Graphene to Polymer/Graphene Nanocomposites: Emerging Research and Opportunities 032390937X, 9780323909372

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Graphene to Polymer/ Graphene Nanocomposites

Graphene to Polymer/ Graphene Nanocomposites Emerging Research and Opportunities

Ayesha Kausar National Centre for Physics, Islamabad, Pakistan

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2022 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-323-90937-2 For Information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Matthew Deans Acquisitions Editor: Edward Payne Editorial Project Manager: Chiara Giglio Production Project Manager: Nirmala Arumugam Cover Designer: Matthew Limbert Typeset by Aptara, New Delhi, India

Contents Preface....................................................................................................................................................IX

CHAPTER 1 Graphene: Structure, properties, preparation, modification, and applications........................................................1 1.1  Introduction.................................................................................................................. 1 1.2  Nanocarbon.................................................................................................................. 1 1.3  Graphene...................................................................................................................... 2 1.4  Structure and properties of graphene........................................................................... 4 1.5  Preparation and modification methods for graphene................................................... 6 1.6  Applications area of graphene nanocarbon.................................................................. 7 1.7  Summary...................................................................................................................... 8 Key terms and definitions.....................................................................................................9 References............................................................................................................................9

CHAPTER 2 Multifunctional polymeric nanocomposites with graphene.............25 2.1  Introduction................................................................................................................ 25 2.2  Polymer nanocomposites........................................................................................... 25 2.3 Prospects on essential properties, processing, and applications of polymeric nanocomposites.................................................................................... 26 2.4  Graphene as remarkable nanofiller............................................................................ 27 2.5  Polymer/graphene nanocomposites........................................................................... 29 2.6  Prospective of polymer/graphene nanocomposites.................................................... 32 2.7  Summary.................................................................................................................... 33 Key terms and definitions...................................................................................................33 References..........................................................................................................................33

CHAPTER 3 Processing strategies in graphene-derived nanocomposites...........45 3.1  Introduction................................................................................................................ 45 3.2  Polymer/graphene nanocomposites via solution method.......................................... 45 3.3  Polymer/graphene nanocomposites via melt blending.............................................. 48 3.4  Polymer/graphene nanocomposites via in situ polymerization................................. 50 3.5  Electrospinning method............................................................................................. 52 3.6  Other processing techniques...................................................................................... 52 3.7  Morphology of polymer/graphene nanocomposites.................................................. 53 3.8  Summary.................................................................................................................... 55 Key terms and definitions...................................................................................................55 References..........................................................................................................................55

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CHAPTER 4 Nano-foam architectures of polymer and graphene........................67 4.1  Introduction................................................................................................................ 67 4.2  Nano-foam nanostructures......................................................................................... 67 4.3  Three-dimensional graphene nanostructures............................................................. 68 4.4  Synthesis and properties of 3D graphene.................................................................. 69 4.5  Polymer/graphene-based nano-foam architectures.................................................... 71 4.6  Application areas of polymer/graphene-based nano-foam architectures................... 73 4.7  Summation................................................................................................................. 76 Key terms and definitions...................................................................................................76 References..........................................................................................................................77

CHAPTER 5 Graphene quantum dots, graphene nanoplatelets, and graphene nanoribbons with polymers.....................................91 5.1  Preamble.................................................................................................................... 91 5.2  Graphene quantum dots, graphene nanoplatelets, and graphene nanoribbons.......... 92 5.3  Polymer/graphene quantum dots nanocomposites..................................................... 93 5.4  Polymer/graphene nanoplatelets nanocomposites..................................................... 95 5.5  Polymer/graphene nanoribbons nanocomposites...................................................... 97 5.6  Significance of polymeric nanocomposites with graphene derivatives..................... 99 5.7  Challenges, future, and summary............................................................................ 100 Key terms and definitions.................................................................................................101 References........................................................................................................................101

CHAPTER 6 Stimuli responsive graphene-based materials.............................117 6.1  Introduction.............................................................................................................. 117 6.2  Shape memory polymers......................................................................................... 117 6.3  Stimuli responsive polymeric nanocomposites........................................................ 119 6.4  Stimuli responsive polymer/graphene nanocomposites........................................... 121 6.5  Potential applications, future forecasts, and conclusion.......................................... 124 Key terms and definitions.................................................................................................126 References........................................................................................................................126

CHAPTER 7 Advances in anti-corrosive coatings of polymer/graphene nanocomposites........................................................................145 7.1  Introduction.............................................................................................................. 145 7.2  Corrosion inhibition by polymers............................................................................ 146 7.3  Corrosion inhibition by polymeric nanocomposites................................................ 146 7.4  Anti-corrosive coatings of polymer/graphene nanocomposites............................... 149 7.5  Role of polymer/graphene nanofibers in anti-corrosion.......................................... 152 7.6  Challenges and summary......................................................................................... 153 Key terms and definitions.................................................................................................154 References........................................................................................................................154

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CHAPTER 8 Polymer/graphene nanocomposites as versatile platforms for energy and electronic devices................................173 8.1  Preface..................................................................................................................... 173 8.2  Polymers in energy applications.............................................................................. 173 8.3  Polymer/graphene nanocomposites in energy sector............................................... 174 8.3.1 Supercapacitor................................................................................................174 8.3.2  Li-ion batteries................................................................................................178 8.3.3  Fuel cells.........................................................................................................178 8.4  Polymer/graphene nanocomposites in electronics sector........................................ 180 8.4.1 Sensors............................................................................................................180 8.4.2  EMI shielding devices, transistors, and other electronics...............................181 8.5  Significance, future, and summary.......................................................................... 182 Key terms and definitions.................................................................................................182 References........................................................................................................................182

CHAPTER 9 Gas separation and filtration membrane applications of polymer/graphene nanocomposites.........................................197 9.1  Introduction.............................................................................................................. 197 9.2  Polymeric nanocomposite membranes.................................................................... 197 9.3  Polymer/graphene nanocomposite-based gas separation membranes..................... 199 9.4  Water filtration membranes of polymer/graphene................................................... 199 9.5  Polymer/graphene nanofibers in membrane technology.......................................... 203 9.6  Future and summary................................................................................................ 204 Key terms and definitions.................................................................................................205 References........................................................................................................................205

CHAPTER 10 Graphene nanomaterials in aerospace applications...................223 10.1  Introduction........................................................................................................... 223 10.2  Composite in aerospace industry........................................................................... 223 10.3  Polymer/graphene nanocomposites in aerospace.................................................. 224 10.4  Epoxy reinforced graphene nanocomposites for aerospace.................................. 228 10.5  Future and summary.............................................................................................. 231 Key terms and definitions.................................................................................................231 References........................................................................................................................232

CHAPTER 11 Cutting-edge polymer/graphene nanocomposites for biomedical applications......................................................245 11.1  Primer.................................................................................................................... 245 11.2  Polymer/graphene nanocomposites in drug delivery............................................. 246 11.3  Polymer/graphene nanocomposites in tissue engineering..................................... 248 11.4  Antibacterial properties of polymer/graphene nanocomposites and nanofibers.... 249

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11.5  Significance of bionanocomposites based on polymer/graphene.......................... 252 11.6  Future and summation........................................................................................... 253 Key terms and definitions.................................................................................................254 References........................................................................................................................254 Glossary����������������������������������������������������������������������������������������������������������������������������������������������269 Index���������������������������������������������������������������������������������������������������������������������������������������������������273

Preface Discovery of graphene instigated a significant drift in the modern nanoscience and technological fields toward the graphene-based nanostructures and nanocomposites. Advancements in the graphene-derived nanomaterials have led to the development of numerous versatile polymer/graphene nanocomposites. Recently, graphene nano-reinforcement has attracted academic and industrial research interest owing to dramatic material property improvement in a facile way. Appropriate fabrication strategies may lead to the remarkably enhanced physicochemical features and material performance. Substantial electrical conductivity, optical properties, thermal stability, thermal conductivity, mechanical strength, barrier properties, anti-corrosion, shape memory, biocompatibility, and several other physical features of the polymer/graphene nanocomposites have escort to the cutting-edge high-performance nanomaterials, high-tech devices/systems, and radical solicitations. This innovative book offers a widespread impression on the state-of-the-art knowledge in the field of graphene and polymer/graphene nanocomposites. Herein, the systematic coverage of the structure, essential features, processing, and widespread advanced applications of the graphene and polymer/ graphene nanocomposites have been presented in terms of topical scientific literature. In addition to the nanocomposites, polymer and graphene have been conversed for the formation of marvelous threedimensional interconnected hierarchical nano-foams and nanofibers, further enhancing the potential of these multifunctional nanomaterials. Various forms of graphene such as graphene quantum dots, graphene nanoplatelets, graphene nanoribbons, etc., have been surveyed with reference to the polymeric nanomaterials. The progressive application areas of the polymer/graphene nanocomposites have been acknowledged for the shape memory, anti-corrosion, gas transport membrane, filtration membrane, electronics and energy devices, aerospace, and biomedical relevance. The debate also points toward the predictable challenges and future opportunities in the field of polymer/graphene nanocomposites. The inventive comprehensive script is systematically prearranged into 11 chapters, focusing the emerging research and technical opportunities, briefly described as follows: Chapters 1–5 ensures indispensable facets related to structure, properties, and fabrication of graphene, graphene nanostructures, polymer/graphene nanocomposites, and nano-foam architectures. Chapter 1 (inaugural chapter of the book) emphasizes the unique two-dimensional graphene structure. Graphene is made up of monolayer of sp2 hybridized carbon atoms densely packed in honeycomb lattice. Graphene has remarkable features like transparency, electronic transport, thermal conductivity, mechanical robustness, and range of other useful characteristics. Graphene preparation and modification methods have also been considered. Accordingly, graphene has gained enormous interest for myriad of systems, devices, and engineering and industrial applications. Succeeding Chapter 2 establishes multifunctional aspects of polymer/graphene nanocomposites owing to superior mechanical, thermal, electrical, barrier, flame retardant, and other important physical properties. The polymer/graphene nanocomposites have opened new dimensions in the field of materials science via potential applications in energy—to—aerospace—electronics industries. Chapter 3 forms an important section of this book comprising several preparation methods for graphene reinforced polymeric nanocomposites. Solution casting, solvent dispersion, melt blending, in-situ polymerization, and other techniques have been frequently used. Fine quality and performance of polymer/graphene nanocomposites have been obtained through selecting appropriate processing technique. Several challenges need to be overcome to fabricate high-performance polymer/graphene nanocomposites to achieve unique functional properties.

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Sequential Chapter 4 deals with the unique three-dimensional interconnected hierarchical nanostructures designed using polymer and graphene. Preformed graphene nano-foam has also been incorporated in the polymer matrices to enhance the intrinsic material properties. Polymer/graphene nanofibers have also been deliberated with the nano-foam architectures. In addition to the essential features and processing, the chapter also discusses structural and engineering skills of graphene foambased nanocomposites. Next, Chapter 5 grades the importance of graphene quantum dots, graphene nanoplatelets, and graphene nanoribbons with polymers. Various forms of graphene have varying structural aspects, fabrication route, and high-performance characteristics. Chapters 6–11 are exclusively dedicated to the application fields of the polymer/graphene-based nanocomposites covering shape memory, anti-corrosion, electronics, energy, aerospace, and biomedical materials. Specifically, Chapter 6 comprises graphene-filled shape memory polymeric nanocomposites. Shape memory polymers are smart materials having ability to change their shape upon exposure to external stimulus, such as heat, light, electricity, pH, moisture. Inclusion of graphene has considerably improved the shape recovery behavior of the polymer/graphene nanocomposites. The fabrication, characterization, actuation ways, and multifunctional properties of shape memory polymer/graphene nanocomposites have been engrossed. The potential of these materials has been observed in self-healing composites, automobile/aerospace actuators, smart textiles, civil engineering, and biomaterials. After that, Chapter 7 deliberates connections between graphene and polymer matrices as a key factor governing the anti-corrosion performance. Moreover, dispersibility and miscibility of graphene with conducting and nonconducting polymers have enhanced the corrosion resistance of the nanocomposite coatings. The formation of interconnected percolation network in the matrix also prevents rusting phenomenon. Several facile approaches have been researched toward the development of graphenebased anti-corrosion coatings and also the polymer/graphene nanofibers. Thenceforth, Chapter 8 has focused on the latent of polymer/graphene in electronics and energy sectors including batteries, supercapacitors, sensors, biosensors, electronics, electromagnetic interference shielding devices, transistors, fuel cells, and 3D printed nanocomposites. Owing to high specific surface area and high electrical/thermal conduction/properties, graphene has found wide-ranging solicitations in energy and electronics related systems. Graphene has been frequently blended with the polymers to fabricate nanocomposites for new-generation advanced flexible devices. Subsequently, Chapter 9 provides an impression of current developments in the polymer/graphene nanocomposite membranes with special emphasis on gas separation and water filtration membranes. Chapter 10 consequently debates an important applicability of graphene-based nanomaterials, i.e., aerospace relevance, in an all-encompassing manner. Chapter 11 (as a final stance) estimates cutting-edge polymer/graphene nanocomposites for biomedical applications. Various polymer/graphene nanocomposites and bio-nanocomposites have been employed for drug delivery, tissue engineering, and other biomedical zones. To conclude, the above-designed chapters of this novel and all-inclusive manuscript presents thorough coverage of the essential forecasts related to the fundamentals and applications of the graphene and polymer/graphene derived nanomaterials. Ayesha Kausar 2021

CHAPTER

Graphene: Structure, properties, preparation, modification, and applications

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1.1  Introduction Graphene is an important technological material [1-3]. Graphene is one atom thick two-dimensional nanosheet of sp2-bonded carbon atoms [4, 5]. It has been considered as the thinnest material, ever found. The sp2 hybridized carbon atoms are compactly packed in the honeycomb crystal lattice structure. Graphene possesses range of the extraordinary properties including mechanical strength, electrical conductivity, thermal conductivity, optical transparency, and thermal constancy [6, 7]. Graphite, a common carbon structure, consists of a layers of graphene [8-11]. The word “graphene” is actually derived from graphite with the suffix “-ene.” The graphene nanosheets are stacked together via the weak dispersion forces. Graphene has been prepared using various top down and bottom up approaches [12]. The most common, inexpensive, and facile method is the production of graphene from graphite using the mechanical, thermal, exfoliation or other routes [13-15]. The isolated graphene is considered as a free-standing nanosheet. The individual graphene nanosheet may have unusual electronic transport properties. For the production of the large surface area graphene on large scale having fine chemical and physical properties, the chemical vapor deposition (CVD) technique has been used [16]. Advance properties and applications of graphene have also been observed via incorporation in the polymer matrices [17-19]. Consequently, the graphene nanosheet has been considered as a remarkable candidate for the functional nanocomposites [20, 21]. Graphene and graphene oxide (GO) have been used to form the useful nanomaterials [22]. Graphene-based nanomaterials have shown performance in the photovoltaics, catalysis, supercapacitors, sensors, Li-batteries, fuel cells, and radiation shielding [23-27]. However, the challenges and future research directions of the graphene materials need to be further explored [28-30]. This chapter focuses on the fundamentals of structure, properties, synthesis of graphene, and graphene modification methods along with the advancements for the advance applications [31-34]. Fabrication, properties, and structural applications of the high-performance graphene-based nanocomposites have been discussed in the succeeding chapters of this book [35-39].

