Progress in Polymer Science 36 (2011) 638670

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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

A review on the mechanical and electrical properties of graphite and

modied graphite reinforced polymer composites
Rajatendu Sengupta a , Mithun Bhattacharya a , S. Bandyopadhyay b , Anil K. Bhowmick a,
a
Rubber Technology Centre, Indian Institute of Technology Kharagpur, 721302, India
b
School of Materials Science and Engineering, UNSW, Sydney, NSW 2052, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Carbon materials particularly in the form of sparkling diamonds have held mankind spell-
Received 9 August 2010 bound for centuries, and in its other forms, like coal and coke continue to serve mankind as
Received in revised form 1 November 2010
a fuel material, like carbon black, carbon bers, carbon nanobers and carbon nanotubes
Accepted 4 November 2010
meet requirements of reinforcing ller in several applications. All these various forms of car-
Available online 19 November 2010
bon are possible because of the elements unique hybridization ability. Graphene (a single
two-dimensional layer of carbon atoms bonded together in the hexagonal graphite lattice),

Abbreviations: 100% modulus, modulus at 100% elongation (MPa); 300% modulus, modulus at 300% elongation (MPa); 2D, two-dimensional; ABS,
acrylonitrilebutadienestyrene terpolymer; a-PP, atactic polypropylene; AS, acrylonitrilestyrene resin; ATRP, atom transfer radical polymerization;
Br-GNP, bromine doped GNP; CB, carbon black; CCB, conducting carbon black; CMG, chemically modied graphene; CNT, carbon nanotube; CNT-MA-PP,
polypropylene-wrapped carbon nanotubes via maleic anhydride grafting; CPAN, conjugated polyacrylonitrile; DMF, dimethyl formamide; EB, elonga-
tion at break (%); EG, expanded graphite; EG-g-PS, expanded graphite grafted with polystyrene; EM, electromagnetic; EPDM, ethylene propylene diene
monomer; ER, electrical resistivity ( cm); EVA, ethylene-co-vinyl acetate; FG, foliated graphite (EG in which the worm-like structure has been broken
into separated platelets); FGS, functionalized graphene sheets; FM, exural modulus (GPa); FS, exural strength (MPa); f-SWNT, functionalized single
walled carbon nanotube; GIc , fracture energy (J m2 ); GIC, graphite intercalated compound; GO, graphene oxide; GNP, graphite nanoplatelet; HDPE, high
density polyethylene; HFFR, halogen free ame retardant; HIPS, high impact polystyrene; IIS, Izod impact strength (J/m); iPP, isotatic polypropylene; ISP,
in situ polymerization; KB, ketjenblack (nanosized high structure carbon black); KC48 , stage IV K-GIC compound; KIc , mode I fracture toughness (Pa m2 );
K-THF-GIC, potassiumtetrahydrofurangraphite intercalation compound; LC, latex compounding; LCVG, liquid cooling and ventilation garment; LLDPE,
linear low density polyethylene; MA-g-PE, maleic anhydride grafted polyethylene; MA-g-PP, maleic anhydride grafted polypropylene; MAI, macroa-
zoinitiator; MAI-GO, GO intercalated with macroazoinitiator; MB, melt blending; MBFP, master batch lling process; MEG, modied expanded graphite;
MEMS, micro-electro-mechanical systems; MMA, methyl methacrylate; MMB, masterbatch melt blending; MPEO, poly(ethylene oxide) methyl ether;
MWNT, multi walled carbon nanotube; NBR, acrylonitrilebutadiene rubber; NCIS, notched Charpy impact strength (J/m2 ); NCO, isocyanate group; NTC,
negative temperature coefcient; ODA-MMT, octadecylamine modied montmorillonite; PA6, polyamide 6; PAN, polyacrylonitrile; PAN-CF, PAN based
carbon ber; PAS, poly(arylene sulde); PC, polycarbonate; PE, polyethylene; PEFC, polymer electrolyte fuel cell; PEN, poly(ethylene-2,6-naphthalate);
PEO, poly(ethylene oxide); PETI, phenylethynyl-terminated polyimide; phr, parts per hundred parts rubber; PMMA, poly(methyl methacrylate); POBDS,
poly(4,4 -oxybis(benzene)disulde); POM, polyoxymethylene; PPEn, poly(phenylene ethynylene); PP, polypropylene; PPCR, positive pressure coefcient
of resistivity; PPCP, propylene ethylene random copolymer; PPE, poly(phenylene ether); PPS, poly(phenylene sulde); PS, polystyrene; PT, percolation
threshold; PTC, positive temperature coefcient; PU, polyurethane; PVC, polyvinyl chloride; PVDF, poly(vinylidene uoride); RPUF, rigid polyurethane
foam; RTC, room temperature conductivity (S/cm); RTV, room temperature vulcanization; SAN, poly(styrene-co-acrylonitrile); SBR, styrenebutadiene
rubber; SC, solution compounding; SGN, sulfur/graphite nanocomposite; SR, silicone rubber; SMI, solid state pan milling intercalation; SSSP, solid state
shear pulverization; SWNT, single walled carbon nanotube; TC, thermal conductivity (W m1 K1 ); TD, thermal diffusivity (m2 /s); THF, tetrahydrofuran;
TPU, thermoplastic polyurethane; TPV, thermoplastic vulcanizate; TRGO, thermally reduced graphene oxide; TS, tensile strength (MPa); UG, natural unmod-
ied graphite; UPR, unsaturated polyester resin; UTS, ultimate tensile strength (MPa); UV/O3 , ultraviolet and ozone treatment; VGCNF, vapor grown carbon
nanober; xGNP, exfoliated GNP; Y, Youngs modulus (GPa).
Corresponding author. Current address: Indian Institute of Technology Patna, 800013, India. Tel.: +91 3222 283180/612 2277380;
fax: +91 3222 220312/612 2277384.
E-mail addresses: anilkb@rtc.iitkgp.ernet.in, director@iitp.ac.in (A.K. Bhowmick).

