Materials Research - Nanocomposites

5/6/2015
MaterialsResearchNanocomposites:synthesis,structure,propertiesandnewapplicationopportunities
Nanocomposites:synthesis,structure,propertiesandnew
applicationopportunities
PedroHenriqueCuryCamargoKesturGundappaSatyanarayana*FernandoWypych
DepartamentodeQumica,CentroPolitcnico,UniversidadeFederaldoParan,Jardimdas
Amricas,81531990CuritibaPR,Brazil
ABSTRACT
Nanocomposites,ahighperformancematerialexhibitunusualpropertycombinationsandunique
designpossibilities.Withanestimatedannualgrowthrateofabout25%andfastestdemandto
beinengineeringplasticsandelastomers,theirpotentialissostrikingthattheyareusefulin
severalareasrangingfrompackagingtobiomedicalapplications.Inthisunifiedoverviewthe
threetypesofmatrixnanocompositesarepresentedunderliningtheneedforthesematerials,
theirprocessingmethodsandsomerecentresultsonstructure,propertiesandpotential
applications,perspectivesincludingneedforsuchmaterialsinfuturespacemissionandother
interestingapplicationstogetherwithmarketandsafetyaspects.Possibleusesofnatural
materialssuchasclaybasedminerals,chrysotileandlignocellulosicfibersarehighlighted.Being
environmentallyfriendly,applicationsofnanocompositesoffernewtechnologyandbusiness
opportunitiesforseveralsectorsoftheaerospace,automotive,electronicsandbiotechnology
industries.
Keywords:composites,layeredcompounds,polymers,metals,ceramics
1.Introduction
Nanocompositesarecompositesinwhichatleastoneofthephasesshowsdimensionsinthe
nanometrerange(1nm=109m)1.Nanocompositematerialshaveemergedassuitable
alternativestoovercomelimitationsofmicrocompositesandmonolithics,whileposing
preparationchallengesrelatedtothecontrolofelementalcompositionandstoichiometryinthe
nanoclusterphase.Theyarereportedtobethematerialsof21stcenturyintheviewof
possessingdesignuniquenessandpropertycombinationsthatarenotfoundinconventional
composites.Thegeneralunderstandingofthesepropertiesisyettobereached2,eventhough
thefirstinferenceonthemwasreportedasearlyas19923.
Thenumberofpublishedpaperscontainingwordssuchasnanoscience,nanotechnology,
nanomaterials,etc.,doubledin1.6years4inthelate1990s.Also,aliteraturesurveymadeby
theauthorsrevealsthatabout13.420papers(ofwhich4028containthekeywords
nanocompositeandpolymerinWebofScienceISI:updatedon10February2009)havebeen
publishedonnanocompositesinthelasttwodecade(19882008).Similarly,patentswith
completedocumentonnanocompositesaccountforabout4663duringthesameperiodasper
Sciruswww.scirus.com).Additionally,specificconferencesandspecialissuesofsomejournals
havebeendevotedexclusivelytotheemergingscienceandtechnologyofnanomaterials.
Ithasbeenreportedthatchangesinparticlepropertiescanbeobservedwhentheparticlesizeis
lessthanaparticularlevel,called'thecriticalsize'(Table1)5.Additionally,asdimensionsreach
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thenanometrelevel,interactionsatphaseinterfacesbecomelargelyimproved,andthisis
importanttoenhancematerialsproperties.Inthiscontext,thesurfacearea/volumeratioof
reinforcementmaterialsemployedinthepreparationofnanocompositesiscrucialtothe
understandingoftheirstructurepropertyrelationships.Further,discoveryofcarbonnanotubes
(CNTs)in19916andtheirsubsequentusetofabricatecompositesexhibitingsomeoftheunique
CNTrelatedmechanical,thermalandelectricalproperties79addedanewandinteresting
dimensiontothisarea.ThepossibilityofspinningCNTsintocompositeproductsand
textiles10madefurtherinroadsfortheprocessingandapplicationsofCNTcontaining
nanomaterials.Nowadays,nanocompositesoffernewtechnologyandbusinessopportunitiesfor
allsectorsofindustry,inadditiontobeingenvironmentallyfriendly11.
Asinthecaseofmicrocomposites,nanocompositematerialscanbeclassified,accordingtotheir
matrixmaterials,inthreedifferentcategoriesasshowninTable2.
CeramicMatrixNanocomposites(CMNC)
MetalMatrixNanocomposites(MMNC)and
PolymerMatrixNanocomposites(PMNC).
Nanocompositesystems,includingthosereinforcedwithCNTs,havebeenextensivelystudied
sincethe1990sand,accordingly,therehasbeenasteadyandcontinuousincreaseinthenumber
ofpublicationsonthesubject,includingreviewsfromtimetotime2,1235.Inspiteofthisgrowth,
themajorityofthereviewsdescribethecurrentstatusofonlyonetypeofnanocomposite.Thus,
thereareonlytworeviewsonCMNC16,32andthreeonCNTreinforced
nanocomposites17,20,27andaquitelargenumberonPMNC16,18,19,21,2835.InthecaseofPMNC,
reviewsdealwithprocessingaspects,includingthoseonlayeredsilicates18,26,conductingand
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biodegradablepolymerbasedsystems19,34,35,fibrereinforced17,20and
structure/morphology/propertyaspects16,35,aswellaswithapplicationsandperspectives,
includingkeyopportunitiesandchallengesinthedevelopmentofstructuralandfunctionalfibre
nanocomposites18,26,29.
Conductingpolymerbasedcompositesarenovelmaterialswithlessthanadecadeofhistory.It
isbelieved19thatthetotalcontrolofthewholeconductingpolymerbasedcompositesystemand
theoptimisationoftheirphysicalproperties(suchaselectricalconductivityandcolloidal
stability)areyettobeachieved,whileboththeircommercialavailabilityinthenearfutureanda
bigleapforwardformaterialsscienceareexpectedwiththeirappropriateutilization.Inthecase
ofbiodegradablepolymerbasednanocomposites,recentdevelopmentsinpreparation,
characterizationandproperties,includingcrystallizationbehaviourandmeltrheology,ofboththe
matrixandthelayered(montmorillonite)nanocompositeshavebeendiscussed34,35.Similarly,
anemphasisontoughnessandinterfacialbondingbetweenCNTsandpolymermatricesis
criticallydiscussed27tounderlinethestresstransferfromthematrixandthepotentialofthese
compositesforpossiblemacroscaleCNTpolymerproduction.Here,problemsencounteredsofar
areconsidered,andhintsgivenregardingacriticalvolumefractionofCNTstogetappropriate
strengthening(asobservedinmicrocomposites)possiblefailuremechanismsinsuchcomposites
arealsopresented.Finally,tothebestofourknowledge,andinviewoftheverylimitedworkon
metalbasednanocompositesincludingtheoneswithCNTreinforcements,noreviewisavailable
todateonthissystem.
Consideringthesefactsandalsotheabsenceofamoregeneralreviewcomprisingthethree
differentkindsofnanocomposites(metal,ceramicandpolymerbased),thispapergivesan
overviewofthem,includingthosewithincorporationofCNTs.However,whiledoingsoonlya
fewrelevantpublications2,4,79,11,14308areconsideredhere.Themainfeatures,currentstatus
andrecentdevelopmentsintheareaareprovided,focussingonthepreparationmethods,
structure,propertiesandapplicationsofthesesystemstoavoidrepetition.Also,thepotential
usesofnanocompositesandtheopportunitiestheyprovide,alongwithperspectivesforthe
futureandmarketandsafetyaspectsarealsopresented.Nanocompositecoatingisnotcovered,
inordertokeepthefocusofthereview.
1.1.Potentialsandopportunitiesinnanocomposites
Beforegoingintodetailsregardingprocessing,structure,propertiesandapplicationsofthethree
typesofnanocomposites,letuslookatthepotentialsofthesesystemsandthegeneral
opportunitiestheyprovide.Ceramicshavegoodwearresistanceandhighthermalandchemical
stability.However,theyarebrittle.Inthiscontext,thelowtoughnessofceramicshasremained
astumblingblockfortheirwideruseinindustry.Inordertoovercomethislimitation,ceramic
matrixnanocompositeshavebeenreceivingattention,primarilyduetothesignificant
enhancementonmechanicalpropertieswhichcanbeachieved.Forexample,theincorporationof
energydissipatingcomponentssuchaswhiskers,fibres,plateletsorparticlesintheceramic
matrixmayleadtoincreasedfracturetoughness309311.Thereinforcementsdeflectthecrack
and/orprovidebridgingelements,hinderingfurtheropeningofthecrack.Inaddition,the
incorporatedphaseundergoesphasetransitioninconjunctionwiththevolumeexpansioninitiated
bythestressfieldofapropagatingcrack,contributingforthetougheningandstrengthening
processes,eveninnanocomposites36.
Thepotentialofceramicmatrixnanocomposites(CMNC),mainlytheAl 2O3/SiCsystem,was
revealedbythepioneeringworkofNiihara37,38.Moststudiesreportedsofarhaveconfirmedthe
noticeablestrengtheningoftheAl 2O3matrixafteradditionofalow(i.e.~10%)volumefraction
ofSiCparticlesofsuitablesizeandhotpressingoftheresultingmixture.Somestudieshave
explainedthistougheningmechanismbasedonthecrackbridgingroleofthenanosized
reinforcements39.Consequently,theincorporationofhighstrengthnanofibresintoceramic
matriceshasallowedthepreparationofadvancednanocompositeswithhightoughnessand
superiorfailurecharacteristicscomparedtothesuddenfailuresofceramicmaterials40.
Metalmatrixnanocomposites(MMNC)refertomaterialsconsistingofaductilemetaloralloy
matrixinwhichsomenanosizedreinforcementmaterialisimplanted.Thesematerialscombine
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metalandceramicfeatures,i.e.,ductilityandtoughnesswithhighstrengthandmodulus.Thus,
metalmatrixnanocompositesaresuitableforproductionofmaterialswithhighstrengthin
shear/compressionprocessesandhighservicetemperaturecapabilities.Theyshowan
extraordinarypotentialforapplicationinmanyareas,suchasaerospaceandautomotive
industriesanddevelopmentofstructuralmaterials41.BothMMNCandCMNCwithCNT
nanocompositesholdpromise,butalsoposechallengesforrealsuccess.
Polymermaterialsarewidelyusedinindustryduetotheireaseofproduction,lightweightand
oftenductilenature.However,theyhavesomedisadvantages,suchaslowmodulusandstrength
comparedtometalsandceramics.Inthiscontext,averyeffectiveapproachtoimprove
mechanicalpropertiesistoaddfibres,whiskers,plateletsorparticlesasreinforcementstothe
polymermatrix.Forexample,polymershavebeenfilledwithseveralinorganiccompounds,
eithersyntheticornatural,inordertoincreaseheatandimpactresistance,flameretardancyand
mechanicalstrength,andtodecreaseelectricalconductivityandgaspermeabilitywithrespectto
oxygenandwatervapour 25.Furthermore,metalandceramicreinforcementsofferstriking
routestocertainuniquemagnetic,electronic,opticalorcatalyticpropertiescomingfrom
inorganicnanoparticles,whichaddtootherpolymerpropertiessuchasprocessibilityandfilm
formingcapability42.Usingthisapproach,polymerscanbeimprovedwhilekeepingtheir
lightweightandductilenature31,4347.Anotherimportantaspectisthatnanoscalereinforcements
haveanexceptionalpotentialtogeneratenewphenomena,whichleadstospecialpropertiesin
thesematerialsaswillbeseenlater.Itmaybepointedoutthatthereinforcingefficiencyof
thesecomposites,evenatlowvolumefractions,iscomparableto4050%forfibresin
microcomposites34.
Additionofreinforcementstoawidevarietyofpolymerresinsproducesadramaticimprovement
intheirbiodegradability.Thisunderlinesagoodexampleofpolymermatrixnanocomposites
[PMNC]aspromisingsystems24forecofriendlyapplications.Besides,futurespacemission
conceptsinvolvelargeultralightweightspacecraftstermed"Gossamer"48.Thematerials
requiredforsuchspacecraftsshouldpossessandmaintainaspecificcombinationofproperties
foroveralongperiod(1030years)inrelativelyharshenvironmentssuchas173to373Kfor
satellitesandcyclingtemperaturesof1273Kforreentryvehicles,exposuretoatomicO2and
solarradiation.SomeoftheGossamerspacecraftdevicesaremovablemechanicalpartssuchas
gearsandgyroscopes,andothersincludesolararrays/sails,antennaeanddrives,sunshields,
rovers,radars,solarconcentrators,andreflectorarrays.Itisreported48thatthesepartswill
havetobefabricatedfromflexible,appropriatematerials,whichcanbefoldedorpackagedinto
smallvolumes,similarlytothoseavailableinconventionallaunchvehicles,andshouldpossess
manyofthecommonmissionconcepts.Thisisneededsincethestructureconsistingofultra
lightweightpartswouldbedeployedmechanicallyorbyinflationintoalargeultralightweight
functioningspacecraftonceitachievestherequiredorbit.Itisimperativethattheabove
mentionedcharacteristicsshouldbeavailableinonesinglematerial.Metaloxideincorporated
polymernanocompositesseemtomeettheserequirements.Itisexpectedthatsuchspacecrafts
offerasignificantcostadvantagecomparedtoonorbitconstruction,andthelargesizecan
enablesomeuniquemissions.Similarly,rocketpropellantsarepreparedfromapolymer
Al/Al 2O3nanocompositetoimproveballisticperformance306.Inaddition,recentinformationon
nanomaterials,nanoindustriesandahostofpossibleAtoZapplicationsofpolymer
nanocompositeshavebeenreported312.
