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 mechani- cal, 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 permis- sions 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. 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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 G raphene: 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 v vi Contents 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 G raphene 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 A dvances 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 Contents vii CHAPTER 8 P olymer/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 G as 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 C utting-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 viii Contents 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 three- dimensional interconnected hierarchical nano-foams and nanofibers, further enhancing the potential of these multifunctional nanomaterials. Various forms of graphene such as graphene quantum dots, gra- phene 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 gra- phene, graphene nanostructures, polymer/graphene nanocomposites, and nano-foam architectures. Chapter 1 (inaugural chapter of the book) emphasizes the unique two-dimensional graphene struc- ture. 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 modifi- cation 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 materi- als 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. ix x Preface Sequential Chapter 4 deals with the unique three-dimensional interconnected hierarchical nano- structures designed using polymer and graphene. Preformed graphene nano-foam has also been in- corporated 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 foam- based 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, fab- rication 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 biomedi- cal 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, characteriza- tion, actuation ways, and multifunctional properties of shape memory polymer/graphene nanocompos- ites have been engrossed. The potential of these materials has been observed in self-healing compos- ites, 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 nanocom- posite coatings. The formation of interconnected percolation network in the matrix also prevents rust- ing phenomenon. Several facile approaches have been researched toward the development of graphene- based 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 interfer- ence 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 so- licitations 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 bio- medical 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 thor- ough coverage of the essential forecasts related to the fundamentals and applications of the graphene and polymer/graphene derived nanomaterials. Ayesha Kausar 2021