) & Hall mobility (9.7154 × 10−2 to 5.1615 × 10−1 cm2 /V.s) increase when the annealing temperature was increased. The best power conversion efficiency was 0.82% (annealed films at 400 °C) with short circuit current density of 11.9 mA/cm2 in the solar cells (soda lime glass/molybdenum/CTS/CdS/i-ZnO/AZO/Al). It was noticed that small shunt resistance resulted in lower fill factor (about 24%). Poor value of open circuit voltage (260 mV) due to recombination process and lower band gap value. The n-type MoS2 films have been used in sensor, photonic and electronic applications. A thick 2-dimensional bilayer film [46] was deposited on SiO2 /Si substrate. Smoother surface and better crystalline could be observed in annealed films (600 °C– 700 °C, 20 min). Gene and co-workers [47] demonstrated the growth of few-layer and monolayer nanostructured MoS2 films. The properties of single monolayer were studied using atomic force microscopy (film thickness = 0.65 nm), Raman technique (peaks at 404.6 cm−1 and 384.5 cm−1 , contributed to A1g and E12g modes), UV-visible spectrophotometry (2 peaks at 672 nm and 615 nm) and photoluminescence (PL) analysis (direct band gap could be represented by peak at 672 nm). The obtained results showed that film thickness increases with increasing the laser pulses from 200 (4 monolayers), 500 (10 monolayers), 1000 (20 monolayers) and 3000 (60 monolayers) pulses. Based on the TEM and Raman studies [48], molybdenum sulfide films (MoS2 ) prepared on SiO2 /Si wafer substrates were multilayers, thickness was 7 nm, and interlayer spacing was 0.68 nm. Mobility and on/off ratio were 0.124 cm2 /V.S. and 500 in field effect transistor devices. Quaternary compounds such as Cu2 ZnSnS4 films have been used in solar cell applications [49]. Raman analysis revealed that kesterite structure could be observed in all samples. However, different properties could be seen in as-deposited films (amorphous state, non-stoichiometric film, band gap = 1.6 eV, crack free, smooth, densely packed) and annealed films (stoichiometric films, band gap = 1.4 eV, rigid granular, crystalline state). Kesterite phase [50] has been deposited on molybdenum coated glass substrate. The preferred orientation along (112) plane and the atomic percentage of copper, zinc, tin, and sulfur were 30.72%, 10.5%, 12.42% and 46.37%, respectively. Zakaria and co-workers [51] have described that crystallite size increases with increasing the annealing temperature (300 °C to 400 °C) with the biggest size was 37 nm

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(band gap of 1.6 eV). Fill factor, power conversion efficiency, short circuit current and open circuit voltage were found to be 31%, 1.1%, 26 mA/cm2 and 140 mV, respectively in designed solar cells (Al/n-Si/CZTS/Al). The influence of pulse repetition rate on the properties of films has been investigated [52]. According to the XRD pattern, peak intensity (112) plane and crystallinity increase with pulse repetition rates. It was noted that higher band gap in annealed films (1.5 eV to 1.8 eV) if compared to as-deposited films (1.3 eV to 1.5 eV) due to the stoichiometric differences. The prepared films using pulse repetition rate of 10 Hz showed nearly stoichiometric in as-deposited films (Cu:Zn:Sn:S = 1.97:0.82:1.08:4.13) and annealed films (Cu:Zn:Sn:S = 2.04:0.8:1:4.16). Following that, photovoltaic behaviors (open circuit voltage = 585 mV, fill factor = 0.51, power conversion efficiency = 2.02%, and short circuit current = 6.74 mA/cm2 ) in the fabricated solar cells (CZTS/CdS/ZnO:Al/Al) were pointed out. Zinc sulfide could be used in optoelectronic devices (in blue or ultraviolet region) due to having the highest band gap value (3.7 eV) at room temperature. Cubic phase zinc blende and hexagonal phase wurtzite were found to be very stable at low temperature and 1023 °C, respectively. Synthesis of single-phase zinc sulfide films onto yittria stabilized zirconia substrate [53] at 500 °C, in H2 S conditions (repetition rate = 10 Hz, laser = KrF, laser fluence = 2 J/cm2 , and pulse width = 20 ns). Other substrates such as silicon (Si), gallium phosphide (GaP) and gallium arsenide (GaAs) showed similar lattice constants to ZnS, however, they showed smaller band gap value if compared to ZnS. The femtosecond Yb:KGW laser [54] was used to synthesize thin films on silicon substrate in argon gas atmosphere (wavelength = 1.03 microns, pulse duration = 280 fs, pulse energy = 150 μJ, repetition rate = 10 kHz). In the SEM studies, spherical shapes with various sizes (1 to 160 nm) and main fraction value (10–20 nm) were reported. According to the XRD pattern, major peak corresponding to (002) plane, and confirmed hexagonal phase.

4 Metal Telluride Thin Films It is worth nothing that bismuth telluride films could be used in thermoelectric, heat pump and power generation applications. Tellurium excessive target was used to avoid the production of unwanted phases [55] during the preparation of films (substrate = Al2 O3 (001) substrate). According to XRD studies, several peaks such as (003), (0015) and (006) planes attributed to the rhombohedral phase, confirming c-axis oriented and polycrystalline in nature. In addition, higher intensity, narrower width, and crystallite size (24 nm to 54.2 nm) increases when the substrate temperature was increased. Noticeably, the crystallite sizes are 50–60 nm with lattice spacing of (006) planes (0.51 nm among the caxis) as highlighted in the High-resolution transmission electron microscopy (HRTEM) images, matched well with the XRD results. In the SEM analysis, all samples indicated polygonal granular morphology and layered structures (film thickness = 1154 to 1428 nm). It was noted that tellurium content (60.12% to 59.48%) has been reduced significantly (especially at higher substrate temperature) due to faster re-evaporation of the tellurium process. Other mechanical properties such as hardness (5.2 to 3.4 GPa), Young modulus (125.2 to 62.5 GPa), shear stress (2.2 to 1 GPa), fracture toughness (1.42 to 0.88 MPa.m1/2 ), fracture energy (0.15 to 0.12 J/m2 ) reduced with increasing the temperature from 225 °C to 300 °C. Matthieu and co-workers [56] demonstrated nanosecond pulsed laser melting of bismuth telluride films. Experimental findings confirmed

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that columnar microstructure, fine-grained, could be seen in melted region. Morphology (highly irregular, small particles, and large number of aggregates) of the starting materials, namely Bi2 Te3 powder was studied using SEM. Noticeably, no subsurface consolidation was detected in 1 W and 2 W, however, subsurface melting could be observed using 3 W to 5 W. The p-type antimony telluride (Sb2 Te3 ) has been used in the cadmium telluride solar cells (back contact) due to very stable ohmic and low electric resistance. Deposition of films on the glass substrate has been described by Jiyang and co-workers [57]. Based on the Hall studies, high mobility and high carrier concentration could be observed. According to the XRD studies, different results could be seen at room temperature (amorphous), 100 °C & 200 °C (comprised of tellurium and antimony), 300 °C (rhombohedral phase) and 400 °C (diffraction peaks became more intense). Also, different morphologies could be found (300 °C = uniform surface, 400 °C = dense packed with larger size, 500 °C = smaller grain size, faceted feature lost) based on SEM images. Power conversion efficiency, fill factor, short circuit current and open circuit voltage were 8%, 51.77%, 22.34 mA/cm2 and 691.62 mV, respectively using Au-only back contact in designed solar cells (glass/FTO/CdS/CdTe/Sb2 Te3 /Au contact). The obtained results confirmed that significantly improvement in fill factor (53.61%–62.45%), short circuit current (23.29 mA/cm2 to 24.88 mA/cm2 ), power conversion efficiency (8.62% to 11.92%) and open circuit voltage (723.5 mV to 767.03 mV) using Sb2 Te3 as buffer layer. Biswajit and co-workers [58] successfully synthesize highly oriented stoichiometric films. Larger grains size could be seen when the substrate temperature was increased. XRD pattern (highly oriented films) and TEM images confirmed the best temperature was 300 °C. Raman spectroscopy exhibited two major peaks at 114 cm−1 (E2 ) and 168 cm−1 (A2 .mode). g1g Gallium telluride films have been used as phase-change materials in memory applications. Because of unique properties such as fast switching rate, higher melting and crystallization temperature, and low switching power. Homogeneous Ga2 Te5 films were produced [59], indicating a strong crystallization peak (at 545 K) and typical glass transition (491 K). Band gap was 0.98 eV and 0.4 eV for glass and crystalline, respectively. In terms of thermal properties, bulk glassy GaTe3 indicated two significant features at 492 K (primary tellurium crystallization) and 602 K (cubic and rhombohedral phase). The p-type thermoelectric materials (Bi2 Te3 Sb1.5 ) have been synthesized on polyimide substrate [60]. Based on the experimental results, film thickness was affected by different conditions such as distance (H), pressure (P) and temperature (T) and the highest film thickness was 151 nm. It was noted that reduction in prepared sample could be seen at lower temperature and higher pressure. Experimental findings showed that electric power factor reached 5.25 μW/cmxK2 with the grain size of 0.14 μm, and relative frequency (25%). Shupenev and co-workers [61] demonstrated the synthesize of p-Bi0.5 Sb1.5 Te3 and n-Bi2 Te2.7 Se0.3 on polyimide substrate. The obtained films showed high electrical resistance with thickness of 300 nm. In the p-Bi0.5 Sb1.5 Te3 films, Seebeck coefficient and electrical power factor were found to be 220 μV/K and 9.7 μW/cm.K2 , respectively. While, in the n-Bi2 Te2.7 Se0.3 films, the Seebeck coefficient and electrical

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power factor were observed to be −200 μV/K and 5 μW/cm.K2 , respectively based on the obtained experimental findings. Formation of hexagonal (band gap = 1.54 eV) and cubic CdTe films (band gap = 1.6 eV) have been deposited onto various substrates [62], at 200 mJ and 50 mJ, respectively. Samples with different thickness could be formed using SnO2 /glass (0.182 nm to 0.339 nm) and Corning 7059 glass (0.152 nm to 0.315 nm). AFM images showed that good morphology with grain size = 0.03 nm. The p-type CdTe films have been synthesized on corning glass when target was CdTe powder [63]. Crystallite size (22 nm to 28 nm), band gap (1.34 eV to 1.5 eV), thickness (1.5 μm to 5.03 μm) and cadmium content (43.77% to 48.96%) increase with increasing temperature (25 °C to 300 °C). Polycrystalline CdTe films [64] were grown on glass substrate. XRD data confirmed the presence of wurtzite (300 K) and zinc blende structure (more than 573 K). There are two peaks that could be seen at 921 nm and 863 nm in all samples based on photoluminescence studies. Fourier transform infrared spectroscopy (FTIR) investigations exhibited several peaks attributed to OH stretching vibration (3360 cm−1 and 1549 cm−1 ) and vibration of oxygen compound (620 cm−1 to 820 cm−1 ). Ulrich and co-workers [65] have prepared Ge2 Sb2 Te5 films on silicon substrates at intermediate temperature. Film thickness (154 to 19 nm) and germanium content (23% to 10%) reduce, but tellurium (53% to 57%) and Sb content (24% to 33%) increase with increasing the temperature (110 °C to 280 °C). Bulai and co-workers [66] have reported the growth of Ge-Sb-Te films using different pulse durations. It was noticed that droplets decrease when the laser fluence is diminished using nanosecond laser ablation. The lowest tellurium content in these samples is due to lower vaporization heat. In single-junction solar cells, CuInTe2 significantly showed greater Bohr radius and stronger quantum confinement effect than CuInS2 and CuInSe2 . Cu2 Te films [67] have been synthesized on the Corning glass at 300 °C. In addition, XRD studies revealed that there are several phases could be observed when the temperature was room temperature (amorphous), 100 °C (mixture of phases) and 200 °C (Cu2-x Te phase). The p-type conductivity of CuInTe2 films [68] have been deposited on Corning glass using XeCl laser at different substrate temperatures (80 °C to 430 °C). Band gap (0.96 eV), absorption value (104 cm−1 ), and resistivity (10−1 to 10−1 cm) of the prepared films have been highlighted. XRD studies showed chalcopyrite phase with preferred orientation along (112) plane when the temperature was more than 270 °C. Ag-doped PbTe films [69] have been deposited on alumina substrate using femtosecond laser ablation. Higher laser intensity could be observed with ultra-short pulses, creating multi-photon absorption processes. In addition, higher rate of ablation was achieved, the growth rate was 0.11 μm/minute, finally layer of micrometers could be reached in few minutes. Noticeably, ratio of [Pb]/[Te] = 1 and significantly reduced when the Ag content was up to 8.8% and more than 8.8%, respectively. According to XPS studies, several peaks at 368.3 eV (Ag 3d5/2 ), 137. 5eV (Te 3d5/2 ) and 572.2 eV (Pb 4f7/2 ) could be identified when the amount of Ag was 10%. The highest power factor was 14.9 μW/K2 .cm when the amount of Ag was 14.4% and at 540 K. Pal and co-workers [70] demonstrated preparation of ZnTe films onto glass substrates using Nd:YAG laser. EDX results showed that different compositional could be seen when the films were prepared at lower (tellurium rich) and higher temperature (zinc

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rich). XRD data highlighted mixed phases of zinc telluride when the temperature was less than 573 K. Noticeably, film deposited at 773 K displayed a strong peak related to (111) plane for cubic ZnTe. The fused silica glass slides [71] have been used to prepare films (thickness = 2 μm) using nanosecond pulse of Nd:YAG laser (wavelength = 1064 nm & 532 nm) at room temperature. There are different structures that could be observed when the films are produced at shorter (amorphous) and longer ablation wavelength (mixture of amorphous, wurtzite and zincblende). The growth of films on silicon wafers [72] were described (laser = Nd:YAG with 10 Hz & 6 ns, fluence = 0.72 J/cm2 ). When the ablation wavelength was 532 nm, deposition rate achieved the highest point using 1 J/cm2 , then dropped due to scattering process hindered laser power to reach target effectively. At 1064 nm, the deposition rate was quite low, the highest point was moved to 1.5 J/cm2 because of higher fluence is required to provide energy density for ablation.

5 Conclusion As we know, many efforts have been made on the preparation of pulsed laser deposited thin films over the last twenty years. Because of these materials could be used in sensor, solar cell applications, thermometry, fluorescence microscopy, and optoelectronic devices. The mechanism of pulsed laser deposition is based on the principle of laser induced ablation. It uses high-powered laser to vaporize a target material, later depositing it onto a substrate. Based on the experimental results, the growth rate, desired structural, electrical, compositional and the optical properties could be controlled using different deposition parameters during the preparation of films.