Ontheotherhand,evenafteradecadeofresearch27,CNTshavenotfullyrealizedtheir
potentialsasnanoscopicreinforcements313334inpolymermatrices.Thusgreatchallengesand
opportunitiesarestillexpectedforthesystem.Thesearebasedonthefollowing:
a)CNTswithsmallnumberofdefectsperunitlengthpossess27500timesmore
surfaceareapergramonthebasisofequivalentvolumefractionofatypicalcarbon
fiber,highaspectratio(~1000),veryhightensilepropertiesandelectricaland
thermalconductivities(moredetailsaregiveninthenextsection).
b)ResearchonCNTrelatedareashasbeenmostactive,withpublicationsdoubling
withinsixmonths335.Eventhepatentingactivityinthisareahasbeenimpressive,
withabout3,000applicationsfiledfrom2001toJune2006aspertheliterature
survey.
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c)Becauseoftheirhollownature,CNTscanbeopenedandfilledwithavarietyof
materialsincludingbiologicalmolecules335,generatingtechnologicalopportunities.
Addedtothis,thechallengesinobtaininghomogeneousdispersionsandstrong
interfacialinteractions,whichcanbebetterdonebysurface
grafting/functionalizations,maketheuseofCNTsincompositesmoreintriguing49.
d)VariousapplicationsofCNTsincompositeshavebeenreported
extensively 30,33,313334.
e)Thepossibilityofspinningpolymerstoobtaintextiles10certainlyconstitutesa
greatpromisefortheirextendeduseinavarietyofapplications,particularlyinthe
electronicandthermalmanagementsectors.
f)Nanoreinforcementswithbiodegradablepolymershaveahighpotentialforthe
designofenvironmentallyfriendly'greenmaterials'forfutureapplications.
Onthewhole,opportunitiesandrewardsappeartobegreatwithnanocompositesandhence
thereisatremendousworldwideinterestinthesematerials.
2.ProcessingofNanocomposites
2.1.Rawmaterials
Aswithmicrocomposites,CMNCmatrixmaterialsincludeAl 2O3,SiC,SiN,etc.,whilemetal
matricesemployedinMMNCaremainlyAl,Mg,Pb,Sn,WandFe,andawholerangeof
polymers,e.g.vinylpolymers,condensationpolymers,polyolefins,specialitypolymers
(includingavarietyofbiodegradablemolecules)areusedinPMNC.Ingeneral,itisthe
reinforcementthatisinthenanorangesizeinthesematerials.Bothsyntheticandnatural
crystallinereinforcementshavebeenused,suchasFeandothermetalpowders,clays,silica,
TiO2andothermetaloxides,althoughclaysandlayeredsilicatesarethemostcommon176.This
issoduetotheiravailabilitywithverylowparticlesizesandwellknownintercalation
chemistry18,50,51,inadditiontogeneratingimprovedpropertiesevenwhentheyareusedat
verylowconcentrations252.Mostofthesereinforcementsarepreparedbyknowntechniques:
chemical,mechanical(e.g.ballmilling),vapourdeposition,etc.detailsofthesemaybefound
inmanyofthereferencesgiveninthefollowingsections.
Similarly,CNTsarepreparedmostlybychemical/vapourdepositionmethodsanddetailsare
availableelsewhere319327.AbibliometricanalysisofCNTsmadein2000335revealedthatabout
49%ofthepatentsfiledbetween19921999wererelatedtotheprocessingofCNTsandabout
14%totheirstructure,propertiesandmodels.CNTsconsistofgraphenecylindersandare
availableintwovarieties,assinglewalled(SWCNT)andmultiwalled(MWCNT),withabout70%
yieldinthecaseofSWCNT317.WhileSWCNTsaresinglegraphenecylinders,MWCNTsconsistof
twoormoreconcentriccylindricalsheetsofgraphenearoundacentralhollowcore.Bothtypes
exhibitphysicalcharacteristicsofsolids,eithermetallicorsemiconductinginnature,with
microcrystallinityandveryhighaspectratiosof103.
Surfacemodificationsofreinforcementsarecarriedouttogivehomogeneousdistributionwith
lessagglomeration,andtoimproveinterfacialbondingbetweenthematrixandthenanosized
reinforcements.Detailsonthesecanbefoundinthereferencesgivenforeachtypeof
nanocompositesinlaterSections.InthecaseofCNTs,useofsurfactants,oxidationorchemical
functionalizationofsurfacesaresomeofthetechniquesemployed27.Chemicalmethodsmaybe
moreeffective,particularlyforpolymerandceramicmatrices.Physicalblendingandinsitu
polymerizationareusedforimprovingdispersioninthecaseofCNTreinforcedpolymer
composites,whilealignmentofCNTscouldbeachievedbytechniquessuchasexsitutechniques
(filtration,templateandplasmaenhancedchemicalvapourdeposition,forcefieldinducements,
etc.)33.
2.2.Processingmethods
Despitetheirnanodimensions,mostoftheprocessingtechniquesofthethreetypesof
nanocompositesremainalmostthesameasinmicrocomposites.ThisisalsotrueevenforCNT
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reinforcedcomposites.Detailsonthesetechniquesaregivenbelow.
2.2.1.CeramicMatrixNanocomposites(CMNC)
Manymethodshavebeendescribedforthepreparationofceramicmatrix
nanocomposites 20,38,53112.Themostcommonmethodologies,asusedformicrocomposites,
areConventionalpowdermethodPolymerprecursorrouteSpraypyrolysisVapourtechniques
(CVDandPVD)andChemicalmethods,whichincludethesolgelprocess,colloidaland
precipitationapproachesandthetemplatesynthesis.WhileTable3alistssystemspreparedby
someofthesemethods,Table3bshowstheiradvantagesandlimitations.Scheme1adepictsthe
conventionalpowdermethodandScheme1billustratesthepolymerprecursorrouteusedinthe
synthesisofanAl 2O3/SiCnanocomposite.
Alargevarietyofparametersaffectingthesolgelprocess,suchastypeofsolvent,timing,pH,
precursor,water/metalratio,etc.,allowaversatilecontrolofstructuralandchemicalproperties
ofthefinaloxidematerials61.Regardingtheprocessingofcarbonnanotubes(CNT)reinforced
ceramicnanocomposites,manyapproacheshavebeendescribed20,74112.Severaloftheseare
listedinTable3c.
2.2.2.MetalMatrixNanocomposites(MMNC)
Themostcommontechniquesfortheprocessingofmetalmatrixnanocompositesare113
150SpraypyrolysisLiquidmetalinfiltrationRapidsolidificationVapourtechniques(PVD,CVD)
ElectrodepositionandChemicalmethods,whichincludecolloidalandsolgelprocesses.Table
4alistsvarioussystemspreparedbythesemethodsandTable4bshowstheiradvantagesand
limitations.Onlytworeportsarefound,forexample,onFebasednanocompositespreparedby
solidificationtechniques.Thefirstone,byBranagan121,iscalled"devitrifiednanocomposite
steel".ThiswasobtainedbyquenchingthemetallicglassobtainedfromaFebasedalloy,
followedbydevitrifyingtheglassprecursorthroughheattreatmentaboveitscrystallization
temperature.Thisresultedinamaterialshowingacrystallinemultiphasemicrostructure.The
formationofnanophaseswasexplainedbythehighnucleationfrequencywithinthelimitedtime
forgrowthofgrainsbeforeimpingement.InordertoexplaintheveryhighhardnessoftheseFe
basednanocomposites,BranaganandTangstudied122novelnanostructuresobtainedinbulkFe
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alloysbydesigningalloycompositionswithdifferentamountsofWandCtogetmaximum
solubility.Difficultieshavebeenencounteredinpreparingcompositeswithveryfineparticlesdue
totheirinducedagglomerationandnonhomogeneousdistribution.Useofultrasoundhelpedto
improvethewettabilitybetweenthematrixandtheparticles.
AnumberofCNTreinforcedMMCshavebeensynthesisedbydifferenttechniques87,135141since
thefirstreportin2002137.SomeofthesetechniquesarelistedinTable4c.
2.2.3.PolymerMatrixNanocomposites(PMNC)
Manymethodshavebeendescribedforthepreparationofpolymernanocomposites,including
layeredmaterialsandthosecontainingCNTs 151308.Themostimportantonesarei)
Intercalationofthepolymerorprepolymerfromsolutionii)Insituintercalative
polymerizationiii)Meltintercalation(Figure1)iv)Directmixtureofpolymerandparticulates
v)Templatesynthesisvi)Insitupolymerizationandvii)Solgelprocess.Publicationsdealing
withvariousmethodsfortheincorporationofnanodispersoidsintoconductingpolymersarealso
available19,201,234themostprominentoneisprobablytheincorporationofinorganicbuilding
blocksinorganicpolymers.
Table5ashowstheproceduresadoptedinsomeoftheseprocesses,whiletheiradvantagesand
limitationsarelistedinTable5b.
Intercalativeprocessesemployedforthepreparationofpolymerbasednanocomposites,
includingthosecontaininglayeredsilicates,areshowninScheme2.Itmaybenotedthat,inthis
method,arangeofnanocompositeswithstructuresfromintercalatedtoexfoliatedcanbe
obtained,dependingonthedegreeofpenetrationofthepolymerchainsintothesilicate
galleries.Asaresult,thisprocedurehasbecomestandardforthepreparationofpolymer
layeredsilicatecombinations.
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ThepreparationofCNTreinforcedpolymernanocompositesisgenerallyperformedbydifferent
methods,includingdirectmixing,solutionmixing,meltmixingandinsitupolymerisation.These,
asapplicabletovarioussystems187,202,arelistedinTable5c.
Similarly,differentprocessingtechniques,mostlychemicalandelectrochemicalmethods,have
beenemployedforthepreparationofconductingpolymernanocomposites19.Table
6asummarizesthesemethods,whilearelevantcategorizationofthesenanocompositesis
presentedinTable6b.
Inthecaseofnanocompositescontaininglayeredreinforcements,dependingonthenatureofthe
components(layeredsilicate,organiccationandpolymermatrix),themethodofpreparationand
thestrengthofinterfacialinteractionsbetweenthepolymermatrixandthelayeredsilicate
(modifiedornot),threedifferenttypesofPLSnanocompositesmaybeobtained,asillustrated
inFigure218.
Whenthepolymerisunabletointercalatebetweenthesilicatesheets,aphaseseparated
composite(Figure2)isobtained,whosepropertiesstayinthesamerangeasthatoftraditional
microcomposites.Ontheotherhand,inintercalatednanocomposites,theinsertionofapolymer
matrixintothelayeredsilicatestructureoccursinacrystallographicallyregularfashion,
regardlessoftheclaytopolymerratio.Awellorderedmultilayermorphologybuiltupwith
alternatingpolymericandinorganiclayersisgenerated.Normally,onlyafewmolecularlayers
ofpolymercanbeintercalatedinthesematerials.
Theinsitumethodcanbeusedwithmineral/vegetalfibres,withthepossibilitytoattachthe
polymertothegraftedsurfacethroughlinkinggroups(couplingagents),whichoptimizethe
interfacebondingand,consequently,themechanicalproperties176.
Despitethesuccessfuluseofthesedifferentmethodsforthepreparationofpolymerbased
nanocomposites,informationonvariousfactorsisstilllacking,suchasi)theuseofan
appropriatemethodforaspecificmatrixreinforcementcombinationorii)themaximumamount
ofreinforcementstogiveoptimumpropertycombinationsandlowerthecostoftheprocesses,
etc.Therefore,itisstillnecessarytolookintotheseaspectsincludinguseofsimulationand
modellingtechniques.
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3.StructureandProperties
Thestructureofnanocompositesusuallyconsistsofthematrixmaterialcontainingthenanosized
reinforcementcomponentsintheformofparticles,whiskers,fibres,nanotubes,etc.93.Different
investigatorshaveemployedvariousequipmentsandtechniquesforthecharacterizationof
nanocomposites,includingatomicforcemicroscopy(AFM),scanningtunnellingmicroscopy
(STM),Fouriertransformedinfraredspectroscopy(FTIR),Xrayphotoelectronspectroscopy
(XPS),nuclearmagneticresonance(NMR),differentialscanningcalorimetry(DSC),scanningand
transmissionelectronmicroscopy(SEM/TEM),etc.Forexample,AFMisapowerfultooltostudy
thesurfaceevendowntothenanometrescale,asevidentfromtheworkofVeithetal.303,304.
SimultaneoussmallangleXrayscattering(SAXS)andXraydiffractometry(XRD)studieshave
beenrecentlyusedforquantitativecharacterizationofnanostructuresandcrystallitestructures
insomenanocomposites34,307,308.Inaddition,theoreticalcalculations/simulationshavebeen
workedouttopredictstrengthproperties,includingstress/straincurves41,52,166,169,207
212,290,291.
Beforediscussingstructureandpropertiesofnanocomposites,includingthosecontainingCNTs,a
briefdescriptionofCNTswillbemadehere313334,becauseoftheiruniquepropertiescompared
tootherreinforcements.Briefly,thedensityofSWCNTsislessthanonesixthofthatof
steel 335whilethedensityofMWCNTisonehalfofthatofAl 30.TensilestrengthsofSWCNTand
MWCNTsarereported313316,335tobeinarangemuchhigherthanofhighstrengthsteel,while
Young'smodulusvaluesarecomparabletothoseofdiamond.Theyexhibittremendous
resilience,inthattheycansustainbendingtolargeanglesandrestraighteningwithoutdamage,
inwhichtheydifferfromtheplasticdeformationofmetalsandthebrittlefractureofcarbon
fibres.Similarly,theoreticalthermalandelectricalconductivitiesarecomparablewiththatof
diamond,withanalmostnegligiblethermalexpansioncoefficient30.Theyalsoexhibithigh
thermalstabilitybothinairandinvacuum,comparedtothelowervaluesobtainedformetal
wiresinmicrochips,andhighparallelandperpendicularmagneticsusceptibilities.Theoretical
surfaceareavaluesofthesematerialsareca.3,000m2/g 318321,whiletheexperimentally
reportedvaluesvarydependingonthegasusedduringthemeasurements.Thisinformationis
summarizedinTable7.