1.2  Nanocarbon Nanocarbon materials have gained success in the cutting-edge applications of material science [40-42]. Since the discovery of carbon nanotube, other nanocarbon materials have also been researched [43-46]. Nanocarbon with the large surface area and exclusive properties are the graphite, nanodiamond, fullerene, and graphene [47-52]. Fullerene, carbon nanotubes, carbon nanoonion, and graphene are the Graphene to Polymer/Graphene Nanocomposites. DOI: https://doi.org/10.1016/B978-0-323-90937-2.00010-1 Copyright © 2022 Elsevier Inc. All rights reserved.

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archetypal nanocarbons with zero-, one-, and two-dimensional structures, respectively [53-56]. These nanocarbon materials have attracted attention for the diverse technical and engineering applications such as aerospace, solar cells, batteries, supercapacitors, water treatment, and other relevance [57-60]. Among the nanocarbons, graphene is a fascinating nanocarbon containing single-, bi-, or few layers of carbon atoms [61-63]. When a single layer of graphene is rolled, it forms a single-walled carbon nanotube. Similarly, a wrapped graphene nanosheet may lead to fullerene nanostructure. In addition to graphene, carbon nanotube also possesses remarkable electrical, mechanical, and thermal features for energy storage, solar cell, electrochemical sensing, and biomedical relevance [64-67]. Consequently, graphite, nanodiamond, and fullerene also have progressive solicitations in diverse fields such as Li-ion batteries, fuel cells, photovoltaics, supercapacitors, biomedical, etc. [68-73]. Naocarbons have also been used to form the light, inexpensive, strong, and high-performance nanocomposite structures [74-76]. The nanocomposites have found applications for the aerospace, automotive, electronics, construction, textile, sports, and biomedical industries.

1.3  Graphene Graphene is a single layer hexagonal lattice of the carbon atoms [77-79]. It is a nanocarbon having sp2 hybridized C–C bonding with the π-electron clouds (Fig. 1.1) [80-82]. Graphene has a zero-band gap and linear band dispersion at Fermi-level. Graphene also possesses the large interfacial adhesive energy. In 2004, graphene was first identified by Novoselov, Geim, and coworkers at The University of Manchester [83]. Fig. 1.2 shows that the graphene can be obtained using the top-down and bottomup approaches for graphene [84-87]. Various routes involved are the mechanical cleavage of graphite, exfoliation, intercalation, organic synthesis, CVD, etc. The most sophisticated technique to form the pure large surface area graphene is CVD [88-91]. Graphene has been synthesized on the different substrates [92-94]. In this technique, carbon containing gases are adsorbed on catalytic metal surfaces. Graphene is formed by a dominant growth process. However, it is an expensive technique and removing graphene layers from the metallic substrate without the structure damage is quite challenging [95-97]. Ultrathin epitaxial graphene can also be grown on the single crystal silicon carbide through the vacuum graphitization and nanolithography [98-100]. These methods are high quality but expensive. Graphene may lead to several carbon nanoallotropes including the carbon nanotube, fullerene, nanodiamond, etc. (Fig. 1.3) [101-105]. Graphene has several interesting structural and physical characteristics [106-108]. However, the neat graphene nanosheets have tendency of crumpling owing to strong vander Waals forces [109-111]. In this regard, the surface modified graphene may facilitate the formation of stable structures.

FIG. 1.1  Graphene.

1.3  Graphene

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FIG. 1.2  Top-down and bottom-up approaches for graphene.

FIG. 1.3  Graphene leading to carbon nanoallotropes.

The promising properties, processibility, and functionalization of graphene render it an ideal material for the incorporation into the functional materials. Recent research has led to several breakthroughs in the graphene materials [112].

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1.4  Structure and properties of graphene Graphene is a nanoallotrope of carbon [113]. It is a two-dimensional monolayer of carbon atoms arranged in the hexagonal honeycomb lattice nanostructure [114]. Structure of graphene has been examined using the Raman spectroscopy, X-ray diffraction, scanning tunneling microscopy, transmission electron microscopy, and atomic force microscopy [115-117]. Fig. 1.4 reveals the transmission electron microscopy image of the graphene nanosheet grown on the platinum (Pt) substrate and using ethane (C2H6) gas as carbon source [118]. The carbon growth was found dependent on the catalyst nanoparticle size. The growth of the graphene layers needs minimum energy in the growth. In a graphene nanosheet, the sp2-bonded atoms have the molecular bond length of 0.142 nm. Graphene is a thinnest known material (1 sqm) of 0.77 mg. Graphene is a transparent/translucent material [119]. Graphene has capability to transmit 97–98% of light. Optical properties of graphene are beneficial for the solar panels, touch screens, and light emitting diodes [120-122]. In the layered graphene structure such as graphite, interplanar spacing of the graphene layers is 0.335 nm [123-125]. The graphene layers are held together by vander Waals forces. Graphene is 200–300 times stronger than steel. Graphene has the tensile strength of 130 GPa and Young’s modulus of 1 TPa [126]. Graphene has the electron mobility of 200,000 cm2/V/s, so it is a best electronic conductor [127, 128]. It has been considered as a semimetal. Graphene has high thermal conductivity of graphene in the range of 3000–5000 W/Mk. Graphene nanosheets have been used for holding, trapping, and detecting gases. In the polymers, graphene may impart marvelous electrical conductivity, heat conductivity, strength, and heat confrontation [129]. Various routes for the graphene synthesis are shown in Fig. 1.5. Among

FIG. 1.4  Transmission electron microscopry (TEM) image of the grown graphene layers on platinum (Pt) [118].

1.4  Structure and properties of graphene

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FIG. 1.5  Graphene synthesis routes.

modified forms of graphene, GO is a unique structure with the hydrophilic functional groups such as epoxy, hydroxyl, carbonyl, and carboxyl groups [130]. Graphene has grown in various morphologies comprising different dimensionalities such as graphene nanosheet, graphene nanoplatelet, graphene quantum dot, graphene nanoflower, and graphene nanoribbon (Fig. 1.6) [131-133]. Different morphologies have led to the varied physical and chemical

FIG. 1.6  Graphene morphologies: graphene nanoplatelet, quantum dot, and graphene nanoribbon.

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properties [134]. Graphene has also been doped with the heteroatoms such as N, P, and S [135-139]. The N-doping of graphene has been used to enhance the electronic, optical, chemical, and physical properties of the nanostructures [140-142]. Graphene has gained success in both the fundamental and applied research fields due to the huge surface area, high electrical conductivity, thermal conductivity, mechanical properties, and chemical features. Owing to the exceptional properties and morphologies of the graphene and derived nanostructures, it has found importance in the methodological areas of nanoelectronics, energy storage, sensing, catalysis, biomedical, and nanocomposites [143-146]. Surface modification of graphene may avert the agglomeration problem. In polymer nanocomposites, modified graphene nanofiller has effective compatibility for solar cells, supercapacitors, sensors, electronics, and biomedical systems [147-149].

1.5  Preparation and modification methods for graphene The preparation methods of graphene has been largely focused in literature in search of a facile, low cost, and high yield route [150-152]. The yield and graphene quality depend on the method used for the production. Use of graphite powder has been observed for the bulk production of graphene nanosheets [153-155]. Graphite is an inexpensive source of graphene. Initially, in 1975 the mono-layer of graphite was extracted using the thermal decomposition method and Pt substrate [156]. The graphene production on large scale has also been performed using the micro-mechanical cleavage and exfoliation [157-159]. Among CVD, the plasma enhanced CVD [160-162] and the thermal CVD techniques [163-165] have been used. Different chemical methods have been used for the proficient synthesis of graphene on the large scale [166-168]. The chemical or liquid phased exfoliation of graphite have been performed through the strong oxidants to form the oxidized graphene. Using such methods, graphite oxide has been prepared. In this regard, the Brodie method has used the mixture of potassium chlorate and nitric acid to form the GO from graphite [169]. Hummers and Offeman methods have been proposed using the sodium nitrate, sulfuric acid, and potassium permanganate to form the GO from graphite [170174]. Fig. 1.7 demonstrates summarized form of the numerous approaches to prepare the graphene and graphene derivatives [175]. Numerous methods have been industrialized to form the modified graphene [176]. These methods include the noncovalent method [177-179], covalent reaction [180-182], chemical deposition [183185], hydrothermal method [186-188], solvothermal development [189-191], electrochemical route [192-194], electrophoresis approach [195-197], and physical deposition methodologies [198-200].

FIG. 1.7  Production techniques for graphene and graphene oxide [175].

1.6  Applications area of graphene nanocarbon

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Noncovalent method involves the noncovalent interactions between the graphene nanosheets and the desired organic or inorganic species [201-203]. In this method, the graphene surfaces may interact with the small molecules through π–π stacking [204-208], electrostatic interactions [209-214], or hydrophobic connections [215-219]. Covalent functionalization of graphene promotes the covalent bonding of the nanosheet surfaces with the desired molecules using the click chemistry [220-223], atom transfer radical polymerization [224-226], and other methods. In situ chemical deposition method has been used to deposit the nanoparticles on the graphene surface [227-229]. Range of metal and metal oxides nanoparticles such as Ag, Au, Pt, Cu, SiO2, TiO2, Fe2O3, etc. have been deposited on the graphene surface using this route [230-234]. The hydrothermal and solvothermal growth have been used to form the modified graphene nanosheets [235-240].

1.6  Applications area of graphene nanocarbon Due to unique graphene nanostructure and properties, it is a remarkably useful material in materials science and technology. Industrial applications of graphene have been immensely focused owing to its exclusive features [241-244]. Pristine graphene has found promising applications in range of technical fields related to the nanomaterials and devices [175, 245, 246]. Graphene in the polymeric nanocomposites have been applied in the energy devices [247-250], electronics [251-253], sensors [254256], membranes [257-259], etc. (Fig. 1.8). Supercapacitors is an important application of graphene. In supercapacitors, the graphene electrodes possess the facile flexibility, electrical conductivity, thermal conductivity, chemical stability, and mechanical robustness [260-262]. The specific capacitance of the graphene electrodes for the supercapacitors was about 48–132 F/g [263-265]. The electrochemical performance of devices with the graphene electrodes were found better than the traditional powder production techniques.

FIG. 1.8  Applications of graphene.

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Chapter 1  Graphene

Then spintronic application of graphene has been studied. Graphene has been employed as electrode for the spintronics [266-268]. Graphene has found potential in the spin polarized electrodes [269271]. Graphene maintained the fine spin polarization and tunneling spin values. The graphene coated electrodes may cause the specific sign reversal of magneto-resistance [272-274]. In this regard, the innovation of novel graphene architectures may lead to the promising materials for spintronic technologies. Another important use of graphene has been discovered in the lithium-ion batteries. It has been used in the electronic components in the lithium-ion batteries [275-278]. Graphene nanosheets may be used to detach the electrical current collector. The electrodes possess capacity of 60–400 mA/hg at current density of 100 mA/g. High power lithium-ion batteries demand the use of flexible, light weight, and thin graphene electrodes [279-282]. The research on graphene has turned toward the range of sensing applications. Graphene microelectrode arrays have been used in the nanosensors [283-288]. Moreover, fabrication of 3-dimensional graphene aerogels-based sensors have been focused [289-292]. Magnetic field sensors have remarkable electron transport and magnetotransport properties [293-298]. Graphene strain sensors have shown optimum piezoresistive properties under tensile strain up to 7.1% [299-302]. Strain sensors with graphene has found applications in body monitoring, fatigue detection, displays, robotics, etc. [302-307]. Graphene woven fabrics were developed with ultralight weight, good sensitivity, robustness, and reversibility for human motion detection [308-313]. Graphene-based gas sensors have also attained realization for detection of NO2, H2, CO, CO2, NH3, H2S, etc. [314-318]. High-performance graphene-based CO2 gas sensor was conceived by mechanical cleavage [319]. Reduced GO has been used as NO2 gas sensor [320-322]. The applications of graphene have also been observed for the transistor like electronic devices [323-327]. Performance of graphene-based nanoelectronic devices were analyzed [328-332]. Graphene field effect transistors have charge carrier ability, quasiballistic mobility, intrinsic capacitance, and channel charge density [333-337]. Modern flexible and robust touch screen devices, mobile devices, wireless data transfer, and self-powered electronics have been incorporated with graphene [338-341]. Stimuli-responsive smart materials derived from graphene has potential for aerospace, automobiles, construction, and electronic industries [342-347]. Similarly, anticorrosion coatings based on multilayer graphene have been developed for metallic structures and relevant industrial uses [348-353]. The nanostructures with one atom thick honeycomb graphene has fine potential for hydrogen storage [354-358]. Graphene can absorb hydrogen through physisorption (vander Waals forces) or by chemisorption (chemical bonding) [359-363]. Graphene-based membranes have found potential in selective separation of gases, water contaminants, and fuel cell [364-367]. Besides the success of graphene in innumerable technical fields, there are several limitations and challenges which need to be overcome to achieve future success and research directions [368].

