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Materials Science Mukhopadhyay Gupta GRAPHITE, GRAPHENE AND THEIR POLYMER NANOCOMPOSITES GRAPHITE, GRAPHENE P G O R POLYMER Perhaps the first of its kind, this book explores emerging research trends in graphene- L A AND THEIR based polymer nanocomposites, including the underlying physics and chemistry. Covering Y P the entire spectrum of graphene-based materials topics, from synthesis to characterization NANOCOMPOSITES to processing and practical applications, this state-of-the-art book provides the point of M H departure for future polymer-based nanocomposites research. The chapter authors, drawn I from experts from around the globe, summarize their recent research and provide their T E perspectives for the future. E R , “The book … covers fundamentally important aspects, starting from graphite, moving on to graphene, and then to their polymer nanocomposites. I find a nice balance between G theoretical aspects and experimental studies. … This is a reference work that should find N R its place among its peers in a scientific library.” —D r. Vassilios Galiatsatos, Fellow SPE, Leibniz Institute of Polymer A A Research, Dresden, Germany N P “… relevant to real-world applications for graphene, graphene-like, and near graphene H O materials that are now reaching the marketplace. … Researchers, applications engineers, manufacturing chemists, polymer scientists, formulators, and other individuals involved in E C graphene materials will be enticed to read further.” N —Albert V. Tamashausky, Asbury Carbons Inc., New Jersey, USA O E “The editors have skillfully compiled virtually the complete spectrum of graphite, graphene, M A and their nanocomposites technology. … Each chapter has been written by a well-known individual possessing extensive firsthand experience combined with complete familiarity P N with the contemporary literature. This handbook has all the ingredients to become one of the most influential resources in this emerging field.” O D —Dr. Raj Chhabra, Indian Institute of Technology (IIT), Kanpur, India S T “This book brings together key players from all over the world, and these researchers I T H present the state of the art in this convenient and easy-to-read edited volume. ... It is Edited by extremely well done … and this book has the potential to act as the guide for those E E contemplating their own journey into this emerging area of materials science and Prithu Mukhopadhyay I engineering.” S R —Dr. Henk Verhoogt, SABIC, Sittard, the Netherlands Rakesh K. Gupta K11372 ISBN: 978-1-4398-2779-6 90000 9 781439 827796 K11372_COVER_final.indd 1 9/14/12 4:17 PM Graphite, Graphene, polymer and their nanocomposites Edited by prithu mukhopadhyay rakesh K. Gupta CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2013 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20120627 International Standard Book Number-13: 978-1-4398-2780-2 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com To the memory of my father who taught me the value of true education. Prithu Mukhopadhyay To my mother who helped me become what I am today. Rakesh K. Gupta Contents Preface.....................................................................................................................vii Editors...................................................................................................................xvii Contributors..........................................................................................................xix 1. Graphite: Structure, Properties, and Applications...................................1 John W. Zondlo 2. Electronic Transport in Graphene: Theory and Applications..............59 Pierre Carmier 3. Different Characterization Techniques to Evaluate Graphene and Its Properties........................................................................95 Viera Skákalová, Dong Su Lee, and Alan B. Kaiser 4. Electrochemical Exfoliation:.A Cost-Effective Approach to Produce Graphene Nanoplatelets in Bulk Quantities.........................139 Martin Matis, Urszula Kosidlo, Friedemann Tonner, Carsten Glanz, and Ivica Kolaric 5. Exfoliation of Graphite toward