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48. Lei, J., Wang, Y., Jie, W., Wu, Z.: Fabrication and characterization of two-dimensional layered MoS2 thin films by pulsed laser deposition. Adv. Condens. Matter Phys. (2018). https://doi. org/10.1155/2018/3485380 49. Gujar, T.P., Shinde, V.R., Katiyar, R.S.: Characterization of pulsed laser deposited Cu2 ZnSnS4 thin films for Solar cell. MRS Online Proc. Libr. (2012). https://doi.org/10.1557/opl.2012. 1165 50. Lin, S., He, J., Chen, Y., Yue, F.: Comparative study on Cu2 ZnSnS4 thin films deposited by sputtering and pulsed laser deposition from a single quaternary sulfide target. J. Cryst. Growth 361, 147–151 (2012) 51. Zakaria, O., Rajesh, P., Ali, E.: Pulsed laser deposition of CZTS thin films, their thermal annealing and integration into n-Si/CZTS photovoltaic devices. In: 2016 International renewable and Sustainable Energy Conference, Marrakech, Morocco, 14–17 November 2016. https://doi.org/10.1109/IRSEC.2016.7983988 52. Moholkar, A., Patil, S., Kim, J., Sim, K.: Development of CZTS thin films solar cells by pulsed laser deposition: influence of pulse repetition rate. Sol. Energy 85, 1354–1363 (2011) 53. Hidenori, H., Ohta, H., Hirano, M.: Heteroepitaxial growth of single-phase zinc blende ZnS films on transparent substrates by pulsed laser deposition under H2 S atmosphere. Solid State Commun. 124, 411–415 (2002) 54. Chernikov, A., Kochuev, D., Egorova, A.: Synthesis of spherical zinc sulfide nanoparticles produced by femtosecond laser ablation and deposited on a silicon substrate under the action of an electrostatic field. J. Phys. Conf. Ser. (2021). https://doi.org/10.1088/1742-6596/2077/ 1/012002 55. Huiping, C., Juang, J., Chung, Y., Teng, I.: Effects of substrate temperature on nanomechanical properties of pulsed laser deposited Bi2 Te3 films. Coatings (2022). https://doi.org/10.3390/ coatings12060871 56. Matthieu, A., Saniya, L., Carter, M.: Pulsed laser melting of bismuth telluride thermoelectric materials. J. Manuf. Process. 43, 35–46 (2019) 57. Jiyang, L., Liu, X., Li, W., Lu, H.: Preparation and characterization of pulsed laser deposited Sb2 Te3 back contact for CdTe thin film solar cell. Appl. Surf. Sci. 453, 126–131 (2018) 58. Biswajit, S., Pragati, C., Anil, K., Saha, D.: Pulsed laser deposition of highly oriented stoichiometric thin films of topological insulator Sb2 Te3 . J. Vac. Sci. Technol. B 34 (2016). https://doi.org/10.1116/1.4943026 59. Tverjanovich, A., Benmore, C., Khomenko, M., Sokolov, A.: Decoding the atomic structure of Ga2 Te5 pulsed laser deposition films for memory applications using diffraction and firstprinciples simulations. Nanomaterials (2023). https://doi.org/10.3390/nano13142137 60. Shupenev, A., Melnik, S., Korshunov, I., Karpoukhin, S.: Growth features of Bi2 Te3 Sb1.5 films on polyimide substrates obtained by pulsed laser deposition. Materials (2022). https:// doi.org/10.3390/ma15248993 61. Shupenev, A., Korshunov, I., Grigoryants, A.: On the pulsed-laser deposition of bismuthtelluride thin films on polyimide substrates. Semiconductors (2020). https://doi.org/10.1134/ S1063782620030173 62. Pandey, K., Umesh, T., Raman, R.: Growth of cubic and hexagonal CdTe thin films by pulsed laser deposition. Thin Solid Films 473, 54–57 (2005) 63. Flores, F., Galvan, G., Salazar, J., Cruz, S.: CdTe thin films grown by pulsed laser deposition using powder as target: effect of substrate temperature. J. Cryst. Growth 386, 27–31 (2014) 64. Hussain, S., Pal, K., Bhar, R.: Studies on CdTe films deposited by pulsed laser deposition technique. Physica B 407, 4214–4220 (2012) 65. Ulrich, R., Erik, T., Bernd, R.: Microstructure evolution in pulsed laser deposited epitaxial Ge-Sb-Te chalcogenide thin films. J. Alloy. Compd. 676, 582–590 (2016)

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Review on Current Research of Fabrication, Properties and Applications in Zeolite Ho Soonmin(B) Faculty of Health and Life Sciences, INTI International University, 71800 Putra Nilai, Negeri Sembilan, Malaysia [email protected]

Abstract. Zeolites consisted of aluminum ion and silicon ion, surrounded by oxygen anions. These materials could be categorized into natural zeolite and synthetic zeolite, respectively. The uses of zeolites include ion exchanger, agricultural, catalysis, adsorption process and water purification. Formation of zeolite could be carried out using solvothermal, ionothermal synthesis method, microwaveassisted method, and hydrothermal. The quality of the obtained zeolites depends on experimental conditions such as pH, adsorbent dosage, contact time, composition of precursors, and temperature. Characterization of zeolite has been studied using x-ray diffraction technique, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray fluorescence spectroscopy, and scanning electron microscopy technique. Surface properties, pore size distribution, thermal stability, acidic/alkaline behaviors, mobile cation, and pore size have been reported based on the literature review. In this work, the adsorption of heavy metal, carbon dioxide gas, dye and phenolic compounds onto natural and modified zeolite has been investigated. Sometimes, cobalt, copper, iron, and sodium were used to modify the zeolite surface. The adsorption data was investigated using Langmuir, Temkin, Freundlich isotherm models. Kinetic study was studied using pseudo first-order and pseudo second-order models. The adsorption process was spontaneous (negative Gibbs free energy), exothermic (negative enthalpy) and randomness of the system decreases (negative entropy) based on the thermodynamic parameters. Keywords: Zeolite · adsorbent · surface area · air purification · catalysts · water treatment

1 Introduction Zeolite has unique chemical and structural properties. It could be used in catalysis, gas separation, adsorbent and ion exchange [1]. Generally, zeolite could be classified as natural zeolite, and synthetic zeolite [2]. Natural zeolite is hydrated aluminosilicate material, can be found in rock and volcanic origin [3]. Currently, China is the biggest manufacturer of natural zeolite, followed by South Korea and Slovakia. The physical properties of some natural zeolites (heulandite, analcime, clinoptilolite, erionite, mordenite, chabazite, and philipsite) were highlighted in Table 1. On the other hand, there are more than 150 zeolites that have been produced through slow crystallization process © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 94–109, 2024. https://doi.org/10.1007/978-981-97-1594-7_12

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(silica-alumina gel) in the presence of organic and alkali [4]. Some common synthetic zeolites are zeolite X, zeolite Y, zeolite A and ZMS-5. The synthetic zeolite market reached USD 5.2 million (in 2018), is expected to achieve USD 5.9 billion in 2023 due to high demand in detergent industry and specialty applications. Figure 1 shows the structure of zeolite [5]. It was noticed that it is three-dimensional crystalline [6], rigid, microporous [7], and consisted of oxygen, silicon, and aluminium. The aluminium atom and silicon atom were tetrahedrally coordinated via shared oxygen atom [8]. We can observe that the channel sizes [9] and the pores were nearly uniform (the crystal could be acted as molecular sieve). The advantages and disadvantages of zeolite were described (Table 2).

Fig. 1. The structure of the zeolite [5]

Table 1. Physical properties of several types of zeolites [3]. Natural zeolite

Porosity (%)

Heat stability

Exchange capacity (meq/g)

Specific gravity (g/cm3 )

Bulk density (g/cm3 )

analcime

18

High

4.54

2.24 to 2.29

1.85

chabazite

47

High

3.84

2.05 to 2.1

1.45

clinoptilolite

34

High

2.16

2.15 to 2.25

1.15

erionite

35

High

3.12

2.02 to 2.08

1.51

heulandite

39

Low

2.91

2.18 to 2.2

1.69

mordenite

28

High

4.29

2.12 to 2.15

1.7

philipsite

31

Moderate

3.31

2.15 to 2.2

1.58

Several adsorbents have been studied and used in wastewater treatment. Activated carbons have been produced using carbonaceous materials through carbonization and

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activation process [10]. Sometimes, different activating agents such as sodium hydroxide [11], zinc chloride, potassium hydroxide, phosphoric acid [12], sulfuric acid, and nitric acid [13] were used. Prepared activated carbon showed high surface area [14], microporous structures [15], and high hydrophobicity. Clay consisted of small earth metal, stone, and metal oxide [16]. Bentonite clay is low-cost absorbent and abundant [17]. It contained MgO, SiO2 , CaO, Al2 O3 , K2 O and Fe2 O3 . It was noted that it has high adsorption capacity due to high cation exchange capacity [18], and high porosity structure. Fly ash is a coal combustion product, consisting of fine particles [19]. The chemical composition of fly ash depends on the coal type. The percentage of SiO2 , Al2 O3 , Fe2 O3 , and CaO were 20−60%, 5−35%, 10−40%, 1−12% in bituminous coal, 40–60%, 20−30%, 4−10%, 5−30% in sub-bituminous coal, 15–45%, 20–25%, 4–15%, 15–40% in lignite coal. Specific gravity, size, shape and colour were found to be 1.9 to 2.96, 10 to 100 micron, spherical shaped, brownish, dark grey or black, respectively [20]. The world zeolite market is valued at about USD 12.1 billion (in 2021) and is expected to achieve USD 14.1 billion (in 2026) due to the rising demand in various industries. Currently, the leading companies such as Tosoh, Zeolyst International, Clariant, Chemiewerk Bad Kostritz GmbH, KMI zeolite Inc., Zeocem, Grace, Resonac Corporate and Huiying Chemical Industry (Xiamen) Co. Ltd (Table 3). Natural zeolite has been used in the wastewater treatment, animal feed, soil remediation, building and construction industry. While the synthetic zeolite was employed in detergent (to replace sodium tripolyphosphate due to environmental regulation), catalysts and absorbent [30]. In this work, the properties of zeolite and adsorption capacity were reported. Several tools such as thermogravimetric analysis, scanning electron microscopy, x-ray diffraction technique, Fourier transform infrared spectroscopy and X-ray fluorescence spectroscopy have been used to investigate the obtained zeolites. Following that, the prepared zeolite was used to adsorb heavy metal ions, dye, carbon dioxide gas and phenol in specific conditions. Adsorption data was studied using different isotherms such as Langmuir, Freundlich, and Temkin isotherm models. Kinetic study was studied using pseudo firstorder and pseudo second-order models. Table 2. Advantages and limitations of zeolite Advantages

Disadvantages

No corrosion

Low catalytic site density

No disposal problems

Replace magnesium and calcium ion by sodium ion

High thermostability

Treated water contained more salts

Easy set-up of continuous process If inhaled zeolite dusts, lead to pulmonary disease, health, and safety concerns It needs less time for softening

Limitation on pore size

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Table 3. World zeolite manufacturer Company name

Description

Zeolyst International [21]

• Produce zeolite Y (660–925 m2 /g), zeolite beta (620–710 m2 /g), zeolite ZSM-5 (400–425 m2 /g), ferrierite (400 m2 /g), and mordenite (surface area = 425 to 500 m2 /g)

Clariant [22]

• Pentasil zeolite (odor removal) • Mordenite zeolite (volatile organic compounds reduction) • Beta zeolite (automotive emission control) • SAPO-11 zeolite (active carbon replacement) • Chabazite zeolite (conversion of methanol to olefins)

KMI zeolite Inc. [23]

• Produce natural cliptilolite zeolite (granular form, 50 lbs per cubic foot) • Prepared zeolite could be used as filtration media, to absorb heavy metal and ammonia

Zeocem [24]

• • • •

Huiying Chemical Industry (Xiamen) Co. Ltd. [25]

• 4A zeolite powder detergent grade (employed in homecare product) • 3A Molecular sieve powder (desiccation of ethanol, ethylene, and propylene) • 13 X Molecular Sieve Powder (purification of air) • 5A Molecular Sieve powder (air purification)

Grace [26]

• Sylobead (petrochemical and refining industries) • Phonosorb silica (gravimetric spacer filling) • Cryosiv molecular sieve (refrigeration adsorbent) • Sylosiv zeolite powder (low sensitivity to temperature and improved dispersibility)

Resonac Corporate [27]

• High silica zeolite was produced in Aizu (Fukushima), Japan (continued)

ZeoAqua (pool water treatment) ZeoTraction Ultra (anti-frosting) ZeoCem Micro (anti-caking effect) ZeoCem Eco (flue gas cleaning)

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H. Soonmin Table 3. (continued)

Company name

Description

Tosoh [28]

• Zeolum is synthetic zeolite (powder, bead, and pellet form), could be used for purifying, drying and separating purposes • High silica zeolite (high acid and thermal stability) could be employed in absorbent and catalyst applications

Chemiewerk Bad Kostritz GmbH [29]

• Zeolite A, X and Y were synthesized (spherical granular, grain sizes = 0.5 to 5 mm) • These zeolites could be used in purification of exhaust air, energetic applications, natural gas and petroleum processing

2 Removal of Pollutant Using Zeolite The 5A zeolite was loaded with iron through the ozonation process [31]. In the Fourier transform infrared spectroscopy (FTIR) investigations, sharp peak could be seen at 970 cm−1 (Si-OH and Al-OH stretching vibration) and 1442 cm−1 (Fe-OH stretching vibration). The percentage of iron (5%) and smooth morphology could be seen also. The surface area and pore size were 93.25 m2 /g and 0.5 nm, respectively. In the advanced oxidation processes, we can observe that the removal efficiency (1 h) was 73.4% (O3 /Fe-zeolite/UV), 65.6% (O3 /zeolite), 57.1% (UV/O3 ) and 49.3% (O3 ). Catalytic ozonation (O3 ) with ultraviolet (UV) irradiation formed hydroxyl radicals (Fig. 2). Also, decomposition of ozone using UV-rays will enhance the removal of ciprofloxacin and formation of active oxygen species. Ciprofloxacin is an antibiotic, was employed to treat bacterial infections (typhoid fever, diarrhea, skin infection, bone, and joint infection). Residual ciprofloxacin endangers human health and ecosystems. The conventional technique cannot remove ciprofloxacin effectively due to stable chemical structure.

Fig. 2. Mechanism of ultraviolet (UV) assisted catalytic ozonation (O3 ) on the iron loaded zeolite [31].

