Inconclusion,effortstoachievemorphologicalcontrol overtheconductivenetworksinCPCshaveattracted signif-icantattentionduetothevitalrolethatmorphologyplays inelectricalproperties.Recentandextensiveprogresson severalefficientmethodsforcontrollingthemorphology of conductive networks has beenreviewed. Conductive networksendowCPCswiththeirelectricalproperties.In addition,themajorityoftheresistanceinaparticulartype ofCPCisderivedfromthetunnellingresistancebetween local conductive networks; therefore, tunable electrical properties can beobtainedby adjusting theconductive networks.
Variousdirectandindirectobservationmethodshave beenusedtocharacteriseconductivenetwork morpholo-gies,includingOM,SEM,TEM,andAFM,aswellasRaman spectroscopyand electricalconductivitymeasurements,.
Tofullyutilisethelargeaspectratioofconductivefillers (suchasCNTs orgraphene)and furtherreducethe per-colation threshold of CPCs, various methods have been proposedforcontrollingconductivenetworks,including theuseofpolymerblendsand thermalannealing. Poly-mer blendsallowconductive networkstobeselectively dispersedat oneofthepolymerphasesorinterfacesby
Please cite this article in press as: Deng H, et al. Progress on the morphological control of conductive network carefullycontrollingthethermodynamic(e.g.,controlling
interfacial energy through careful selection of polymer types) and kinetic parameters (e.g., mixing procedures andsequence,blendingtime,shearstrength,etc.)ofthe system.Thermalannealingenablestherepairofcontacts betweenlocal conductivenetworks for CPCscontaining varioustypesofconductivefillers,includingCB,CNT,and carbonnanofibres.Othermethods,suchastheuseofshear force,mixedfillers(hybridfillers),electricalormagnetic fields,orlatex particles,canalsobeusedtocontrolthe morphologyofconductivenetworks.Thesemethodsare effectiveattuningtheconductivenetworkstructure,and thustheelectricalproperties,inacontrolledfashion. More-over, a combination ofdifferentmethods hasalsobeen showntobeefficientatcontrollingnetworkmorphology.
TheelectricalpropertiesofCPCscanbetunedovera relativelywiderangeusingvariousmethods.However,the maximumconductivityobservedintheresultingCPCsis oftenmuch lower thantheintrinsic conductivityofthe conductivefillers.Itisthoughtthatthecontactresistance betweenconductivefillersisresponsibleforthis.The abil-ity toenhance theconductivity of CPCstovalues close to that of the conductive fillers through morphological controlwouldthereforeprovideatremendousadvantage.
However,thistaskremainsachallenge.Moreover,as var-ious morphologicalcontrol methods can confer distinct characteristicstothenetwork(forinstance,shearor elec-tricalfieldscontrolorientation,thermalannealingrepairs local contacts, and polymer blends produce selectively distributednetworks),amoresystematicstudyusing com-binationsofdifferentmorphologicalcontrolmethodscould leadtobettercontrolovertheconductivenetwork struc-ture.Finally, theuseof novelprocessingmethods,such ashighspeedinjectionmoulding[102]orlayer-by-layer assembly,tocontroltheconductivenetworkstructurein CPCsisalsoaninterestingresearchdirection.
Asamaterialwithnumerousapplications,the multi-functionality of CPCshasbeen extensively investigated.
Thesefunctionalitiesincludestrainanddamagesensing, vapour/liquidsensing, andtemperature sensing,aswell aselectroactiveshapememoryproperties,thermoelectric properties,anduseasstretchableconductors.For sensing-basedfunctionalities,effortshavebeenmadetoenhance thesensitivityofCPCsusingvariousmorphologicalcontrol methods.Forstrain/damagesensing,tuningtheresistance betweenlocalconductivenetworkswasreportedtobevital forsensing.Otherstrategies,includingtheuseofmixed fillers,conductivefillerswithdifferentaspectratios,and conductive fillers withdifferent polymercoatings, have been consideredfor the modificationof strain sensitiv-ity.Nevertheless, therange oftunablesensitivityis still relativelysmall,andfundamentalaspects,suchasthe con-ductive networkstructure and interfacialstresstransfer between filler and matrix, need to be re-evaluated for thepreparationofhighperformanceCPCsstrain/damage sensors.In terms oftemperature sensing,thetransition temperaturecanbedeterminedbythemelting temper-ature, the glass transition temperature of the polymer matrix,orthedifferencein thethermal expansion coef-ficient between the polymer and conductive filler. In some cases, a wide range of transition temperatures
canbeobtainedby adjustingthefiller contentor poly-mer blend composition. These materials can be used fortemperature-sensingandcurrent-limitingapplications.