3.1.Ceramicmatrixnanocomposites
Ceramicsareusuallybrittleandeasilyfracturedasconsequenceofcrackpropagation.There
havebeenattemptstomakeceramicssuitableforengineeringapplicationsthroughthe
incorporationofaductilemetalphaseoranotherceramicintothematrix.Thisleadstoimproved
mechanicalpropertiessuchashardnessandfracturetoughness,whichoccurasaresultofthe
relationshipbetweenthedifferentphases,matrixandreinforcements,atthephaseboundaries
throughoutthematerial.Thesurfacearea/volumeratioofthereinforcementmaterialsisof
fundamentalimportanceintheunderstandingofthestructurepropertyrelationshipinCMNCs.
Weshallthereforefirstdiscusstheseimprovementsinsomeceramicbasednanocompositesand
relatethemwiththeobservedmorphologies.
3.1.1.Ceramicmatrixdiscontinuousreinforcementnanocompositesystems
Table8showsexamplesofceramicnanocompositesandoftheobservedimprovementsintheir
propertiescomparedtotherespectivemonolithicmaterials.Table9comparesthemechanical
propertiesoftheAl 2O3/SiCsystemanditsmicrocompositecounterpart39,103105.
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Itcanbeseenfromthesetablesthatthereisasignificantimprovementinthestrengthofthe
nanocompositecomparedwithitsmicrocounterpart.Thefracturestrength,asanexample,is
noticeablyhigherbecauseofthehigherinterfacialinteractionbetweentheparticlesin
nanocomposites.Besides,Al 2O35to15%SiCsystemsexhibited90superficialgroovesofplastic
deformationcomparedtotheintergranularfractureobservedinmonolithicmaterials.Therewas
notimedependantweartransitionforthesecompositesevenatloadsof20100N,butpre
transitionwearratesof12x108mm/Nmwereobservedforboththemonolithicandcomposite
materials.Thespecificwearratedecreasedwithslidingdistance.Thisenhancementof
propertiesobservedinceramicnanocompositescanalsobeillustratedbytheSi 3N4/SiCsystem
(Table10)106,107.
Itcanbeseenthatthenanocompositepresentssignificantimprovementsinfracturestrengthand
toughness,hightemperaturestrengthandcreepresistancecomparedwithitsmicrocounterpart
andtothemonolithicmatrixcomponent.Forexample,theSi 3N4/30%SiCsystemhasstrengthof
1080MPaupto1673K,whereasthestrengthofthemonolithicsampledecreasesconsiderablyat
hightemperatures.Furthermore,at1673Kandtensionof200MPa,Si 3N4failsafter0.4hoursat
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0.3%strain,whereastheSi 3N4/10%SiCnanocompositedoesnotfailevenafter1,000hoursat
1.5%strain.
Comingtomorphologicalstudies,Figure3acshowsthemicrostructuresofsomeceramicmatrix
nanocompositesofAl 2O3andFe2O3containingagooddistributionofCoandNinanoparticlesor
ofCNTs.Thepresenceofmetalparticlesleadstotheimprovementofelectricalandthermal
conductivitiesandofmagnetic,electronicandopticalproperties,aswellastothedevelopment
ofnovelanduniquefeaturesduetothenanosizedcomponents.
Figure4showsSEMandTEMimagesoftheAl 2O3SiCnanocomposites,whileFigure5showsthe
highresolutionTEMphotographs.SEMresults(Figure4a)revealagglomerationofthematrix
particles.Thegrainsare~2minsize.TEManalysis(Figure4b)showsacharacteristic
intra/intergranularstructure.TheintragranularSiCparticleisapproximately500nminsize
(Figure4c).Inaddition,intheupperpartoftheHRTEMimage(Figure5),alayerofan
amorphousphaseisclearlyvisibleinatypically(local)edgeonorientationattheinterfaceof
twocrystallinephases.However,thislayerfadesawayinthelowersectionoftheimage,where
thetwophasesseemtomergewithanatomiclevellatticematchpattern39,103105.
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Figure6showsthemicrostructureoftheSi 3N4/SiCnanocomposite.Onecanobservethatthe
nanosizedSiCparticlesareintimatelydispersedthroughoutthematrixmaterial.Inaddition,
theyareembeddedwithinthematrixoflargeSi 3N4grainsandatgrainboundaries,havinginter
andintragranularenvironments106,107.Thesemorphologieshelpunderstandingtheobserved
properties.
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Anotheraspecttobenotedisthemechanismofgrowthofthetwophasesinnanocomposites,as
illustratedbyAFMphotographs111.Figure7showsAFMimagesoftwometaloxidebased
nanocompositesystems,viz.,Fe2O3/Co3O4andNiO/Co3O4.FromFigure7bc,onecanseethe
productionofbigparticlesintheNiO/Co3O4systemwithincreasingsupportedoxide
concentration.TEMimagesoftheseoxidesystemssupportdifferentgrowthmechanisms.Inthe
caseofFe2O3/Co3O4,smallclustersofFe2O3gotwettedonthesurfaceofCo3O4,whileNiO
grewasisolatedparticles,showingalargerdiameterintheNiO/Co3O4system.
3.1.2.CeramicmatrixCNTSystems
TheeffectofCNTloadingonmechanicalpropertiesoftheSiO2/CNTnanocompositesisshown
inFigure874.WhenthevolumecontentofCNTislowerthan5vol.%,bothbendingstrengthand
fracturetoughnessincreasewithincreasingvolumeofCNTs.However,loadingshigherthan5%
causedecreaseinthesetwoproperties.At5vol.%,theincrementinstrengthandfracture
toughness,comparedwiththatofmonolithicSiO2,isupto65and100%,respectively.This
increaseinmechanicalpropertiesisduetothelargeaspectratioandexcellentmechanical
propertiesofCNTs,accordingtothetheoryofshortfibrereinforcedcomposites 4.Thedecrease
inbendingstrengthathighloadingisduetothehindrancecausedbyCNTsduringdensification,
astheyshowahigherprobabilityforagglomeration.Consequently,theincreasedagglomeration
leadstothelossofbonding.Also,thehighertheloadingofCNTs,thehigheristheirpullout
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fromthematrixduringstresstransfer 274.
Unusualbehaviourssuchashighcontactdamageresistancewithoutacorresponding
improvementintoughnesshavealsobeenreportedinAl 2O3/nanotubecomposites91,92.The
microhardnessofthesesystemsincreasesastheCNTcontentisincreasedupto4wt.(%).This
isprobablyduetograinsizeeffectsandthereinforcementroleofCNTs,asshowninFigure9a.
However,theeffectdecreasesagainabove4wt.(%),probablyduetothedifficultyindispersing
CNTshomogeneouslyinthecompositeandtotheproblemofpoorcohesionbetweenCNTsand
thematrix107.Thistrendisalsoobservedinthewearlossandfrictioncoefficient,asshown
inFigure9b.Itcanbeseenthatthewearlossofthe4wt.(%)compositedecreasedbynearly
45%ascomparedtothatofthepurematrix.AstheCNTcontentincreasedabove10wt.(%),
wearlossesalsonotablyincreased.FrictioncoefficientsdecreasedgraduallyastheCNTcontent
increasedfrom0to10wt.(%),andthendroppedsharplyat12.5%CNTcontent.Thistrendis
attributedtothelubricatingpropertiesoftheCNTs(graphite)76.
MaandcoworkerspreparedSiC/CNTswhichshoweda10%improvementinthestrengthand
fracturetoughnessascomparedtothemonolithicceramics108.Thesemodestresultswere
attributedtonanotube/matrixdebondingandcrackdeflection20.Asaconsequence,many
attemptshavebeenmadetodevelopimprovedmechanicalpropertiesthroughtheincorporation
ofCNTsinceramicmatrices.However,theobservedimprovementswerenotasdramaticas
expected.Inthiscontext,recently,Zhanetal.109successfullyappliedSWCNTsinthe
reinforcementofceramiccompositesthroughsparkplasmasintering(SPS),whichresultedina
194%increaseinfracturetoughnessoverpurealumina[~9.7MPam1/2inthe10vol.%
SWCNT/Al 2O3nanocomposite].Also,theelectricalpropertiesofceramic/CNTsnanocomposites
havebeensharplyenhanced,asillustratedinTable11,duetotheoutstandingelectrical
propertiesofCNTs110.
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UsingGriffith'stheoryandresidualstressaroundnanoparticlesinthematrix,Awajietal.36have
proposedamechanismfortougheningandstrengtheninginceramicbasednanocomposites.They
observedthatthecoefficientofthermalexpansionofbothmatrixandnanoparticleshadaneffect
onresidualstresseswhichwassufficienttocauselatticedefectssuchasdislocationsaround
particlesinceramics.Dislocationswerealsogeneratedaroundtheparticlebythenanoparticles
inthematrix.
A24%increaseinfracturetoughness(3.44.2MPam1/2)overthematrixwasobservedin
nanograinedAl 2O3composite(averagediameter39nm)containing10vol.%MWCNT85,which
wasattributedtotheoxidationofCNTsbeforedispersion.Inthiscasethematerialwasproduced
inthreeconditions,viz.,mixed,hotpressed(1573K)andsinteredtoneartheoretical
density.Figures10and11showTEMandSEMimagesoftheSiO2/CNTandAl 2O3/CNTsystems
respectively74,76,whereitcanbeseenthatCNTsarehomogeneouslydispersedinbothmatrices.
Thiscouldexplaintheobservedstrengthproperties.
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Itcanbeseenthateachprocessingmethodhasitsownadvantagesinyieldingappropriate
structuresandpropertiesforeachsystem,andhencethereisneedtofindoutproper
combinationsofprocessing,togetherwiththesuitablesystems,toarriveatoptimumproperties.
3.2.Metalmatrixnanocomposites
3.2.1.Metaldiscontinuousreinforcementsystems
Table12illustratesexamplesofsomemetalmatrixnanocompositesandtheirrespective
properties.
TheFe/Fe23C6/Fe3Bsystemprovidesagoodexampleofhowuniquepropertiesmayarise
frommetalnanocomposites.Table13showsthemeasuredhardnessvalues(GPa)oftheingot
andribbonsamplespreparedfromthissystem122.Vickershardnessvaluesofthesetwoforms
ofthealloyproducedbyBranaganandTang122werefoundtobe10.3and11GPaintheas
solidifiedcondition.Theribbonvarietyshowedincreasedhardnesswithincreasingheat
treatmenttemperature,showingamaximumof16.2GPaat973K[higherthananyexisting
commercialsteelandhardalloys]andthereafterdecreasingto10.5GPaat1123K.Thiscanbe
comparedtothedecreasingtrendoftheingottype(8and6.6GPaat873and973K
respectively).
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TheAl/SiCsystemalsoillustratestheadvantagesofmetalnanocompositescomparedtotheir
microcounterparts145147.Figure12ashowsplotsofVickershardnessvs.SiCcontent,
whileFigure12bpresentsplotsofYoung'sandshearmodulusasafunctionofSiCcontent.There
isalinearincreaseinhardnesswithincreasingvolumefractionoftheharderphase(SiC)until
themaximumvalueof2.6GPaforthesamplethatcontains10vol.%ofSiC.Thevaluesof
Young'sandshearmodulusincreasesignificantlywithincreasingSiCcontent,suggestingthe
formationofananocompositematerialcontainingabrittlephase(SiC)embeddedintheductile
Almatrix.Table14showssomemechanicalpropertiesofbothnanoandmicrocompositesof
Al/SiC.
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ItcanbeclearlyseenthattheAl/SiCnanocompositeexhibitsnotablyhigherYoung'smodulusand
hardnessthanitsmicrocounterpart.Forexample,thenanocompositeshows12.6%increasein
hardnessand105.1%inYoung'smodulus145147.Also,Al/Pbnanocompositesexhibitedimproved
frictionalfeatures119121.Thenanosizeddispersoidsloweredthecoefficientoffriction[0.3for
nanocompositecomparedto0.42forthemicrocomposite]duetotheformationofauniform
leadrichtribolayer,withmaterialtransferbeinganorderofmagnitudelowerthaninthemicro
sizedcounterpart.ThecomparativewearlossofnanoandmicrosizedAl/Pbcompositesisshown
inFigure13119.
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Comingtothemorphologicalstudiesofmetalmatrixbasednanocomposites,analysisofthe
structureandidentificationofthenanophasesinFe/Fe23C6/Fe3BalloysusingXraydiffraction
andTEMwithEDAXrevealedtheexistenceoftwocubicandonetetragonalphase.Thethree
phasesexhibitedthesizeof4m[4,000nm]intheingotalloy,whileintheheattreatedribbon
alloythesizeofthephaseswasintherangeof100130nm.Basedonthese,theobserved
hardnesswasattributedtothenanostructureandtothesupersaturationofCrandWabovetheir
equilibriumsolubilityinFe.Thesestudiesalsosuggestedthepossiblesynthesisofveryhardand
inexpensivematerialsforthreebodieswearapplicationsandtoreplaceexpensivehardmetals
suchasincobaltbasedmaterials.Figure14showsTEM/SAEDimagesofthisnanocomposite.The
threeironcontainingphasesarehomogeneouslydistributedovertheentirematerial 122.
InthecaseofAl/SiCnanocomposites(Figure15),onlytwophasesarevisibleintheTEMimages:
SiC(granularfinegrains)andAl(overallmatrix).Nomoresharpringspotpatternshave
appearedintheelectrondiffractionpattern(SAED),indicatingtheformationoffine,nanosized
powders147containingthebrittleSiCphaseembeddedintheductileAlmatrix.
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OthermetalceramicnanocompositesareshownintheSEMandTEMphotographsofFigure
16.Figure16aisaSEMmicrographofFe/MgOcompositeheattreatedat873Kandreducedat
1073K11.VolumechangesoccurredduetoO2atomsreleasedfromFe2O3during
reduction.Figure16b,cpresentsTEMmicrographsofuniformlydistributednanosizeceramic
particlesinAlandAgmetalmatrices95,96respectively.NearlysphericalparticlesofAgisolated
fromeachothercanbeseeninFigure16c.ThisstudyrevealedthatAgparticlesofsizesmaller
thanporesize(10nm)aresizedefinedandstabilized.Similarobservationshavebeenmade
withothernoblemetalssuchasAuandPd.