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Chitosan is nontoxic, and shows different types of functional groups (methyl, amino and hydroxyl groups). Chitosan cross-link (various ratios of acetic acid was 0.5:1 (ZLCHa) and 1:1 (ZLCH-b)) with zeolite was prepared to adsorb methylene blue [32]. Surface area, carbon, oxygen, sodium, aluminum, and silica were found to be 5.98 m2 /g, 2.6%, 49.15%, 4.11%, 9.08%, 35.07% and 1.08 m/g, 3.11%, 45.37%, 12.69%, 7.99%, 30.84% in ZLCH-a and ZLCH-b, respectively. General characteristics (molecular weight = 319.85 g/mol, chemical formula = C16 H18 ClN3 S, dye type = thiazine, dye nature = cationic, maximum absorbance value = 665 nm) of methylene blue were reported. Removal of dye achieved 97% (adsorption capacity was 242.5 mg/g) for 1 h, at pH 10. Adsorption data supported Freundlich model (R2 = 0.9926) and pseudo second order isotherm (R2 = 0.9978). The influence of other ions on the adsorption process was studied. Results reflected removal percentage reduced after added sodium chloride, glucose, and citric acid (due to dye could not be trapped on the surface of adsorbent). However, removal percentage increased (83.4% to 85.3%) after added hydrogen peroxide, representing the adsorption and oxidation process happened (Fig. 3). In the desorption investigations, desorption percentage was 1.64% (NaOH), 49.75% (HCl) and 57.05% (H2 SO4 ), respectively. Furthermore, desorption percentage was increased to 99.65% when the temperature was increased to 45 °C. Coal fly ash (Brazilian) was employed as starting material to produce zeolite via hydrothermal treatment [33]. Some physical properties including pH (pH 11), specific surface area (131.5 m2 /g), specific gravity (2.36 g/cm3 ), pore volume (0.25 cm3 /g), and CEC (152.2 meq/100 g) were reported. According to SEM images, rough morphology and most of the crystallite was small (less than 1 mm in length) in the obtained zeolite. The higher R2 value indicated that the adsorption process obeyed pseudo second kinetic order model and Freundlich model. Thermodynamic studies confirmed the spontaneous process (free energy changes = − 2.06 to −5.05 kJ/mol), exothermic reaction (enthalpy changes = −6.49 to −19.7 kJ/mol) and reduced randomness at the solid/solution interface (entropy changes = −14.5 to − 49.1 J/K.mol). Cubic zeolite/bentonite composite has been prepared via alkaline treatment for 240 min, at 150 °C [34]. The obtained zeolite has unique properties such as surface area of 512 m2 /g, swelling capacity of 5.62, micropores volume of 0.244 ml/g, mesopores volume of 0.175 ml/g, cation exchange capacity (CEC) of 387 meq/100g and average pore diameter of 5.8 nm. The percentage of removal was 94% in specific conditions (initial concentration = 5 mg/L, contact time = 720 min). The monolayer adsorption process (Langmuir model, maximum capacity was 36.23 mg/g) was described and chemisorption process (pseudo second order model) was observed. Chromium happens naturally in soil, volcanic emission, rock, water, animal, and plant [35]. Chromium (III) ion was essential nutrient (for organism), while chromium (VI) was carcinogenic, poisonous, and teratogenic. Natural zeolite has been coated with Fe3 O4 to enhance adsorption capacity, surface characters and recoverability process [36]. Pore volume, surface area and pore diameter were 0.099 cm3 /g, 21.2 m2 /g & 1.867 nm and 0.264 cm3 /g, 78.69 m2 /g & 1.34 nm in raw zeolite and magnetic zeolite (25% Fe3 O4 ). The point of zero charge was higher in raw zeolite (pH = 4.9) if compared to magnetic zeolite (pH = 3.47 to 3.76). The highest uptake of chromium was 72.39% and 90.2% for natural zeolite and magnetic zeolite (33.3% Fe3 O4 ). FTIR analysis displayed OH vibration in Fe3 O4 (1425 cm−1 ), FeO vibration (570 cm−1 ), O-H

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Fig. 3. Mechanisms of the adsorption process and oxidation reaction simultaneously [32].

stretching vibration (3425 to 3441 cm−1 ), Si-OH-Al (3610 to 3740 cm−1 ), Si-OH (3740 to 4000 cm−1 ), and O-Si-O/O-Al-O asymmetry stretching groups (1049 to 1635 cm−1 ) in spectra. The highest removal of chromium reached 93.57% in the best experimental conditions (contact time = 75 min, adsorbent dose = 2g/L, initial chromium concentration = 10 mg/L, pH = 1.5). Adsorption data supported Langmuir model (R2 = 0.9966) with adsorption capacity of 43.93 mg/g. Adsorption kinetic fitted to pseudo first order model (R2 = 0.994) with rate constant of 5.59 min−1 . Low-cost zeolite has been made using exhausted fluidized bed catalytic cracking catalysts through hydrothermal method [37]. The results obtained confirmed that the chromium (III) concentration was reduced from 40.3 ppm to lower than 1.2 ppm. XRD studies indicated that all diffraction peaks (20 < 2θ < 25) correspond to silica glasses. However, high percentages of zeolite were observed at longer deposition times. The particle size and morphology were reported with (cubic structure, smaller than 1 μm) and without the alkaline fusion (special shaped, 60–100 μm). Alkaline fusion process could be used to improve high content of zeolitic phase, enhanced the adsorption capacity of Cr (III) ion from aqueous solution. Deyi and co-workers [38] have reported the synthesis of zeolite using coal fly ash (thermal power plant in China). The chemical composition of zeolites revealed mainly silicon (29.3% to 39.86%) and aluminum components (14.47% to 42.36%), followed by calcium (2.49% to 13.26%) and iron content (4.13% to 10.27%). Adsorption of chromium (III) ions was studied at pH 4 (exclude precipitation happened and to protect adsorption process). According to Langmuir isotherm, higher R2 value (0.982 to 0.999) with maximum capacity of 13.95 mg/g to 50.5 mg/g could be seen. Nickel was silvery white, hard, and so-called heavy metal (high density value). Exposure to nickel could lead to irritation to skin, harmful to stomach, lung, and kidneys [39]. Nickel was released to environments through nickel mining activity and industrial process (battery, electroplating, rubber, and plastic). The HZSM-5 zeolite was treated with phosphoric acid [40], was stirred at 60 °C for 180 min. Phosphoric acid modified zeolite (surface area = 422 m2 /g) indicated higher uptake if compared to Na+ modified zeolite (surface area = 385 m2 /g) due to more exchangeable sodium ion. The uptake efficiency increased with increasing the pH (pH 3 to pH 4). Precipitation was observed when the pH is above 4. Both zeolites fitted the Langmuir model (maximum capacity was 39.96 mg/g) and pseudo second order model. The adsorption process was endothermic, removal efficiency increased when the temperature was increased. It was noticed that the

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best pH value for adsorption process was pH 4. Jordanian zeolite tuff was prepared and treated with NaCl for nickel ion removal [41]. Based on the XRF studies, main content was SiO2 (35.63%), followed by Fe2 O3 (11.71%), MgO (11.27%), Al2 O3 (9.71%), CaO (6.65%), TiO (1.73%), Na2 O (1.42%), K2 O (1.29%), P2 O5 (0.53%) and MnO (0.12%). It was noted that increase in particle size from the 45 μm–90 μm, 90 μm–180 μm, 180 μm–355 μm, to 355–710 μm, resulted in decreases in equilibrium removal (qe) for nickel ions (1.005 meq/g, 0.681 meq/g, 0.409 meq/g to 0.358 meq/g). Adsorption data supported Langmuir model and the correlation coefficient was 0.991. Jordanian zeolite (philipsite) was treated with bentonite (high in ion exchange capacity) to remove nickel ion [42]. High value of correlation coefficient showed that the adsorption process was well described by Langmuir model (R2 = 0.967, maximum capacity was 33 mg/g), Freundlich model (R2 = 0.999) and Dubinin-Radushkevich isotherm (R2 = 0.954). The adsorption process was spontaneous (negative value of free energy) and the removal process is well highlighted with the pseudo second order reaction model. Phenol contains the phenyl group (C6 H5 ) that bonded to hydroxyl (OH) group. The properties of phenol have been highlighted in Table 4. Exposure to phenol resulted in pain, weight loss, irritation to the eyes and nervous system. Phenol is used in plastic industry, cosmetic industry, medicine industry, and produce phenolic resin. Zeolite (NaP1) was synthesized using fly ash with sodium hydroxide solution through hydrothermal process [43]. It consisted of 0.18% sodium, 21.52% aluminium, 47.4% silicon, 5.65% potassium, 14.71% iron, 0.06% copper, 2.96% calcium and 0.8% magnesium. On the other hand, chitosan will be used to modify the obtained sample, and namely as NaP1CS. Surface area, total pore volume and average pore width were 98.5 m2 /g, 0.302 cm3 /g, 11.38 nm and 53.5 m2 /g, 0.134 cm3 /g, 11.17 nm in NaP1 and NaP1Cs, respectively. Based on the FTIR studies, several peaks at 1638 cm−1 (bending vibration of water), 3420 cm−1 (O-H stretching vibration), 977 cm−1 (Si-O-Si), 1000–1100 cm−1 (C-O-C), and 1600–1650 cm−1 (N-H) in NaP1 sample. In the thermogravimetric analysis (TGA), two weight losses could be observed at 40 °C to 120 °C (evaporation of water) and 300 °C to 450 °C (degradation of saccharide ring) in chitosan. Thermogram of NaPI indicated water loss at 100 °C to 200 °C, then remain stable conditions. In NaP1Cs sample, evaporation of water (up to 150 °C) and degradation of saccharide ring (more than 300 °C) could be seen. The highest removal of phenol was observed at pH 7 (NaP1) and pH 6 (NaP1CS) representing different surface charges on the adsorbent. The adsorption data showed a higher R2 value in Freundlich model (R2 = 0.966) if compared to Langmuir model (R2 = 0.629), Temkin model (R2 = 0.683) and Dubinin-Radushkievich model (R2 = 0.945) on NaP1 sample at 293 K. The adsorption kinetic obeyed pseudo second order isotherm on both samples (R2 = more than 0.974). In the thermodynamic studies, enthalpy, entropy, and free energy were found to be −13.08 kJ/mol, −76.6 J/K.mol, −6.6 to −7.4 kJ/mol and −26.67 kJ/mol, 114.3 J/K.mol, −6.21 to −11.48 kJ/mol, in NaP1 and NaP1CS, respectively. Nonylphenol was derivative of phenol. It has hydroxyl group (OH) and other organic group (carbon, hydrogen, oxygen, or sulfur) attached to benzene ring. It appears as liquid (at room temperature), moderately water-soluble, and soluble in alcohol. Natural zeolite (from San Luis Potosi, Mexico) with desired size (1– 2.5 mm) was produced [44]. It consisted of SiO4 and AlO4 , the percentage of aluminum and silicon were 3.85% and 27.92%, respectively. It was noted that equilibrium will be

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reached within 30 min using 0.4 g adsorbent. The adsorption data confirmed pseudo second order model (R2 = mor than 0.999) and Temkin model (R2 = 0.994). Table 4. Properties of phenol Chemical formula

C6 H6 O

Molar mass

94.113 g/mol

Density

1.07 g/cm3

Odor

Tarry and sweet

Melting point

40.5 °C

Boiling point

181.7 °C

Solubility in water

8.3 g/100 mL

Dipole moment

1.224 D

Malachite green is a very toxic cationic dye. The 4A zeolite has been prepared from the gas dehydration unit of TFT plant [45]. Chemical components such as SiO2 (55.39%), Al2 O3 (27.18%), Na2 O (4.49%), K2 O (1.03%), CaO (3.34%), P2 O5 (0.79%), Fe2 O3 (4.47%), TiO2 (0.32%), and MgO (2.99%) were studied by X-ray fluorescence spectroscopy (XRF) technique. As shown in FTIR spectrum, some peaks included 3441 cm−1 (stretching vibration H-O-H), 1660 cm−1 (bending vibration H-O-H), 994 cm−1 (asymmetric stretching vibration Si-O-Si or Al-O-Al), 787 cm−1 (symmetric Si-O-Si), 684 cm−1 (stretching vibration Si-O-Al) and 464 cm−1 (bending vibration OSi-O) could be observed. Surface area and point of zero charge (pHpzc) were 35.5 m2 /g and pH 10.5, respectively. The adsorbent surface is positive when the pH was less than pHpzc. However, surface was predominantly negative if the pH was greater than pHpzc. The highest removal capacity reached 99.5% when the pH was 8. According to the adsorption data, the Langmuir model (R2 = 0.994) and pseudo second order kinetic model [R2 = 0.99] provided higher R2 value if compared to other isotherms. In thermodynamic studies, entropy (204.5 J/mol.K), free energy (−35.4 to −40.5 kJ/mol) and enthalpy (25.5 kJ/mol) have been described, representing spontaneous reaction, and endothermic in nature. Congo red is an azo dye, organic compound, and water soluble. This dye was toxic, may cause dermatitis. Some characteristics of Congo red such as molar mass (696.6 g/mol), molecular formula (C32 H22 N6 Na2 O6 S2 ), nature of charge (anionic) and absorbance maximum (497 nm). Carboxymethyl cellulose agar polyvinyl alcohol zeolite (6%) biomembrane [46] showed excellent thermal stability (68.28% weight loss) and high hydrophobicity (89°), could be used to adsorb Cong Red dye. The highest adsorption capacity was 96% in specific conditions (pH = 2, adsorbent dosage = 6%, initial concentration of dye = 20 mg/L). The adsorption kinetic data indicated pseudo second order model (R2 = 0.992) was more fitted if compared to other isotherms. Monolayer and multilayer adsorption happened at the same time. Thermodynamic parameters such as enthalpy (−83.6 kJ/mol), entropy (−257 J/mol.K) and free energy (−0.49 to − 9.1 kJ/mol) were reported. It was noted that all small pores were sealed when the zeolite