1.7  Summary This chapter aims to offer insights into the graphene structure, properties, synthesis, and applications. Graphene has gained scientific fame owing to unusual structure and extraordinary properties. Fabrication strategies have focused upscaling the graphene production with improved structural characteristics. Graphene modification methods have also been considered to upgrade the properties of graphene and related materials. Its potential for high-performance applications has also been realized. Despite of

 References

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the research and studies so far, several aspects of graphene are yet to be explored, counting new rapid and facile synthetic stratagems for high quality nanomaterials, synergistic features, and uncharted application area.

Key terms and definitions Graphene

graphene is a nanoallotrope of carbon

Nanocarbon

it is a carbon nanostructure

Nanoallotrope

two or more different physical forms of a nanomaterial

vander Waals forces weak intermolecular forces of attraction and repulsions between the surfaces Synergistic

phenomenon relating to interaction/cooperation of two or more effects

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[312] Y. Jia, et al., Multifunctional stretchable strain sensor based on polydopamine/reduced graphene oxide/electrospun thermoplastic polyurethane fibrous mats for human motion detection and environment monitoring, Compos. Part B: Eng. 183 (2020) 107696. [313] L. Zhang, et  al., Three-dimensional binary-conductive-network silver nanowires@ thiolated graphene foam-based room-temperature self-healable strain sensor for human motion detection, ACS Appl. Mater. Interf. 12 (39) (2020) 44360–44370. [314] M.G. Chung, et al., Highly sensitive NO2 gas sensor based on ozone treated graphene, Sens. Actuat. B: Chem. 166 (2012) 172–176. [315] T.V. Cuong, et al., Solution-processed ZnO-chemically converted graphene gas sensor, Mater. Lett. 64 (22) (2010) 2479–2482. [316] H.J. Yoon, et al., Carbon dioxide gas sensor using a graphene sheet, Sens. Actuat. B: Chem. 157 (1) (2011) 310–313. [317] H.R. Jappor, Electronic and structural properties of gas adsorbed graphene-silicene hybrid as a gas sensor, J. Nanoelectron. Optoelectron. 12 (8) (2017) 742–747. [318] S. Bandi, A.K. Srivastav, Graphene-based chemiresistive gas sensors, Anal. Applic. Graphene Comprehens. Anal. Chem. 91 (2020) 149. [319] E. Akbari, et al., Monolayer graphene based CO2 gas sensor analytical model, J. Comput. Theor. Nanosci. 10 (6) (2013) 1301–1304. [320] S. Deng, et al., Reduced graphene oxide conjugated Cu2O nanowire mesocrystals for high-performance NO2 gas sensor, J. Am. Chem. Soc. 134 (10) (2012) 4905–4917. [321] H.Y. Jeong, et  al., Flexible room-temperature NO2 gas sensors based on carbon nanotubes/reduced graphene hybrid films, Appl. Phys. Lett. 96 (21) (2010) 213105. [322] H. Ding, et al., Recent advances in gas and humidity sensors based on 3D structured and porous graphene and its derivatives, ACS Mater. Lett. 2 (11) (2020) 1381–1411. [323] T. Albrecht, et  al., Transistor-like behavior of transition metal complexes, Nano Lett. 5 (7) (2005) 1451–1455. [324] S.C. Caliga, C.J. Straatsma, D.Z. Anderson, Transport dynamics of ultracold atoms in a triple-well transistor-like potential, New J. Phys. 18 (2) (2016) 025010. [325] S. Wang, et al., Skin electronics from scalable fabrication of an intrinsically stretchable transistor array, Nature 555 (7694) (2018) 83–88. [326] J. Locklin, et  al., Ambipolar organic thin film transistor-like behavior of cationic and anionic phthalocyanines fabricated using layer-by-layer deposition from aqueous solution, Chem. Mater. 15 (7) (2003) 1404–1412. [327] J.A. Rogers, et  al., Like electronic displays: large-area rubber-stamped plastic sheets of electronics and microencapsulated electrophoretic inks, Proc. Natl. Acad. Sci. 98 (9) (2001) 4835–4840. [328] A.K. Upadhyay, S.K. Vishvakarma, A.K. Kushwaha, Compact modeling of graphene field effect transistors for RF circuit applications, Discipline of Electrical Engineering, IIT Indore, India, 2019. [329] M. Saiz-Bretín, F. Domínguez-Adame, A. Malyshev, Twisted graphene nanoribbons as nonlinear nanoelectronic devices, Carbon 149 (2019) 587–593. [330] H. Mizuta, et al., Recent progress of graphene-based nanoelectronic devices and NEMS for challenging applications, 2016 13th IEEE International Conference on Solid-State and Integrated Circuit Technology (ICSICT), IEEE, 2016. [331] A. Kadri, F. Menacer, F. Djeffal, Simulation and analysis of graphene-based nanoelectronic circuits using ANN method, Mater. Today: Proc. 5 (8) (2018) 15959–15967. [332] Y.-M. Lin, J.-B. Yau, Fabrication of Graphene Nanoelectronic Devices on SOI Structures, Google Patents, 2014. [333] L. Vicarelli, et al., Graphene field-effect transistors as room-temperature terahertz detectors, Nat. Mater. 11 (10) (2012) 865–871.

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Chapter 1  Graphene

[359] H. Tang, et al., van der Waals correction to the physisorption of graphene on metal surfaces, J. Phys. Chem. C 123 (22) (2019) 13748–13757. [360] X. Liang, et al., Strain-induced switch for hydrogen storage in cobalt-decorated nitrogen-doped graphene, Appl. Surface Sci. 473 (2019) 174–181. [361] F. Presel, et al., Translucency of graphene to van der Waals forces applies to atoms/molecules with different polar character, ACS Nano 13 (10) (2019) 12230–12241. [362] R. Nagar, et al., Recent advances in hydrogen storage using catalytically and chemically modified graphene nanocomposites, J. Mater. Chem. A 5 (44) (2017) 22897–22912. [363] L. Ma, J.-M. Zhang, K.-W. Xu, Hydrogen storage on nitrogen induced defects in palladium-decorated graphene: a first-principles study, Appl. Surface Sci. 292 (2014) 921–927. [364] G. Amato, Properties and applications of graphene membranes grown on Co, Mater. Today: Proc. 20 (2019) 1–6. [365] A. Kausar, Poly (methyl methacrylate-co-methacrylic amide)-polyethylene glycol/polycarbonate and graphene nanoribbon-based nanocomposite membrane for gas separation, Int. J. Polym. Anal. Characterization 23 (5) (2018) 450–462. [366] Z.U. Khan, et al., A review of graphene oxide, graphene buckypaper, and polymer/graphene composites: properties and fabrication techniques, J. Plastic Film Sheeting 32 (4) (2016) 336–379. [367] A. Kausar, S. Anwar, Graphite filler-based nanocomposites with thermoplastic polymers: a review, Polym.Plast. Technol. Eng. 57 (6) (2018) 565–580. [368] A. Kausar, Emerging research trends in polyurethane/graphene nanocomposite: a review, Polym.-Plast. Technol. Eng. 56 (13) (2017) 1468–1486.

CHAPTER

Multifunctional polymeric nanocomposites with graphene

2

2.1 Introduction Polymer nanocomposites involve the dispersion of nanoparticles (nanosheet, nanosphere, nanotube, nanorod, and nanowire) in polymers [1]. The resulting nanomaterials have gained enormous success in academic and industrial sectors [2]. Addition of very small nanoparticle content offer remarkable property enhancements relative to neat resins. As compared with pristine polymeric matrices, strength, conductivity, barrier, corrosion resistance, heat stability, and nonflammability properties of nanocomposites have shown considerable development. Consequently, the nanocomposites possess entirely new amalgamation of properties from polymers and nanofillers. Graphene owns several beneficial characteristics for polymers [3]. Graphene has been successfully used as nanofiller in the polymer matrices. Various conducting, thermosetting, and thermoplastic polymers have been reinforced with the graphene nanofiller [4, 5]. For example polyaniline, polypropylene, polythiophene, polyurethane, polystyrene, poly(methyl methacrylate), polybutyl acylate, polyethylene, polypropylene, poly(vinyl fluoride), poly(ethylene oxide), poly(N‐isopropylacrylamide), epoxy, polycarbonate, etc. have been used as matrix materials for graphene nanofiller. Effect of the nanocompositing has been observed in the form of remarkable characteristics and advanced applications of these materials. Progressive polymer/ graphene nanomaterials have stimulating applications in energy sector, transportation field, aerospace industry, construction area, electronic devices, textile, and biomedical relevances. High-performance polymer/graphene nanocomposites demand proper control of the nanoparticle arrangement, distribution, and processing in the polymer matrices. In this chapter, the importance of graphene nanofiller in the polymer/graphene nanocomposite and the significant prospects of these materials are outlined.

2.2  Polymer nanocomposites Nanocomposite is combination of various components, where one constituent must have dimensions on nanoscale [6]. In polymeric nanocomposites, nanoscale particles are usually added as reinforcement [7]. In this regard, range of nanomaterials has been used such as metal nanoparticles [8], inorganic nanoparticle [9], nanoclay [10], and nanocarbon [11]. The added nanoparticles are named as nanofiller. The nanofillers can be classified according to their dimensions such as one-dimensional, twodimensional, and three-dimensional nanoparticles. Among nanofillers, carbonaceous nanoparticles possess high surface area, aspect ratio, and fine structural and physical properties. Most of the nanofillers need to be loaded in small amount to enhance the properties and minimize the processing problems [12]. Neat thermoplastic and thermosetting polymers have useful properties for industrial applications such as low density, flexibility, and easy processibility [13]. However, polymeric nanocomposites Graphene to Polymer/Graphene Nanocomposites. DOI: https://doi.org/10.1016/B978-0-323-90937-2.00008-3 Copyright © 2022 Elsevier Inc. All rights reserved.

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Chapter 2  Multifunctional polymeric nanocomposites with graphene

have been developed to markedly enhance the properties relative to pristine polymer. Consequently, polymeric nanocomposites offer entirely new combinations of properties and permits newfangled applications for polymers [14]. There are innumerable polymer/graphene nanocomposites and range of techniques available for their synthesis. The ex situ method, in situ processing, ball milling, extrusion, solution casting, sonication, and dry mixing are to name the few [1]. Polymeric nanocomposites have found potential in energy—to—aerospace—electronics. High-performance nanocomposites necessitate design, material selection, and synthesis innovations. Current challenges are connected to the modification, processing, and scalability of nanocomposites and future perspectives.

2.3  Prospects on essential properties, processing, and applications of polymeric nanocomposites Particularly, the nanofillers with at least one dimension smaller than 100  nm are dispersed in the polymers [9, 15-18]. One-dimensional nanofillers have one dimension less than 100 nm [19, 20]. They are generally in the form of nanosheets. Common one-dimensional nanofillers are nanoplates, nanodisks, nanosheets, nanowalls, etc. [21-23]. Example is montmorillonite nanoclay. Two-dimensional nanofillers usually have two dimensions less than 100 nm [24]. They exist in the form of tubes or fibers. Examples are carbon nanotubes (CNTs), two-dimensional graphene, nanowires, etc. [25-27]. Threedimensional nanofillers have three dimensions in the nanometer scale [28, 29]. These are nanospheres or nanogranules like particles. Examples are nanosilica, nanotitanium oxide, nanoalumina, polyhedral oligomeric silsesquioxane, etc. [30-33]. Nanofillers are significant reinforcement for polymers. The inclusion of low nanofiller contents has been known to enhance the essential polymer properties as thermal, mechanical, electrical or thermal conductivity, barrier, nonflammability properties [7, 34]. The nanofiller inclusion must improve the polymer characteristics without distressing their processability [35, 36]. Ideal polymeric nanocomposite designs must involve the uniformly and homogeneously dispersed nanoparticles in the polymer matrices [37]. However, achievement of ideal dispersion state of nanoparticles and potential of property enhancement are the challenging factors [38-40]. This unvarying nanofiller dispersion may offer large interfacial area between the matrix and the reinforcement. Thus, reinforcing effects of the nanofillers involve several aspects such as nanofiller type, nanoparticle aspect ratio, nanoparticle orientation, polymer matrix type, polymer/nanofiller ratio, nanofiller concentration, and nanofiller dispersion in the matrix [41]. The most successful types of nanofillers used with polymers in enhancing the properties are graphene [42, 43], CNT [44-46], nanodiamond [47-49], nanoclay [50-52], halloysite [53, 54], metal nanoparticle [55-57], and some natural nanofillers [5860]. These nanofillers have been blended with lots of natural and synthetic polymers [61, 62]. Various studies have been carried out to study the synergistic effects of nanofiller dispersion on the morphology, mechanical, and thermal properties of the polymers [2, 63-66]. The degree of nanoparticle separation in the matrix through exfoliation has also been studied for the polymeric nanocomposites [67, 68]. The polymer/nanofiller nanocomposites with well-ordered morphology have shown high performance. The reinforcement of large surface area nanofiller may develop better contacts between the matrix and nanoparticles [69]. The matrix/nanofiller interactions owing to fine nanoparticle dispersion have resulted in improved properties compared with the traditional composites [70, 71]. Better matrix/nanofiller interactions have led to the nanocomposite compatibilization. Comprehensive modeling techniques have been used to study the polymer-filler bridging and nanoparticle disaggregation [51, 72-74].