Graphene from Lab to Industry......169 Weifeng Zhao and Guohua Chen 6. Graphene-Based Materials for Clean Energy Applications...............199 Bin Luo, Minghui Liang, Michael Giersig, and Linjie Zhi 7. Electrochemistry of Graphene-Based Nanomaterials..........................263 Martin Pumera 8. Graphene–Polymer Composites for Pulse Lasers.................................283 Qiaoliang Bao, Dingyuan Tang, Han Zhang, and Kian Ping Loh 9. Epoxy Nanocomposites: Graphene a Promising Filler........................315 Iti Srivastava, Mohammad A. Rafiee, Fazel Yavari, Javad Rafiee, and Nikhil Koratkar 10. Nanoparticles and Polymer Nanocomposites........................................353 Musa R. Kamal and Jorge Uribe-Calderon v vi Contents 11. Polymer-Functionalized Graphene via Atom Transfer Radical Polymerization Route for Graphene-Based Polymer Nanocomposites...........................................................................393 Arun K. Nandi, Rama K. Layek, Sanjoy Samanta, and Dhruba P. Chatterjee 12. Synthesis and Properties of Graphene-Based Nanocomposites in a Biodegradable Polymer.......................................423 Gui Lin, Isao Noda, and James E. Mark 13. Effect of Modified Graphene on Properties of Polypropylene Nanocomposites...........................................................................................447 Olga Shepelev and Samuel Kenig 14. Diffusion through Polymers Containing Platelike Nanomaterials.............................................................................467 Matthew S. Thompson, Sushant Agarwal, Prithu Mukhopadhyay, and Rakesh K. Gupta 15. Using Functionalized Graphene Sheets to Restrain Chemically Driven Composite Aging.....................................................495 J. S. van der Wal 16. Graphene/Polymer Nanocomposites.......................................................513 Hyunwoo Kim, Ahmed A. Abdala, and Christopher W. Macosko 17. Highly Filled Graphite–Polymer Composites: Synthesis, Processing, and Characterization.............................................................557 Sadhan C. Jana and Ling Du Preface Here.we.go.again..After.intercalated.compounds.of.graphite.(1974),.fullerenes. (1985),.and.carbon.nanotubes.(CNTs).(1991),.it.is.time.for.another.allotrope.of. elemental.carbon.to.be.at.the.forefront.of.scientific.curiosity.(Boehm.2010).. The.allotrope.is.“graphene.”.By.graphene,.we.mean.the.basal.plane.of.graphite,.a.one-atom-thick.two-dimensional.honeycomb.layer.of.sp2-bonded.carbon..Conversely,.when.many.graphene.layers.are.stacked.regularly.in.three. dimensions,.graphite.is.created. Why.such.an.interest.in.graphene?.It.is.all.about.the.digital.world,.and.the. search.for.materials.that.will.make.integrated.circuits.smaller,.faster,.and. cheaper!.Graphene.is.a.semiconductor.with.a.zero.band.gap.and.an.excep- tionally.high.charge.mobility..In.fact,.electron.mobilities.in.graphene.could. reach.values.that.are.more.than.an.order.of.magnitude.higher.than.those. encountered.in.an.Si.transistor..This.opens.up.the.tantalizing.possibility.that. one.day.graphene.might.replace.silicon.as.the.building.block.of.the.electronic. industry.and.revolutionize.nanoelectronics..Although.the.existence.of.graphene.had.been.known.for.a.long.time,.the.material.had.never.actually.been. synthesized..This.had.to.await.the.work.of.Andre.K..Geim.and.Konstantin.S.. Novoselov.of.the.University.of.Manchester,.U.K.,.who.were.awarded.the.2010. Nobel.Prize.in.Physics.for.their.ability.to.isolate.a.defect-free,.single.sheet. of.carbon.atoms.through.micromechanical.cleavage.of.graphite,.whereby. monolayers.are.peeled.from.graphite.crystals.(Novoselov.et.al..2004)..This. method,.however,.produces.a.very.small.amount.of.pristine.graphene,.which. makes.it.unsuitable.for.efficient.and.scalable.high-volume.manufacturing.. Nevertheless,.this.pioneering.work.paved.the.way.to.the.rise.of.intense.graphene.research. Important.characteristics.of.graphene.are.that.it.is.nanoscale.in.dimension,. and.it.is.derived.from.graphite,.an.inexpensive.precursor..Consequently,.a. key.goal.of.worldwide.research.has.been.to.produce.a.large.enough.volume. of.pristine.graphene.safely.and.in.a.cost-efficient.manner..Other.researchers. are.seeking.practical.applications.of.graphene.that.will.benefit.society,.espe- cially.in.the.electronics.area. In.the.technical.literature,.a.number.of.methods.have.been.described.for. producing.graphene,.which.can.broadly.be.classified.as.