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was treated with algae [47]. The average diameter of the pores, hydrodynamic diameter and surface area are 817 nm, 91.4 nm, and 117.3 m2 /g, respectively. The highest adsorption capacity increased when the Congo Red concentration was increased from 5 mg/L (4.3 mg/g), 10 mg/L (7.4 mg/g), 15 mg/L (9 mg/g), 20 mg/L (10.7 mg/g) and 25 mg/L (11.3 mg/g) at 25 °C and pH was 7. It was noticed that fast removal rate could be observed at the early adsorption stage, because of large number of uncovered active sites on the surface of the adsorbent. Repulsion force increases between the dye and the adsorbent when the active site was occupied by dye molecules. The zeolite/algae composites indicated removal percentage of 72.3% (pH 2), 61.4% (pH 5), 74.5% (pH 7) and 67.9% (pH 10), respectively. At high pH values, positive charged (adsorbent surface) has competitive interaction with anionic Congo Red dyes or hydroxide ion. A decrease in dye removal was highlighted when the temperature was increased due to the destruction of active sites. In the reusability test, dye removal reduced (45.27% in first cycle to 25.09% in seven cycle) due to agglomeration of dye on the surface of the adsorbent, hind the pores and the surface of zeolite/algae composites. Higher correlation coefficient could be seen in the Langmuir model (R2 = 0.995) if compared to Freundlich model (R2 = 0.982) and Temkin model (R2 = 0.992). The highest removal percentage reached 78.89% in the best conditions (temperature = 25 °C, pH = 7, concentration of dye = 20 mg/L, adsorbent dose = 0.02 g and contact time = 480 min). Characteristics of acid red 88 dye including molecular weight (400.39 wasl), dye type (azo), nature (anionic), absorbance maximum (503 nm) were reported. Surface morphology of raw zeolite (non-adhesive), modified zeolite chitosan hydrogen (interlayer structure, adhesive on the surface) and after adsorption (rough texture) was reported based on the SEM analysis [48]. Experimental findings indicated adsorption capacity increased when initial dye concentration was increased (33.2 mg/g to 326.2 mg/g). However, reduction in the uptake when the adsorbent dosage (30 to 80 mg/100 mL) and the pH value (pH 2 to 8) was increased. As shown in FTIR analysis, several peaks (3453.16 to 3225.3 cm−1 , 1650.65 to 1615 cm−1 ) have reduced after adsorption process. Also, some peaks (745.99 and 681.22 cm−1 ) appeared because of bending vibration C-H groups. The mechanism of updating of dye onto zeolite has been described. Adsorption data revealed that higher correlation coefficient value (R2 ) in the Freundlich model (R2 = 0.9938) and pseudo second order kinetic model (R2 = 1) if compared to other isotherms. Desorption investigations indicated that the 0.01M of sodium hydroxide (NaOH) could be a better desorbing agent and achieved equilibrium (25 min) with a percentage of 93.8%. A recycling process was carried out (up to three cycles), demonstrated excellent dye removal. Zeolite Na-ZK-4 (Si/Al = 1.8, 2.3 and 2.8) has been produced through hydrothermal method [49]. Based on the infrared (IR) spectroscopy, physisorbed (peaks at 2360 cm−1 , 3599 cm−1 and 3715 cm−1 ) and chemisorbed carbon dioxide gas (peaks at 1668 cm−1 , 1366 cm−1 ) were observed. Higher removal percentage (55%) could be detected in zeolite NaK-ZK-4 (2.8) if compared to NaK-ZK-4(1.8) due to smaller amount of sodium ion (Na+ ) and potassium ion (K+ ) cations in the prepared zeolite (in the 6 rings). The carbon dioxide gas physisorption rate was reduced in other samples, because of potassium ion populating the 8-rings. Zeolite NaK-ZK-4(1.8) takes 10 min to achieve 80%

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of maximum capacity (due to it containing 28% of potassium ions). Ranjani and coworkers [50] have demonstrated that lower adsorption capacity at 120 °C if compared to ambient temperature. Also, higher adsorption could be observed [51] at high pressure (pressure of 300 psi). On the other hand, more intense FTIR bands could be seen (due to have more surface-active sites) when the material pretreatment temperature and adsorption temperature were 350 °C and 120 °C, respectively. Zeolite was added to monoethanolamine (MEA) in methanol solution [52]. Surface area (9.15 m2 /g), pore volume (0.059 cm3 /g) and average pore size (1.1 nm) in the case of 13X-MEA-50 were reported. In the carbon (C), hydrogen (H) and nitrogen (N) analysis, higher amount of carbon (37.1 mg/g, 48.8 mg/g and 47.3 mg/g) could be seen in the first, second and third cycles. The hydrogen (from 27.5 mg/g to 24.1 mg/g) and nitrogen content (18.8 mg/g to 10 mg/g) reduced after the first cycle. It was noticed that carbon dioxide gas breakthrough adsorption capacity dropped when the adsorption temperature was increased (from 30 °C to 120 °C), due to the surface area was reduced. Carbon dioxide contained one carbon and two oxygen atoms. It is a chemical compound and absorbs infrared radiation (greenhouse gas). Properties of carbon dioxide have been described in Table 5. Exposure of carbon dioxide caused headaches, sweating, coma, asphyxia, dizziness, convulsions, and restlessness. Also, global temperature rises by adding more carbon dioxide gas to the atmosphere. Table 5. Properties of carbon dioxide.

3 Other Applications Bio oil was viscous liquid, dark, and consisted of many oxygenated compounds (sugar, furan, ketone, aldehyde, and carboxylic acid) and water. The bio-oil was prepared using rape biomass (pods, leaves, and straw) via pyrolysis process [53]. Pore volume, total acidity, pore diameter and surface area were described (Table 6) in the 13X zeolite modified with iron, copper, and cobalt. Research findings confirmed that these zeolites can improve catalytic selectivity towards the aromatic hydrocarbon. Furthermore, bio-oil

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quality has been successfully improved using Fe-Cu/13X zeolite catalyst. The obtained zeolite showed high deoxygenation activity (62.45% to 20.56%), reduced oxygen content in bio-oil (34.98% to 16.06%), formed the highest monoaromatic hydrocarbon (27.45%), and calorific value was increased. Also, the pH value was increased, but corrosion effect and the viscosity reduced were reported. Table 6. Porosity texture and surface area of metal modified zeolite and pure 13X zeolite [53]. Catalyst

Surface area (m2 /g)

Pore volume (cm3 /g)

Pore diameter (nm)

Total acidity (mmol/g)

13X zeolite

620

0.434

11.95

4.75

Fe/13X

327

0.254

11.12

6.24

Co/13X

435

0.268

10.35

6.75

Cu/13X

468

0.278

10.72

6.84

Fe-Co/13X

308

0.255

11.25

8.85

Fe-Cu/13X

303

0.234

10.64

9.21

Co-Cu/13X

301

0.262

10.72

7.36

Synthesis of micro mesoporous Y-zeolite alumina for olefin production from heavy oil was proposed [54]. Specific surface area (274.8 to 559.2 m2 /g) increases, but total pore volume (0.691 to 0.282 cc/g) and average pore diameter (6.6 to 5.7 nm) decreases when the alumina content was reduced (100% to 25%). In the FTIR studies, several peaks at 950 cm−1 (Si-O-Al), 3600–3560 cm−1 (hydroxyl groups), and 3690 cm−1 (undissociated water). Based on the results, the conversion was 0.65% and 0.45% for propylene and ethylene, respectively when the temperature was 395 °C. Higher conversion could be observed for propylene (double) and ethylene (1.5 folds) at 400 °C. The properties of such as boiling point, melting point, density, molar mass, solubility in water were described (Table 7). Methanol was converted to highly aromatic gasoline [55] via CuO-ZnO/HZSM5 zeolite (ultrasound radiation). Experimental findings confirmed the co-impregnation can enhance aromatic yield and reduce benzene content. Soares and co-workers [56] have reported that ripening rate reduced when packed in specific packing system (silver impregnated zeolite NaY, incorporate into chitosan Kraft paper). Also, this packing system can maintain the nutritional composition and could prolong the shelf-life of cherry tomatoes (weight loss reduction of 29% after 30 days at 25 °C). The immobilized cell technology was employed in ethanol fermentation process because of easier separation, high cell density and tolerance to higher concentrations of product and substrate. The natural zeolite (diameter = 5–100 μm, and high porosity structure) was utilized to immobilize Saccharomyces cerevisiae (3.6 × 108 cells/mL carrier). Experimental results showed that the capacity for alcohol fermentation activity and immobilization were found to be 1.2-fold and 2-fold higher if compared to glass beads [57].

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4 Conclusions In this work, the removal of dye compounds, heavy metal, carbon dioxide gas, and phenolic compounds using natural and modified zeolite (treated with sodium, cobalt, iron, and copper) has been reported. The obtained experimental results confirmed that adsorption capacity depended on different conditions (adsorbent dosage, temperature, pH, contact time, initial concentration). A spontaneous reaction could be observed when the sign of free energy was negative value. The endothermic process could be seen when the enthalpy is positive value based on the thermodynamic parameters.

References 1. Veronique, V., Karen, H., Catlow, C., Bell, G.: Advances in theory and their application within the field of zeolite chemistry. Chem. Soc. Rev. 44, 7044–7111 (2015) 2. El-Sayed, D.: Electronic band structure and density of state modulation of amphetamine and ABW type–zeolite adsorption system: DFT-CASTEP analysis. J. Mol. Model. (2023). https:// doi.org/10.1007/s00894-023-05501-y 3. Ersin, P., Mehmet, K., Naci, A., Halil, D.: Use of natural zeolite (clinoptilolite) in agriculture. J. Fruit Ornam. Plant Res. 12, 183–189 (2004) 4. Lim, C.K., Seow, T.W., Neoh, C.: Treatment of landfill leachate using ASBR combined with zeolite adsorption technology. 3 Biotech (2016). https://doi.org/10.1007/s13205-016-0513-8 5. Broclawik, E., Kozyra, P., Mitoraj, M., Rado, M., Rejmak, P.: Zeolites at the molecular level: what can be learned from molecular modeling. Molecules (2021). https://doi.org/10.3390/ molecules26061511 6. Abolpour, B., Sheibani, S., Eskandari, A.: Modeling the influent and effluent parameters concentrations of the industrial wastewater treatment under zeolite filtration. Appl. Soft Comput. 27, 5855–5872 (2023)

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31. Amir, I., Rahat, J., Fei, Q., Umair, Y.: Application of attapulgite clay-based Fe-Zeolite 5A in UV-assisted catalytic ozonation for the removal of ciprofloxacin. J. Chem. (2022). https:// doi.org/10.1155/2022/2846453 32. Endar, H., Seiichiro, Y., Yoshiharu, M., Hiroyuki, H.: Methylene blue removal by chitosan cross-linked zeolite from aqueous solution and other ion effects: isotherm, kinetic, and desorption studies. Adsorpt. Sci. Technol. (2022). https://doi.org/10.1155/2022/1853758 33. Denise, A., Mariza, B., Lucas, C.: Adsorption and kinetic studies of methylene blue on zeolite synthesized from fly ash. Desalin. Water Treat. 2, 231–239 (2009) 34. Shaban, M., Suzan, I., Shahien, M.: Novel bentonite/zeolite-NaP composite efficiently removes methylene blue and Congo red dyes. Environ. Chem. Lett. (2017). https://doi.org/ 10.1007/s10311-017-0658-7 35. Nur-E-Alam, M., Mia, M., Ahmad, F.: An overview of chromium removal techniques from tannery effluent. Appl. Water. Sci. (2020). https://doi.org/10.1007/s13201-020-01286-0 36. Asanu, M., Dejene, B., Adisu, B.: Removal of hexavalent chromium from aqueous solutions using natural zeolite coated with magnetic nanoparticles: optimization, kinetics, and equilibrium studies. Adsorpt. Sci. Technol. (2022). https://doi.org/10.1155/2022/8625489 37. Elena, I., Andrea, M., Gonzalez, M.: Trivalent chromium ion removal from aqueous solutions using low-cost zeolitic materials obtained from exhausted FCC catalysts. Adsorpt. Sci. Technol. 29, 629–636 (2011) 38. Deyi, W., Sui, Y., He, S., Li, C.: Removal of trivalent chromium from aqueous solution by zeolite synthesized from coal fly ash. J. Hazard. Mater. 155, 415–423 (2008) 39. Shaker, O.A., Safwat, S.M., Matta, M.E.: Nickel removal from wastewater using electrocoagulation process with zinc electrodes under various operating conditions: performance investigation, mechanism exploration, and cost analysis. Environ. Sci. Pollut. Res. 30, 26650–26662 (2023) 40. Panneerselvam, P., Sathya, V., Sivanesan, S.: Removal of nickel (II) from aqueous solutions by adsorption with modified ZSM- 5 zeolites. E-J. Chem. 6, 729–736 (2009) 41. Ahmad, A., Ribhi, E.: Removal of lead and nickel ions using zeolite tuff. J. Chem. Technol. Biotechnol. 69, 27–34 (1997) 42. Reyad, A., Aiman, E.: Removal of cobalt and nickel from wastewater by using Jordan low-cost zeolite and bentonite. J. Univ. Chem. Technol. Metall. 47, 69–76 (2012) 43. Lidia, B., Małgorzata, F., Jarosław, M., Dorota, K.: Zeolites in phenol removal in the presence of Cu(II) ions—comparison of sorption properties after chitosan modification. Materials (2020). https://doi.org/10.3390/ma13030643 44. Ucan, C., Abatal, M., Miguel, A., Denis, C.: Removal of an ethoxylated alkylphenol by adsorption on zeolites and photocatalysis with TiO2 /Ag. Processes (2019). https://doi.org/10. 3390/pr7120889 45. Imessaoudene, A., Cheikh, S., Bollinger, J., Belkhiri, L.: Zeolite waste characterization and use as low-cost, ecofriendly, and sustainable material for malachite green and methylene blue dyes removal: Box-Behnken design, kinetics, and thermodynamics. Appl. Sci. (2022). https:// doi.org/10.3390/app12157587 46. Radoor, S., Nandi, D., Suchart, S.: Efficient removal of organic dye from aqueous solution using hierarchical zeolite-based biomembrane: isotherm, kinetics, thermodynamics and recycling studies. Catalysts (2022). https://doi.org/10.3390/catal12080886 47. Asmaa, R., Hamd, A., Ahmed, A., Abu, A.: Design, characterization, and adsorption properties of Padina gymnospora/zeolite nanocomposite for Congo red dye removal from wastewater. Sci. Rep. (2021). https://doi.org/10.1038/s41598-021-00025-y 48. Hidayat, E., Harada, H., Mitoma, Y., Yonemura, S.: Rapid removal of acid red 88 by zeolite/chitosan hydrogel in aqueous solution. Polymers (2022). https://doi.org/10.3390/polym1 4050893

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A Comprehensive Review of Recent Progress on the Removal of Pharmaceutical Compounds Ho Soonmin1(B) , Sie Yon Lau2 , Abdul Zahir2,3 , Sankha Chakrabortty4 , and Ajala Oluwaseun Jacob5 1 Faculty of Health and Life Sciences, INTI International University, 71800 Putra Nilai,

Negeri Sembilan, Malaysia [email protected] 2 Department of Chemical and Energy Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009 Miri, Sarawak, Malaysia 3 National Textile Research Centre, National Textile University, Faisalabad 37610, Pakistan 4 Kalinga School of Biotechnology/Chemical Technology, Kalinga Institute of Industrial Technology (Deemed to be University), Bhubaneswar 751024, Odisha, India 5 Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, Ogbomoso, Nigeria

