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Hybrid Polymer Composite Materials Related titles Environmentally-friendlyPolymerNanocomposites(ISBN978-0-85709-777-4) CeramicNanocomposites(ISBN978-0-85709-338-7) Polymer-carbonNanotubeComposites(ISBN978-1-84569-761-7) Woodhead Publishing Series in Composites Science and Engineering Hybrid Polymer Composite Materials Properties and Characterisation Edited by Vijay Kumar Thakur Manju Kumari Thakur Asokan Pappu WoodheadPublishingisanimprintofElsevier TheOfficers’MessBusinessCentre,RoystonRoad,Duxford,CB224QH,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates TheBoulevard,LangfordLane,Kidlington,OX51GB,UnitedKingdom Copyright©2017ElsevierLtd.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronicormechanical, includingphotocopying,recording,oranyinformationstorageandretrievalsystem,withoutpermissioninwritingfrom thepublisher.Detailsonhowtoseekpermission,furtherinformationaboutthePublisher’spermissionspoliciesandour arrangementswithorganizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency,canbe foundatourwebsite:www.elsevier.com/permissions. ThisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythePublisher(otherthanas maybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperiencebroadenour understanding,changesinresearchmethods,professionalpractices,ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluatingandusingany information,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethodstheyshould bemindfuloftheirownsafetyandthesafetyofothers,includingpartiesforwhomtheyhaveaprofessional responsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeanyliabilityfor anyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceorotherwise,orfromany useoroperationofanymethods,products,instructions,orideascontainedinthematerialherein. BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress ISBN:978-0-08-100787-7(print) ISBN:978-0-08-100788-4(online) ForinformationonallWoodheadPublishingpublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:MatthewDeans AcquisitionEditor:GwenJones EditorialProjectManager:CharlotteRowley ProductionProjectManager:DebasishGhosh CoverDesigner:GregHarris TypesetbyMPSLimited,Chennai,India List of Contributors H.P.S. Abdul Khalil Schools of Industrial Technology, Universiti Sains Malaysia, Penang, Malaysia; Cluster for Polymer Composites, Science and Engineering ResearchCenter,UniversitySainsMalaysia,Penang,Malaysia Sandro Campos Amico PPGEM, Federal University of Rio Grande do Sul (UFRGS),PortoAlegre,Brazil Alireza Ashori Department of Chemical Technologies, Iranian Research OrganizationforScienceandTechnology(IROST),Tehran,Iran Vajiheh Behranvand Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Islamic Republic of Iran Jarosław Bienias´ Department of Materials Engineering, Faculty of Mechanical Engineering,LublinUniversityofTechnology,Lublin,Poland Grzegorz Bubak Robotics, Brain and Cognitive Sciences Department, Italian Institute of Technology, Genoa, Italy; Italian Institute of Technology, Graphene Labs,Genoa,Italy Ana M. D´ıez-Pascual Analytical Chemistry, Physical Chemistry and Chemical Engineering Department, Faculty of Biology, Environmental Sciences and Chemistry,Alcala´ University,Madrid,Spain David Gendron Robotics, Brain and Cognitive Sciences Department, Italian Institute of Technology, Genoa, Italy; Italian Institute of Technology, Graphene Labs,Genoa,Italy Patryk Jakubczak Department of Materials Engineering, Faculty of Mechanical Engineering,LublinUniversityofTechnology,Lublin,Poland Mohammad Jawaid Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang,Selangor,Malaysia x ListofContributors Ayesha Kausar Nanoscience and Technology Department, National Center For Physics,Quaid-i-AzamUniversity,Islamabad,Pakistan Elham Khadem Organic Polymer Chemistry Research Laboratory, Department of Chemistry,IsfahanUniversityofTechnology,IslamicRepublicofIran Shadpour Mallakpour Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Islamic Republic of Iran; Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Islamic Republic of Iran; Center of Excellence in Sensors and Green Chemistry, Department of Chemistry, Isfahan University of Technology, Islamic RepublicofIran Jose Roberto Moraes d’Almeida Materials Engineering Department, Pontifical CatholicUniversityofRiodeJaneiro(PUC),RiodeJaneiro,Brazil Hiroshi Mutsuyoshi Department of Civil & Environmental Engineering, Saitama University,Saitama,Japan Hai Nguyen College of Information Technology & Engineering, Marshall University,Huntington,WV,UnitedStates M.R. Nurul Fazita Schools of Industrial Technology, Universiti Sains Malaysia, Penang,Malaysia Wagner Mauricio Pachekoski Federal University of Santa Catarina (UFSC), Joinville,Brazil Sergio Henrique Pezzin Center of Technological Sciences, Santa Catarina State University(UDESC),Joinville,Brazil MasoudRais-Rohani