Forvapour/liquid-sensingapplications,thematchbetween polymerandvapourplaysanimportantroleinsensitivity.
AchangeinelectricalpropertiesupontheexposureofCPCs tochemicalsiscausedbymatrixswellinginducedbythe absorptionofvapourorliquid.Thesensitivityand selectiv-ityofthesesensorscanbemodifiedbygraftingfunctional chemicalgroupsorpolymermoleculesontothesurfaceof theconductivefillers.Animprovedunderstandingofthe fundamentalsensingmechanismsandmaterialprocessing couldleadtoarangeofnewapplicationsinleakage detec-tionusingCPC-basedvapour/liquidsensors.
Movingbeyondsensingapplications,variousmethods havealso beenproposedforthefabrication ofCPCsfor useasstretchableconductors.However,thesefabrication methods requirecomplicated and potentially expensive methodsormaterials(suchas1mmlongSWNTs). Recog-nising that the conductive network structure plays an importantroleinthestrain-electricalpropertiesofCPCs, our recent work observed that an interface-mediated method could be used to align the randomly oriented fillerduringstretchingandinducebucklingoftheMWNTs during relaxation. Using this simple approach, the fab-rication of high-performancestretchable conductorsfor arbitrarilyshapedobjectsinlargescaleapplicationscan beachieved.SMPsexhibit a shape-memoryeffect; they canbedeformedandfixedintoatemporaryshape,then recovertheiroriginalshapeinresponsetoexternal stim-uli.Thisstimuluscanbeprovidedbyelectricity-induced heatinginCPC-basedSMPs.Variousshape-memoryCPCs containingdifferentconductivefillershavebeenreported to provide a rapid response as electroactive materials.
The ability of thermoelectric CPCs to transform tem-perature gradients into electricity (and vice versa) has recently attracted tremendous research attention. The useof organicpolymer-based materialsas thermoelec-tricmaterialshastheadvantageofbeinggreener,more flexible,andlowerincostcomparedtoinorganic equiv-alents.Nevertheless,thehighestZTachievedforpolymers isonly0.25,whereastheZTofinorganicmaterialscanbe ashighas2.Someofthecurrentresearchfocusaimsto increase theelectrical conductivityofCPCssignificantly withoutincreasingtheirthermalconductivity.Inthenear future, developing a systematic approach for the selec-tionofappropriateconductivepolymersand conductive nanofillers,withtheaimofachievinghighthermopower andelectricalconductivitywhilemaintainingcontrolover structure,morphologyanddopinglevels,hasthepotential toimprovetheperformanceofcurrentorganic thermoelec-tricmaterials.
Finally,manypotentialapplicationshavebeen demon-strated for electroactive CPC-based materials. However, morphological control over the conductive networks is oftenlackinginthesematerials,eventhoughthe morpho-logicalcontrolofconductivenetworksiscrucialtothefinal electricalpropertiesofCPCs.Futureworkinthisareahas thepotentialtoleadtointerestingandexcitingresults. Fur-thermore,theindustrialuseofthemulti-functionalitiesof CPCsoftenrequiressignalorpropertystabilityandease
Please cite this article in press as: Deng H, et al. Progress on the morphological control of conductive network ofpreparation. Many obstaclesneedto beovercometo
addresstheseissues.
Acknowledgements
We expressour sincere thanksto theNational Nat-ural Science Foundation of China for financial support (51273117,51003063and51121001).Thisworkwas sub-sidizedbythespecialfundsforMajorStateBasicResearch ProjectsofChina(2011CB606006).Thisworkwasalso sup-portedbytheMinistryofEducation(20111568-8-1).The authorsacknowledgetheusewithpermissionoftext pub-lishedinref.[158],Copyright2013byJohnWiley&Sons.
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