Abstract. Adsorption is one of the most tried-and-true methods when it could be used to remove several pollutants from wastewater. Adsorption can remove a wide variety of pollutants. In its most basic form, the adsorption process does nothing more than collect the pollutants that are present in the wastewater on the surface of the adsorbent. The capacity of the adsorbent is dependent on factors such as its porosity, surface area, pore diameter, and the type of adsorbent. Photodegradation of pharmaceutical compounds using graphene oxide has been extensively studied, and the results have shown promising outcomes under various operating conditions. Graphene oxide is consisted of carbon atoms arranged in honeycomb lattice, showed larger surface area and excellent electron transport capabilities. Graphene-based composites received great attention due to providing good visible light activity, could capture a significant portion of solar radiation. In conclusion, several pharmaceutical compounds such as ibuprofen, carbamazepine, diphenhydramine, sulfamethoxazole, tetracycline, sulfamethazine, and chloramphenicol have been successfully removed using various techniques based on the experimental findings. Keywords: Adsorption · phenol · wastewater treatment · water pollution · pharmaceutical compounds · water quality

1 Introduction Adsorption is a versatile wastewater remedial technique and has been employed for many years due to its excellent potential for the abatement of pharmaceutical drugs from wastewater. An impetus of its application for the said purpose is its ease of operation and © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 110–124, 2024. https://doi.org/10.1007/978-981-97-1594-7_13

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low operational cost as adsorbents can be regenerated and reused and thus proves an economical solution for pharmaceutical wastewater treatment [1]. Various adsorbents have been reported to control the concentration of pharmaceutical pollutants in the waste effluent [2]. Based on the origin, these adsorbents can be classified as carbon-based carbon material [3] such as (i) granular activated carbon (GAC), single-walled carbon nanotubes [4], multiwalled carbon nanotubes, carbon-based nanocomposites [5], graphene oxide and its derivatives [6] (ii) mineral based adsorbents such as montmorillonite [7], aluminum oxide [8], silica-supported iron nanocomposite [9], hydrated ferric oxide [10] and (iii) polymeric adsorbents such as chemically modified chitosan [11]. Among all the available adsorbents, graphene oxide (GO) has gained much attention in the wastewater treatment, especially for the adsorption of organic pollutants [12]. The key features that make GO a good choice for the adsorption process are high surface area (600–900 m2 /g), chemical stability, availability of functional groups, high adsorption kinetics and ease of regeneration [13]. However, the kinetics and the adsorptive potential of the GO can be further enhanced by various physicochemical treatments or by synthesizing its composites. The physiochemical and the composite formation enhances the adsorption of the GO by either altering the surface charge, enhancing the surface area, or inducing the vulnerable surface functional groups [14]. The adsorptive potential of GO and its derivates for pharmaceutical and phenolic pollutants are highlighted (Table 1). Despite its various desirable features, such as low operational cost, high efficiency, high surface area and chemical stability, there exist some drawbacks associated with the graphene oxide which hinder its successful application in the field of wastewater treatment, which are as follows: (i) Aggregation: The graphene oxide tends to form aggregates in the aqueous media, which reduces its surface area and, therefore, the adsorption efficiency compromises. (ii) Low thermal stability: The graphene oxide has low thermal stability as compared to its derivatives. At high temperatures, graphene oxide undergoes thermal degradation, which causes the loss of oxygen from its chemical structure. This loss of oxygen function group decreases the active functional groups, which is a favorable attribute for the reactive absorption [22]. (iii) Cost: The graphene oxide has a high synthesis cost as compared to the other available adsorbent due to the requirement of multiple chemicals and reagents and a very controlled environment for the synthesis of graphene oxide [23]. Several different approaches are utilised in the process of transforming the hazardous molecules that are present in water into non-hazardous ones and removing waste from the water [24]. Photodegradation, phytoextraction, phytovolatilization, phytostabilization, biodegradation, phytofiltration (also known as rhizofiltration), and phytoaccumulation are some of the processes that are included in this category [25, 26]. Both aerobic and anaerobic processes, which use living things like bacteria, are necessary for the breakdown of the waste materials that are present in pharmaceutical wastewater. Studies on desorption showed that the antibiotic had been adsorbed onto the sludge rather than being broken down [27]. It has been demonstrated that advanced

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anaerobic methods, such as the moving bed biofilm reactor (MBBR), anaerobic sequencing batch reactor (AnSBR), anaerobic membrane bioreactor (AnMBR), and an up-flow anaerobic sludge blanket (UASB), are effective in the removal of pharmaceuticals [28, 29]. Membrane Incorporated Bioreactor is defined as ccombining a biological procedure with membrane filtration results in a bioreactor [30–33]. A membrane module removes microorganisms from treated wastewater while biomass is broken down inside the bioreactor tank [34, 35]. The addition of microwave (MW) irradiation to UV/H2O2 wastewater treatment results in lower activation energies, simpler operations, faster reaction times, smaller equipment footprints, and higher product yields. For instance, UV/H2 O2 system and 2.5 GHz MW irradiation enhance phenol’s oxidative breakdown. Enzymatic treatment, which draws its inspiration from biological treatment, transforms phenolic chemicals such that they are removed from water by means of a biocatalyst, or an enzyme. If the required enzyme is readily available as a commodity at a reasonable price, this technique can have considerable advantages over traditional biological and chemical therapies. In this work, removal of phenol and pharmaceutical compounds has been reported using different techniques. Percentage removal of pollutant or photodegradation efficiency will be reported based on the literature review. Each technique has its own advantages and limitations as well. However, selection of techniques strongly depends on the several factors such as efficiency, costs, simplicity, and investment. Table 1. Adsorption efficiency of graphene oxide (GO) and its derivates for the adsorption of different pharmaceutical pollutants Adsorbate

pharmaceutical

Adsorption capacity (mg/g)

Graphene oxide [15]

Trimethoprim & Isoniazid

204, 13.8

graphene oxide nanoplatelets [16]

ibuprofen

3.72

1.0-β-CD/rGO-MWCNTs-12

Naproxen [17]

132

maltodextrin/reduced graphene and maltodextrin/reduced graphene/copper oxide

Diclofenac & Amoxicillin [18]

12.836 & 526.3

AC/GO

bisphenol A & Paracetamol [19]

239.9 & 222.6

Fe3 O4 /graphene oxide/citrus peel-derived biochar-based nanocomposite

Ciprofloxacin & Sparfloxacin

283.4 & 502.37

Fe2 O4 @mSiO2 /GO

p-nitrophenol [21]

1548.78

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2 Removal of Pharmaceutical Compounds Biological Treatment of Pharmaceutical Compounds Biological treatments are one of the mature and reliable treatments for the abatement of pharmaceutical pollutants from wastewater. Compared to alternative treatment approaches, biological treatment of pharmaceutical pollutants offers several significant advantages, such as complete understanding of the insights of the process, better removal efficiency and the absence of toxic byproducts [36]. Aerobic Biological Treatment of Pharmaceutical Wastewater Aerobic biological treatment involves the employment of microorganisms (bacteria) in combination with oxygen to decompose the organic pollutants into nontoxic byproducts (carbon dioxide and methane). Activated sludge is a conventional aerobic biological wastewater treatment and has been extensively used for pharmaceutical wastewater treatment [37]. The systematic process flow diagram of activated sludge is shown in Fig. 1.

Fig. 1. The flow diagram of activated sludge for the degradation of pharmaceutical wastewater

The activated sludge is used for the biological treatment of pharmaceutical heterogeneous microbial culture comprised of bacteria, protozoa, rotifer, and fungi [38]. The bacteria in the culture decompose the pharmaceutical drugs, such as antibiotics and analgesics, into CO2 and CH4 . At the same time, the protozoa and rotifer target the freely dispersed bacteria, which upon exclusion from the reactor, may cause additional illhealth effects. The factors that make the activated sludge an ideal consideration are good removal efficiency, low-pressure drop, and generation of nontoxic waste. Several factors that affect the efficiency of the AC for the degradation of antibiotics and analgesics, include dissolved oxygen, hydraulic retention time (HRT), pH value, sludge retention time (SRT), type of pollutant, composition of AS, type of microbial culture used for the AS, and temperature (Fig. 2b and 2c) [39]. The biodegradation of pharmaceutical pollutants occurs in two ways (primary metabolic and co-metabolic mechanisms). During primary metabolic mechanism, heterotrophic microorganisms utilize pharmaceutical active compounds (PhACs) in primary metabolism, utilizing them as a carbon and energy source to support cell growth and development. The microorganism in the activated sludge directly breaks down the pharmaceutical pollutants and degrades them.

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In co-metabolism, bacteria (both heterotrophic and autotrophic) chemically change the pharmaceutical active compound (PhAC) without using it as their main source of growth. They do this while consuming a different substance as their primary energy source and growth [40]. However, there are some considerable factors that need to be considered while designing the activated sludge process in the pharmaceutical wastewater treatment [42]: (i) High capital and working cost. (ii) Need for excessive mechanization. Can only treat the high flow rate of wastewater.

Fig. 2. (a) removal efficiency of different antibiotics using activated carbon and (b and c) Effect of HRT and SBR on the removal efficiency of activated carbon [41]

Anerobic Biological Treatment of Pharmaceutical Wastewater Anerobic biological treatment, unlike aerobic biological treatment, does not need oxygen environment to decompose the pharmaceutical pollutants. Anerobic biological treatment involves different processes. This technology [43], just like aerobic biological treatment possesses some considerable advantages which are as follows: (i) Anaerobic treatment of pharmaceutical wastewater exhibits enhanced degradation efficiency. (ii) Anerobic treatment generates less waste sludge as compared to aerobic treatment. (iii) Anerobic biological treatment operates at a slow bacterial growth rate and produces less biomass as waste and, therefore, requires fewer chemicals to treat and dispose of waste sludge.

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(iv) Anerobic treatment shows better process stability and robustness when subjected to any variation in the effluent flow rate or change in pollutants concentration in the effluent stream. The degradation efficiency of anerobic biological treatment for different pharmaceutical wastewater is summarized in Table 2. Table 2. Removal efficiency of various pharmaceutical drugs using different anerobic biological treatment. Anerobic treatment type

Pharmaceutical pollutant

Removal efficiency (%)

Reference

UASB

Amoxicillin

21.6

[44]

UASB

6-Aminopenicillanic Acid

26.3

[44]

UASB

Tylosin

95

[45]

ABR

Erythromycin

40

[46]

ABR

Sulfamethaxazole

37

[46]

ABR

Amoxicillin

97.2

[47]

ABR

Etodola

99

[48]

ANSBR

etracycline

85–95

[49]

Photodegradation of Pharmaceutical Compound Using Graphene Oxide The structural, formula and molar mass of several pharmaceutical compounds have been highlighted in Table 3. Removal efficiency has been reported using graphenebased composites. These composites received great attention due to providing good visible light activity, could capture a significant portion of solar radiation. Researchers have highlighted that the limitations of conventional options could be solved easily after adding photocatalysts into graphene compounds. Therefore, the prepared graphenemodified photocatalysts successfully indicated excellent performance activity, improved pollutants adsorption process and reduced recombination of electron-holes. Both physiochemical and biological treatment of water have their own limitations, which limit their application for the successful removal of pharmaceutical pollutants from the waste effluent. Generally, adsorption process could be considered as the best technique for eliminating pharmaceutical pollutants. However, one of its highlighted drawbacks is the generation of secondary pollutants either due to the disposal of absorbent or from the regeneration/recycling of adsorbents [64]. Furthermore, biological treatment sometimes requires long treatment time and is not effective for the waste effluent containing high concentrations of pharmaceutical pollutants [65]. Alternatively, the photodegradation of pollutants could overcome the limitations of the conventional physiochemical and biological treatments as it does not produce any toxic byproduct during the degradation process and can be employed for the wastewater enriched with pharmaceutical pollutants [66]. Photodegradation of pollutant uses the semiconductive catalyst (photocatalyst) which generates hole pair when exposed to light and absorb photons from the three electromagnetic regions of light (visible, infrared, and ultraviolet) [67]. The

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Name/Structure

Formula, molar mass (g/mol)

Highlighted results

Ibuprofen

C13 H18 O2 , 206.285

• Adsorption removal rate reached 34.8% using graphene oxide membranes while, achieved 44.9% by GO-EDA (ethylenediamine as cross-linking agent) [50]

Carbamazepine

C15 H12 N2 O, 236.274

• Removal efficiency (sulfamethoxazole, ibuprofen, and carbamazepine) were higher in TiO2 -rGO (improved photocatalytic activity) if compared to TiO2 -Fe. [51] • Higher degradation efficiency could be seen in BiVO4 graphene quantum dots (improved optical properties) if compared to bare BiVO4 [52]

Sulfamethoxazole

C10 H11 N3 O3 S, 253.28

• Removal of sulfamethoxazole reached 98% (within 180 min) using rGO-WO3 (RW-200) under visible light illumination [53]

Diphenhydramine

C17 H21 NO, 255.361

• Higher adsorption capacity in GO-TiO2 (larger surface area) if compared to P25 TiO2 . [54] • The highest pseudo-first order rate constants (56 × 10−3 min−1 ) was found in GO-TiO2 (P25) composites [55]

17-α-ethinylestradiol

C20 H24 O2 , 296.41

• Higher efficiency photocatalytic degradation of 17-α-ethinylestradiol could be observed in ZnFe2 O4 -Ag/rGO (minimize agglomeration and enhance charge carrier generation and separation) if compared to ZnFe2 O4 alone and ZnFe2 O4 -Ag [56]

Sulfamethazine

C12 H14 N4 O2 S, 278.33

• High degradation efficiency of 99% could be seen in Fe3 O4 /Mn3 O4 -rGO nanocomposite under optimized conditions [57] (continued)

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Table 3. (continued)

Name/Structure

Formula, molar mass (g/mol)

Highlighted results

Tetracycline

C22 H24 N2 O8 , 444.44

• Bi3.84 W0.16 O6.24 -graphene oxide has been prepared [58] through inorganic salts-assisted hydrothermal method. The composite gives additional active sites (pollutant adsorption) and facilitates charge separation • Highly active degradation of tetracycline using rGO-CdS/ZnS composites (15% RGO) because of facilitates the transformation of electrons [59]

Ciprofloxacin

C17 H18 FN3 O3 , 331.347

• Graphene oxide magnetite was synthesized [60]. The composite showed excellent efficiency values than bare Fe3 O4 • The degradation rate was 98.3% (in 4 h) and maintained for 80% after 10 cycles using Fe3 O4 @Bi2 O3 -rGO photocatalysts [61] • Excellent ciprofloxacin hydrochloride degradation performance in ZnO-GO nano composite (pH was 6) [62] and could be reused without significant loss of efficacy

Chloramphenicol

C11 H12 Cl2 N2 O5 , 323.13

• Excellent chloramphenicol degradation performance of Ce(MoO4 )2 /GO could be seen in the presence of visible light irradiation [63]

absorption of photons produces photo-induced electron and hole pairs which when react with oxygen and water molecules yield reactive oxygen species [68]. The efficiency of the photocatalysis to degrade the pollutant can be enhanced by incorporating the suitable adsorbent in the photocatalyst [69]. Adsorption facilitates the degradation of the pharmaceutical pollutants process by increasing the probability of interaction between photoexcited charges generated by the photocatalyst and the adsorbed pollutant [70]. Graphene oxide (GO), being a carbon-based material, showed high surface area, high chemical and thermal stability, ease of functionalization, hydrophobicity which makes it an ideal absorbent. GO is also considered as the favorable material in photocatalysis. The