UniversityofMaine,Orono,ME,UnitedStates Shima Rashidimoghadam Organic Polymer Chemistry Research Laboratory, Department of Chemistry, Isfahan University of Technology, Islamic Republic of Iran E. Rosamah Faculty of Forestry, Mulawarman University, East Kalimantan, Indonesia MohammadRouhi ConcordiaUniversity,Montreal,QC,Canada Naheed Saba Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang, Selangor,Malaysia ListofContributors xi Fabrizio Sarasini University of Rome “La Sapienza” Department of Chemical EngineeringMaterialsEnvironment,Rome,Italy N.A. Sri Aprilia Department of Chemical Engineering, Syiah Kuala University, BandaAceh,Indonesia Barbara Surowska Department of Materials Engineering, Faculty of Mechanical Engineering,LublinUniversityofTechnology,Lublin,Poland Tham Mun Wai Schools of Industrial Technology, Universiti Sains Malaysia, Penang,Malaysia Wael Zatar College of Information Technology & Engineering, Marshall University,Huntington,WV,UnitedStates 1 Functional materials from polymer derivatives: properties and characterization GrzegorzBubak1,2andDavidGendron1,2 1Robotics,BrainandCognitiveSciencesDepartment,ItalianInstituteofTechnology, Genoa,Italy,2ItalianInstituteofTechnology,GrapheneLabs,Genoa,Italy ChapterOutline 1.1 Introduction 1 1.2 Section1.Electro-photoactivepolymermaterialsforoptoelectronics 2 1.2.1 Historyandbasicsparametersofanorganicsolarcell 2 1.2.2 Architectureofapolymersolarcelldevice 4 1.2.3 Morphologyofthepolymer(cid:1)PCBMcomposite(activelayer)performancerelationship 8 1.2.4 Thermalannealingandpostannealing 9 1.2.5 Polymerchemicalmodification 11 1.2.6 Chargetransportandeffectofchargecarriermobility 11 1.3 Section2.Polymericmaterialsforsupercapacitorsand electroactivepolymeractuators 17 1.3.1 Polymerderivativesinelectrochemicalsupercapacitors 18 1.3.2 Polymerichybridmaterialsforelectroactivecarbon-basedactuators 26 References 36 1.1 Introduction Nowadays, the presence of functional polymeric materials can be found in a broad range of application. They offer unique and attractive properties that can be tuned tofitoureverydaytechnologicalneeds.Thischapteraimstosummarizeanddiscuss the physicochemical properties of a broad range of functional polymeric materials. The first section of this chapter introduces electro-photoactive polymer material for optoelectronic. The optoelectronic field has grown steadily in the past decade and can therefore be declined in many subfields such as materials for organic photovol- taics, photodetectors, light-emitting diodes and transistors. In this section, we will discuss the optical and electronic properties of novel functional materials (polymer composites)aswellastheirperformancesinpolymersolarcell. HybridPolymerCompositeMaterials:PropertiesandCharacterisation.DOI:http://dx.doi.org/10.1016/B978-0-08-100787-7.00001-9 Copyright©2017ElsevierLtd.Allrightsreserved. 2 HybridPolymerCompositeMaterials:PropertiesandCharacterisation Thesecondsectionofthechapterwillbecenteredonhybridpolymercomposites for electroactive devices. More precisely, we will glance at functional materials for storing or transducing energy as well as their corresponding devices such as super- capacitors. At last, polymeric materials used in electroactive actuators will be describedandthemaincharacterizationtechniqueswillbereviewed. 1.2 Section 1. Electro-photoactive polymer materials for optoelectronics Electroactive polymers have attracted great attention in the past decade as active materialsinoptoelectronicdevicessuchasorganicphotovoltaiccell(OPV),organic field-effect transistor (OFET), light-emitting diodes, and photodetector. In this sec- tion, we will discuss the optical, structural, and electronical properties of polymer compositesusedasactivematerialinthesedevices. Before reviewing the main classes of polymer composites, we will briefly intro- duce the conceptofpolymersolarcell anddiscuss the main characterizationtechni- ques commonly used to obtain information about the active layer (also referred to the conjugated polymer—fullerene derivative composite) such as optical, structural, andelectronicproperties. 1.2.1 History and basics parameters of an organic solar cell ThefirstorganicsolarcellwasreportedbyTangin1986(Tang,1986).Atthetime, a power conversion efficiency (PCE) of about 1% as well as a fill factor of 65% was reached. However, it is important to note that the architecture of Tang’s solar cell was different from the one usually used today. Indeed, Tang constructed a bilayer device using a p-type copper phthalocyanine and a n-type bisbenzimidazo (2,1-a:20,10-a0)anthra(2,1,9-def:6,5,10-d0e0f0)diisoquinoline-10,21-dione. Both were vacuum-evaporated in order to construct the device. Then the concept of bulk het- erojunction (BHJ) was introduced to address the exciton diffusion length problem (the exciton is defined as a Coulombically bonded hole(cid:1)electron