2.4  Graphene as remarkable nanofiller

27

Modeling approaches have confirmed the interphase layer formation in polymer nanocomposites [75]. The polymer nanocomposites with finely dispersed nanophase and better matrix/nanofiller interactions have shown enhanced strength and stiffness properties, thermal stability, electrical transport, thermal conduction, permeation features, flame resistance, biocompatibility, and biodegradability properties [76-78]. In addition to structure and properties, processing and manufacturing of polymeric nanocomposites according to the relevant applications have been focused [7, 63, 79, 80]. Various processing techniques have been used for the formation of polymeric nanocomposites including solution mixing, melt method, in situ polymerization, resin infiltration, and several other methods [8183]. In situ polymerization technique involves the dispersion of monomer in a solvent and the addition of suitable initiator or catalyst [84-86]. Later the addition of nanofiller may lead to polymer chain formation and diffusion to form the nanocomposites [87, 88]. In situ polymerization may also involve the adsorption of monomers on the nanofiller surface and subsequent polymerization. In the case of solution method, polymer solution is formed and nanofiller is dispersed in the dissolved matrix to form the nanocomposites [89, 90]. Sometimes, sonication method is used to disperse the nanofiller in the polymer solution [91-93]. Using melt technique, the polymer matrix is formed in molten state and nanofiller is dispersed in it [94, 95]. In this method, no solvent is used. The polymer chains can be wrapped with the nanofillers to form nanocomposites. Consequently, the polymeric nanocomposites have been employed in several commercial goods [14, 96]. The application areas of polymeric nanocomposites are very wide having potential uses in automotive parts [97, 98], packaging [99, 100], construction [101, 102], biomedical material, etc. [103, 104]. Particularly, these materials have been employed in car interiors, building materials, computer housings, etc. In packaging industry polymeric nanocomposites may form permeable nanofiller layers to promote the diffusion of molecules through tortuous pathway in the matrix [105, 106]. In optoelectronic industry, CNTs and graphene nanofillers have been employed in devices [107, 108]. The high surface area, structural stability, chemical constancy, dispersion, and processability of the nanofillers affect the optoelectronic properties [109111]. The polymeric nanocomposites have also been employed in photovoltaics, supercapacitor, field emission devices, etc. [112-114]. The field of polymeric nanocomposites has opened several promising and emerging research zones [115-117]. The field of polymeric nanocomposites has gained immense attention owing to light weight, flexibility, and ease of production [63, 118, 119]. Novel design of polymeric nanocomposites may provide future platform for several concealed areas of these materials [1, 120-122].

2.4  Graphene as remarkable nanofiller Graphene has been categorized as two-dimensional carbonaceous nanofiller. Currently, graphene nanofiller has been considered as one of the most promising nanofiller material [123]. Graphene is a good source of several other derived nanofillers [124, 125]. Graphene usually consists of monolayers of carbon atoms arranged in honeycomb network structure [126, 127]. Graphite has stacks of graphene layers [128]. Graphite has also been used as reinforcement in polymers [129, 130]. The graphene layers are held together through weak interactions, that is, vander Waals interactions [131, 132]. Graphene has large specific surface area, high Young’s modulus, strength, thermal conductivity, electrical conductivity, and biocompatibility. Graphene has high aspect ratio and surface area to interact with the polymers [5, 133, 134]. However, vander Waals forces may cause nanosheet crinkling. The graphene

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Chapter 2  Multifunctional polymeric nanocomposites with graphene

oxide (GO) and reduced GO have also been developed as the modified forms of graphene [135, 136]. The GO is usually synthesized by modified Hummer’s method [137, 138]. The as prepared GO can be electrochemically or photocatalytically reduced to form reduced GO [139]. The GO and reduced GO have also been employed as nanofillers for polymer matrices. Graphene has found application in nanoelectronics, catalysis, energy devices, engineering, biomaterials, and nanocomposites. For an ideal high-performance nanocomposite, nanofiller should be well-dispersed and agglomeration must be evaded [140, 141]. As demonstrated in Fig. 2.1, a common source of graphene is graphite [142]. Generally, graphite lead to economical large-scale production of graphene. Graphene can be prepared via direct exfoliation of graphite [143]. Mechanical cleavage of graphite may also lead to graphene material. Modified graphene nanosheet can be produced using exfoliation route from graphite. Consequently, better compatibility of polymer and graphene is demanded for superior physical properties of the nanocomposites [144]. Bonding between graphene and polymer is indispensable to permit stress transfer between matrix/ nanofiller. The functional graphene may further improve the interaction among matrix and reinforcement [145]. The preparation of polymeric nanocomposites with functional graphene nanosheets may also overcome the dispersion difficulties and offer superb polymer–nanoparticle interactions [146]. Better dispersed graphene nanofillers may exhibit low nanofiller weight fraction. Thus, it is extremely critical to attain better dispersion of graphene nanoparticles [147]. Improved graphene dispersion may help to attain fine load transfer and uniform stress distribution in the matrix. Highly loaded graphene

FIG. 2.1  Graphene production from graphite.

2.5  Polymer/graphene nanocomposites

29

nanocomposites have pronounced dispersion complications, weak synergetic enhancement effects, and poor solution viscosity control in the nanocomposites. The composition of nanocomposite, use of modified graphene, interaction in matrix/nanofiller, and synergistic properties are desired for advanced polymer/graphene materials [148].

2.5  Polymer/graphene nanocomposites Graphene attained exclusive stance among carbon nanofillers owing to easy production, reasonable cost, and stimulating physical properties [149]. This section elaborates various aspects of graphenebased polymeric nanocomposites (Fig. 2.2). Graphene can be incorporated in different polymers and using numerous processing methods. Dispersion of graphene in polymers depends on method from which graphene is obtained and nanocomposite processing technique. Functional groups on graphene and nature of polymer may also affect the nanofiller dispersal in the matrix. Polymer/graphene nanocomposites are the most versatile materials. The excellent combination of properties has led to multifunctional applications. Graphene inclusion directly affects the essential characteristics of the polymer/graphene nanocomposites. Various series of graphene-based nanocomposites have been developed in the literature with remarkable mechanical, electrical, thermal, and nonflammability properties [150]. The synergic effects of polymer and graphene have also been observed. The polyaniline/graphene nanocomposites have been prepared using solution/in situ techniques [151]. The aniline monomer is polymerized using suitable initiator and surfactant to form emeraldine salt [152]. During in situ polymerization, graphene can be added. The aniline monomers can be adsorbed on the graphene surface, and can be subsequently polymerized. In dispersed graphene nanosheets, aniline micelles are adsorbed and polymerized on graphene surface. A route to polyaniline/graphene nanocomposite is shown in Fig. 2.3. Zhang et al. [153] incorporated chemically modified graphene in polyaniline nanocomposite. The modified graphene was homogeneously dispersed in solvent and polyaniline was uniformly adsorbed on the nanoparticle surface. Polyaniline/graphene nanocomposite was also

FIG. 2.2  Polymer/graphene nanocomposites.

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Chapter 2  Multifunctional polymeric nanocomposites with graphene

FIG. 2.3  Polymerization of polyaniline/graphene nanocomposites.

used to form flexible carbon paper [154]. Polyaniline/graphene nanocomposite has been employed in dispensable component in stretchable electronic systems [155]. Structure, preparation, and properties of epoxy/graphene nanocomposites have been intensely explored [156]. Luo et al. [157] researched on epoxy/graphene nanocomposites. The cationic reduced GO was denoted as RGO-ID+ through in situ synthesis. The functional graphene was then dispersed in epoxy matrix to form nanocomposites. The functional graphene developed epoxy-grafted-graphene materials (Fig. 2.4). Epoxy/graphene nanocomposites have shown enhanced interfacial strength and adhesion properties [158, 159]. Epoxy nanocomposites have superior mechanical, thermal, electrical, and flame retardant properties. Zhang et al. [160] formed polyethylene glycol (PEG) and functional graphene nanosheet hybrids. Dispersion and thermal stability of nanocomposites have been studied. Liu et al. [161] used freezing-drying masterbatch approach for graphene dispersion in PEG. The PEG functional GO material was used to form efficient biocompatible systems [162]. The PEG/graphene have been used to produce efficient immune response materials. The waterdispersible poly(lactide)/graphene and PEG/graphene nanocomposites have been developed [163]. The electrical conductivity of PEG/graphene materials have been used for engineering applications [164]. The PEG/GO materials have been used in drug delivery [165]. Thus, pristine and functionalized graphene nanosheets have been effectively employed to develop hybrid materials. Consequently, graphene has been used to enhance the electrical, thermal, and mechanical properties of the nanocomposites [166, 167]. Low graphene contents may reveal considerable enhancements in their multifunctional characteristics [168, 169]. Conductive polymers are also known as intrinsically conducting polymers. Conductive polymers may show metallic conductivity or semiconducting properties. However, conducting polymers are more biocompatible and processable compared with

2.5  Polymer/graphene nanocomposites

31

FIG. 2.4  Formation of epoxy/graphene nanocomposites.

the semiconducting materials. The mechanism of electrical conductivity in the conducting polymers may be through the transmission of polarons/bipolarons through the conjugated backbone [170]. For specifically enhanced electrical conductivity properties, graphene decorated with metal nanoparticles may reveal fine results [171-173]. Combination of graphene or functional graphene with the conducting polymers may show good electrical properties. Graphene may form percolation pathways in the conducting matrix to further enhance the conducting properties [91, 174]. The conducting polymer/graphene nanocomposites may also show a very important phenomenon of electromagnetic interference (EMI) shielding [175, 176]. Such conducting nanocomposites may own both the electrical and magnetic properties for EMI shielding [177, 178]. In this regard, the processing method must be opted to improve the interface bonding and interactions between the matrix and filler [179, 180]. Both the weak secondary forces and covalent linkages have been used to promote the stronger interfacial bonding [181-183]. Consequently, dispersive forces in the polymer–graphene assemblies have been enhanced [184]. The π-conjugated conducting polymers can better interactions with the functional or nonfunctional graphene [185, 186]. The conjugated polymer/graphene nanocomposites have fine electrical and optical properties [187]. Usually, neat conducting polymers have poor solubility, intractability, processability,

32

Chapter 2  Multifunctional polymeric nanocomposites with graphene

and low mechanical strength [188, 189]. The conducting polymer nanocomposites prepared through in situ polymerizations have shown high performance. Research on polyaniline [190], polypyrrole [191], polythiophene [192], and poly(3,4-ethylenedioxythiophene) PEDOT [193, 194] must be focused for the incorporation of graphene and enhancement of properties and performance [195, 196]. Poly(3,4ethylenedioxythiophene) has high conductivity and thermal stability relative to the polypyrrole [197, 198]. Doping of PEDOT can further enhance the conductivity of these polymers [199-201]. In addition to conductivity improvements, interfacial bonding between the polymer and graphene may remarkably enhance the strengthening and other physical aspects [202-204]. The theoretical analysis and simulation tools may play important role in thoughtful structure–property investigations [168, 205-209]. The understanding of fabrication mechanisms, molecular–level interactions, and physical properties of the polymer/graphene nanocomposites may lead to advanced potential applications for various technical fields ranging from energy and electronics to engineering and biomedical sectors [210-212]. Consequently, the polymer/graphene nanocomposites have been used in emerging areas as fuel cells, batteries, light-emitting displays, coatings, membranes, biomedical devices, and other structural materials [213-217]. Polymer/graphene nanocomposites are the industrially important nanomaterials [218, 219].

2.6  Prospective of polymer/graphene nanocomposites Graphene has been preferred over other conventional fillers and nanofillers such as CNT, nanoclay, carbon fiber, and glass fiber for various polymers. The electrical, optical, barrier, mechanical, and thermal properties of these materials are suitable for electronics, sensors, light emitting displays, solar cell, and supercapacitor electrodes [220]. Polymer/graphene nanocomposites are also applicable in electrostatic discharge, EMI, and biomedical applications. High electrical conductivity, carrier mobility, and optical transmittance of graphene-based materials render them useful in field emission devices, liquid crystal devices, light-emitting diode, organic light-emitting diode, and dye-sensitized solar cell electrodes [221]. Poly(dimethyl siloxane)/graphene nanocomposites have been used in these applications [222-225]. EMI shielding materials have been prepared with polymer/graphene having electrical conductivity and corrosion resistance [226]. Electrostatic discharge devices were also prepared with polymer/graphene nanocomposites [227]. Graphene-based nanocomposites have been used in high-performance microbial fuels, so are advance source of green energy [228, 229]. Polymer/graphene nanocomposites have large specific area for surface adsorption of moisture and gas molecules. These materials are promising candidate for gas sensors to detect a variety of molecules [230, 231]. Poly(N-vinylcarbazole) and graphene-based materials have been recognized for antimicrobial properties [232, 233]. Biodegradable poly(ε-caprolactone)/graphene nanocomposites have also been reported [234]. Barrier and transport properties of graphene have been used to form nanocomposite membranes [235]. Graphene-based nanomaterials also have fine adsorbent and photocatalytic properties for relevant applications [235]. The photocatalytic materials have found scope for air and water decontamination. Graphene-based membranes have shown fine separation performance for gas pairs with commercial viability [236]. In drug delivery, aromatic regions of graphene nanosheets may develop interactions with aromatic drug structure [237, 238]. PEG/ graphene nanocarriers have been used in this regard [239]. Graphene-based polymer nanocomposites are still at early stage of developments and there are growing interests in overcoming the challenges and applications of these materials.