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following are the characteristics of GO that make it a desirable choice for the adsorption process [71]. Electron transport: GO in its pristine form, is an insulator and does not contribute to dissipating the electrons and photoexcited charges to the adsorbed sites to degrade the pollutant [72]. However, the electrical properties of the GO can be enhanced up to several times by the chemical and thermal treatment of GO]. The GO with superior electrical conductivity assists in transporting the electrons and photoexcited charges to the target locations and thus enhances the photocatalytic reaction and the performance of the process. Functionalization of photocatalyst: Graphene oxide acts as the surface modifier when deposited on the catalyst surface. This surface modification could enhance the surface properties of the catalyst (zeta potential and surface area), resulting in better interaction between the pollutant and photoexcited charges [73]. Photostability enhancer: The surface modification of the photocatalyst with GO provides chemical stability to the catalyst. GO shields the catalyst from the adverse effect of chemicals in the wastewater [74]. The harnessing of GO in the photocatalysis can enhance the reaction’s overall performance and thus increase the pollutant’s degradation [75]. The photocatalytic degradation of different pharmaceutical pollutants using graphene oxide has been summarized (Table 4). Table 4. Degradation efficiency of different pharmaceutical pollutants using GO based photocatalyst. GO composite

Pollutant

Degradation Efficiency (%)

ZnSnO3 /RGO

Metronidazole [76]

72.5

Fe3 O4 /rGO/TiO2

Metronidazole [77]

98

ZnONP

Levofloxacin [78]

99.2

cobalt ferrite/reduced graphene oxide

Oxytetracycline [79]

84.7

Graphene oxide decorated ZnWO4

Cetirizine hydrochloride [80]

89

pectin-graphene oxide-magnesium ferritezinc oxide nanocomposite

Diclofenac [81]

38.7

CoFe2 O4 nanoparticles decorated onto graphene oxide

Bisphenol-A [82]

62

BiVO4 /reduced graphene oxide

Tetracycline [83]

99

rGO/GNW hydrogel

Ethenzamide [84]

99

GO@Fe3 O4 /ZnO/SnO2 nanocomposites

Azithromycin [85]

90

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3 Conclusions Several treatment technologies (traditional method and advanced technique) have been used to remove the pharmaceutical compounds. Adsorption process could be considered as the most popular method. Because of several advantages include high efficiency, simple method, less toxic by-product could be formed, and very low maintenance cost is required. The mechanism of the photo-degradation process using graphene oxide as a photocatalyst involves a series of complex interactions between graphene oxide, light, and the target pollutant (pharmaceutical compounds). Graphene oxide is a 2-dimensional carbon material, exhibits excellent photocatalytic properties due to its unique electronic structure and large surface area. When graphene oxide is irradiated with light, typically ultraviolet or visible light, electron-hole pairs are generated through photoexcitation. These photoexcited electrons and holes play a crucial role in initiating redox reactions with the adsorbed organic pollutant, leading to its degradation. The obtained experimental findings confirmed that the photodegradation of pharmaceutical compounds using graphene oxide has been extensively studied, and the results have shown promising outcomes under various operating conditions. In addition, removal of pharmaceutical compounds has been carried out by other techniques as well.

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On Hidden Reason for Fractals from Water Vijayakumar Mathaiyan1

, Vijayanandh Raja2 , Beena Stanislaus Arputharaj3 and Dong Won Jung4(B)

,

1 Accenture, Bangalore 560103, India 2 Kumaraguru College of Technology, Coimbatore 641006, India 3 Saveetha School of Engineering, SIMATS, Chennai 602105, India 4 Jeju National University, Jeju-si 63243, South Korea

[email protected]

Abstract. Fractals in nature follows the Fibonacci series and shows angular rotation mostly in anticlockwise direction. The recent study suggests that fluids especially water stores its molecules in a series. The chirality of water molecules can allow vortex generation only in counter clockwise direction. If both these properties are combined, any viscoelastic materials like elastomers added in water and undergoes the forced vortex will turn these materials to fractals. The article is a detailed discussion about fractals from water. Keywords: Fractals · Fibonacci Series · Chirality of molecules

1 Introduction Fractals in nature is always intrigued physicist all around world. The fractals elements are giving fractals in macro level. These elements are usually not available as fractals in its nature state but in mixture with other elements inside living organism. Water is the major content in all living organism, the changes of any sort inside it should be its effect. If the hidden property of water is known, then the mystery behind fractals will be solved. Though there is numerous research and theories are there to describe this phenomenon, authors believe that this article explains it much better than existing theories.

2 Literature Review Bantawa et al. (2023) mentioned that there is a hidden fractal elements in viscoelastic fluids. When the droplet at almost zero velocity is allowed to impact the surface of liquid bath and allowed to coalescence in the liquid bath. The droplet coalescence takes place in 5 stages with gradual size reduction. In nature, it is noted that Fibonacci series are seen mostly in masses. The droplet masses in all stages of coalescence followed a Fibonacci series. Now, if we consider the fluid bath, it actually storing the water molecules from droplet in the series. Since the water molecules are added and removed only in series, the water can be considered as well structured. The reason for the presence of Fibonacci © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 125–131, 2024. https://doi.org/10.1007/978-981-97-1594-7_14

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series in water molecules is because of the golden ratio in hydrogen bonding. The growth direction and the Fibonacci series creates fractals in plants (Mathaiyan 2023, 2023a). Since the atomic masses of all elements in periodic table follows Fibonacci Series, the authors believe that almost everything in nature follows Golden ratio or Fibonacci Series. Even quark, an elementary particle in atom, follows the series. This may be a rule for existence in universe and might be a property of any known or unknown force which governs everything. The chirality of molecules combined with this Fibonacci series results in fractals.

3 Hidden Property of Water As previous mention, water is the major content in all living organism. Keshavarz et al., (2022) showed that curing elastomer poured and stirred in glycerine liquid bath resulted in Mandelbrot granular raft and Cheerios effect arranges them in order. From observation, the bubbles from water are also showing similar effects and discussed in appendix section. Let us consider the elastomer is added in water and a forced vortex is generated. According to the literature review, the water stores molecule in golden ratio or Fibonacci series. The surface tension can be considered as force per unit length acting on an imaginary line on surface of water. Surface tension usage is not limited to the surface of fluid but also under the surface. If we combine the theory of golden ratio and concept of surface tension, then we can draw the imaginary lines (surface tension) in Fibonacci series.

Fig. 1. Shows (a) schematic representation of water stored in container with imaginary lines drawn in it with markings and measurements and (b) schematic representation of droplet with imaginary lines marked in it. Note that the lines are just depiction and not scalable or countable.

The Fig. 1 shows the schematic representation of water stored in container, and droplet with the imaginary lines of surface tension. In Fig. 1a, the imaginary lines of surface tension are drawn with markings o, a, b, etc., and the respective length from bottom of the containers are l1, l2, etc. The lengths are assumed to follow golden ratio based on Fig. 1b. The presence of Fibonacci series in droplet is well proven and depicted with imaginary lines as shown in Fig. 1b. Since the water is static in a container, the

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pressure and kinetic energy can be neglected. The only energy acting on the water molecules on each layer is the potential energy. Let E be the total energy acting on the system and E 1 , E 2, etc., be the energy due to the molecules stored between imaginary line o to a, a to b, and so on. According to the conservation of energy, the total energy acting on system should be equal to energy acting in each section divided with imaginary lines. E ≈ E1 + E2 + . . .

(1)

If we substitute the potential energy term and cancel the common terms on both sides, then we can rewrite Eq. (1) as follows. h ≈ l1 + l 2 + . . .

(2)

where h is the total height measured from bottom to top surface of liquid. Since we have assumed that the length follows golden ratio, then the Eq. (2) can be rewritten as follows.   h ≈ l1 1 + 1.618 + 1.6182 + 1.6183 . . . + 1.618n (3) where n is the total number of Fibonacci series following imaginary lines in the fluid stored in any form. Since the right-hand side of the above equation follows geometric progression, we can simplify the Eq. (3) as follows.   1.618n − 1 h ≈ l1 (4) 0.618 It is noted that the foreign molecules passing through these imaginary layers will be impacted in a series. From Marangoni effects, the concentric circles are formed on surface of fluid when it is in contact with other fluids. Surface tension change on surface of fluids is usually seen as concentric circles. This suggest that the imaginary lines not necessarily found in vertical direction but also in horizontal direction. In the horizontal direction, these imaginary lines will be concentric to each other. If we visualize these horizontal lines with the previously mentioned imaginary lines as in Fig. 1a, then we can depict these lines as shown in Fig. 2.

Fig. 2. Shows the depiction of imaginary lines in horizontal direction. These lines may be seen in similar pattern for the lines in vertical direction. Note that all these lines should be following the golden ratio. Images are just depiction and not to be scaled or counted.

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The exact length of these imaginary lines following the series are not clear, but bubble movement in water can be used to guess these lines. Moreto et al., (2022) shows the variation of centroid vertical velocity in vertical direction. The results show that there is a sharp change in velocity at 1mm, ~3 mm, ~5 mm, ~8 mm, ~15 mm, and ~20 mm vertical distance from bottom of the container. Though the changes are not completely following Fibonacci series, it is a considerable match. The hidden property of water suggests that the energy distribution to the entire system will happen in a series. If energy damping in the droplet has to be simplified, then we can depict the arrangement of droplet masses as shown in Fig. 3. The energy transfer between masses inside the droplet can be devised as a system with spring and damper. If the understanding about the imaginary lines is clear, the prediction of bubble movement and its change in physical properties like wobbling motion will be easy.

Fig. 3. Shows spring and damper system in the position of imaginary lines in droplets as in Fig. 1b.

4 Fractals from Water The results from water droplet coalescence shows that there Fibonacci series is followed in adding or removing the water molecules. The detailed theory about the arrangement is explained under the Sect. 3. When the elastomer is poured in the container of water, it should have impacted by the hidden property of water. Though there is an impact, the energy applied onto the material is considerably low and the changes are negligible. Let us consider that there is no elastomer inside the water but undergoes the induced vortex. From observation, the chirality of water molecules allows it to create vortex only in counter clockwise direction. For forced vortex, the tangential velocity is directly proportional to the radius. The velocities in cylindrical coordinate system are a function of angle. It is also well known that Fibonacci series can be seen in vortex formation of water. When the water with elastomer is under forced vortex, the materials disintegrate and passes through water molecules. These molecules are arranged in a Fibonacci series,

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therefore the impact on the elastomer will also be in a series. Vortex makes the molecules of elastomer to add its molecules only in a sequence in counter clockwise direction. This in turn can makes fractals of elastomers from water. From the above discussion, it is understood that any viscoelastic material under forced vortex in the water molecules can result in fractals. The same phenomena happen in the plants and animals. The viscoelastic material forms the structure of living organism but when the water passes through it, these materials are turning into fractals. The chirality of viscoelastic molecules is giving the growth direction to its host which is heavily influenced by chirality of water molecules. Whenever the fractals are programmed, the algorithm usually contains the angle at which the turn should takes place. These angles of turn in plants are 90° and the leaf formation always happens at regular intervals with the 90° phase change. Mathaiyan et al. (2022) mentioned that leaves form more in top following the fountain model. The water fountain is streamlined at the bottom than in top. Similarly, the fluid flowing inside the plants are streamlined in the bottom and varies in top. Since the variation in fluid flow is maximum at tip, the leaf generation in top of the plants are considerably high. The author called it as Water Fountain Phenomenon. The shape of leaves and fruits follows fluid physics [4, 7, 8]. In Coccinia grandis, the edges of the plants are seen to be coiled around. If we assume that the flow in the coil is because of vortex flow, then the velocity is known as a function of radius. The considerable change in radius or velocity is happening at regular angle of interval. Any high deviation of the energy may be resulting in formation of leaves. Only sine or cosine curve shows extrema at right angles, the leaf‘s formation should be influenced by these trigonometric functions. The reader can imagine plant as a fluid containing system that produces leaves when it fails to control the fluid or at places where energy is considerable high and directed outwards from the stem. Detailed research on the formation of leaf will be published elsewhere.

5 Conclusion In this article, author showed that the arrangement of molecules in a Fibonacci series and chirality of molecules can wither to fractal formation. The hidden property of water and its effects can make any viscoelastic material into fractals. The author believes that the same phenomenon is responsible for fractals in plants and animals. Periodic table follows Fibonacci series, so almost all materials should follow the same. Solar system shows the same series in the distance between planets from Sun. This suggests that there might be a force with follows the series in universe and reflecting it in all of its matter. It is noted that even the elementary form of atom called quark is following the same series. Gravitational Force is weak force and its influence on strong forces like interatomic forces may be negligible. The detailed research on the forces which can give Fibonacci series to the masses will be discussed elsewhere. Acknowledgement. Author would like to thank Accenture, Bangalore for supporting this research. Special thanks to Srikumar Manda, Deepti Bhutani, Ayan Chakraborty, and Dharanisha Siddalingaiah for all the mentoring and support. Vijayakumar Mathaiyan takes all findings and ideation in this work.

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Funding. This research was funded by the Brain Pool program of the Ministry of Science and by ICT through the National Research Foundation of Korea (RS-2023-00218940).

Appendix When water jet is allowed to impact the bath, bubbles formation on the surface of bath is visualized. The motion of these bubbles is in anticlockwise direction and follows a series. As discussed throughout the article, the anticlockwise direction of bubbles is due to the chirality of water molecules. Figure 4 (a) shows the depiction of liquid jet impacting the surface and Fig. 4 (b) shows top view of the container in which the bubble movement is depicted.

Fig. 4. Shows (a) depiction of liquid jet impacting the container, and (b) top view in which bubble motion is in counter clockwise direction.