InthecaseofAlPbnanocomposites,micrographsshowingthewornsurfaces(notshownhere)
revealeddelaminationintheearlystageofwear,whilethebehaviouratlatestageswasaffected
bytheprocessingtechnique.Inaddition,someelongationofparticleswasalsoobserved,along
withcoarseningofPbparticlesduringsliding,duetodislocationaideddiffusion.
3.2.2.MetalmatrixCNTcomposites
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LetusnowlookintotheCNTcontainingmetalmatrixnanocomposites.Electricalpropertiesofan
Al/CNTsystemmeasuredbetween4.2Kandroomtemperaturerevealedanincreasefrom4.9to
6.6cmatroomtemperaturefor1and4wt.(%)CNTs,butadecreaseto5.5cmfor10
wt.(%)CNT(Figure17),comparedtothevalueof3.4cmfortheAlmatrix.Atlower
temperatures[7080K],resistivitiesofallcompositesdecreasedlinearly,asinthecaseof
metals,withanabruptdropofabout90%.Themechanismofthesechangesisyettobe
understood.
Ontheotherhand,compressiontestingoftheseAlCNTcomposites139showedidenticalstress
straincurvesforboththecompositewithouttheprecursorandpureAl,exceptforlargeelastic
strain,whilethosewiththeprecursor,thoughsimilarinshape,exhibitedincreasedcompression
stresses.AtahigherMWCNTloading(1.6vol.%),proofstressincreasedsevenfold,incontrast
toanotsoremarkableimprovementinpolymerCNTcomposites196,197.Fractographsofthe
compositerevealednoMWCNTaggregates,butinsteadtheiruniformdistributionwithoutany
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pullouts.TheenhancedmechanicalpropertyhasbeenattributedtotheconfinementoftheAl
matrixbytheMWCNTsonnanoscale.
InternalfrictionmeasurementsonMgbasednanocompositesasafunctionoftemperatureupto
500Krevealedalmostidenticalspectraforboththecomposites[AlSaffilcoveredwithCNTand
AlSaffilCNTs]withthermalhysteresis141.Amaximumdampingwasobservedatabout300K
for1Hzfrequency,associatedwiththemaximumshearmodulusforboththecomposites.Onthe
otherhand,largerhysteresisandrapidincreaseofinternalfrictionreachingamaximumat350
Kwasobservedforthethirdcomposite[Mg1vol.%CNT].However,shearmodulusdecreased
forallthreecomposites,beingabout20%higherforMgSaffilCNTthanthatforMgSaffil.SEM
fractographicstudiesshowedanMgmatrixembeddedwithCNTsandcoveringofsaffilfibres
withCNTs.
InthecaseofSn2Sb/CNTnanocomposites,higherspecificcapacitythanthatshownbyCNTsand
improvedcyclabilityrelativetounsupportedSnSballoyparticleswereobserved.Thisbehaviour
wasattributedtothehighdispersionofSn2SbintheCNTmatrix.SEMandTEMexaminations
confirmed136thepresenceofnanometricSn2SbparticleshomogeneouslydispersedintheCNTs
(Figure18).
InthecaseofAl/CNTnanocomposites(Figure19),asinglecarbonnanotubeisseentobe
embeddedintheAlmatrix(Figure19b)138.Furthermore,agglomeratesofcarbonnanotubescan
befoundatthegrainboundariesofthealuminiummatrix.
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3.3.Polymermatrixnanocomposites
Structurepropertycorrelationsinpolymernanocompositeshavebeenextensivelydealtwithina
recentbook292,whichdescribesthemechanicalpropertiesofpolymersbasedonnanostructure
andmorphology.Table15presentsexamplesoftheseproperties.
3.3.1.Polymermatrixdiscontinuousreinforcement(nonlayered)nanocomposites
Thereinforcingmaterialsemployedintheproductionofpolymernanocompositescanbe
classifiedaccordingtotheirdimensions** 18.Forexample,whenthethreedimensionsareinthe
nanometrescale,theyarecalledisodimensionalnanoparticles.Examplesincludesphericalsilica,
metalparticlesandsemiconductornanoclusters219.Thesecondkindofreinforcementisformed
bynanotubesorwhiskers,whichcontaintwodimensionsinthenanometrescaleandonelarger,
forminganelongatedstructure.Carbonnanotubesandcellulosewhiskers,extensivelystudiedas
reinforcingnanofillers,canbeincludedinthissecondcategory.Thethirdtypeofreinforcement
ischaracterizedbyonlyonedimensioninthenanometrerange220222.Inthisgroup,thefiller
containssheetsonetoafewnanometresthickandhundredstothousandsnanometreslong.This
familyiscalledpolymerlayerednanocomposites2,18,26.Thesematerialsareobtainedby
intercalationofthepolymer(oramonomersubsequentlypolymerized)insidethegalleriesofthe
layeredhost.Manysyntheticandnaturalcrystallinehoststhatareable,underspecific
conditions,tointercalateapolymerhavebeendescribed.Examplesincludegraphite,metal
chalcogenides(MoS2,forexample),clays,layeredsilicate(montmorillonite,hectorite,saponite,
fluoromica,fluorohectorite,vermiculiteandkaolinite)andlayereddoublehydroxides.
Nanocompositesbasedonclayandlayeredsilicateshavebeenwidelyinvestigatedduetothe
availabilityofclaystartingmaterialsandtheirwellknownintercalationchemistryasmentioned
earlier 18,50,51,223.
Figure20showsthevariationinquasistaticfracturetoughnessasafunctionofthevolume
percentageofTiO2inthepolyester/TiO2nanocomposite.TheadditionofTiO2particleshasa
greateffectonfracturetoughness.Atloadingsof1,2and3vol.%,anincreaseof57,42and
41%,respectively,canbeobserved,whencomparedwiththatoftheoriginalpolyester.
However,at4vol.%TiO2,toughness(0.55MPam1/2)decreasedapproximatelytothevalue
givenbythepolyestermatrix(0.54MPam1/2).Thisvariationcanbeexplainedintermsof
nanocompositestructure,asillustratedinFigure21.
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Itcanbeobservedthatthespecimenscontaining1,2and3vol.%TiO2showexcellentparticle
dispersion.Conversely,considerableagglomerationwaspresentinthespecimenscontaining4
vol.%TiO2.Authorshaveassignedtheinitialincreaseinfracturetoughness,followedbythe
precipitousdeclineobservedat4vol.%,tothelevelofdispersionofnanoparticleswithinthe
matrixandtotheweakbondingbetweenthetitaniaparticlesandthepolyester 180.
Thestructureofpolymernanocompositesreinforcedwithisodimensionalparticlesissimilarto
thatofceramicandmetalnanocomposites.Inthistype,thereinforcementmaterialisdistributed
alloverthepolymermatrix,asillustratedinFigure22.Themicrostructureofsomeparticle
reinforcedpolymernanocompositesisshowninFigure23.Figure23ashowstheTEMmicrograph
ofpolyacrylicacid/silvernanocomposite,showingsphericalAgparticlesof1080nmsize183.
Secondaryaggregatesareformedduetothelowviscositynatureofthecomposite
solution.Figure23bshowstheTEMmicrographofanoxidisedpoly(4vinylpyridine)
homopolymerFe2O3nanocompositeshowingultrafineandcrystallinesphericalparticlesofthe
dispersoidsinthe20200nmrange223.Inthiscase,theparticlesretainthenanosizedimension
duetotheprotectiveactionofthepolymerlayer.
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SEManalysesofPETuncoatedCaCO3nanocomposites(Figure23c)showlargeparticleswhich
seemtobequiteweldedtoPET181.Oncoating,theseparticlesgetevenlarger,butagainare
wellwelded.Figure23d,onitsturn,isafieldemissionSEMoftransparentpolymaleimide27.4
wt.(%)silicananocompositewithoutanyadditionofcolloidalsilica,synthesisedbythesolgel
processandshowingdiscretedomainsofaninorganicphasewithnarrowparticlesize
distribution(1020nm)224.ThiscompositeshowedbetterthermalstabilitywithhigherTg(527
K254C)comparedto458K(185C)fortheNbutylsubstitutedpolymaleimides,andahigher
decompositiontemperatureof834K(561C)comparedtoNalkylsubstitutedpolymaleimides.
Mostofthepropertiesobservedinpolymersdiscontinuousreinforcementsystemsaredirectly
relatedtotheirstructure.Forexample,PSM/CdSenanocomposite(PSM=poly(styrenealt
maleicanhydride)showedanemissionpeakat540nminitsphotoluminescencespectrum,which
wasclosetotheabsorptionedgeoftheobtainedCdSeparticles225.Accordingtotheauthors,this
typeofnearbandedgeemissionistypicalofsurfacepassivatednanocrystallineCdSe.For
nanoparticles,alargepercentageofdefectsarelocatedatthesurface.Ifthesedefectsarenot
passivated,nonradiativerecombinationwilloccur,astheyactastrapsforelectronandhole
annihilation.Therefore,itisconceivablethatPSMmodifiedthesurfacestructureandenhanced
theluminescencepropertiesofCdSenanoparticles225.AscanbeseenfromTEMimagesofthis
material(Figure24),CdSenanoparticlesareuniformandmonodisperse,withanaveragesizeof
about17nm.Inthiscase,itisfeasiblethatPSMplayedanimportantroleincontrollingthesize
andthemonodispersionofthenanoparticles225.InteractionsbetweenPSMandCdSeparticles
werealsoinvestigatedandaresupportedbyIRandUVvisiblespectroscopy.
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InthePVA/Agnanocompositesystem,astronginfluenceoftheAgnanofiller(~20nm)was
observedonthematerialstrengthandthermalproperties,evenatlowconcentration(<1wt.
(%))178.Forexample,theglasstransitionwasshiftedtowardshighertemperaturesby20Kand
thethermalstabilitywasimprovedbyabout40Kinthecaseofthenanocompositecontaining
0.73wt.(%)Ag.Also,nanocompositefilmsshoweddeformationbehaviourcharacteristicof
semicrystallinematerials,withaclearlydistinguishedyieldpoint,whilenoyieldpointwas
observedinthedeformationofthepurePVAmatrix.Thesechangesinthethermaland
mechanicalbehaviourofPVAinthepresenceoftheAgnanofillerwerediscussedintermsof
polymerchainsattachedtothesurfaceofAgnanoparticles.Theimprovedthermalstabilitywas
explainedonthebasisofthereducedmobilityofthePVAchainsinthenanocomposite.Inthis
system,astronginfluenceofnanoparticlesonthematerialstrengthwasalsoobserved.The
stressatbreakofthenanocompositefilmwith0.33wt.(%)ofsilverwasalmost100%higher
thanthecorrespondingvalueforthepurematrix.Finally,thestrainatbreakslightlydecreased
withincreasingnanoparticlecontent178.
FromthephasecontrastAFMofpolyparaxylylenecompositescontainingPdorSnnanoparticles
(Figure25ac),preparedbyvacuumcocondensationofboththemetalandthepolymer 47,one
canidentifysurfaceimperfectionsaswellasmetalparticlesizes(710nm).Surfacemorphology
seemedtodependonthetypeofmetal,withgoodsurfaceuniformityforPd.InthePdcase,
particleswereidentifiedasaninorganicphasewithsphericalglobulesof~200nmsize.Inthe
caseoftin,separatedSnparticleslocalizedonpolymerspherulites(Figure25b)andaggregates
ofSnnanoparticlesconnectedincontinuouschainsareevident.Theionicconductivityofthese
nanocompositesisreportedtohaveimprovedwhencomparedwiththatofthepurepolymer.
3.3.2.Polymernanocompositeswithlayeredreinforcements
Polymerlayeredsilicate(PLS)nanocompositeshaveattractedgreatinterestduetotheir
improvedpropertiescomparedwiththepurepolymerandconventionalmicroand
macrocomposites.Someoftheseimprovementsincludehighmoduli,increasedstrengthandheat
resistance,decreasedflammabilityandgaspermeabilityandincreased
biodegradability1,158,166,207,210,211,235243.Twoparticularcharacteristicsoflayeredsilicates
aregenerallyconsideredforPLSnanocomposites.Thefirstistheabilityofthesilicateparticles
todisperseintoindividuallayers(totallydelaminatedorexfoliated).Thesecondistheabilityto
finetunetheirsurfacechemistrythroughionexchangereactionswithorganicandinorganic
cations.Thesetwoare,ofcourse,interrelated,sincethedegreeofdispersionofalayered
silicateinaparticularpolymermatrixdependsontheinterlayerionicspecies.
Althoughtheintercalationchemistryofpolymerstowardslayeredsilicateshaslongbeen
known245,246,thefieldofPLSnanocompositeshasrecentlygainedimpressiveattention,dueto
twoimportantfindings.Firstly,theresultsobtainedonNylon6(N6)/montmorillonite(MMT)
nanocomposites,whichshowedthatasmallconcentrationoflayeredsilicateleadtoremarkable
changesinthermalandmechanicalproperties26.Secondly,theobservationbyVaiaetal.247that
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itispossibletomeltmixpolymerswithlayeredsilicates,withouttheuseoforganicsolvents.
Thestructuralfamilycalledthe2:1phyllosilicatesisthemostcommonlyusedlayeredsilicatein
polymernanocomposites.Theirtwodimensionallayersaremadeupoftwotetrahedrally
coordinatedsiliconatomsfusedtoanedgesharedoctahedralsheetofeitheraluminiumor
magnesiumhydroxide.Thelayerthicknessisaround1nmanditslateraldimensionsmayvary
from300toseveralmicraorlarger,dependingonthenatureofthesilicate26.Stackingof
theselayersgeneratesaregularvanderWaalsgap,whichiscalledthe'interlayer'spaceorthe
'gallery'.Isomorphicsubstitutionwithinthelayersproducesnegativechargesthatare
counterbalancedbyalkalineoralkalineearthcationslocatedintheinterlayer.Thisoccurs,for
example,whenMg2+orFe2+replacesAl 3+orwhenLi +replacesMg2+.Becausetheforcesthat
holdthestackstogetherarerelativelyweakvanderWaalsinteractions,theintercalationof
smallmoleculesbetweenthelayersissimple143.Insomecases,thehydratedinterlayercations
canbeexchangedbyionexchangereactionswithcationicsurfactantsincludingprimary,
secondary,tertiaryandquaternaryalkylammoniumoralkylphosphonium.Inorganosilicates,
thesealkylammoniumoralkylphosphoniumcationslowerthesurfaceenergyoftheinorganic
hostandimprovethewettingcharacteristicsofthepolymermatrix,resultinginalarger
interlayerspacing.Moreover,thesecationsprovidefunctionalgroupsthatcanreactwiththe
polymermatrixorinitiatethepolymerizationofmonomerstoimprovethestrengthofthe
interfacebetweentheinorganiccomponentandthepolymermatrix50,245,248,249.