 References

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2.7 Summary Graphene has been used as an effective nanomaterial to form low cost, light weight, and processable high-performance nanocomposites with polymers. Graphene has been incorporated in various polymers including thermoplastics, thermosets, and conjugated polymers. Various methods have been used to incorporate graphene in the polymers. Both the functional and nonfunctional graphene has been incorporated in the polymeric matrices. Functional graphene may form better interactions and interfacial bonding with the polymers to enhance the conductivity, mechanical, thermal, and other physical properties. Owing to superlative properties, graphene nanofiller led to functional nanocomposites for several technical applications. There are challenging problems which need to be addressed for large-scale production of uniformly dispersed efficient nanocomposites. Mainly fine dispersion and alignment of nanofiller and interaction between matrix/nanofiller is a major challenge.

Key terms and definitions Nanocomposite

a combination of two or more components with one constituent on nanoscale

Nanofiller

nanoscale reinforcement used in polymeric matrix

Processability

ability to be processed

Electrical conductivity property of a material to conduct electrons or charge Flame retardant

ability of a material to resist fire

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CHAPTER

Processing strategies in graphene-derived nanocomposites

3

3.1 Introduction Incorporation of graphene in polymers has resulted in the combined properties of both the components (synergy effects) for improving the performance of high-performance polymer/graphene nanocomposites [1]. Poor processability and compatibility of polymer and graphene may result in deprived mechanical features, brittleness, electrical conductivity, and optical properties [2-4]. Efficient processing technique promotes stronger interfacial bonding in matrix/nanofiller [5-7]. Thermoplastic polymers such as polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(vinyl chloride), poly(vinyl alcohol), polyaniline, polypyrrole, polythiophene, polyethylene (PE), poly(ethylene oxide) (PEO), poly(vinyl fluoride) (PVDF), etc. have been processed with graphene using three common polymerization techniques including solution casting, melt blending, and in situ polymerization for compositing [810]. Other fabrication methods such as interfacial polymerization, microwave irradiation, atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT), Ziegler–Natta polymerization, latex technology, and colloid methods have also been employed for polymer/graphene materials. Polymer/graphene nanocomposites usually interact through weak dispersive forces [10-12]. Though, covalent linkages between matrix/nanofiller promote better graphene dispersion in polymers [13-15]. Choice of a good technique causes improve bonding interaction at the interface between the filler and matrix [16-18]. Poorly processed nanocomposites are usually insoluble, intractable, and may decompose before melting or technical casting [19-21]. This chapter essentially focuses the formation of nanocomposites using polymer matrix, graphene nanofiller, and facile technique.

3.2  Polymer/graphene nanocomposites via solution method The solution mixing, solution processing, or solvent casting method has been effectively used for the production of polymer/graphene nanocomposites [8, 9, 22]. In this method, graphene nanosheets are dispersed in a solvent. Polymer is also dissolved in desired solvent. Later, graphene nanosheets are dispersed in polymer solution and mixed (Fig. 3.1). The mixture was cast in mold via solvent evaporating. Various thermoplastic and thermosetting polymers have been processed using solution route [23]. Zeng et al. [22] prepared PMMA/graphene nanocomposites using solution blending technique. The electrical conductivity was found to increase with nanofiller content. Inclusion of 2.0 wt.% nanofiller led to electrical conductivity of 0.037 S/m (Fig. 3.2). At this concentration, graphene nanoparticle Graphene to Polymer/Graphene Nanocomposites. DOI: https://doi.org/10.1016/B978-0-323-90937-2.00005-8 Copyright © 2022 Elsevier Inc. All rights reserved.

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Chapter 3  Processing strategies in graphene-derived nanocomposites

FIG. 3.1  Solution mixing set-up.

formed percolation network to facilitate flow of electron. Glass transition temperature (Tg) of the nanocomposites was also enhanced with the graphene addition. Balasubramaniyan et al. [24] reported PMMA/graphene nanocomposites using solution blending method. The electrical conductivity of nanocomposites was enhanced up to 0.039 S/m, with nanofiller loading. The storage modulus and Tg of the nanocomposites were also enhanced with graphene addition. Yu et al. [25] designed PS/graphene nanocomposites. Addition of 2 wt.% graphene led to increase in Tg from 298 to 372 °C. The storage modulus was also amplified from 1808.76 to 2802.36 MP. He et al. [26] also prepared syndiotactic PS and graphene nanocomposites by solution blending. The nanocomposites

FIG. 3.2  Electrical conductivities as a function of nanofiller content [22].

3.2  Polymer/graphene nanocomposite via solution method

47

FIG. 3.3  Transmission electron microscopy (TEM) image of polyethylene (PE) nanocomposites with 3 wt.% graphene [29].

with 10 wt.% graphene had electrical conductivity of 1.5 × 10−7 S/m. Vadukumpully et al. [27] produced poly(vinyl alcohol) (PVA) and graphene nanomaterials by this route. The 2 wt.% graphene caused 58% upsurge in Young's modulus and 130% enhancement in tensile strength. Inclusion of 6.47 vol.% graphene caused electrical conductivity of 0.058 S/cm. Yang et al. [28] used solution processing route to attain PVA/ graphene nanocomposites. The PVA/graphene nanocomposites have shown fine nanoparticle dispersion and increase in Tg with graphene loading. Kuila et al. [29] studied solution processed PE/graphene nanocomposites. Fig. 3.3 shows the transmission electron microscopy (TEM) image of PE/graphene nanocomposites with 3 wt.% graphene. Homogeneous dispersion of graphene nanosheets in the matrix may be attributed to fine interfacial interactions between the matrix and graphene. Yao et al.[30] formed well-dispersed epoxy/graphene materials. The thermal conductivity epoxy/graphene nanocomposites with 5 wt.% graphene nanosheets was 0.56 W/mK, that is, 2.5 times higher than neat epoxy [31-33]. Kim et al. [34] prepared polyurethane/graphene nanocomposites using solution blending and melt compounding. Solution blending was found to efficiently dispense graphene nanosheet in the matrix, compared with the melt processing. Nanocomposites of graphene have also been attempted with several other polymers through solution casting [35-37]. Mahmoud et al. [38] studied the morphology of properties of PEO/graphene nanocomposites. According to TEM, morphology of solution blended nanocomposites depicted fine graphene dispersal in PEO matrix compared with the melt route. Polyaniline [39-41], polythiophene [42-44], polypyrrole [4547], polyethers [48-50], polyesters [51-53], etc. have been processed using solution method. Solution blending has been found effective to enhance the glass transition temperature [54-56], electrical conductivity [57-59], thermal conductivity [60-62], strength [63-65], modulus [66-68], toughness [69-71], and thermal properties [72-74] of polymer/graphene nanocomposites. This method led to fine dispersion of graphene nanosheet in polymer matrices, which in turn may enhance the interfacial interactions and physical properties of the nanocomposites. However, it has been observed that the organic solvents may be adsorbed between the graphene layers [75-77]. The adsorption of organic

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Chapter 3  Processing strategies in graphene-derived nanocomposites

solvents influences the performance of the polymer/graphene nanocomposites [78-80]. The solvent adsorption has been studied using elemental analysis, Fourier-transform infrared spectroscopy, and nuclear magnetic resonance techniques [81-85]. Graphene oxide has more tendency to adsorb moisture owing to surface functional groups, compared with the graphene [86-88]. Studies have also been carried out regarding the removal of solvent molecules inserted in the graphene layers [89-91]. However, it is quite difficult to remove solvent molecules entirely from graphene layers even at high temperatures. Highly polar aprotic solvent such as dimethyl sulfoxide, N,N-dimethylformamide, hydroxymethylfurfural, acetone, etc. are among the solvents having high removal temperatures [9294]. The chloride solvents such as chlorobenzene, dichloromethane, chloroform, and carbon tetrachloride are also retained in the graphene layers [95-97]. Due to toxic nature of organic solvents, solution blending is not an environmentally friendly method for large-scale production [98-102]. Consequently, this method may not be preferred for large-scale manufacturing of polymer/graphene, relative to the melt blending technique.

3.3  Polymer/graphene nanocomposites via melt blending Melt blending has been used as an ideal method for preparing polymer/graphene nanocomposites [103105]. In this method, polymer is melted and fed into an extruder. The desired amount of graphene is also introduced into the compounding set-up (Fig. 3.4). It is also carried out in the presence of an inert gas (argon, nitrogen, or neon). Tan and Thomas [106] reviewed melt cast polymer/graphene nanocomposites. Nanosheet orientation, stacking, and polymer chain confinement in the nanocomposites have been discussed. Owing to the absence of organic solvents, this method has been considered as an environment friendly. Melt blended polyamide 6 (PA6)/graphene nanocomposites were prepared by Scaffaro and Maio [107].

FIG. 3.4  Melt compounding set-up of polymer/graphene nanocomposites.

3.3  Polymer/graphene nanocomposite via melt blending

49

FIG. 3.5  Transmission electron microscopy (TEM) of polyamide 6 (PA6) with 0.5 wt.% nanofiller [107].

Fig. 3.5 shows graphene nanosheet totally wetted by PA6 melt matrix. Uniform dispersion and no aggregates were observed with the nanofiller. Yan et al. [108] filled graphene in polyamide 12 matrix by melt compounding. The electrical conductivity of neat polyamide 12 was low ∼2.8 × 10–14 S/m. Insertion of 1.38 vol.% graphene enhanced the electrical conductivity to 6.7 × 10–2 S/m. Kausar [109] introduced graphene in polyamide1010 matrix. Nonflammability and strength of the nanocomposites were found to increase with graphene loading. Graphene has found to enhance the strength, stiffness, heat stability, and chemical resistance of engineering polyamides [110-113]. Bao et al. [114] dispersed graphene in poly(lactic acid) using melt blending. The percolation threshold was achieved at 0.08 wt.% graphene. Istrate et al. [115] designed polyethylene terephthalate (PET)/ graphene nanocomposites. The PET/graphene nanocomposites with 0.07 wt.% graphene enhanced the tensile strength up to 40%, relative to pristine PET. Maiti et al. [116] also reported PET/graphene nanomaterials with melt method. Shen et al. [117] reported melt blending of PS/graphene nanocomposites. The materials exhibited homogeneous dispersion and enhanced electrical properties owing to π–π stacking interactions between PS and graphene. El Achaby et al. [118] prepared polypropylene (PP)/ graphene nanocomposites via melt mixing. Graphene loading caused superior mechanical and thermal properties of these nanocomposites. Ryu and Shanmugharaj [119] studied interfacial interactions in melt processed PP/graphene nanocomposites. Jiang et al. [104] incorporated graphene into PMMA matrix through melt technique. During melt mixing, PMMA developed good compatibilization and interfacial between the matrix and graphene. Mittal et al. [120] introduced graphene in PP, PS, polycarbonate, high-density polyethylene, and linear low-density polyethylene through melt mixing. Ansari et al. [121] formed PVDF and graphene nanosheet nanocomposites by compression molding. Storage modulus of the  nanocomposite was found to enhanced with graphene loading. Consequently, melt blending is an adaptable technique for various thermoplastic polymers. It is a cost-effective, mass production, and ecofriendly technique [122]. This method is also well-matched with the current industrial processes in advance fields. However, the disadvantages of this technique lie in poor graphene dispersion and stacking in the polymer matrix [13]. Compared with the other fabrication methods, melt blending has been used as an efficient and environmental friendly method for polymer/graphene

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Chapter 3  Processing strategies in graphene-derived nanocomposites

nanocomposites [123]. There is no use of organic solvents involved in this method. In this method, the direct addition of graphene in polymers is advantageous [124]. Moreover, the parameters such as temperature, blending time, and twin-screw extruder speed can be easily adjusted [125]. Thus, the production of large-scale commercial products is facile using this technique. Wide range of polymers (PS, styrenic copolymers, PP, poly(ethylene terephthalate), polyurethane, epoxy, etc.) have been processed with graphene using the melt method [126]. Nevertheless, the melt method may lead to deprived dispersion of graphene in the polymer matrices. Poor dispersion may lead to low mechanical properties and performance parameters of polymer/graphene nanocomposites [127, 128].