References 1. Bantawa, M., et al.: The hidden hierarchical nature of soft particulate gels. Nat. Phys. 19, 1178–1184 (2023) 2. Moreto, J., et al.: Free rising bubble in quiescent water. In: 75th Annual Meeting of the APS Division of Fluid Dynamics, Gallery of Fluid Motion. American Physical Society (2022). https://doi.org/10.1103/APS.DFD.2022.GFM.V0098 3. Keshavarz, B., Geri, M.: A Mandelbrot granular raft. In: 75th Annual Meeting of the APS Division of Fluid Dynamics, Gallery of Fluid Motion. American Physical Society (2022). https://doi.org/10.1103/APS.DFD.2022.GFM.V0115 4. Mathaiyan, V.: Fluid leaves: effects of fluid flow on leaf shapes and Fibonacci series. Int. J. Fluid Mech. Res. 50(5), 33–50 (2023). https://doi.org/10.1615/InterJFluidMechRes.202304 9415 5. Mathaiyan, V., et al.: Coalescence property of droplet in liquid bath. In: AIAA Aviation Forum, CA, 2023, pp. 1–18. AIAA Conference Publications (2023) 6. Mathaiyan, V., Vijayanandh, R., Srinivasamoorthy, S., Kumar, T.R., Sivalingam, S., Jung, D.W.: Theory of shape for living and non-living things–based on thin fluid flows in Hele-Shaw cell. In: Tadepalli, T., Narayanamurthy, V. (eds.) Recent Advances in Applied Mechanics. LNME, pp. 337–352. Springer, Singapore (2022). https://doi.org/10.1007/978-981-16-9539-1_24

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7. Mathaiyan, V., et al.: Parametric study of interaction behavior of laminar jets. In: AIAA Scitech 2022 Forum, San Diego, CA, pp. 1–14 (2022) 8. Mathaiyan, V., Srinivasamoorthy, S., Vijayanandh, R., Won, J.D.: Shape of a leaf or liquid leaf. In: 75th Annual Meeting of the APS Division of Fluid Dynamics, Gallery of Fluid Motion (2022)

Residual Stresses Characterization in Friction Stir Welding of 2017 A-T451 Alloy Using Eddy Current Control Sari Elkahina1(B) , Benachenhou Kamel1 , Bennoud Salim1 , Kirad Abdelkader2 , Boucherou Nacer3 , and Mimouni Oussam4 1 Aeronautics and Space Studies, Energetic Process and Nanotechnology Laboratory, Blida I

University, Blida, Algeria [email protected] 2 Mechanical Engineering Department, Energetic Process and Nanotechnology Laboratory, Blida I, Blida, Algeria 3 Scientific and Technical Research Center in Industrial Technology (CRTI), Chéraga, Algeria [email protected] 4 Research and Development Center of Aeronautical Mechanics, Dar El Beida, Algeria Abstract. This work involves identifying residual stresses in friction stir welding (FSW) soldered aeronautical structures using nondestructive testing. The used alloy is 2017 A-T451, which is used for welding aircraft structures that are difficult to weld using conventional fusion techniques. The solid-state nature of the sintering process allows for the elimination of defects associated with solidification and the absence of any material addition, but the process also involves phenomena as diverse as the microstructural modification of smelted materials, heat transfer, and the emergence of residual stresses. These residual stresses are capable of altering the material’s initial structure and mechanical properties. And to reduce the probability of failure, preventive maintenance is required to determine the level of allowable stress for the operational structure. Eddy current’s method of control was utilized in this work to determine these stresses. Keywords: FSW · aluminum alloy · 2017 A-T451 · residual stresses · eddy current · NDT

Nomenclature  B:  J: : H  E: ρ:  D: Z: R: L: σ: μ:

Magnetic field density (T) Current density (A/m2 ) Magnetic field (H/m) Electric field (A/m) Charge volume density (C/m3 ) Electrical density flow (C/m2 ) Impedance () Resistance () Reactance (H) Electrical conductivity (m)(-1) Magnetic permeability (F/m)

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 132–143, 2024. https://doi.org/10.1007/978-981-97-1594-7_15

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1 Introduction Aluminum alloys with structural hardening are utilized in the assembly of air transportation structures. In contrast, this type of alloy is difficult to weld using conventional methods, and the most common method of assembly is riveting, which presents numerous disadvantages in addition to mass and an uneven joint between the two tubes. In the first place, riveting involves high concentrations of non-negligible stresses, which are obviously detrimental to the mechanical integrity of assemblies and are especially responsible for the formation of fatigue cracks. The second issue relates to the poor corrosion resistance of riveted structures. Finally, riveting is difficult to automate and therefore expensive. The replacement of rivets with soldering is an option. The study of welding processes appears to be both a straightforward and difficult field of research, as it requires the integration of knowledge from different branches of physics and mechanics. The vast majority of processes involve such diverse phenomena as microstructural changes in molten materials, heat transfer, the emergence of residual stresses, etc. The conventional fusion welding of aluminum alloys presents a challenge due to their inherent properties: high hydrogen solubility, a tenacious oxide layer that must be eliminated to prevent contamination of the joint, high thermal conductivity that requires high welding energy, and a high thermal expansion coefficient that causes distortion. The thermal conductivity, deformation of the joint, and length of the solidification interval render welded joints susceptible to hot cracking. Structural-strengthening alloys present additional challenges due to the presence of additional elements. The series 6000 alloys are difficult to weld, while the series 2000 and 7000 alloys are practically not-weldable. The presence of copper and magnesium, essential elements for improving the mechanical properties of these alloys, increases their susceptibility to fissuring after forging. Friction Stir welding is a new assembly method introduced in 1991, and it is considered the greatest innovation in the field of welding. The novelty of this process lies in the fact that the base materials to be melted are never melted during the melting process. This eliminates defects related to solidification and results in weaker internal stresses compared to conventional casting. Obviously, this has allowed many technological doors to be opened. It is then possible to assemble “difficult-to-weld” alloys, such as aluminum alloys from the 2000 and 7000 series, which are regarded as not-weldable using conventional fusion techniques. The benefits of FSW sowing are readily apparent: it’s a cost-effective process with significant advantages. However, this is a relatively new procedure that must be mastered. This method does not require any input metal, consumes less energy than fusionwelding processes, and does not require any shielding gas. Compared to fusion-welding processes, it is considered more environmentally friendly. The analysis and characterization of welded joints is also part of our research; we can distinguish multiple zones within the weld. The available scientific literature indicates that FSW can produce joints with superior fatigue performance compared to riveted joints. However, residual stress-induced deformations, the loss of hardness in the thermally affected zone, process control, the cost of equipment and dies, and the lack of data on fatigue life are the primary factors limiting the use of this process at the moment.

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Residual constraints can alter the fundamental structure and mechanical properties of a material. Their presence within this entity can have both positive and negative effects. In fact, it is generally observed that residual compression constraints have a beneficial effect on the durability of a piece because they prevent the formation of cracks. In contrast, residual tension stresses promote the development of cracks. Therefore, it is necessary to determine residual constraints as precisely as possible [1]. Traditional techniques for measuring residual constraints can be divided into two categories: destructive and nondestructive techniques. Eddy current’s method is one of the non-destructive methods with which we are concerned in our research. The determination of residual stresses with eddy current is based on the interpretation of the variation of impedance across the four zones of the suction cord. The objective of our work is to find a relationship between the residual stresses of a joint welded by FSW and the impedance by comparing the shape of the impedance curve with the residual stresses curve obtained by the ultrasonic method.

2 Theory Study 2.1 FSW Process Friction Stir welding is a relatively new technique; it is still the subject of active research in order to gain a better understanding of certain aspects, such as material flow, tool shape, and microstructure simulation. This method is suitable for a variety of materials, including steel, titanium, and copper, and especially for structurally hardened (series 2000, 6000, and 7000) aluminum alloys that are difficult to weld using conventional methods. Its operating principle is to tightly compress the two parts to be welded. Then, the tool, which is primarily composed of a shoulder and a rotating axis (spinning pedal rotating at 400 to 1400 tr/min), penetrates the substance. Putting the pawn on the piece causes the temperature at the contact to rise, which causes the material to roll up. This

Fig. 1. Friction Stir Welding (FSW) Process.

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makes it possible to transfer the pion to the interface between the parts to be assembled, and the tool moves along the assembly point at a speed of approximately 30 to 1,000 mm/min [2], as shown in Fig. 1. As shown in Fig. 2, the friction welding method creates joints that are different from each other by having four clear zones: • Zone A: It’s far from the welded area, so welding doesn’t change the base metal at this level. This means that the metal’s mechanical properties and nanostructures stay the same during welding. • Zone B is the ZAT area that is thermally affected. This is where the material changes as the temperature rises (from 150 to 350 °C), affecting its mechanical properties and even its microstructure, but it doesn’t seem to deform. • Zone C is the area that is thermo mechanically damaged (from 350 to more than 500 °C). This time, the metal deforms more plastically than the area that is thermally affected because the tool is moving. The mechanical properties and microstructure are changed not only by the heat effect but also by mechanical effects on the metal’s plastic deformations. • Zone D: The mechanical properties and microstructure of zone D and the area of the welded core are affected by both thermal (about 500 °C) and mechanical forces, but more so than in the area that is only affected by thermal forces.

Fig. 2. Macro graphic section of AA7020 welding cored split into four separate zones [3].

2.2 Eddy Current’s Electromagnetic Modeling The distribution of magnetic fields and induced currents in a conductive material is governed by the fundamental laws of electromagnetism. These include the links between magnetic and electric phenomena [4]. The Maxwell equation in dynamic mode is given by: (1)  =0 ∇.B

(Magnetic flow conservation law)

(2)

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 =− ∇ ×E

 ∂B ∂t

 =ρ ∇.D

(Faraday law) (Gauss Theorem)

(3) (4)

The impedance equation is done by: Z = R + jωL

(5)

Electromagnetic energy of system (probe-piece) is equal to dissipated energy by Joule effect: ˚ J PJ = dV (6) v σ and PJ = RI 2

(7)

As the same that stored energy can be deduced the system inductance: 1 X = 2

˚ v

B2 dV μ

(8)

and X =

1 2 LI 2

(9)

3 Experimental Study 3.1 Description of the FSW Process The welding process is used to put together two plates of aluminum alloy 2017 A-T451 with 100 mm width, 200 mm length, and 6 mm thick. They are put together on a standard PMER VST300 shear, which is shown in Fig. 3. The two plates were welded at maximum speeds of 1500 rpm for rotation and 900 mm/min for forward. The tool is made of AISI-H11 steel (tool steel AFNOR-Z38CDV5.1), which has a higher melting point and hardness than the 2017 A-T451 alloy used for the plates. The chemical composition of it is shown in Table 1 below: The tool’s geometry was designed so that air can flow well around it and keep it cool. In Table 2, you can see the parameters of the joint that were used to make the welded joint: A welded joint is made up of different zones, as presented by Fig. 4, with strong metallurgical evolution: • For the base metal, the original mechanical and metallurgical parameters are retained.

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Fig. 3. Conventional milling machine PMER VST300.

Table 1. The chemical composition of the tool AISI-H11. Elements

C

Si

Mn

P

S

Cr

V

Mo

Weight %

0.3. 0,3–0.0.0,45

0,8–1,25

0,2–0,6

0,03

0,03

4,75–5,5

0,3–0,6

1,1–1,6

Table 2. Welding parameters. Rotational speed (tr/min)

Forward speed (mm/min)

Inclination angle (°)

1250

36

2

Fig. 4. Welded joint with different zones of eddy current control.

• Concerning thermally affected zone (ZAT), we notice a structural evolution such as the grains coarsening. • For the thermo mechanically-affected zone (ZATM), the grains are deformed according to the tool movement. • For the zone of the core (N) there are plastic deformation and high level of heat which make it possible to trigger the phenomena of grains crystallization and obtain the grains with very small size from 20 μm to a few microns.

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These situations are presented by Fig. 5.

a

b

c Fig. 5. Optics micrographic with enlargement (50X) of different zone of FSW: a) ZAT ; b) N ; c) MB

3.2 Description of Eddy Current Control and Measuring Device In order to check the piece that was charged by eddy current, an Agilent 4284A-LCR meter with a frequency range of 20 Hz to 1 MHz was used (see Fig. 6). The achievement of the probe is done in our lab. It is made of ferrite and has 100 spikes with a 0.2 mm diameter, shaped like a cylinder and measuring 6.5 mm in diameter (see Fig. 7). The assembly of this control is given in Fig. 8 below:

Residual Stresses Characterization in Friction Stir Welding of 2017 A-T451 Alloy

Fig. 6. Impédence metre type Agilent 4284A.

Fig. 7. Eddy current probe.

Fig. 8. The measuring device of eddy current control.

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4 Results and Discussions To find a relationship between the residual stresses and the impedance, first we prepare the simples of 2017 A-T451 Alloy without any defects, and then we create the thermal residual stresses by quenching them in liquid nitrogen. The results of eddy control current are given by the Table 3. Table 3. Relationship between impedance and residual stresses. R()

L(H)

Z()

Plate without residual stresses

19.005

0.0117

41.681

Plate with thermal residual stresses

19.477

0.01207

42.637

The results of the Table 3 show the presence of residual stresses increase the impedance. The results of eddy current control for different areas of the welded plate by FSW can be seen in Fig. 9 and Fig. 10:

Fig. 9. Impedance diagram for the four FSW welding zones.

Analyzing the impedance diagrams of the various zones on the solid surface reveals that:

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Fig. 10. Superposition of impedance diagram for the four FSW welding zones.

• All of the impedance curves for the different zones have the same shape of the impedance curve; • The superposition of the curves shows a variation in the electromagnetic parameters due to the presence of residual stresses. The following Fig. 11 and Fig. 12 show the results of impedance profiling for several FSW welding zones at various frequencies:

Fig. 11. Normalized impedance profile for various FSW zones at 500 Hz.

Analyzing the results of Fig. 11 and Fig. 12, we might conclude: • The normalized impedance profile has the shape of a ‘M’. • The normalized impedance increases with frequency. • A reduction in impedance at the zone N level is due to the presence of minor residual stresses due to the high and persistent temperature in this zone. This zone undergoes dynamic recrystallization as a result of the combined effort of metal flow and thermal cycling, resulting in grain refinement and the softening of stresses.

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Fig. 12. Normalized impedance profile for various FSW zones at various frequencies.

• Because of the presence of the most residual stresses, the largest impedance is found at the level of the zone affected thermo mechanically (ZATM) (at the tool’s extremities). These constraints are caused by the friction heat between the shoulder and the matter, which is insufficient to activate the dynamic recrystallization mechanism. Then the residual stresses decrease and converge to zero when the welded cord is moved away from the base metal, which has not undergone any thermal, mechanical, or chemical changes. • The obtained results are consistent with residual stress profiles determined by other methods published in the literature [5–7]. • The eddy current control is extremely sensitive to micro-variations of subsurface residual stresses which are the origin of Bloch domain. These last are the transition zone between Weiss domain that generate a change of the magnetic moment [8].

5 Conclusion The FSW is a solid-state bonding process that offers significant economic and financial benefits. This method requires no metal input, uses less energy, and does not require any protective gas. It is seen as more environmentally friendly than fusion-based processes. The characterization of residual stresses caused by the FSW process in an aluminum alloy structure was carried out experimentally using eddy current non-destructive control. The results show that the profile of impedance is symmetric with respect to the center of the suture cord and has the same shape of M as residual stresses determined by other methods published in the literature. The maximum impedance is found at the level of the ZATM zone, which corresponds to the maximum of residual stresses. These latter are caused by friction heat between the element and the matter. The minimum is found at the level of zone N, which synchronizes with a low residual stresses since the temperature in this zone, is quite high, causing weakening of residual stresses. As a result of this work, we can say that eddy current control is extremely sensitive to micro-variations caused by the generation of residual stresses.