Montmorillonite,hectoriteandsaponitearethemostcommonlyusedlayeredsilicates.Their
structureispresentedinFigure26andtheirformulaeinTable16235.Whenthehydratedcations
areionexchangedwithbulkierorganiccations,alargerinterlayerspacingisusuallyobtained
(Figure26).
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Themainreasonfortheremarkableimprovementsobservedinpolymer/layeredsilicate
nanocompositesisthestrongerinterfacialinteractionbetweenthematrixandthesilicate,
comparedtoconventionalfillerreinforcedsystems.Someexampleswillbegivenbelowinorder
toillustratethisstatement.
TheincorporationofMMT(montmorillonite)intoaNylon6matrixhasledtoasignificant
improvementinitsmechanicalproperties.TheYoung'smodulus(ortensilemodulus),for
example,ofpureNylon6(1.11GPa)wasstronglyimprovedwhenthenanocompositewas
formed.TheNylon6/MMTwithafillercontentof4.1wt.(%)gaveavalueof2.25GPa,which
correspondstoanincreaseof102.7%208,209.Figure27representsthedependenceoftensile
modulusE,at393K(120C),onclaycontentfororganomodifiedmontmorilloniteand
saponitebasednanocomposites208.ResultsclearlyshowthattheincreaseinYoung'smodulusin
thesesystemsisrelatedtotheaveragelengthofthelayersand,consequently,totheaspect
ratioofthedispersednanoparticlesaswellastheextentoftheirexfoliation.Also,regarding
Nylon6nanocomposites,astronginteractionbetweenmatrixandsilicatelayersoccursvia
formationofhydrogenbonds.
Thisbehaviourcanalsobesupportedbymaleicanhydridemodifiedbypropylene(PPMA)/LS
anocomposites.Table17representsthevariationoftheYoung'smodulusasafunctionoffiller
andmaleicanhydridecontentsforboththenanoandthemicrocomposite.Theseresultsindicate
thatthenanocompositeshowshigherYoung'smodulusthanthepurePPmatrix.Also,a
significantincrease,ascomparedtothePPmicrocomposite,wasobservedastheamountofMA
addedtothepolymermatrixwasincreased250.
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ImportantimprovementsonthestressatbreakwerealsoobservedinPolymer/LSsystems.In
thermoplasticbasednanocomposites,thestressatbreak,whichexpressestheultimatestrength
thatthematerialcanbearbeforebreaking,variesdependingonthenatureoftheinteractions
betweenthematrixandthefiller.Table18showssomeexamplesoftensilestressindifferent
nanocompositesystems.Accordingtotheseresults,someimportantconclusionscanbedrawn,
asdiscussedbelow.
ExfoliatedNylon6andintercalatedPMMAnanocompositesexhibitedagreatincreaseinthe
stressatbreak251.Thiscanbeduetothepolar(PMMA)andionicinteractions(Nylon6grafted
ontothelayers)betweenthematrixandthesilicatelayers.ThisincreaseislargerinNylon6
nanocomposites250252.Ontheotherhand,propylenebasednanocompositesshowedonlya
slightenhancementintensilestress,whichcanbeexplainedbythelackofinterfacialadhesion
betweennonpolarPPandpolarlayeredsilicates.However,additionofmaleicanhydride
modifiedpolypropylenetothepolypropylenematrixhasconfirmedtobeeffectiveinthe
intercalationofthePPchainsandthemaintenanceoftheultimatestressatanacceptable
level 18.Finally,regardingPSintercalatednanocomposites,theultimatetensilestressis
significantlydecreasedcomparedtothatgivenbythePPmatrixanddropsdownathigherfiller
contents252.Theauthorshaveattributedthisfindingtotheweakinteractionsatthepolystyrene
clayinterface.Itisimportanttonotethatinpreviouscompositionsinwhichpolarinteractions
weredeveloped,strengtheningatthefillermatrixinterfacewasobserved18.
Usually,whenLSaredispersedinthermoplasticssuchasPMMA,PSorPP,theelongationat
breakisreduced251,252.Thereporteddecreaseinelongationisfrom150%inpurePPmatrix,to
105%fora6.9wt.(%)nonintercalatedclaymicrocomposite.Ontheotherhand,ina
nanocompositefilledwith5wt.(%)silicatelayers,themorepronounceddropwas7.5%.
Conversely,thislossinultimateelongationdidnotoccurinelastomericepoxyorpolyol
polyurethanematrices253,254.Inthesecases,introductionofthenanoclayincrosslinked
matricescausesanincreaseoftheelongationatbreak.ThisisshowninFigure28forepoxy
nanocomposites,whicharepreparedfrommagadiitemodifiedwithmethyloctadecylammonium
ortrimethyloctadecylammoniumionsandaconventionalcompositepreparedfrommagadiite
modifiedwithoctadecylammonium254.Whileadropintheelongationatbreakcanbeobserved
fortheconventionalcomposite,aslightimprovementinthispropertycanbeobservedforthe
intercalatednanocomposite.
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Finally,exfoliatednanocompositesdisplayalargeincreaseintheelongationatbreak.Thisis
probablyduetotheplasticizingeffectofthegalleries,theircontributiontotheformationof
danglingchainsandconformationaleffectsattheclaymatrixinterface.Thecombinationof
improvedstiffness(Young'smodulus),toughness(stressatbreak)andelasticity(strainatbreak)
makeselastomericnanocompositessuitablecandidatesforthegenerationofanewfamilyof
highperformancematerials.
Polyimideisanotherexampleofapolymermatrixmaterialshowinganincreaseinbothstress
andelongationatbreak 255.Forexample,whenfilledwithmontmorilloniteexchangedwith
hexadecylammonium,thesepropertiesincreasewiththefillerloadingatleastupto5wt.(%).
Athigherfillercontents,bothpropertiesdroptowardsvalueslowerthanthosedescribedforthe
fillerfreematrixduetotheformationofnonexfoliatedaggregateswhichmakethese
compositesmorebrittle.
AnothernanocompositesystemstudiedingreatdetailisNylon6/protonatedaminododecanoic
acid,whichhasbeenstudiedforitsimpactresistanceproperties.Thenanocompositesynthesized
byinsituintercalativepolymerizationhaditsIzodimpactstrengthreducedfrom20.6to18.1
J/mcomparedwiththepurematrixwhen4.7wt.(%)ofnanoclaywasincorporated.Charpy
impacttestingshowedasimilarreductionfrom6.21kJ/m2to6.06kJ/m2forthe4.7wt.(%)
nanocomposite52,256.Table21presentstheeffectofMMTcontentandNylon6molecularweight
onthetensilemodulusofMMTmodifiedwith(HE)2M1R1 257.Asubstantialimprovementin
stiffnesscanbeseen,whichincreaseswithincreasingmatrixmolecularweight(atanygiven
concentration)forallNylon6nanocomposites,i.e.,low(LMW),medium(MMW)andhigh
molecularweights(HMW).Aslightlylargermodulusof2.82GPaforLMWmaybetheresultofa
higherdegreeofcrystallinitygivingfastercrystallizationkineticsduringthecoolingofthe
specimenafterinjectionmoulding.Yieldstrength,onitsturn,increaseswiththecontentofMMT,
butwhiletheHMWandMMWbasednanocompositesshowasteadyincreaseinstrengthwiththe
increasingcontentofclay,theLMWbasednanocompositesshowalesspronouncedeffect.Also,
increaseinstrengthrelativetothevirginmatrixfortheHMWcompositeisnearlytwicethatof
theLMWcompositeatthehighestclaycontent.Regardingtheelongationatbreakfortwo
differentratesofextension,resultsshowthatthepurematrixisveryductileatatestrateof
0.51cm/min.Increasingclaycontentleadstoagradualdecreaseinductility.Theelongationat
breakfortheLMWbasednanocompositesdecreasesrapidlyatlowMMTcontent(around1wt.
(%)).ThislargerreductionintheLMWbasedsystemsmaybeduetothepresenceofstacked
silicatelayers,asseeninFigure29257.Thehighertestingrateof5.1cm/minyieldssimilar
trends,buttheabsoluteleveloftheelongationatbreakissignificantlylower.Thestrain
decreasesforallnanocompositeswhencomparedtothepurematrixpolymer.
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Table19
Thisgoodresistancetoimpact,highYoung'smodulus,goodflexuralmodulusandanotable
enhancementintheheatdistortiontemperature,goingfrom338K(65C)forpureNylon6to
morethan423K(150C)forthenanocomposite,haveallowedthismaterialtoreplaceglass
fibrereinforcednylonorpolypropyleneintheproductionoftimingbeltcoversofautomotive
engines258.
Comingtodynamicstrengthproperties,itiswellknownthatdynamicmechanicalanalysis(DMA)
measurestheresponseofagivenmaterialtoacyclicdeformation(usuallytensionorthreepoint
flexiontypedeformation)asafunctionoftemperature.Resultsareexpressedbythreemain
parameters,whicharethestoragemodulus(E'),correspondingtoelasticresponseto
deformationthelossmodulus(E"),correspondingtoplasticresponsetodeformationandtan,
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thatisthe(E'/E")ratio,usefulfordeterminingtheglasstransitiontemperature,forexample.PS
nanocompositeshavebeencharacterizedbyDMAanalysis252.NosignificantdifferenceinE'was
observedbetweenthepurePSandananocompositeintercalatedwith17.2wt.(%)ofNa
montmorilloniteinthetemperaturerangeof293413K(20140C),indicatinglackofinfluence
ofintercalatednanocompositesontheelasticpropertiesofthematrix.However,shiftand
broadeningoftanvaluestowardshighertemperaturesforthenanocompositesuggestsan
increaseintheglasstransitiontemperatureandsomebroadeningofthistransition.Thiscanbe
assignedtorestrictedsegmentalmotionsattheorganicinorganicinterfaceoftheintercalated
systems.
However,adifferentbehaviouronDMApropertiesisobservedwhenblendingcopolymers,such
asthesymmetricstyrenebutadienestyrene[SBS]blockcopolymers,arepreviouslyusedto
modifythematrix259.Forexample,whenSBSismeltblendedwithamontmorillonitemodified
bydimethyldioctadecylammonium,ananocompositeinwhichonlythePSblockscanintercalate
withinthelayeredsilicatesisproduced.Inthismaterial,alargeimprovementofthestorage
modulusat25Cwasobserved.Figure30showstheseresultsforthisnanoandits
microcompositecounterpart259.
Thisfigurecomparesthevaluesofthestoragemodulifortwosetsofsamplesinwhichthe
reinforcementcontentvariedfrom0to30wt.(%).Valueswererecordedfornanocomposites
filledwithorganomodifiedclayandforcompositespreparedbymeltblendingtheSBSmatrix
andNamontmorilloniteunderthesameconditions.Thereisasharpincreaseinelasticmodulus
fornanocomposites,whilemicrocompositesdonotpresentanyimprovementinthisproperty.
DMApropertieswerealsostudiedforthewidelyusedbifunctionaldiglycidyletherofbisphenolA
(DGEBA)containingdifferentamounts(210wt.(%))oflayeredsilicate,andpreparedbyatwo
stepschemicalmethod(173to323Kandfrom323to573K).Resultsindicatedthat,with
increasingorganicclaycontentinthecomposite,therelaxationtemperaturesofthecured
systemdecreased,whilethepresenceofmodifiedlayeredsilicateimprovedbothtoughnessand
stiffnessofthematrix260.AFMphasecontrastimages(Figure31)showstackedlayersof
silicatesintheproduct,eventhoughtheyarenotdistributedhomogeneouslythroughoutthe
material.ThehighmagnificationshowninFigure31(b)revealsthestriatedstructureinthe5wt.
(%)layeredsilicatecontainingnanocomposite,withincreasingphaseintervalsatthetopofthe
surface.However,noindividuallayerscouldbeseenbyTEM.
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Thedependenceofthestoragemodulusforpolyimidebasednanocompositesfilledwith2wt.
(%)oforganicclaysandfortheunfilledmatrixisshowninFigure32.Atanytemperature,
higherstoragemoduliresultfromthebetternanofillerdispersion.Moreover,thelargedifference
betweenexfoliatedmontmorilloniteandexfoliatedmicabasednanocompositescanbeexplained
bytherespectiveaspectratioofthedispersedsilicatelayers,withlengthsof0.218and1.23mm
formontmorilloniteandsyntheticmicarespectively,asobservedbyTEMstudies.
FromFigure32,itisalsoevidentthattheglasstransitiontemperaturedecreases(~288K)with
increasingclaycontentforthisnanocomposite.Theinfluenceofdispersionandlengthofthe
layeredparticleshasthusbeendemonstratedinthecaseofthesenanocompositesusingvarious
organoclays(hectorite,saponite,montmorilloniteandsyntheticmica)210,255.Micaand
montmorilloniteclaysleadtoexfoliatedstructures,whileapartiallyexfoliatedintercalated
structurewasobtainedforsaponiteandamainlyintercalatedmorphologywasattributedtothe
hectoritebasednanocomposite.
