Table Of ContentHybrid Polymer Composite Materials
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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
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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).