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References 1. Lohwasser, D., Chen, Z.: Friction stir welding: from basics applications (2010) 2. Mishra, R.S., Ma, Z.Y.: Friction stir welding and processing. Mater. Sci. Eng. R Rep. 50(1–2), 1–78 (2005) 3. Liechty, B.C., Webb, B.W.: The use of plasticine as an analog to explore material flow in friction stir welding. J. Mater. Process. Technol. 184(1–3), 240–250 (2007) 4. Lorrain, P., Corson, D.P., Lorrain, F.: Electromagnetic Field and Waves. W.H. Freeman and Co., New York (1988) 5. Dattoma, V., De Giorgi, M., Nobile, R.: On the residual stress field in the aluminium alloy FSW joints strain 45(4), 380–386 (2007) 6. Nandan, R., DebRoy, T., Bhadeshia, H.K.D.H.: Recent advances in friction-stir welding–process, weldment structure and properties. Progress Mater. Sci. 53(6), 980–1023 (2007) 7. Lemos, G.V.B., Farina, A.B., Nunes, R.M.: Residual stress characterization in friction stir welds of alloy 625. J. Mater. Res. Technol. 8(3), 2528–2537 (2019) 8. El-Kahina, S., Kamel, B.: Stress influence to Eddy current control of cracked aeronautical material. J. Meas. Eng. 9(4), 231–240 (2021)

Development of an Experimental Methodology to Investigate the Occurrence of the Tribocorrosion Phenomenon in Metallic Materials Gerardo A. Rodriguez-Bravo1 , Manuel Vite-Torres1(B) , Ezequiel A. Gallardo-Hernández1 , and César Sedano-de la Rosa2 1 Instituto Politécnico Nacional-ESIMEZ, Mexico City, Mexico

[email protected] 2 Universidad de Guadalajara, CUCEI, Campus Autlán, Autlán de Navarro, Jal., Mexico

Abstract. Tribocorrosion is a multidisciplinary research field whose importance has been increasing along with technological advances. Basic aspects, concepts, and terminology used in the tribocorrosion research are presented in this work. First, the historical context is explained briefly; followed by the concept of tribocorrosion and synergy. These concepts are then schematically represented. After that the proceedings to calculate the synergy of the process are shown, to continue with an analysis of the content from the main international standards used in tribocor-rosion research along with a description of the most used tribological and electro-chemical techniques. Likewise, a brief introduction of materials of interest used in the study of the tribocorrosion phenomenon is presented. The purpose of this work is to present an overview of some of the most used techniques to understand and analyze tribocorrosion and the problems that generates, as well as its important contributions to mechanical engineering, materials science, and medicine, among others. Keywords: Tribocorrosion · system · abrasion-corrosion · erosion-corrosion · techniques · standards

1 Introduction Although the first scientific approaches relating surface properties of materials and chemical-electrochemical interactions with the medium surrounding it belongs to the mid-XIX century, with Thomas Edison observations about friction coefficient changes due to electric potential application [1, 2]; it was not until the last two decades of XX century when this phenomenon began to catch the attention of more specialists and turn into a formal research area, mainly by the need to develop mechanical components for increasingly complex systems and more extreme work conditions [3, 4]. Tribocorrosion starts then to be short defined as a permanent change in materials due to the joint action

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 144–150, 2024. https://doi.org/10.1007/978-981-97-1594-7_16

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of mechanical wear and corrosion; and can be represented as it is shown in Eq. (1) [5]. Tribocorrosion = (Mechanical wear)+ (Chemical and Electrochemical degradation) + (Synergic effect)

(1)

The effect of tribocorrosion normally is higher (synergistic interaction) or lower (antagonistic interaction) than just the sum of wear and corrosion individually; this change depends on the elements involved in the tribocorrosion system [6]. Main studies of tribocorrosion focus on evaluating metallic alloys and coatings used in components for industries like Biomedical, marine, chemical, hydrocarbon, aerospace, and food; being biomedical applications the most studied field of tribocorrosion by far [7]. The importance of tribocorrosion in studies for medical and biological applications has resulted in a new sub-research field called Biotribocorrosion. In addition to the basic knowledge of tribology and corrosion science, necessary to carry out a tribocorrosion study, there are some other aspects to consider, like the tribocorrosion system characteristics, commonly used materials, techniques to evaluate it, and applicable standards. In the following sections, these aspects are described.

2 Tribocorrosion System J. Peter defines a tribosystem as “any system that contains one or more tribo-elements, including all mechanical, chemical, and environmental factors relevant to tribological behavior”. Being the triboelements “one of two or more solid bodies comprising a sliding, rolling, or abrasive contact, or a body subjected to impingement or cavitation, i.e., each triboelement contains one or more tribosurfaces [8]. The tribological approach of a system tends to propose the environment or medium just as a friction modifying factor; giving bigger importance to the physic-mechanic characteristics of the elements like geometry, surface topography, kind of movement, kinematics, loads, etc. In addition, a tribocorrosion system also considers the chemical and electrochemical properties of the elements, making it more complex but allowing to evaluate the material’s interactions with the medium. According to S. Mischler, tribocorrosion systems are affected by four main factors: Mechanical (load, kinematics, geometry, vibrations.), physic-chemical (viscosity, conductivity, pH, oxidants, agents, ions, species, temperature), Material (hardness, elasticity, microstructure, roughness, surface properties, debris transfer, etc.) and electrochemical (potential, ohmic resistance, passivation, active dissolution, oxidation valence, etc.) [7]. The representation of a tribocorrosion system can be observed in Fig. 1.

3 Synergy Synergy is the effect caused by the wear-corrosion interaction. It can generate an increase or decrease in the wear or corrosion rates depending on the tribocorrosion system conditions. Synergy of process is a phenomenon not yet completely understood, but it can be measured and quantified. If the total tribocorrosion effect (T) is expressed as loss of mass, Eq. (1) can be reformulated in those terms as shown in Eq. (2). T = W0 + C0 + S

(2)

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Fig. 1. Schematic representation of a Tribocorrosion system (abrasion-corrosion).

W0 is the loss of mass due to wear in the absence of corrosion, C0 is the loss of mass due to corrosion in the absence of wear and S is the synergy of the processes. S can be split as the sum of changes due to interactions as shown in Eq. (3). T = W0 + C0 + Cw + Wc

(3)

Cw is the change in corrosion rate due to wear, and Wc represents the change in the wear rate due to corrosion. The total wear component (Wc ), and the total Corrosion component (Cw ) of T can be expressed as shown in Eqs. (4) and (5). Wc = W0 + Wc

(4)

Cw = C0 + Cc

(5)

Synergy can be used to make a tribocorrosion map and regime classification as it is indicated in the corresponding standard [9].

4 Standards There are two main standards for tribocorrosion phenomenon evaluation: the American ASTM G119 [9] and the European UNE 112086 [10]. ASTM G119 is a guide to calculate the synergy of the process using data obtained from wear and corrosion tests combined but does not specify how such tests must be performed. On the other hand, the European UNE112086 was created in 2016 to normalize the procedures but it still takes into consideration the way to perform the tests depending on the material or system to analyze. It is due to this lack of a normalized universal tribocorrosion test that is necessary to be related to the wear and corrosion standards individually i.e. the ASTM G3, G5, G15, G59, and G102 that are related to electrochemical tests to measure corrosion or the G40 that is about the terminology used in wear and erosion.

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5 Techniques to Generate and Evaluate Wear Although the calculation of tribocorrosion synergy regimes and mechanisms is standardized, there are no standardized tribocorrosion testers. Is very common to find in literature experimental arrangements consisting of a regular tribometer with electrochemical cells adapted to perform accelerated corrosion measurements; or test rigs specifically designed to recreate one particular work condition. The contact configuration is defined by the specific needs of the system to recreate. Some examples of tribometer configurations present in literature to generate abrasion-corrosion and erosion-corrosion are shown in Fig. 2.

Fig. 2. Main contact configurations used to tribocorrosion. a) Unidirectional Sliding, b) Reciprocating sliding, c) sliding rubber wheel, d) impinging jet.

Subsection a) shows the typical configuration for the pin on the disc machine, while b) presents the reciprocating sliding. Both configurations work to generate twobody abrasion-corrosion when an electrochemical cell is adapted to contain a corrosive medium; or generate a corrosive medium with hard particles suspended to recreate the three-body abrasion-corrosion [11, 12]. Subsection c) shows the configuration of the Wet sand/rubber wheel apparatus [13], a configuration usually used to generate three body abrasion-corrosion when is adapted to contain a corrosive medium with hard particles suspended [14–17]. Subsection d) shows a schematic representation of a test rig designed to generate erosion-corrosion by impinging jet; where a flux of corrosive slurry with hard particles suspended is shocked against the sample. Is necessary a good sampleelectrodes location to allow the measurements [18]. In all of the examples, tribological testers are modified to perform simultaneous electrochemical tests to evaluate corrosion.

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6 Techniques to Generate and Evaluate Corrosion In most tribocorrosion experiments, corrosion is evaluated using electrochemical techniques, the main reason is the capacity of this kind of test to be carried out in an electrochemical cell adapted to a regular tribometer. Most reported electrochemical procedures for tribocorrosion are the direct current (D.C.) or potentiodynamic, and alternate current (A.C.) or impedance. Both kinds of tests use almost the same configuration, using a potentiostat-galvanostat; and can be performed before, during, or after the tribological process. The usual setup for an electrochemical measurement of a tribocorrosion system is shown in Fig. 3.

Fig. 3. Experimental setup for corrosion measurements in a tribocorrosion system.

Potentiodynamic tests are the most used of both kinds of electrochemical techniques, these are used to calculate important data like corrosion potential (Ecorr), and corrosion rate (Vcorr), and also to identify the passive and active potential regions of a material. The main ‘D.C. Electrochemical techniques’ used to evaluate corrosion in a tribocorrosion system are: • Open circuit potential: The difference of electrical potential between the material and a reference electrode measured versus the time, and without the influence of external charges. This measurement is made for an hour while the system stabilizes. The result of this measurement is the Ecorr . • Polarization resistance: Consists in a potential scanning of ±25 mV from the Ecorr . With this technique is possible to calculate Vcorr in a very fast way. • TAFEL plot: Also, a relatable technique used to calculate Vcorr and other electrochemical aspects, it consists of a potential scanning of ±250 mV from Ecorr . • Potentiodynamic polarization curve: This technique consists of a potential scanning of −250 mV to +1600 mV from the Ecorr . Also works to calculate the TAFEL plot. Potentiodynamic polarization presents a curve generated by confronting the electric potential (expressed in mV) versus the Current density (Icorr ) (Expressed in µA/cm2 ). Curve interpretation is important because shows the most important electrochemical regions of the material [19].

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The most important standards referred to terminology and techniques for corrosion evaluation are mentioned in the “standards” subsection of this work.

7 Materials Good corrosion resistance properties are reached by using materials capable of generating a thin oxide layer (passive layer) that prevents the migration of species to the medium. These materials are known as stainless. Examples of stainless materials are Al, Ti, and Cr. Other materials like Fe are alloyed with other elements like Cr or Mo to become stainless. Counter abrasion properties are reached using harder materials, or making more resistant materials by adding hard phases. Tool steels and white cast iron belong to this group. Also, diverse techniques to produce coatings through deposition are used to generate the ideal surface characteristics [20] (Fig. 4).

Fig. 4. Desirable properties of a tribocorrosion material.

8 Conclusions • The importance of tribocorrosion lies in the need to understand the role of mechanical and electrochemical interactions in the process of degradation of a material. • Due to the current state of technology, materials are demanded to work in every time more aggressive environments and to have a better performance on them. Tribocorrosion is then necessary for a more accurate assessment of the qualities of new materials, alloys, and coatings. • Measurement of synergy is the most important aspect to consider in basic tribocorrosion research; because is an indicator of the role of each element in the tribocorrosion system; also, the calculation and understanding of the synergy of a system can lead to more specific studies like mixed mechanisms presents in the phenomenon, passivation and re-passivation of the surface, corrosion products, and possible chemical reactions. • It is necessary to continue with the efforts to standardize tests and machinery used in the tribocorrosion evaluation.

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Author Index

A Abdelkader, Kirad 132 Akebono, Hiroyuki 20 Alhajj, Mahmood 80 Arputharaj, Beena Stanislaus Aziz, Shahid 63, 73

Karimova, L. M. 45 Katrenov, B. B. 45 Khan, Muhammad Kamran Kharchenko, E. M. 45 Kida, K. 11 Koike, H. 11 Kurita, Naoki 20

125

B Bagautdinov, Bagautdin 1 Bhandari, Krishna Singh 63, 73 Bilal, Muhammad 63 C Chakrabortty, Sankha Chauke, Hasani 34

L la Rosa, César Sedano-de Lau, Sie Yon 110

63

144

E Elkahina, Sari 132

M Madhu, A. 50 Makhatha, Elizabeth 34 Makoana, Nkutwane Washington Mathaiyan, Vijayakumar 125 Matsueda, T. 11 Mazhar, Abdur Rehman 73 Mizobe, K. 11 Moshokoa, Nthabiseng 34

G Gallardo-Hernández, Ezequiel A.

N Nacer, Boucherou

D Diale, Ramogohlo

110

34

144

132

H Haddout, Soufiane 56 Haraguchi, T. 11 Harajiri, T. 11 Hayashi, Miu 20

O Oussam, Mimouni 132

J Jacob, Ajala Oluwaseun 110 Jung, Dong Won 125 Jung, Dong-Won 63, 73

R Raganya, Lerato 34 Raja, Vijayanandh 125 Riaz, Yasser 73 Rodriguez-Bravo, Gerardo A.

K Kairalapov, Ye. T. 45 Kaleem, Muhammad Mubashir 63 Kamel, Benachenhou 132

P Phasha, Maje

34

34

S Salim, Bennoud 132 Shah, Imran 63

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024 D.-W. Jung (Ed.): ICMMPM 2023, SPM 44, pp. 151–152, 2024. https://doi.org/10.1007/978-981-97-1594-7

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152

Author Index

Skopov, Gennady 27 Soonmin, Ho 80, 94, 110 Srinatha, N. 50 Sugeta, Atsushi 20 T Tubtimtae, Auttasit U Ubaid, Ali 73 Uthayakumar, T. 50

80

V Vite-Torres, Manuel

144

W Watanabe, Tadatoshi

20

Y Yaduvanshi, Namrata 50 Yakornov, Sergei 27 Z Zahir, Abdul

110