Furthermore,DMAstudiescarriedoutonorganoclaysexfoliatedwithincrosslinkedmatrices
revealedaverynoticeableimprovementinstoragemodulus,especiallyaboveTg.Forexample,
theepoxy/montmorillonite4vol.%nanocompositebelowTgshoweda58%increase164.Inthis
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case,awellorderedexfoliatednanocomposite(silicatelayersseparatedbyapproximately100
)wasformed.At331K,E'equals2.44and1.55GPaforthenanocompositeandtheunfilled
crosslinkedmatrix,respectively.At423K,whichisaboveTg,thereportedE'valuesare11and
50MPafortheunfilledandfilledepoxy,respectively.Thisenhancementcorrespondstoa
storagemodulusimprovementbyafactorof4.5.Also,aninterestingresultcouldbeobservedin
nitrilerubber/organoclaynanocomposites258.Athreefoldincreaseinthestoragemoduluswas
describedthroughthesimpledispersion/exfoliationof10partsoforganoclayper100partsof
rubber,withamodulusashighas8.8MPa.Thisvalueissimilartowhatcanbeobtainedwiththe
samematrixfilledwith40partsofcarbonblackper100partsofrubber.Asaresult,theamount
offillercanbereducedbyafactoroffour.Overall,thestorageelasticmodulusappearstobe
substantiallyenhancedattemperaturesaboveTgforexfoliatednanocompositesfilledwith
layeredsilicates.Apossibleexplanationforsuchanimprovementcouldbethecreationofa
threedimensionalnetworkofinterconnectedlongsilicatelayers,strengtheningthematerial
throughmechanicalpercolation.
Mechanicalpropertiesoflayerednanocompositestypicallyresemblethoseofceramicmaterials.
Flocculatednanocompositesare,conceptually,thesameasintercalatednanocomposites.Silicate
layersaresometimesflocculatedduetohydroxylatededgeedgeinteractionofthesilicate
layers,andwhentheyarecompletelyanduniformlydispersedinacontinuouspolymermatrix,
anexfoliatedordelaminatedstructureisobtained.Theindividualclaylayersareseparatedina
continuouspolymermatrixbyanaveragedistancethatdependsonclayloading.Usually,the
claycontentofanexfoliatednanocompositeismuchlower(45wt.(%))thanthatofan
intercalated(1134wt.(%))nanocomposite.Figure33showsTEMimagesofintercalatedand
exfoliatedpolymerlayeredsilicatesnanocomposites26.
Letusnowlookatotherphysicalpropertiessuchasthermalstability,ionicconductivitygas
barrier,flameretardancy,etc.,oflayerednanocomposites.Polymer/LSnanocompositesshow
improvementsintheirthermalstability.ThePMMA/montmorillonite10wt.(%)nanocomposite,
forexample,degradedattemperatures405CissuperiortopurePMMA246.Inthepoly
(dimethylsiloxane)(PDMS)/10wt.(%)organomontorillonitenanocomposite,adramaticshiftin
theweightlosstowardshighertemperatureswasrecorded261.Theseimprovementsweredueto
thedecreaseinpermeability,usuallyobservedinexfoliatednanocomposites,whichhindersthe
diffusionofvolatiledecompositionproducts.Inthiscontext,thesilicatelayersactasasuperior
insulatorandmasstransportbarriertothevolatileproductsgeneratedduringdecomposition.
Firerelevantproperties,suchasheatreleaserate(HRR),peakheatreleaserate(PHRR),smoke
productionandCO2yieldarevitaltotheevaluationofthefiresafetyofthematerial.Asaresult,
thedecreasedflammabilityofnanocompositesisoneoftheirmostimportantfeatures.Table
20showsconecalorimeterdataforthreedifferentkindsofpolymersandtheirrespective
nanocompositeswithMMT.ItcanbeseenthatallMMTbasednanocompositesexhibitedreduced
flammability.ThepeakHRRisreducedby5075%forN6,PS,andPPgMA
nanocomposites243.Ingeneral,theflameretardantmechanismofnanocompositesinvolvesa
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highperformancecarbonaceoussilicatechar,whichbuildsuponthesurfaceduringburningand
servesasabarriertobothmassandenergytransport.Thismechanismhasalsobeensupported
byrecentstudiesconcerningPS/MMTnanocomposites262.Studiesofthefireretardantproperties
ofexfoliatedNylon12(2wt.(%)/3wt.(%))orintercalatedPP/montmorillonite2wt.(%)
nanocompositeshaverevealed63%reductionintheHRRpeak.
Anotherimportantfeatureofpolymer/layeredsilicatenanocompositesistheirgasbarrier
properties.Claysarebelievedtoincreasethebarrierpropertiesbycreatingamazeor'tortuous
path'(Figure34)thatretardstheprogressofthegasmoleculesthroughthematrix26.Thiscan
beillustratedbythepolyimide/claynanocomposite,whichshowedsignificantlyimprovedbarrier
properties210,255.Thissystem,containingonlyasmallfractionofOMLS(organicallymodified
layeredsilicates),exhibitedreductioninthepermeabilityofsmallmoleculegases,e.g.O2,H2O,
He,CO2andethylacetatevapours210.Forexample,at2wt.(%)clayloading,thepermeability
coefficientofwatervapourwasdecreasedtenfoldwithsyntheticmicarelativetopristine
polyimide.Figure35showstheoxygengaspermeabilitymeasurementsforPLA/OMLS
nanocomposites(PLA=polylactide)263.Therelativepermeabilitycoefficientvalue,i.e.PPLACN=
PPLA,wherePPLACNandPPLAarepermeabilitycoefficientsofnanocompositeandpurePLA
respectively,isplottedasafunctionofthewt.(%)ofOMLS.DatawerefittedwiththeNielsen
theoreticalexpression263.ThereisasignificantdecreaseintheO2permeabilityforthe
nanocomposites,whichismorepronouncedathigherclaycontents.Polyurethaneurea
(PUU)/OMLSnanocompositesalsoreportedreducedH2Ovapourpermeability.
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Theeffectofdifferenttypes/shapesoffillers(2wt.(%))suchasorganoclay,eitherexfoliated
montmorillonite,syntheticmicaorintercalatedclaytactoids(hectoriteandsaponite),onwater
permeabilityofbothpartiallyandtotallyexfoliatedpolyimidebasednanocompositeshasbeen
reportedbyYanoetal.255.ResultsofthisstudyaregiveninFigure36,whereonecanobservea
drasticdecreaseinrelativepermeabilitywiththeincreasinglengthoftheclay.Inotherwords,
thebestgasbarrierpropertieswillbeobtainedbyfullyexfoliatedratherthanlonglayered
silicates.Consequently,thepresenceofspherical,plate,cylindrical,etc.,fillersintroducesa
tortuouspathforadiffusingpenetrant.Thereductionofpermeabilityarisesfromthelonger
diffusivepaththatthepenetrantshavetotravelinthepresenceofreinforcements.
Nanocompositessystemshavealsoshowntobeabletoincreasetheionicconductivityof
polyethyleneoxide(PEO)167.ThePEO/Limontmorillonite60wt.(%)intercalatednanocomposite
showedasignificantimprovementregardingthestabilityofionicconductivityatlower
temperaturecomparedtoaconventionalPEO/LiBF4mixture(Figure37)167.
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ThisimprovementisduetothefactthatPEOisnotabletocrystallizewhenintercalated.This
eliminatesthepresenceofcrystallites,whicharenonconductiveinnature.Theconductivityof
PEO/Limontmorillonitenanocompositeis1.6x106.cm1at333Kandexhibitsweak
temperaturedependence,withanactivationenergyof2.8kcal/mol.Therefore,thehigherionic
conductivityatambienttemperaturecomparedtoconventionalLiBF4/PEOelectrolytesandthe
singleionicconductorbehaviourmakesPEO/Limontmorillonitenanocompositeanewpromising
electrolytematerial.
AnotheroutstandingfeatureofpolymernanocompositespreparedwithOMLSasreinforcements
istheirnoticeablyimprovedbiodegradabilityproperties.Figure38showsrealpicturesof
PLA/MMT4wt.(%)nanocompositesandtheirbiodegradabilityprocess.Figure39showsthetime
dependenceoftheresidualweightofthereinforcement(Rw)andthematrixmolecularweight
(Mw)forPLAandPLA/4wt.%MMTundercompostat582C 263,265.
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ItisveryclearthatthebiodegradabilityofPLAissignificantlyenhancedaftertheincorporation
ofMMT.Withinonemonth,boththeMwandthepercentageofweightlossareatthesamelevel
forneatPLAandPLA/MMT4wt.(%).AsharpchangethenoccursintheweightlossofPLA/MMT
4wt.(%)afteronemonth.Finally,thenanocompositeiscompletelydegradedafter2months.
Thisbehaviourisaccountedforthepresenceofterminalhydroxylatededgegroupsinthesilicate
layers,whichstartheterogeneoushydrolysisofthePLAmatrixafterabsorbingwater.Sincethis
processtakestimetostart,theweightlossanddegreeofhydrolysisforPLAandPLA/4wt.(%)
MMTarealmostthesameupto1month.Othersystemswhichshowedlargeimprovementsin
theirbiodegradabilityarePCL/OMLSandaliphaticpolyesterbasednanocomposites18,26,266.
Anotherwayofincreasingthebiodegradabilityofresultingmaterialsisbyadditionofnatural
fibres.Theuseofrenewableresourcesformakingbiodegradablepolymersandreinforcements
fornanocompositesmayleadnotonlytotheachievementofdesirableproperties,butalsotothe
replacement,inthenearfuture,ofpolymersobtainedfromnonrenewablesources.Thismay
helpminimizingenvironmentaldegradationandwastedisposalproblemsassociatedwiththe
extensiveuseofthesyntheticpolymersintheworld.
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Itistobenotedthatapersistentstressonuseofhightechnologyreinforcements,suchasCNTs,
inthedevelopmentofpolymernanocompositesmaybealimitingfactorinviewoftheirhigh
cost.Inthisscenario,thepossibilityofusinglargequantitiesofinexpensivenaturalnanofibrous
materialsmaybeexplored.Suchmaterialsincludethenaturalclayserpentinegroup(chrysotile,
antigorite,lizardite,amesite),nanolayersofthekaolingroup(kaolinite,dickite,nacrite),ribbons
ofthesepiolitepaligorskitegroup(sepiolite,paligorskite),imogoliteofvolcanicoriginandother
mineralswithgraftablesurfaces176.Further,syntheticmaterialsmadefromthedouble
hydroxideorhydroxylsaltgroupswithlayeredorfibrousstructures,andevengraftablesingle
hydroxideshavinglowcostandinvolvingverycommonelements,willalsoplayanimportant
roleinthefuture.Inaddition,vegetablefibresdisposedofasagriculturalproductionwastecan
bealsoreducedtonanosizerangematerialsandusedasreinforcementagents336.Eveninsuch
nongraftablereinforcementsurfaces,onecanchooseanappropriatechemicaltreatmentand
mouldingtemperatureandcarefullyselectthepolymertoarriveatthebestchemical
compatibilization,leadingtotheoptimizedpropertiesoftheresultingmaterials.Itisobserved
thatthesetreatmentsusuallyimprovethesurfaceadhesivecharacteristicsofthevegetable
fibresthroughtheremovalofnoncrystallinecomponentssuchasligninandhemicelluloses.
3.3.3.Polymernanofibre/CNTnanocomposites
Carbonnanofibres,whichareknowntorangefromdisordered"bamboolike"tohighlyordered
"cupstacked"graphitestructures,andhavediametersintherangeof50200nm,havebeen
employedasreinforcingmaterialsinavarietyofpolymermatrixcompounds,includingboth
thermosetpolymerssuchasepoxy,polyimideandphenolic,andthermoplasticpolymers,as
polypropylene,polystyrene,PMMA,Nylon12,andPEEK293,299.Propertiesofnanotubeshave
alreadybeengiveninTable12.Young'smodulusandtensilestrengthofthePPnanocomposites
werefoundtoincreaseduetothegoodadhesionofoxidisedcarbonfibres,butstiffnessshowed
areversetrendwiththeincreasingvolumefractionofthefibres.Evencompressivestrengthand
torsionalmoduliofthenanocompositeswerefoundtobehigherthanthatfromthePEEKmatrix.
Thesescantyresultsonnanofibrecontainingpolymercompositesrevealaneedformore
detailedandsystematicstudiesonthedispersionandadhesionaspects,consideringthevarying
morphologiesofthefibres.
ThostensonandChou230,231havedescribedtheelasticpropertiesofalignedMWCNTsina
polystyrenematrixnanocompositesystem.Adopting'micromechanics'approach,theyhave
derivedtheaxialelasticpropertiesofCNTsconsideringequivalenteffectivefibreproperties,viz.,
tubediameter,distributionandvolumedistributionasafunctionoftubediameter.Thisgivesa
relationshipbetweenYoung'smodulusandvariousdimensionsoffibres,includingtheirvolume.
Similarrelationshipsofphysicalandmechanicalpropertieswouldprobablyhelpinproducing
materialsforspecificapplications.
SignificanttougheningofpolymermatricesafterCNTincorporationhasbeenreported.Aphenol
basednanocompositeusingCNTswithtubediameter<50nmandlength>0mshowedan
enhancementinYoung'smodulusandstrength.SEMimagesofbrittletensilefracturesurfaces
showedfairlyuniformnanotubedistributionandnanotubepullout232.Epoxy/DWCNT(doublewall
carbonnanotubes)nanocompositesshowedincreasedstrength,Young'smodulus,fracture
toughnessandstraintofailureatananotubecontentofonly0.1wt.(%)233.Inthissystem,the
nanotubeswerehighlydispersedinthepolymermatrix.Also,phenylethylterminated
polyimide/MWCNTnanocompositesexhibitedincreasedtensileYoung'smodulusandreduced
tensilestrengthandultimatestrain.Inthissystem,thenanotubeswereafewhundredmin
lengthand20100nmindiameter 234.Thepolyethylene/MWCNTnanocompositeshowedan
increaseinstrainenergydensityby150%andinductilityby140%.Polyacrylonitrile/MWNTs
systemsshowed80%increaseinenergytoyieldandenergytobreak27.Finally,silicone
elastomerSWCNTreinforcedcompositeshaveshowndramaticincreasesinbothstiffnessand
strength30.