3.4  Polymer/graphene nanocomposites via in situ polymerization In situ polymerization technique has also been used to polymerize or graft polymer chains on the graphene surface. Polymer can be physisorbed polymer on graphene surface. The chemical bonds can also be formed between the polymer chains and graphene. Henceforth, grafting-to and graftingfrom approaches are also observed. The grafting-to methodology introduce covalent bonds between polymer and graphene. In grafting-from tactic, polymer molecules are covalently anchored on graphene surface. This technique is efficiently used to enhance the nanofiller dispersion and physical properties. The method is also considered as environmental friendly. Different polymers have been in situ polymerized on graphene surface [125]. PA6 nanocomposites were prepared through in situ polymerization of ε-caprolactam monomer, by Zheng et al. [129]. The 1.64 vol.% graphene led to percolation threshold of ∼0.41 vol.% and electrical conductivity of ∼0.028 S/m. Chen et al. [130] prepared PA6 nanocomposites with graphene and graphene oxide through in situ polymerization. Graphene enhanced the thermal conductivity at low nanofiller loading. Ding et al. [131] prepared PA6/ graphene nanocomposites by in situ route. Thermal conductivity of PA6/graphene was enhanced from 0.293 W/m/K (neat polymer) to 0.265 W/m/K. Xu et al. [132] prepared PA6/graphene nanocomposites by in situ polymerization of ε-caprolactam in the presence of graphene oxide. The 0.1 wt.% loading enhanced the tensile strength by 2.1 folds and Young's modulus by 2.4 folds, compared with neat polyamide. The ε-caprolacatam monomer was introduced on functional graphene surface, which was in situ polymerized to formed polyamide chains on graphene surface (Fig. 3.6). Patole et al. [133] used in situ polymerization to form PS/graphene nanocomposites. Graphene formed good compatibility and interaction with the matrix. Hu et al. [134] developed in situ emulsion polymerization. Styrene monomer was dispersed in graphene and surfactant mixture (Fig. 3.7). Styrene monomer was adsorbed on graphene surface and in situ polymerized. The in situ PS/graphene nanocomposites have shown fine electrical conductivity, glass transition temperature, and thermal stability. Lu et al. [135] performed in situ polymerization of graphene and prepolymerized styrene monomer. Wang et al. [136] prepared PMMA/graphene nanocomposites using in situ suspension polymerization. It was observed that the PMMA microspheres of 2 μm were covalently link to graphene surface. Bose et al. [137] in situ generated polypyrrole/graphene nanocomposites with improved conductivity. Lee et al. [138] prepared waterborne polyurethane and graphene nanosheet by an in situ method. The modulus was improved by reinforcing effect of graphene. The low percolation threshold of 0.078 vol.% was observed for polyurethane/graphene [18]. Among the advantages of in situ polymerization are the strong interfacial interaction between matrix/ nanofiller and facile nanocomposite processing [139, 140]. Better interfacial interaction in polymer/

3.4  Polymer/graphene nanocomposite via in situ polymerization

FIG. 3.6  In situ polyamide/graphene nanocomposites.

FIG. 3.7  In situ polystyrene/graphene nanocomposites.

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Chapter 3  Processing strategies in graphene-derived nanocomposites

graphene may lead to better mechanical and physical properties of these materials [141, 142]. In this method, the graphene is dispersed within the liquid monomer [143, 144]. Then an appropriate initiator is diffused for the polymerization [145, 146]. Sometimes, heat or radiations are also used. In situ polymerization technique is also successful to develop covalent bonding between the polymer and functional graphene nanosheets [147, 148]. However, in this method major drawback is the increase in the viscosity of medium as the polymerization proceeds [149, 150]. Beside the disadvantages, in situ polymerization has been employed to form several polymer graphene systems of important uses [151-154].

3.5  Electrospinning method Electrospinning is an advantageous and effectual technology to form continuous nanofibers using electric field [155-157]. Electrospinning method has been used to form graphene reinforced polymeric nanocomposite fibers [158]. Graphene reinforcement has found to enhance the electrical, thermal, and mechanical characteristics of the electrospun nanocomposite [159]. Scanning electron microscopy has been used to study the morphology of fibers [160]. Raman spectroscopy is also used to study fiber structure [161]. In electrospinning process, the basic electrospinning set-up is used containing spinneret, high-voltage system, and collector [162, 163]. The parameters of electrospinning set-up and procedure can be modified to control the electrospun fiber structure and morphology. During electrospinning, the polymer solution is formed and fed into the vessel. Under high supplied voltage, the polymer solution forms droplet at needle tip [164]. The droplet then forms a cone shape under electrostatic forces. The polymer jet is formed and move to the spinneret under strong electrostatic forces [165]. These forces are the driving power for the electrospinning process [166]. Thus, electrospinning is a characteristic method of employing electrostatic field to generate ultrafine nanofibers in short time span. Mostly, this method is successful and no technical problems of low output low efficiency, and poor nonalignment have been observed [167]. For polymer/graphene nanocomposite nanofiber fabrication, scientific community is increasingly using electrospinning technology [168-170]. The electrospinning technique has been recognized as an efficient and convenient method for forming functional polymer/graphene nanofibers [171]. The performance of the electrospun polymer/graphene nanofibers can be enhanced through obtaining fine topography and orientation of the nanofibers. The electrospun polymer/graphene nanofibers have fine morphology, hydrophobic nature, mechanical strength, and compatibility toward the technical systems [172-174]. Advanced polymer/graphene electrospun nanofibers have been applied in membranes, coatings, sensors, energy devices, aerospace related structures, and tissue-engineering applications [158, 175-178]. This method can be combined with other approaches such as solution, melt, and in situ techniques to overcome their disadvantages [179, 180]. Consequently, the electrospun nanofibers have countless potentials for next-generation polymer and graphene nanocomposites. The latest advances in the development of polymer/graphene nanocomposite electrospun nanofibers have stimulated the interests in academia and industry.

3.6  Other processing techniques There are range of other techniques used to fabricate polymer/graphene materials. Interfacial polymerization has been used to develop polyaniline/graphene nanocomposites [181]. However,

3.7  Morphology of polymer/graphene nanocomposites

53

interfacial polymerization has been less frequently used for the polymer/graphene nanocomposites. Emulsion method has been employed to form polymer/graphene nanocomposites [182]. This technique facilitates better sorption, exfoliation, and dispersion of graphene in polymers. This method is also less used for polymer/graphene nanocomposites. ATRP technique has been used to form graphene nanocomposites with styrene, methyl methacrylate, or butyl acrylate [183]. In this way, the PS/ graphene, PMMA/graphene, and polybutyl acylate/graphene nanocomposites. RAFT polymerization has been used to form poly(N‐isopropylacrylamide) and graphene nanocomposites [184]. This technique may lead to better π–π stacking interaction between polymer and graphene. The poly(N‐ isopropylacrylamide)/graphene oxide nanocomposites have been prepared using RAFT [185]. The PMMA/graphene nanocomposites were prepared via bulk polymerization and microwave irradiation [186]. The microwave irradiation caused better nanofiller dispersion, morphology, thermal stability. PP/graphene oxide nanocomposites were developed by the Ziegler–Natta polymerization [187]. The potentiostatic deposition was prepared by the polypyrrole/graphene nanocomposites [188]. The frontal polymerization has also been used to form thermoresponsive poly(N-isopropylacrylamide)/ graphene nanocomposites [189]. The PMMA, PS, PVDF, and graphene colloids have been developed using colloid technique [190]. The colloid method was also used to form graphene-containing hydrogel [191]. In this method, colloidal aggregation/gelation effect must be avoided to obtain the homogeneously dispersed nanocomposites. The latex technology, cryomilling, and lyophilization are also applied to polymer/graphene nanocomposites. The layer by layer (LBL) assembly technique also offers promising way to control the polymer/graphene morphology and physical properties [192-194]. Additionally, the LBL technique allows facile incorporation of graphene in the organic polymers. This processing technique offers very high nanofiller loading compared with the other composite processing techniques [195]. Moreover, this method has high production rate and low cost. All these techniques need essential parameter optimization to obtain high-performance polymer/graphene nanocomposites. The incorporation of low graphene nanofiller content in polymers using appropriate method has found to enhance the structural and functional properties of the nanocomposites. Table 3.1 shows summary of processing methods used for various polymer/graphene nanomaterials.

3.7  Morphology of polymer/graphene nanocomposites Polymeric nanocomposite morphologies are important to understand for the potential industrial applications [196-199]. Micro- or nanofibrillar composites have shown different morphologies compared with the conventional composite materials [200]. The morphology of the nanocomposites depends on the nanofiller type, nanofiller functionality, nanofiller dispersion in matrix, matrix–nanofiller interactions, processing method used, and several other parameters [201-203]. Fine nanofiller dispersion may lead to homogeneous morphology and in turn enhanced thermal stability and excellent mechanical properties [204-206]. The melt method may cause nanofiller aggregation and the morphology may vary at various stages of the extrusion and drawing [207-209]. The final material properties and applications rely on the generated morphology by melt method [210]. Despite of some disadvantages of solution blending, the morphology of the solution processed nanocomposites is reasonably dispersed and found better than the melt processed systems [208, 211, 212]. The nanocomposite membranes containing electrospun fibers have exclusively dispersed and well aligned morphology studied according to scanning electron microscopy, TEM, and other morphological techniques [213-215]. Morphology of the in situ

54

Chapter 3  Processing strategies in graphene-derived nanocomposites

Table 3.1  Processing and properties of polymer/graphene nanomaterials. Matrices

Nanofiller

Processing method

Ref.

PMMA

Graphene

Solution method

[22]

PMMA

Graphene

Solution method

[24]

PS

Graphene

Solution method

[25]

PVA

Graphene

Solution method

[27]

PVA

Graphene

Solution method

[28]

PE

Graphene

Solution method

[29]

Epoxy

Graphene

Solution method

[30]

PMMA

Graphene

Melt compounding

[104]

PS, PC, PP, HDPE, LDPE

Graphene

Melt compounding

[120]

PVDF

Graphene

Melt compounding

[121]

PA6

Graphene

In situ polymerization

[130]

PA6

Graphene

In situ polymerization

[131]

PS

Graphene

In situ polymerization

[135]

PMMA

Graphene

In situ polymerization

[136]

Polypyrrole

Graphene

In situ polymerization

[137]

Waterborne polyurethane

Graphene

In situ polymerization

[138]

Polyaniline

Graphene

Interfacial polymerization

[181]

PMMA, PS, polybutyl acylate

Graphene

ATRP

[183]

Poly(N‐isopropylacrylamide)

Graphene

RAFT

[185]

PMMA

Graphene

Microwave irradiation

[186]

Polypropylene

Graphene

Ziegler–Natta polymerization

[187]

Poly(N-isopropylacrylamide)

Graphene

Frontal polymerization

[189]

PMMA, PS, PVDF

Graphene

Colloid method

[191]

polymerized nanocomposites is also uniform and unvarying [216, 217]. Usually, the high aspect ratios of nanofillers may also result in superior mechanical and thermal performance of the nanocomposites [218, 219]. However, it is quite challenging to achieve uniform dispersion of nanofillers in the polymers and consequently the uniform morphology [220]. In the case of graphene nanofiller, it has high aspect ratio to develop van der Waals interactions between the nanofiller particles [221, 222]. Similarly, the graphene flakes may aggregate with in the polymer matrices. The nanofiller aggregation may also result in the polymer chain entanglement [223, 224]. The inter-planer π–π interactions in graphene also prevent its dispersion in the matrices [225-227]. The nanofiller agglomeration in the polymer matrices may form a phase-separated structure [228-230]. The oxidized graphene filler (also known as graphene oxide) may form better linkages with the polymer matrix [231]. Sometimes chemical bonding may also develop between the functional graphene and polymer matrix [232]. The chemical bonding in turn prevents graphene agglomeration in the matrix due to better adhesion in polymer/graphene [30, 233]. The graphene nanofiller functionalization enhanced the compatibility between graphene oxide and polymer through improved dispersion [234-236]. In polymer and graphene-based materials

References

55

mechanical interlocking and interfacial bonding energy may play significant roles in interfacial bonding characteristics [237, 238]. The molecular dynamics and molecular simulation studies have been carried out to study the polymer and graphene-based materials [239-242]. Functional groups on the surface of graphene may strongly interlock with the polymer chains to enhance the load transfer properties [243, 244]. The interactions between functional graphene and polymers have resulted in well aligned and homogeneous morphology [13]. The polymer/graphene nanocomposites may form well-dispersed structure due to effective filler reinforcement [245, 246].

3.8 Summary Various strategies have been used to prepare the polymer/graphene nanocomposites. The right selection of a method directly affects the electrical, mechanical, thermal, and morphological properties of these polymer/graphene nanocomposites. Common methods used are solution mixing, melt compounding, in situ polymerization, electrospinning, interfacial polymerization, ATRP, RAFT, microwave irradiation, Ziegler–Natta polymerization, frontal polymerization, LBL, and colloid method. The most widely used methods are melt compounding, solution processing, in situ polymerization, and electrospinning. Though, each method has relative advantages and disadvantages. Melt method is found advantageous; however, it has disadvantage of poor dispersion. Solution method lead to fine dispersion but has disadvantage of environmental toxicity. The in situ method also have disadvantage for nonprocessability on large scale. The fine dispersion of graphene nanosheet and morphology is demanding for highperformance graphene-based materials. The nanofiller functionality also enhances the better dispersion and fine morphology of matrix/nanofiller. The research progress is needed to understand the processing parameters and development of new versatile techniques for polymer/graphene nanocomposites. In short, different manufacturing methods have been used to form the polymer/graphene nanocomposites. The materials formed using suitable method have fine morphology and enhanced electrical, mechanical, and thermal properties.