(1).micromechanical. exfoliation,.(2).epitaxial.growth.of.graphene.films,.(3).chemical.vapor.depo- sition.(CVD),.(4).unzipping.of.CNTs,.and.(5).reduction.of.graphene.oxides.. Each.method.has.its.own.benefits.and.related.drawbacks..A.“bottom-up”. approach.using.chemical.synthesis.is.an.interesting.strategy.(Cai.et.al.. 2010;.Choucair.et.al..2009)..However,.scaling-up.to.produce.large.quantities. remains.a.formidable.challenge..Research.efforts.have,.so.far,.established. that.an.easier.route.to.manufacture.large.amounts.of.graphene.is.via.the. vii viii Preface chemical.exfoliation.strategy..During.chemical.exfoliation,.such.as.oxidation. and.subsequent.reduction.of.graphite.oxides,.one.produces.partially.or.highly. reduced.graphene.oxides..From.a.chemical.viewpoint,.these.graphene.sheets. contain.various.types.of.residual.oxygen-containing.species..From.a.physical. viewpoint,.graphene.sheets.become.corrugated,.and.the.graphene.platelets. can.contain.a.variety.of.defects.such.as.topological,.adatoms,.edges/cracks,. vacancies,.loops,.adsorbed.impurities,.and.so.on.within.the.graphene-like. structures.(Terrones.et.al..2010)..When.the.dimensions.of.these.platelets.fall. in.the.nanoscale.range,.they.are.commonly.termed.“graphene.nanoplatelets”. (GNPs)..One.of.the.most.technologically.promising.applications.of.nano- graphene.materials.is.in.polymer.reinforcement..Studies.have.shown.that. stress.transfer.takes.place.from.the.polymer.matrix.to.monolayer.graphene,. indicating.that.graphene.acts.as.a.reinforcing.phase.(Gong.et.al..2010). Polymers.have.been.combined.with.other.polymers.to.form.blends.and. copolymers,.toughened.by.the.addition.of.elastomers,.mixed.with.talc,.cal- cium.carbonates,.and.clays.to.give.filled.systems.and.extruded.and.molded. with.fibers.and.other.anisotropic.reinforcements.to.yield.composites.and. hybrid.materials..This.simple.“mix-and-match”.approach.has.allowed.polymer.scientists.and.engineers.to.utilize.a.small.library.of.polymers.to.produce. a.bewildering.array.of.useful.products.capable.of.possessing.extremes.of. property.values..Traditional.filled-polymer.composites.typically.utilize.high. loadings.of.micron-sized.filler.particles.to.obtain.desired.properties..If.the. filler.particle.size.is.reduced.to.its.nanoscale.dimension.from.its.micron.size,. similar.properties.are.achieved.but.with.a.drastically.reduced.filler.load- ing.level.to.achieve.percolation..Primarily,.this.is.due.to.the.surface.area. to.volume.ratio.of.the.nanoparticles,.which.is.several.orders.of.magnitude. larger.than.that.of.micron-sized.fillers..To.qualify.to.be.called.a.“nanopar- ticle,”.the.particle.has.to.have.at.least.one.dimension.in.the.nanometer.range.. Therefore,.when.nanometer.particles.are.dispersed.in.a.polymer.matrix,.the. result.is.termed.as.“polymer.nanocomposite”.(PNC);.the.matrix.itself.can. be.single.or.multiphase..The.critical.reinforcing.effects.of.nanosized.particles.come.from.their.aspect.ratio,.very.large.specific.surface.area,.and.the. particle–matrix.interactions..The.original.concepts.for.PNCs.owe.their.ori- gin.to.the.invention.of.polyamide–clay.composites.at.the.Toyota.Research. Corporation.in.1985.(Okada.et.al..1988)..At.that.time,.the.objective.was.to. make.plastics.used.in.under-the-hood.applications.heat.resistant.and.lighter. than.metal..Since.then,.the.list.of.nanoparticles.has.grown.and.PNCs.have. seen.numerous.commercial.applications.ranging.from.autoparts.to.packag- ing.to.coatings.(Ashton.2010). The.latest.addition.to.this.palette.of.nanomaterials.is.graphene..Graphene. layers.can.be.stacked,.functionalized,.and.modified.to.provide.numerous. types.of.graphene-based.nanoscale.materials..Rolled-up.graphene,.known. as.CNTs.also.has.some.structural.flexibility..However,.the.performance.and. cost.advantages.of.graphene.challenge.CNTs.in.nanocomposites,.coatings,. sensors,.and.energy.storage.device.applications..For.instance,.the.quality.