ComingtothemorphologicalstudiesofCNTcontainingpolymernanocomposites,Figure
40representsaTEMimageofpolystyerenecontaining5wt.(%)nanocompositefilmprocessed
byThostensonandChou230,231.Largescaledispersionandalignmentofcarbonnanotubesinthe
polymermatrixcanbeobservedfromthisimage,whichcouldexplaintheobservedproperties.
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Similarly,nanotubesareseparatedintoindividualtubesinthemicrostructureofepoxy/CNTsas
showninFigure41,indicatingtheirgooddispersion.Also,theyremaincurvedinthe
nanocompositeasaresultoftheirsharpflexibility150.
Toconclude,CNTpolymercomposites,thoughmayposegreaterchallengesfortheMaterials
Scientists,willexhibituniquepropertiesasmentionedaboveandhenceoffergreaterpotentials
intermsofapplications.ThisispresentedinthenextSection.
4.ApplicationsofNanocomposites2,1635,258,305,310,337378
Fromtheforegoing,itbecomesevidentthatnanocompositesmayprovidemanybenefitssuchas
enhancedproperties,reductionofsolidwastes[lowergaugethicknessfilmsandlower
reinforcementusage]andimprovedmanufacturingcapability,particularlyforpackaging
applications.Tables21to23presentpotentialapplicationsofceramic,metalandpolymer
basednanocomposites,respectively.Asitcanbeobserved,thepromisingapplicationsof
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nanocompositesystemsarenumerous,comprisingboththegenerationofnewmaterialsandthe
performanceenhancementofknowndevicessuchasfuelcells,sensorsandcoatings.Although
theuseofnanocompositesinindustryisnotyetlarge,theirmassiveswitchingfromresearchto
industryhasalreadystartedandisexpectedtobeextensiveinthenextfewyears.
Forinstance,the(Al 1xTi xN)/Si 3N4superhardnanocomposite,whichhasbeendevelopedby
theCzechcompanySHMLtd.asatribologicalcoatingfortools,issuitableforhardanddry
cuttingoperationssuchasdrilling,turningandmilling,andisreportedtobenow
industrialized337,339.Inthiscase,anovelmethod,whichemploysvacuumarccoatingwitha
rotatingcathode,isusedforcommercialproduction.Thissuperhard(Al 1xTi x)N/Si 3N4possess
hightensilestrength,intherangeof10110GPa,andalifetime24timeshigherthanthatofthe
materialscurrentlyemployedaswearresistantcoatings.
Similarly,oneoftheleadingapplicationareasistheautomotivesector,withstrikingimpactdue
toimprovedfunctionalitiessuchasecology,safety,comfort,etc.Detailsonthecommercial
usageofnanocompositesinautomotivesandfuturedevelopmentsinthissector(includingCNT
basednanocomposites)arenowavailable362.Forinstance,therearereportsonthecurrentuse
ofanumberofnanocoatingsindifferentpartsofAudi,EvobusandDiamlerChrysler
automobiles,aswellasongoingtrialsonfuelcells,porousfilters(foams)andenergyconversion
components,whichincludenanoTiO2containingpaints.Additionally,lightweightbodiesmadeof
metalorpolymerbasednanocompositeswithsuitablereinforcementsarereportedtoexhibit
lowdensityandveryhighstrength(e.g.carbonBuckyfibers,withstrengthof150GPaand
weight1/5thofsteel).Also,twophaseheterogeneousnanodielectrics,generallytermed
dielectricnanocomposites,havewideapplicationsinelectricandelectronicindustries338.
Metalandceramicnanocompositesareexpectedtogenerateagreatimpactoverawidevariety
ofindustries,includingtheaerospace,electronicandmilitary305,whilepolymernanocomposites
majorimpactswillprobablyappearinbatterycathodes6,342,microelectronics343,nonlinear
optics344,sensors345,etc.Improvedpropertiesincludesignificantenhancementsinfracture
strength(about2times)andtoughness(aboutonehalftime)notimedependentwear
transitionsevenatverylowloadshigherhightemperaturestrengthandcreepresistance
increasedhardnesswithincreasingheattreatmenttemperaturehardnessvalueshigherthan
thoseofexistingcommercialsteelandalloyspossibilityofsynthesisofinexpensivematerials
andsignificantincreaseinYoung'smodulus[about105%],shearmodulusandfracturestrength
(almost3timescomparedtomicrocomposites).Thesearebroughtoutmainlybythenanosize
reinforcementsused,whichresultinanappropriatemorphologyfortheproducts.Tables
21and22summarizethepossibledevelopmentsassociatedwiththesematerialsincatalysts,
sensors,structuralmaterials,electronic,optical,magnetic,mechanicalandenergyconversion
devicessuggestedbyresearchersinthefield.
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CNTceramiccomposites,ontheirturn,arereported340tobepotentialcandidatesforaerospace
andsportsgoods,compositemirrorsandautomotivesparesrequiringelectrostaticpainting.Such
materialshavealsobeenreported341tobeusefulforflatpaneldisplays,gasstoragedevices,
toxicgassensors,Li +batteries,robustbutlightweightpartsandconductingpaints.Oneexample
istheAl 2O3CNTcomposite,whichshowshighcontactdamageresistancewithouta
correspondingincreaseintoughnessandhardness.Itisreported92tobeacandidatefor
engineeringandbiomedicalapplications.
Despitethesepossibilities,thereareonlylimitedexamplesofindustrialuseofnanocomposite,
mainlyduetothechallengesinprocessingandthecostinvolved,particularlyfornonstructural
applications.Infact,onerecentreview371dealswithvariousmethodsforthepreparationof
superhardcoatingswithmeritsanddemeritsofeachmethod.However,theintenseresearchin
bothmetalandceramicbasednanocompositessuggeststhatthedaysarenotfaroffwhenthey
willbeactuallyinuse.Thecostfactormaybeaparticularlyseriousproblemforgeneral
engineeringapplications,whilethismaynotbethecaseforspecializedapplicationsin
electronics,aerospace,biomedicalandothersectors,sincetheadvantagesmightfaroutweigh
costsandconcernsinthesesectors.
Ontheotherhand,polymerbasednanocompositesareintheforefrontofapplicationsdueto
theirmoreadvanceddevelopmentstatuscomparedtometalandceramiccounterparts,in
additiontotheiruniqueproperties.Theseinclude23foldstrengthpropertyincrease,evenwith
lowreinforcementcontent(14wt.(%))[e.g.102.7%inYoung'smodulus]withcomplete
eliminationofvoids/holesgasbarrierproperties(about200,000timesoverorientedPPand
about2000timesthatofNylon6withtenfoldrequirementsofexpensiveorganicmodifiers) 372,
biodegradationandreducedflammability[about60%reductionofheatreleaserate],etc.In
addition,agoodpossibilityofenhancingtheshelflifeoftheexistingMREpackagingandtrays
usedintheUGRH&Spolymericmaterialshasalsobeenreported350.Thisisduetothe
limitationsofexistingMREpackings,whichdonotmeettheUSmilitarystandardssuchas
minimumshelflifeof6and12monthsatabout322K(120F)and299K(80F)respectively.In
thiscase,nanocomposites,whichexhibitbettergasbarrierproperties,canprovidealongershelf
life.Suchpackaging,withdifferentmatricesandreinforcements,aswellasdifferentprocessing
conditions,isbeingfieldtestedbytheUSarmysince2002toarriveatanoptimumcombination.
Thisisexpectedtoreducecostby1030%(nearlyUS$13million)comparedtothepresently
usedmaterials,inadditiontobetterperformance.
Varioustypesofpolymerbasednanocomposites,containinginsulating,semiconductingor
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metallicnanoparticles,havebeendevelopedtomeettherequirementsofspecificapplications.
Recently,somePLSnanocompositeshavebecomecommerciallyavailable18,beingapplied237as
ablativesandashighperformancebiodegradablecomposites265,267,280,343,346,aswellasin
electronicandfoodpackagingindustries346,347.TheseincludeNylon6(e.g.DurethanLDPU60by
BayerFoodPackages)18andpolypropyleneforpackagingandinjectionmoldedarticles,semi
crystallinenylonforultrahighbarriercontainersandfuelsystems,epoxyelectrocoatingprimers
andhighvoltageinsulation,unsaturatedpolyesterforwatercraftlayupsandoutdooradvertising
panels,andpolyolefinfireretardantcables,electricalenclosuresandhousings.Table24shows
someexamplesofcommerciallyavailablepolymernanocomposites.Asanexample,Nylon
6/surfacemodifiedmontmorillonite2wt.(%)nanocompositesarecurrentlyavailablefromtwo
commercialsources,HoneywellEngineeredPolymers&SolutionsandBayerAG.Someofthe
productsmadefromnanocompositesareshowninFigure42.
Technologicalcontributionsintheareasofgasbarrier,reinforcementandflameretardancyhave
alsobeenextensivelyexploited355,356.Forexample,heatresistantpolymernanocompositesare
usedtomakefirefighterprotectiveclothingandlightweightcomponentssuitabletoworkin
situationsofhightemperatureandstress.Thisincludeshoodsofautomobilesandskinsofjet
aircrafts,asopposedtoheavierandcostliermetalalloys.Theycanalsoreplacecorrosionprone
metalsinthebuildingofbridgesandotherlargestructureswithpotentiallylighterandstronger
capabilities357,358.Also,unsaturatedpolyester(UPE)nanocompositescanbeemployedinfibre
reinforcedproductsusedinmarine,transportationandconstructionindustries359361.Currently,
UPE/fibreglassnanocomposites,whoseformulationsareavailablefromPolymericSupply,Inc.,
arebeingusedinboataccessoriesthatarestrongerandlesspronetocolourfading362.
Regardingthevarietyofapplicationsofpolymernanocomposites,prominentimpactsoverthe
automotiveindustrycanbehighlighted,includingtheiruseintyres,fuelsystems,gasseparation
membranesinfuelcellsandseattextiles,mirrorhousingsonvariousvehicletypes,door
handles,enginecovers,intakemanifoldsandtimingbeltcovers363,364,withsomeofthese
alreadybeingexploited.Forexample,athermoplasticnanocompositecontainingnanoflake
reinforcements(tradenameBasellTPONano)isbeingemployedforthedevelopmentofstiffand
lightexteriorparts,likethestepassistsbyGM348.Also,porouspolymernanocompositescanbe
employedforthedevelopmentofpollutionfilters365.Otherpromisingtechnologicalapplicationin
thehorizonisinairbagsensors,wherenanoopticalplateletsarekeptinsidethepolymerouter
layerfortransmittingsignalsatspeedoflightgainingmillisecondstobringdownthelevelof
possibleimpactinjuries373.Finally,polymer/inorganicnanocompositeswithimproved
conductivity,permeability,watermanagementandinterfacialresistanceattheelectrodeare
naturalcandidatesforthereplacementoftraditionalNafionPEMinfuelcells,andarecurrently
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undertrial 349.
Improvementsinthemechanicalpropertiesofpolymernanocompositeshavealsoresultedin
theirmanygeneral/industrialapplications.Theseincludeimpellersandbladesforvacuum
cleaners,powertoolhousings,andmowerhoodsandcoversforportableelectronicequipment,
suchasmobilephonesandpagers366.Anotherexampleistheuseofpolymernanocompositesin
gluesforthemanufacturingofpressuremouldsintheceramicindustry.
Thedevelopmentofenvironmentallyfriendly,nonfoilandbetterpackagingmaterialscanreduce
theamountofsolidwaste,improvepackagemanufacturingcapabilities,andreducetheoverall
logisticsburdentousers.Inthiscontext,theincorporationofnanoclayparticlesinto
thermoplasticresinshasshowntobehighlyeffectivetoimprovebarrierpropertiesandpackage
survivability351.Suchexcellentbarriercharacteristicshaveresultedinconsiderableinterestin
claynanocompositesinfoodpackagingapplications,bothflexibleandrigid.Specificexamples
includepackagingforprocessedmeats,cheese,confectionery,cerealsandboilinthebagfoods,
alsoextrusioncoatingapplicationsinassociationwithpaperboardforfruitjuiceanddairy
products,togetherwithcoextrusionprocessesforthemanufactureofbeerandcarbonated
drinksbottles367.Theuseofnanocompositeformulationswouldbeexpectedtoenhance
considerablytheshelflifeofmanytypesoffood.Honeywellindustrieshavealsobeenactivein
developingacombinedactive/passiveoxygenbarriersystemforpolyamide6materials368.Itis
mentionedherethatTritonSystemsandtheUSArmyareconductingfurtherworkonbarrier
performanceinajointinvestigation,asmentionedearlier.Theyaretryingtodevelopanon
refrigeratedpackagingsystemcapableofmaintainingfoodfreshnessforthreeyears.
Polymer/claynanocompositesarecurrentlyshowingconsiderablepromiseforthisapplication.
Thereductionofsolventtransmissionisanotherinterestingaspectofpolymer/clay
nanocomposites.AstudyconductedbytheUBEIndustrieshasrevealed347significantreductions
infueltransmissionthroughpolyamide6/66polymersbyincorporationofananoclayfiller.Asa
result,thesematerialsareveryattractiveforthedevelopmentofimprovedfueltanksandfuel
linecomponentsforcars.Inaddition,thereducedfueltransmissionmeanssignificantcost
reductions.Thepresenceoffillerincorporationatnanolevelshasalsobeenshowntohave
significanteffectsonthetransparencyandhazecharacteristicsoffilms369incomparisonto
conventionallyfilledpolymers.Theabilitytominimizetheextenttowhichwaterisabsorbedcan
beamajoradvantageforpolymermaterialsthataredegradedinmoistenvironments370.
Finally,CNTpolymercompositesarereported28tobepotentialcandidatesfordatastorage
media,photovoltaiccellsandphotodiodes,opticallimitingdevices,drumsforprinters,etc.