Key terms and definitions Thermoplastic

a polymer which becomes soft on heating and hardened when cooled

Thermosetting

polymer which is irreversibly hardened by heating

Dispersion

distribution of nanoparticles in polymer matrix

Compatibility

mutual miscibility of two or more materials

Morphology

particular form/shape of a material

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[230] B. Wang, S. Krause, Properties of dimethylsiloxane microphases in phase-separated dimethylsiloxane block copolymers, Macromolecules 20 (9) (1987) 2201–2208. [231] S. Stankovich, et al., Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide, Carbon 45 (7) (2007) 1558–1565. [232] R. Aradhana, S. Mohanty, S.K. Nayak, Comparison of mechanical, electrical and thermal properties in graphene oxide and reduced graphene oxide filled epoxy nanocomposite adhesives, Polymer 141 (2018) 109–123. [233] Y.-J. Wan, et al., Covalent polymer functionalization of graphene for improved dielectric properties and thermal stability of epoxy composites, Compos. Sci. Technol. 122 (2016) 27–35. [234] J. Rivnay, et al., Quantitative determination of organic semiconductor microstructure from the molecular to device scale, Chem. Rev. 112 (10) (2012) 5488–5519. [235] D.R. Kozub, et al., Polymer crystallization of partially miscible polythiophene/fullerene mixtures controls morphology, Macromolecules 44 (14) (2011) 5722–5726. [236] C.R. McNeill, Morphology of all-polymer solar cells, Energy Environ. Sci. 5 (2) (2012) 5653–5667. [237] C. Lv, et al., Effect of chemisorption on the interfacial bonding characteristics of graphene−polymer composites, J. Phys. Chem. C 114 (14) (2010) 6588–6594. [238] K.M. Shahil, A.A. Balandin, Thermal properties of graphene and multilayer graphene: applications in thermal interface materials, Solid State Commun. 152 (15) (2012) 1331–1340. [239] S. Frankland, et al., Molecular simulation of the influence of chemical cross-links on the shear strength of carbon nanotube−polymer interfaces, J. Phys. Chem. B 106 (12) (2002) 3046–3048. [240] L. Yan, et al., Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials, Chem. Soc. Rev. 41 (1) (2012) 97–114. [241] A.N. Rissanou, A.J. Power, V. Harmandaris, Structural and dynamical properties of polyethylene/graphene nanocomposites through molecular dynamics simulations, Polymers 7 (3) (2015) 390–417. [242] J. Zhang, D. Jiang, Molecular dynamics simulation of mechanical performance of graphene/graphene oxide paper based polymer composites, Carbon 67 (2014) 784–791. [243] B. Qi, et al., Enhanced thermal and mechanical properties of epoxy composites by mixing thermotropic liquid crystalline epoxy grafted graphene oxide, Express Polym. Lett. 8 (7) (2014) 467–479. [244] L.-Z. Guan, et  al., Toward effective and tunable interphases in graphene oxide/epoxy composites by grafting different chain lengths of polyetheramine onto graphene oxide, J. Mater. Chem. A 2 (36) (2014) 15058–15069. [245] C. Wan, B. Chen, Reinforcement and interphase of polymer/graphene oxide nanocomposites, J. Mater. Chem. 22 (8) (2012) 3637–3646. [246] M. Bhattacharya, Polymer nanocomposites—a comparison between carbon nanotubes, graphene, and clay as nanofillers, Materials 9 (4) (2016) 262.

CHAPTER

Nano-foam architectures of polymer and graphene

4

4.1 Introduction Recently, scientists have focused the fabrication of graphene nano-foam using two-dimensional (2D) graphene nanosheet [1, 2]. Graphene is a single layer of atoms with crystalline structure. It is a nanoallotrope of carbon. The 2D graphene has potential applications in the solar cell, electronics, semiconductors, and water purification. The layered amalgamation of 2D material due to van der Waals interactions may form structure as graphite or aggregated arrangement [3, 4]. The 2D graphene offers platform for the formation of heterostructure having extraordinary performance–property relationship [5]. Recently, research has switched from the 2D graphene nanosheet toward the three-dimensional (3D) graphene architecture. The 3D graphene architecture is commonly known as the graphene nano-foam. The 3D graphene nanofoam or sponge or aerogel has unique nanoporous and flexible morphology. Microscopic studies have been used to confirm the 3D hierarchical nano-foam nanostructure. 3D graphene network has been developed to obtain advance potential of nano-foam architectures in compositing, energy, environment, and biomedical applications [6]. The 3D graphene nano-foam possesses almost all the inherent properties of graphene nanosheet [7]. The highly porous, flexible, robust, electrically conducting, and thermally transporting 3D graphene nano-foam has been of considerable interest for high-performance technical fields [8]. The graphene nano-foam has been developed using template, sol gel, hydrothermal, chemical vapor deposition (CVD), freeze-drying, supercritical drying, and several other methods [9-11]. In these methods, 2D graphene nanosheets are interconnected to form 3D graphene network. The highly conducting network possesses high surface area, ultrahigh porosity, low density, and exceptional mechanical properties [12, 13]. The integration of graphene nanosheet into nano-foam has enhanced the potential for electronic devices, supercapacitors, batteries, photovoltaics, and other energy-related applications [14]. Potential of graphene nanofibers has also been found in nano-foam architectures. This chapter summarizes recent progress in the design of 3D graphene network, graphene nanocomposite nano-foam, and structure-property characterization. The book section is unique in terms of transformation of 2D graphene nanosheet toward the 3D graphene nano-foam. It is worth noting that the latent of 3D graphene nano-foam is comparable or even better than the 2D graphene nanosheet. This fact is reflected in wide ranging promising application areas of these nano-foam materials.

4.2  Nano-foam nanostructures Carbon nano-foam has been considered as a nanoallotrope of carbon [15-18]. It has a 3D nanostructure. The carbon atoms may form a mist-like arrangement in the aerogel [19, 20]. There is an interconnected nanoclusters of the carbon atoms having a regular hexagonal pattern [21, 22]. The structure of the carbon Graphene to Polymer/Graphene Nanocomposites. DOI: https://doi.org/10.1016/B978-0-323-90937-2.00001-0 Copyright © 2022 Elsevier Inc. All rights reserved.

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Chapter 4  Nano-foam architectures of polymer and graphene

nano-foam was studied by Rode et al. [23, 24]. The laser pulse method was used on the carbon target in an inert atmosphere [25, 26]. These nano-foam are lightweight materials having density of ∼2 mg/cm3 [27, 28]. Carbon nano-foam had extremely high surface area and electrical insulating properties [29]. It has transparent and brittle structure. The carbon nano-foam possesses unpaired electrons leading to the ferromagnetism phenomenon at room temperature [30-32]. Though, the ferromagnetic property of the carbon nano-foam exists below 90  K [33-35]. The carbon nano-foam has high magnetic properties to be employed in spintronic devices [36, 37]. These materials have also been used in the biomedical applications and bioimaging [38, 39]. There is the indication of the schwarzite layers in the graphene nano-foam [40-42]. The high-resolution scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have revealed the knitted patterns of graphene nanosheets [43-45]. The 3D nanostructure has carbon bond length of 5.6 Å [43, 46]. The nanosponge mesophases have also been studied using microscopic techniques [47-50]. The nanostructures of hyperbolic graphitic nanosheets including pore size and diameter have been measured and investigated. The hyperbolic structure can be considered to form the 3D schwarzite nanosheets. The nano-foam or nanoaerogels have been employed in the insulation materials [51]. These materials have nanoholes or nanobubbles in the nanostructures [52-54]. These insulation materials have been used to prevent the greenhouse gas emissions causing the global heating [55-57]. Initially, such materials were produced in 1930s for the thermal insulation on commercial scale [58]. The nano-foam or aerogels are often referred as the solid smoke especially when combined with silica [59-61]. The nano-foam need to be further researched for the construction sector to achieve the high-performance insulation structures [62, 63]. The nano-foam displays low or high dielectric constant, that is, essential for the significant electrical properties [64, 65]. The dielectric constant is usually considered as a force between the charges in the medium [66]. The dielectric effects offer important parameters for the charge transport and polarization through the medium [67, 68]. Usually low dielectric constant leads to the high charge transport through any medium. The speed of the generated electrical signal can also be measured. The nano-foam materials having low dielectric constant have found applications in the microelectronics and the electronic applications [69-71]. The nano-foam nanostructures with high dielectric constant have been found useful for capacitor applications [72-74]. The interfaces of low-density nano-foam nanostructured materials are also important to study [75-77]. The interactions between the nano-foam constituents may lead to a well-formed interface. The periodic provisions in the 3D graphene may lead to the agglomerated or crosslinked nanostructures [78-81]. The simulation or computational studies have been performed on the nanofoam nanostructures with or without the nanoparticles [82-84]. The incorporation of carbon nanotube or carbon nanofibers may also affect the agglomeration or crosslinking in the nano-foam [85-87]. The inclusion of the carbon nanostructures may generate sp3 sites in the 3D nano-foam network. The rigidity of the 3D nano-foam is enhanced with the nanoparticles. The 3D nano-foam may have high thermal conductivity, electrical conductivity, and optical absorption [88-90]. Similarly, the graphene nanoribbons have also been included in the nano-foam structures [91-93]. The mechanism for the formation of low-density 3D interconnected nanostructures with the nanocarbons needs to be studied in the future [94-96].

4.3  Three-dimensional graphene nanostructures Graphene has intrinsic 2D structure with the carbon atoms arranged in the honeycomb-like structure [97-99]. The 2D graphene has potential for the advance applications [100]. The 2D atomically thin graphene nanosheets can be arranged into the 3D macroscopic architectures [100]. The 3D graphene

4.4  Synthesis and properties of 3D graphene

69

FIG. 4.1  Scanning electron microscopy (SEM) images of three dimensional (3D) graphene network/nickel foam at 2 µm [107].

not only owns intrinsic properties of graphene nanosheet, but also offer the innovative physicochemical properties [101]. The unique 3D graphene network structure possesses large specific surface area, ultrahigh porosity, high electrical conductivity, thermal transportation, mechanical robustness, and flexibility [102, 103]. The construction of 3D network also evades the problem of crumbling and restacking of the graphene nanosheets [3]. Various routes have been used to form the 3D graphene network with the different morphologies [104-106]. Initially, the 3D graphene nano-foam was synthesized using the nickel foam template [10]. Deng et al. [107] designed the 3D graphene network/ nickel foam using CVD. Fig. 4.1 depicts the morphology of 3D graphene network/nickel foam. The graphene nano-foam has shown wrinkles due to the thermal expansion of Ni and graphene materials. The wrinkles led to large surface area and mechanical robustness of the graphene nano-foam [108]. This material was used as hybrid supercapacitor electrode with the specific capacitance of 321 F/g. Zhang et al. [109] also designed the 3D nano-foam of titanium dioxide (TiO2)-graphene via one-pot method. The material was used for adsorption-photoelectrocatalytic degradation of the bisphenol A. The inherent features and unique morphology of the 3D graphene have led to several advance technical applications. The 3D graphene is also known as graphene foam (GF) or nano-foam, graphene sponge (GS), and graphene aerogel (GA) [110]. Similar to a sponge, the graphene nano-foam owns efficient absorption and recyclability [111, 112].

4.4  Synthesis and properties of 3D graphene Graphene is a 2D layer of the hexagonally packed carbon atoms [113-115]. In the graphene hexagonal lattice, sp2 hybridized carbon atoms form out of plane π bonding [116-118]. The sp2 hybridized carbon atoms donate to the delocalized electron network. While the in-plane C–C connection is due to the σ bonding. The σ bonds form a stable and strong structure. The π bonds are accountable for the electron conductivity in the graphene structure. The π bonding also provides weak interactions between the

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Chapter 4  Nano-foam architectures of polymer and graphene

individual graphene layers [119-121]. Owing to the conjugated graphene structure, the scientific research has focused the exceptional physical properties of this important nanocarbon [122-124]. Graphene has shown the unique charge carrier behavior increasing its remarkable physical properties. It has been observed that the charge transfer is due to Dirac fermions, that is, massless relativistic particles [125, 126]. These particles are also responsible to some charge scattering in graphene. Moreover, Dirac fermions may lead to several other extraordinary phenomena of graphene [127, 128]. Graphene often consists of overlapping valence and conduction bands leading to a zero-bandgap 2D semiconductor material [129-131]. Graphene possesses very high charge carrier mobility at room temperature. It also exhibits strong ambipolar electric field effect [132]. An important phenomenon observed in graphene is quantum Hall effect [133-135]. According to the quantum Hall effect, using an electric field effect can potentially transport the electrons and holes in graphene [136-138]. Graphene has a transparent structure having visible light absorption of ∼2.3%. The single graphene layer nanosheet has thermal conductivity of ∼5000 Wm/K (room temperature) [139-141]. Graphene has fine mechanical strength properties, so it is a very strong material [142, 143]. The intrinsic mechanical properties of a free standing graphene monolayer were studied using nanoindentation [144-146]. The Young’s modulus of graphene is ∼1.0 TPa [147, 148]. Graphene may form variety of multifunctional architectures. Graphene has found potential in number of field such as sensors, actuators, energy devices, electronics, and composite structures [149-155]. However, the advanced applications of graphene need several design opportunities for exceptionally enhanced physical properties. The individual graphene nanosheets have been employed to form unique macroscopic structures such as 3D graphene nano-foam or 3D macroassemblies [156-158]. Various fabrication methods have been employed for the fabrication of 3D graphene assemblies [13, 108, 159]. The 3D graphene assemblies have been developed using physical interactions especially the van der Waals forces. These forces may form a stable 3D network structure [160-163]. The stable 3D graphene has considerably enhanced physical properties compared with the 2D graphene structures. The 3D graphene assemblies have high Young’s moduli of 102 kPa [164, 165]. The 3D graphene assemblies are also bonded by covalent σ bonds and conjugated π bonds. The 3D graphene assemblies have reasonably high specific surface area (1000 m2/g) and electrical conductivity [166-168]. However, the specific surface areas and electrical conductivity of 3D graphene are considerably lower than the theoretical values studied. Both the 2D graphene and graphene oxide have been used to form the 3D graphene. The sol–gel method has been used to form covalently cross-linked graphene oxide nanosheets with 3D structure [169, 170]. The thermal treatment is also used to form the 3D graphene network through covalent crosslinking [171, 172]. The 3D graphene has high surface area, porosity, thermal conductivity, and electrical conductivity due to the formation of covalently cross-linked structures [173, 174]. Sometimes a covalent binder is also used. These values are definitely higher than the physically cross-linked structures [175, 176]. The chemistry of sol–gel method and thermal treatment is also need to be understand. Graphene oxide behaves better than the graphene during 3D crosslinking using varying chemical approaches. The presence of epoxide, hydroxyl, carbonyl, and other functionalities has enhanced the potential of graphene oxide during chemical crosslinking [177-179]. The thermal reduction of graphene oxide has also led to the formation of a macroassembly network. The crosslinking provides better structural provision and conductivity to the 3D assembly. The crosslinking also limits the aggregation tendency of individual graphene nanosheets. Consequently, these 3D graphene monolith may form carbon bridges to form network [180, 181]. The 3D graphene has shown superelastic structure and mechanical stiffness. To approach the theoretical values of surface area and electrical conductivities of the 3D graphene, new fabrication approaches