pair) (Yu et al., 1995). Indeed, contrary to the bilayer approach, in the BHJ, the donor (conjugated polymer)and the acceptor (fullerene derivative) are mixed togetherthus forming an interpenetrating network (which can also be seen as a polymer composite) with large interfacial areas to enhance the exciton dissociation. This polymer(cid:1)fullerene mixture is also named “active layer.” We will see later in this chapter that several routes can be used to optimize the morphology of the active layer, therefore improvingtheexcitondiffusionandenhancingthesolarcelldeviceperformance. Before entering into the details concerning the chosen materials, let us first dis- cuss how to calculate the PCE of a solar cell. Plainly, the PCE can be defined as the product of the open circuit potential (V ), the short-circuit current density OC (J ) and the fill factor (FF) divided by the light intensity incident on the device SC (P ) (Li et al., 2010). In short, the V is related to the energy levels of the donor IN OC and acceptor and to the nanomorphology of the active layer. The J depends on SC the charge mobility in the polymer and on the number of absorbed photons. At last, Functionalmaterialsfrompolymerderivatives:propertiesandcharacterization 3 the FF is determined by the number of charge reaching the electrodes when the electricfieldisdecreasedtowardstheV . OC It is generally accepted that the BHJ solar cell mechanism can be described according to the following steps: (1) light absorption and generation of highly local- ized Coulombically bonded pair hole(cid:1)electron (exciton), (2) exciton diffusion to the donor(cid:1)acceptor interface, (3) exciton dissociation at the interface creating a charge- transferstatewhich thendissociateintofreechargecarriers(holesandelectrons),and (4)chargetransportandcollection(Chengetal.,2009;Gu¨nesetal.,2007). Few years later, conjugated polymers were introduced and used as electron donor together with a fullerene derivative (PC BM) as electron acceptor. In the 61 second generation of organic solar cell, conjugated polymers were used as the electron donor. The following list represents the main classes: poly(phenylenevi- nylene) PPV derivatives (for example: poly(2-methoxy-5-(3,7-dimethyloctyloxy)- 1,4-phenylene, also named MDMO-PPV), poly(thiophene) derivatives (for example: poly(3-hexylthiophene, also named P3HT), and poly(fluorene) deriva- tive (for example: poly(2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene-co-5,5-(40,70-di- thienyl-20,10,30-benzothiadiazole) PFDTBT). As for the third generation of organic solar cell, recent advances in the polymer design have brought forward the concept of donor(cid:1)acceptor (D-A) copolymer (also named push(cid:1)pull copolymer) which led to very efficient devices. It is important to avoidconfusingthisdonor(cid:1)acceptor(D-A)copolymerconceptwiththeelectrondonor (conjugated polymer) and the electron acceptor (fullerene derivative). Unlike P3HT, whichisahomopolymer,donor(cid:1)acceptorcopolymerspossesslowbandgapsandtheir energylevels(HOMO,LUMO)aswellastheirmolecularstructurescanbeoptimized. Morespecifically,D-Acopolymersincorporateanelectron-richmoiety(donor)andan electron-deficientmoiety(acceptor).Thishastheeffectofincreasingthedoublebond character(quinodal effect) ofthesinglebonds inthe polymer backbone which results in a reduction of the bond length alternation and thus, a reduction of the band gap of thecopolymer(Dennleretal.,2009;ZhangandTour,1998).Moreover,aninteresting featureoftheD-AcopolymeristhattheirHOMOandLUMOenergylevelsaregreatly determined by the HOMO energy level of the donor moiety and the LUMO energy leveloftheacceptormoiety(Bredas etal.,2009).Therefore, it ispossible totunethe energy levels of the copolymer by choosing appropriately the donor and acceptor moietiesor/andbyengineeringoftheirchemicalstructures.Fig.1.1showsaseriesof donorandacceptorfragmentunitscommonlyusedforefficientpolymersolarcells. Concerning the acceptor component (fullerene derivative), the most commonly used derivatives are the PC BM ((1-(3-methoxycarbonyl)propyl-1-phenyl[6,6] 61 C )) and the PC BM ((1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C ) (Fig. 1.2). 61 71 71 PCBM has been chosen as electron acceptor as it possesses the right energy levels (LUMO located at 24.3eV, HOMO located at 26.0eV) compared to conjugated polymerandallowsanefficientexcitondissociationtofreechargecarriers. As the aim of this subchapter is to discuss the different characterization techni- ques available to study the polymer(cid:1)fullerene composite we will not go into the details of the preparation of such polymeric materials. If the reader wishes to explore in depth the field, we refer him to the following reviews (Hoppe and Sariciftci,2004;Luetal.,2015;Huangetal.,2014;ThompsonandFre´chet,2008).

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