5.Perspectives
Outstandingpotentialsofnanocompositescanbeexemplifiedbythemassiveinvestmentsfrom
manycompaniesandgovernmentsthroughouttheworld.Asaresult,nanocompositesare
expectedtogenerateagreatimpactinworldeconomyandbusiness.Thisisverymuchevident
fromthepublicationspouringin,particularlyonavarietyofpropertiessuitedfordifferent
applications350.AccordingtoareportfromPrincipiaPartners,whichisillustratedinTable25,a
marketsizeofoverthanU$1,834billion(USD)isestimatedby2009,consideringonlythe
differentapplicationsofpolymer/claynanocomposites350.Theestimativemaynotbe
exaggerated,sincemanyoftheapplicationareasalreadyusethesecomposites,withsomeof
thembeingcommercializedbymanyleadingindustries.Packaging,coatingandautomotive
sectorsareintheforefrontfortheuseofthesenewmaterials.
Withincreasingdemandforhighperformancesystemssuchasnanofillersandtheircomposites
andmanysectorslookingforthematlowcosts,optimisticestimatesdonotseembeyond
reach372.Abrightfutureisevidentasmanyleadingindustriallaboratories,suchasArgonne
NationalLaboratory,arereadyforcommercializationoftheirnanoproducts[organoclays]and
lookingforindustrialpartnerstodevelopand/ortesttheminawiderangeofapplications.Many
oftheseareconsumerproducts,andhencetheenvisagedmarketisexpectedtoestablishitself.
Forexample,electroconductivepolymers,nanosmartswitchesandsensorsforautomotivesare
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alreadyinusebyGEandCabotinUSA,whilesince2002GeneralMotorshassuccessfullyused
nanocompositescontainingclayandtalcintheirexteriorstructuralcomponents.
Further,asnewpowerproductionandstoragedevicesareattractiveproducts,othernanotech
revolutionsexpectedtotakeplaceinthenearfuturearereported373tobehydrogenstorage,
fuelcells,supercapacitorsandbatteries.Infact,ithasbeenpointedoutthattheinfrastructure
costofautomotiveswoulddecreaseby10100timesbytheuseoffuelcellsalone,withother
nanotechnologieshavingsimilarimpact.Futureareasofresearch,particularlyfortheautomotive
industrycouldbei)improvedfireretardancyofnanocomposites,whichcanbeusedasinterior
parts,ii)improvedweatherabilityforuseasexteriorparts,andiii)bipolarity,obtainedbythe
useofnanocarbons,fortheproductionoffuelcells.Similarly,thecoatingandinternalstructure
ofcombustionenginesmayreceiveattentioninthecaseofceramicbasednanocomposites.
Nanoclaysareexpectedtohave50%ofthetotalnanomaterialsmarketby2020.Also,withthe
expecteddecreaseincostofCNTs,theirnanocompositesarealsoexpectedtogainlargesharein
themarkets,therebyleadingtotherapidcommercializationofCNTsthemselves374.Itisalso
reportedthattwoofthesectors,automotiveandpackaging,whichwillaccountforabout40%of
demandby2020,willbemostimportantforthenextdecadeorso.Then,theconstructionsector
willprobablydominate,whileCNTbasednanocompositeswillreplacethepresentlyused
conductingmaterialsintheelectricalandelectronicindustries375.
Consideringtheuseofpolymerbasednanocompositesduring2003at11,000tons(11millionkg)
atUS$90.8million,BusinessCommunicationsCo.Inc.,initsreportonnanocomposites
publishedinApril2004,hasestimatedthismarkettoincreasebynearly3times(35,960tons)at
US$211.1duringthecurrentyear(2008),withanannualgrowthrate(AAGR)of18.4%377.Of
this,thermoplastics,whichwereabout5.68millionkgatUS$70.7in2003,wouldgrowto27.74
millionkgwithabout20.4%AAGRatUS$178.9million,whilethermosets,with5.45millionkg
atUS$20.1million,wouldgrowto8.22millionkgwithabout9.9AAGRatUS$32.2million.
Evenifsomedifficultiesaretobeencounteredforthis,presentapplicationsofthesematerials
areexpectedtogrowhigherthan20%ofthetotaldemandofpolymercomposites,withthe
fastestdemandinengineeredplasticsandelastomers374,376.Ontheotherhand,withthermoset
basednanocompositesbeingnotsodiversecomparedtotheirthermoplasticscounterparts,their
marketisexpectedtogrowattheratementionedabovebasedonthecurrentusesofthese
compositesinprefinishedwoodflooringandothersectors.
ThereareotherforecastsforUSsuchastheonesfromFreedoniaIndustry,whichreportsonthe
profilesofmajorindustriesintheareaofnanocompositesinUSA,markettrendsandindicators
forthesematerialsforeveryfiveyearsfrom2010375.Accordingtothem,thedemandfor
nanocompositeswillbeabout159millionkgby2010andabout3.2billionkg,valuedatUS$15
billion,by2020.Theotherestimate376fortheglobalnanocompositemarketrisestoUS$250
millionwithAAGRbetween1825%by2008.Itisalsoreported374thatthepackagingindustry
alonewoulduseabout1.7millionkgofpolymernanocompositesinthebeverageandfood
industriesby2009,andthatthiswillgrowtoabout45millionkg.Alltheabovementioned
projections,thoughvaryingmarginally,maynotbeexaggeratedinviewoftheresearchoptions
madebysomeofthedevelopedcountries,withUSAleadingwith400researchcentresand
industrieswithinvestmentstothetuneofUS$3.4billion,Europewith175
organizations/industrieswithaboutUS$1.7billionandJapanwith100organizations350.
Someofthechallengestobefacedforthesuccessoftheaboveprojections,whichwillalsogive
futureresearchdirections,include:suitablereinforcementssuchasnanofibreswithorwithout
spinning,whichwillhavehigherstrengthproperties,beinglighterthantheirmicrocounterparts
andhenceappearingassuperiorstructuralcomponentsuseofnanofibresindifferentareassuch
asbiomedical,electricalandoptical,forvariousfunctionaldevicesconductingpolymerbased
nanomaterialsforelectrochemicalapplicationsmodificationofthemechanicalbehaviourof
nanocompositestogethigherperformancessurfacemodificationofpolymernanofibresfortheir
useinpolymermatricestoovercomethepoorinterfacialbondingmodellingandsimulationof
mechanicalpropertiesofnanofibrecontainingcomposites,etc.377.
Otherissues,whicharealsoexpectedtogetdueattention,includevariousprocessing
parametersinthecaseofthethreetypesofnanocomposites,withoutwhichtheirwidespread
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commercializationwouldnotcomethrough.Theseincludeproblemswithcompatibilityandde
agglomeration,whichcanbeovercomethroughsurfacemodificationofreinforcementsfor
homogeneousdispersionwithoutagglomeration.Theabove,alongwithappropriatepositioningof
reinforcements[exfoliationandorientation]inthecaseofpolymerbasedcompositesarealso
issuestobesolved.
Otherpromisingareaforfutureresearchonproperinexpensivereinforcementsistheuseof
cheapandabundantlyavailablepolymeric(mayberecyclable)andreinforcingmaterialsof
naturaloriginforwideapplications.Ifthelattercanreplaceexpensivecarbonnanotubes,the
costoftheirnanocompositeproductsmaybereducedtoextendthemtopopularapplications.
Hence,concentratedeffortswillbeneededtofindnewformulationswithmaterialsfrom
renewableresources(suchaspolymersderivedfromplasticizedsaccharides,polylactide(PLA),
polyhydroxylalkanoates(PHAs),poly(caprolactone),etc.),reinforcedwitheasilyavailable
mineral/vegetalmaterialsorsyntheticreinforcementsbasedoncommonelementslike
hydroxides,layereddoublehydroxidesandlayeredhydroxidesalts.Thesameprocedurecan
alsobeusedtoimprovethepropertiesofsyntheticbiodegradablepolymers.Researchinthese
directionswillbeacertainty,keepinginviewtheincreasedattentiononcleanerenvironment
andecology.
Thestudyofnanocompositesisaninterdisciplinaryarea,encompassingphysics,chemistry,
biology,materialsscienceandengineering.Therefore,theknowledgearisingfromscientistswith
differentbackgroundswillundoubtedlycreatenewscience,andinparticularnewmaterials,with
unforeseentechnologicalpossibilitiessuchascreationofmacroscopicengineeredmaterials
throughnanoscalestructures.Itisthereforerightlypointedoutthatthiscallsforbasicresearch
onstructurepropertycorrelationsinnanocomposites,leadingtonewchallengesinthe
developmentofsuitablefabricationtechniquesfordealingwithnanoscalematerials,fortheir
characterizationandmechanics,inordertounderstandinteractionsatsuchsizes30.Another
excitingaspectisthatnanocompositeswillbenefitmanysectorsofoursociety,including
electronicsandchemical,spaceandtransportationindustries,aswellasmedicine,healthcare
andenvironmentalprotection.Becauseofthis,nanocompositesareexpectedbeofhighimpactin
theimprovementofourqualityoflifeinthecomingyears.
Asthepropertiesofnanostructuredcompositesarehighlystructure/sizedependent,many
researchstudiesstillhavetobeperformedtoprovideabetterunderstandingofthestructure
propertyrelationshipinsuchsystems.Thisisanessentialrequirementtoallowthenanoscale
designofmultifunctionalmaterialsforengineeringapplications.Inthisregard,criticalissuesto
belookedintoincludeaspectsofdispersion,alignment,volumeandrateoffabricationand,
finally,costeffectiveness.Somelighthasbeenthrownontheseaspects30.Probably,processing
structurepropertiesmapssimilartothosedevelopedformetalsandalloysbyAshby379may
furtherenhancethepotentialsofnanocomposites.Thisisbecausestructure,whichisdictatedby
theprocessingmethod,inturndictatesthepropertiesofmaterials.Addedtothisisthe
engineeringaspectofdesign.
Formaterialsscientists,designcouldbeoneofthefollowing380:i)designofmaterialshaving
combinationsofuniquepropertiesorii)selectionofmaterialshavingbettercharacteristicsfora
specificpurposeoriii)developmentofanewprocessforprovidingoneoftheabovementioned
materials.Besides,inengineeringatermcalled'performanceindex'(P)isdefined,which
correlatesthepropertiesofmaterialsforagivenproduct,andhelpsintheirselectionforspecific
applications.ThehigherthevalueofP,thebetterwillbetheperformance380.Further,another
correlationgenerallyusedisbetweentherelativecostandtheperformanceindex,wherebyone
canarriveattheeconomicalmaterialselectionforagivenproduct.Theaboveconceptsshould
alsobeappliedinthecaseofnanocomposites,sothatonecouldgetthemaximumbenefitfrom
theminanyapplication.
Finally,aspartofthesocialimplicationsofthisnascentandpotentialtechnology,therearesome
safetyaspectstobeconsideredwhiledealingwithnanosizedparticlesandtheircomposites.For
example,fabricscoatedwithnanoparticlesareavailable,whichcanbeconfiguredtoimbuethe
fabricwithvariousattributes.Aerosolisedchemicalandbiologicalagentsareaclearthreatthat
islikelytogrowinthefuture.Thereleaseofnanoparticlesintotheenvironmentisamajor
healthandsafetyissue.Hencethereisanincreasingneedforresearchintoemissionof
nanocompositesandnanoparticles.Potentiallyharmfulcharacteristicsofnanotechnology
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productsbasedontheirlargesurfacearea,crystallinestructureandreactivitymayfacilitate
theireasytransportintotheenvironmentorinteractionwithcellconstituents,thusexacerbating
manyharmfuleffectsrelatedtotheircomposition.Onerecentconferencewasdevotedtothe
studyofthesafetyandrisksofnanoparticles381,whiletheU.S.EnvironmentalProtectionAgency
(EPA),aspartofitsSciencetoAchieveResults(STAR)program,isseekingapplicationsthat
evaluatethepotentialimpactsofmanufacturednanomaterialsonhumanhealthandthe
environment.Thisisimportantasnewnanomaterialsareconstantlybeingmanufacturedthere
isalwaysapossibilityofhumanandenvironmentalexposuretowastestreams,orother
pathwaysenteringtheenvironment382.
6.Conclusions
Inconclusion,newtechnologiesrequirematerialsshowingnovelpropertiesand/orimproved
performancecomparedtoconventionallyprocessedcomponents.Inthiscontext,nanocomposites
aresuitablematerialstomeettheemergingdemandsarisingfromscientificandtechnologic
advances.Processingmethodsfordifferenttypesofnanocomposites(CMNC,MMNCandPMNC)
areavailable,butsomeoftheseposechallengesthusgivingopportunitiesforresearchersto
overcometheproblemsbeingenclunteredwithnanosizematerials.Theyofferimproved
performanceovermonolithicandmicrocompositecounterpartsandareconsequentlysuitable
candidatestoovercomethelimitationsofmanycurrentlyexistingmaterialsanddevices.A
numberofapplicationsalreadyexists,whilemanypotentialsarepossibleforthesematerials,
whichopennewvistasforthefuture.Inviewoftheiruniquepropertiessuchasveryhigh
mechanicalpropertiesevenatlowloadingofreinforcements,gasbarrierandflamerelated
properties,manypotentialapplicationsandhencethemarketforthesematerialshavebeen
projectedinvarioussectors.Thusallthethreetypesofnanocompositesprovideopportunities
andrewardscreatingnewworldwideinterestinthesenewmaterials.
Acknowledgements
Wearegratefultoallauthorsofthepapers,publishersofthejournalsfromwheretablesand
figureshavebeenreproduced[TheAmericanChemicalSociety,AmericanInstituteofChemical
Engineers,AmericanInstituteofPhysics,Elsevier,InstituteofPhysics,JapanSocietyofPowder,
PowderMetallurgy,JohnWiley&Sons,MaterialsResearchSociety,PlasticsTechnology
Magazine,SpringerVerlag,WileyVCHVerlagGmbh&Co,websites],fortheircourtesyandkind
permission.TheauthorssincerelyexpresstheirgratitudetoProfessorJaisaF.Soaresof
DepartmentofChemistry,UFPRforherreadingofthefullmanuscript,editingbothtechnicaland
languageaspectsaswellforhercriticalsuggestions.WealsoacknowledgeMr.Gregorio
GuadalupeCarbajalArizaga,DepartmentofChemistry,UFPR,MaheshKesturSatya,USA,for
theirreadingofthepaperandusefulsuggestions.
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