4.5  Polymer/graphene-based nano-foam architectures

71

must be focused for physical or chemical crosslinking. Li et al. [182] studied chemical cross-linking method for the formation of the 3D graphene oxide. The hydrolytic condensation technique was used to form covalently assembled 3D graphene oxide. Functional graphene oxide nanosheets were reacted with pyrrole monomers to form 3D polypyrrole/graphene oxide with cross-linked structure [183-185]. The nano-foam morphologies with the mesopores were studied using various techniques as SEM and transmission electron microscopy. The N2 adsorption was used to study the high specific surface area of the nano-foam. The nano-foam structures were also explored using Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. Such type of 3D polypyrrole/graphene oxide foams were useful for enhanced oil and solvent sorption capacities >100 g/g. The formation of 3D covalent network was responsible for the high performance and properties of the nanocomposite foams [186-188]. In addition to CVD, several other techniques have been used to form 3D graphene nano-foam [189-191]. Then, freeze-drying and supercritical drying methods were also used to form cross-linked graphene network. GA has also been prepared using liquid phase self-assembly technique [192]. Moreover, 3D graphene nano-foam and Fe3O4-graphene nanocomposite have been synthesized through direct hydrothermal grafting method [193]. The graphene nanocomposite nano-foam architectures have shown potential for microwave absorption. Template method is also frequently used for nano-foam synthesis [108]. GFs produced using all these techniques possess high surface area, porosity, low density, high electric conductivity, and mechanical features [103]. These 3D graphene materials have been employed in sensors, catalysis, absorbents, energy storage and conversion devices, and biomedical relevances [102].

4.5  Polymer/graphene-based nano-foam architectures Various design strategies have been employed to fabricate 3D nanoarchitectures [194]. The nanocomposite nano-foam materials have been applied in sensors, supercapacitors, solar cells, resonators, nanophotonics, and other applications. The nano-foam impregnated with polymer has high specific surface area, low density, high electrical conductivity, and mechanical characteristics [195]. Yao et al. [196] synthesized the 3D reduced graphene oxide hybrid monolith and composited with polymer using one-pot surfactant-free method. The nano-foam was used to form the supercapacitor electrode. The material has high specific capacitance of 952.85 F/g. Wang and Liu [197] infiltrated epoxy resin into porous graphene nano-foam to form the nanocomposites. Rinaldi et al. [198] developed the poly(dimethylsiloxane) and the graphene nano-foam-based materials. The nano-foam was used to develop pressure sensor to detect the pressure variations of ∼1 Pa. The nano-foam sensor may detect compressive stress of 10 kPa. Salvatierra et al. [199] reported the polythiophene and graphene nano-foam-based nanocomposite through one-pot in situ polymerization reaction. Yuan et al. [200] prepared the polystyrene and 3D nanocomposite nano-foam architectures. The nano-foam were formed by the vacuum filtration of the mixture of the PS matrix and rGO. The field emission SEM images of the polystyrene-wrapped rGO nano-foam and self-supported 3D porous rGO film (rGOF) are given in Fig. 4.2. The GO-wrapped PS formed uniformly packed microstructure. The self-supported 3D porous rGO film has shown the well-defined 3D porous network structure. Thus, the rGOF formed better ionic and electronic transport pathways. The nano-foam had large specific capacitance of 141-206 F/g.

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Chapter 4  Nano-foam architectures of polymer and graphene

FIG. 4.2  Typical field emission SEM images of polystyrene (PS)/graphene oxide (GO) hybrid film (polystyrene wrapped rGO nano-foam) (a); self-supported 3D porous rGO film (rGOF) (b, c); and top-view (d) [200]..

The nano-foam have been used for the thermal management. Loeblein et al. [201] reported the polymer/3D nano-foam nanocomposite (Fig. 4.3). The nano-foam has shown the thermal conductivity of 62-86 W/m/K. The materials were stable up to the 330 °C. Gnanasekaran et al. [202] prepared the polybutylene terephthalate filled with graphene nano-foam. The material was used for the printing of the electrically conductive structures. Jia et al. [203] formed the graphene nano-foam filled epoxy nanocomposites. The material has high fracture toughness of 1.78 MPa•m1/2. The inclusion of 0.2 wt.%

FIG. 4.3  Polymer/ three-dimensional (3D) graphene nano-foam structure.

4.6  Application areas of polymer/graphene-based nano-foam architectures

73

FIG. 4.4  Preparation of 3D reduced graphene oxide (3D-rGO) and 3D-rGO/polyaniline [2].

GF enhanced the electrical conductivity up to 3 S/cm and strength was increased by 38% relative to neat epoxy. Ormategui et al. [204] also prepared the reduced graphene oxide nano-foam and epoxy nanocomposite. Shao et al. [205] prepared the boron nitride nanosheet-based graphene nano-foam and introduced in the polyamide 6 matrix. The nano-foam was introduced during the in situ polymerization of the polyamide. The thermal conductivity of the polyamide 6/boron nitride/graphene nano-foam nanocomposite was 0.891 W/m/K. Tang et al. [2] used the hydrothermal method to form the 3D reduced graphene oxide (3D-rGO) nano-foam. The 3D-rGO was impregnated with the polyaniline. Fig. 4.4 shows the formation of the nanocomposite. The polyaniline /3D-rGO nanocomposite was used as the supercapacitor electrode and has high capacitance of 243 F/g. Li et al. [182] prepared the polypyrrole and graphene nano-foam-based nanocomposite. Better interactions were observed between the polymer and nano-foam. The material has fine oil sorption capacities of >100 g/g. Thus, all the attempts on polymer and nano-foam-based nanocomposites have shown the enhanced properties and mechanical uses.

4.6  Application areas of polymer/graphene-based nano-foam architectures Polymer/graphene-based nano-foam architectures have gained attention in several technical fields. The applications of polymer/3D graphene materials are concisely depicted in Fig. 4.5. By fabricating the 2D graphene into the 3D network, excellent performance in the industrial applications has been achieved. The immense developments and use of electronic devices have led to the unsolicited electromagnetic

74

Chapter 4  Nano-foam architectures of polymer and graphene

Applications of 3D graphene-based materials

Solar cell

3D graphene

Fuel cell

Batteries

Supercapacitor EMI shielding

FIG. 4.5  Applications of three-dimensional (3D) graphene nano-foam.

pollution. The high-performance electromagnetic interference (EMI) shielding materials have been developed using the 3D graphene nano-foam [206, 207]. The high electrical conductivity of GSs is responsible for excellent EMI shielding performance. Moreover, the enhanced elasticity and durability of nano-foam architectures are desirable for the radiation protection. The efficient EMI shielding materials are demanding in the aerospace, soldierly, and range of electronic industries. In this regard, the polyurethane and self-assembled GS-based nanocomposites have been developed using the two-step hydrothermal technique [208-210]. These nanocomposite sponges have EMI shielding effectiveness of 969-1578 dB/cm2/g. The high EMI shielding performance was attributed to the superconductivity of the polyurethane/GSs. For the energy storage and the conversion devices such as batteries, fuel cells, supercapacitors, solar cells, etc., 3D graphene materials have been found competent [211-213]. The poly(methyl methacrylate) reinforced with the graphene nano-foam has been used to form the transparent conductive electrodes for the light-emitting diode [214-217]. For the solar cells, the 3D graphene nano-foam architectures have been used [218-220]. Tang et al. [221] designed the dye sensitized solar cell-based on the 3D graphene using CVD technique. The material was used as photoanode to improve the photovoltaic performance (Fig. 4.6 and Table 4.1). A Pt counter electrode was also used [222-225]. The SEM image of nanocomposite electrode has shown better interconnected architecture. Addition of 1 wt.% graphene nano-foam has shown superior power conversion efficiency (η) and short-circuit current density (Jsc) of 6.58% and 15.4 mA/cm2, respectively. The dye absorption for the 2 wt.% graphene nano-foam loading has shown higher dye absorption of 1.28 × 10−7 mol/cm2. The material has also shown better dye absorption and protracted electrode lifetime [226-228].

4.6  Application areas of polymer/graphene-based nano-foam architectures

75

FIG. 4.6  Indium tin oxide (ITO) dye sensitized solar cell with graphene nano-foam-based photoanode and counter electrode, along with SEM images [221].

Table 4.1  Results of photovoltaic properties and dye loading of the Dye sensitized solar cell (DSSC) with varied photoanodes [221].

Photoanode 3D graphene 0.5 wt.% 3D graphene 1 wt.% 3D graphene 2 wt.%

Short circuit current density (Jsc) (mA/cm2)

Photovoltaic bias (Voc) (mV)

Fill factor (FF) (%)

Efficiency η (%)

Absorbed dye (×10−7 mol/cm2)

13.6

671

63.4

5.79

1.03

15.4 14.1

673 674

63.5 63.2

6.58 6.01

1.15 1.28

In fuel cells, 3D graphene has been employed as catalysts or catalyst supports [229-231]. In addition, graphene nano-foam has been used as anode in microbial fuel cell [232-236]. The anode has resulted in high power density of 427.0 W/m3. In lithium-ion batteries and lithium-sulfur batteries, graphene nano-foam-based electrodes prepared using CVD have been utilized [237-239]. Supercapacitor electrodes of nano-foam graphene were also designed [240-242]. The polypyrrole/3D GA-based electrode has shown specific capacitance of 253 F/g. The electrode also possesses high electrochemical performance and cycle stability [243-245]. Additionally, nano-foam-based materials have revealed ≥95% capacitance, after 1000 galvanostatic charge/discharge cycles. Highly conductive electrodes of graphene-Ag nano-foam with epoxy have also been prepared [246-249]. The electrode has capacitance

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Chapter 4  Nano-foam architectures of polymer and graphene

of 38 mF/cm2 and current density of 0.67 mA/cm2 [250]. Thus, supercapacitors are a useful class of energy storage devices with long lifetime and power efficiency [251-253]. They have function to fulfill electronic transport properties for future applications [254-256]. Graphene nano-foam has been used in textile-based flexible electronics [257-259]. The 3D graphene-based fabrics has fine thermal and moisture transport properties in addition to elasticity and rigidity [260-262]. Graphene-based nanofibers has also been developed for the mentioned energy and technical applications [263]. Electrospun nanofibers have been used to form the aerogel nanostructures [264-266]. Such nanofibers have diameter 10–1000 nm [267-269]. Aerogels have been prepared through the electrospun nanofibers of 2D graphene nanosheets [270-272]. Graphene nanofibers have been used to form mechanically robust multifunctional nanocomposite aerogels [273-275]. The polymer/graphene nanofibers have high surface area, surface wettability, and mechanical properties [276-278]. The polymer/ graphene nanofiber in nano-foam architectures has been applied in membrane application [279-282]. Freeze-drying has been applied to form the nano-foam structures [283-285]. The polymer/graphene nanofiber-based nano-foam possesses low density and high porosity [286-288]. Future attempts are needed for the production of flexible 3D graphene nanofiber-based foams on large scale [289-293]. The polymer/graphene nanofiber-based nano-foam have been found efficient for energy applications, tissue engineering, dyes adsorption, oil–water separation, and other separation and purification applications [294-299].

4.7 Summation Graphene is a one atom thick 2D analog of carbon. The 2D graphene has been used to form a network structure known as nano-foam, aerogel, or nanosponge. Exceptional properties of graphene have been incarnated in graphene nano-foam. The 3D graphene nano-foam is a unique nanomaterial having several advantageous features, relative to neat graphene. The 3D nano-foam architectures have been developed using various techniques. The 3D graphene nano-foam possesses several useful solicitations. Henceforth, the progress has been attained on the design and application of graphene nano-foam nanocomposite with polymers. The particular control of nano-foam nanocomposite nanoarchitectures, using appropriate fabrication technique, has led to high-performance applications of these materials. However, there are several challenges need to be overcome such as pore size, pore distribution, porosity, morphology, and resulting flexibility, durability, conducting, and mechanical properties of the materials.

Key terms and definitions Nano-foam

porous nanostructured material with pore diameter