0079-6700/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2010.11.003
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 639

Keywords: the basic building block of graphite, is at the epicenter of present-day materials research
Graphite because of its high values of Youngs modulus, fracture strength, thermal conductivity,
Graphite intercalation compound specic surface area and fascinating transport phenomena leading to its use in multifarious
Graphene oxide applications like energy storage materials, liquid crystal devices, mechanical resonators
Graphite nanoplatelet
and polymer composites. In this review, we focus on graphite and describe its various
Graphene
modications for use as modied llers in polymer matrices for creating polymercarbon
Expanded graphite
nanocomposites.
2010 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
2. Modications of graphite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
2.1. Graphene oxide (GO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.2. Graphite intercalation compounds (GICs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.3. Expanded graphite (EG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
2.4. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 643
3. Methods of manufacturing polymer/graphite nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.1. In situ polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.2. Solution compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.3. Melt blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
3.4. Combination of mixing techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
4. General conclusions and remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667

1. Introduction energy gap between the 2s and 2p orbitals facilitates the

promotion of one 2s electron to a vacant higher energy 2p
Carbon, the sixth element in the Periodic Table of Ele- orbital. This electron promotion allows carbon to hybridize
ments, is truly remarkable for its extraordinary ability of into sp, sp2 and sp3 congurations leading to fascinating
catenation to combine with itself and other chemical ele- and diverse molecular structures. The sp bonding gives
ments in different ways and thereby form the basis of rise to chain structures, sp2 bonding gives rise to planar
organic chemistry and of life. In nature, it is abundantly structures and sp3 bonding to tetrahedral structures. The
available as coal or as natural graphite, and in lesser quan- hybridization states of some typical carbon nanomaterials
tities as diamonds. Diamond and graphite, the well-known are summarized in Fig. 1.
allotropes of carbon have now been joined by fullerenes In this era of nanocomposites research, a lot of empha-
(C60, C70) [1,2], fullerene-related materials (like carbon sis has been directed towards the study of carbon based
onions) [3], carbon nanobers [4,5] and also carbon nan- nanollers mostly carbon nanotubes (CNTs) and to a lim-
otubes [68]all of which are carbon based nanomaterials. ited extent to graphite and vapor grown carbon nanobers
The study of carbon nanostructures became very important (VGCNFs). However, the use of CNTs in nanocomposites to
with the discovery of fullerenes in 1985 [9] and carbon nan- date has been limited by challenges in processing and dis-
otubes in 1991 [10]. This is due to the fact that fullerenes persion, but the biggest hurdle for extensive use is their
serve as prototypes for zero-dimensional quantum dots exorbitant price. Multiwall carbon nanotubes (MWNTs) are
while nanotubes serve as prototypes for one-dimensional priced at $8/g, single wall carbon nanotubes (SWNTs) cost
(1D) quantum wires [7]. $170/g and graphite nanoplatelets are priced at $2/kg
Man has also created several other forms of carbon [14]. As a matter of fact, from a geometric perspective
(engineered carbons) and some of these are: synthetic (Fig. 2), carbon nanostructures like CNTs and VGCNFs can be
graphite and synthetic diamonds, adsorbent carbon, cokes, obtained by the coiling up of the covalent graphene build-
carbon black, carbon and graphitic bers, glassy carbons, ing units resulting in a three dimensional structure [15].
diamond-like carbon, etc., for application in various end Several excellent reviews are available which specif-
uses like electrodes and electrical contacts, lubricants, shoe ically deal with graphene [16], chemical methods for
polish, gemstones, cutting wheels, gas adsorption, catalytic
support, helium gas barrier, tire and elastomer reinforce-
ment, toner for photocopying machines and printing inks,
high performance tennis rackets, aircraft and spacecraft
composites, heat sinks for ultrafast semiconductors, etc.
[1113]. All these various carbon forms can be ascribed to
carbons unique hybridization properties. The ground state Fig. 1. Hybridization states of some typical carbon nanomaterials.
orbital conguration of carbon is 1s2 2s2 2p2 . The narrow
640 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Fig. 2. Rolling up of graphene sheet to form CNT.

Figure reprinted with permission from Ref. [15]. Copyright 2008 CRC Press.

the production of graphene [17] and processing of 2. Modications of graphite

nanographene platelets and the corresponding nanocom-
posites [18]. However, to the best of our knowledge, the In its bulk state, graphite exists as a layered material.
mechanical and electrical properties of polymer nanocom- For the efcient utilization of graphite as a ller in a poly-
posites comprising of the different members of the mer composite, its layers must be separated and dispersed
enormous graphitic ller family have not been compared throughout the polymeric matrix. Graphite nanoplatelet
extensively to date [19] and this is exactly what we have (GNP), the basic unit obtained by exfoliation of the natu-
pursued here. ral aky graphite and having a platelet thickness varying
In this review we provide a brief introduction to from less than 0.34 to 100 nm, is a promising low cost and
graphite, discuss its structure and properties, the various lightweight alternative to metal- and carbon-based elec-
modications studied till date solely for applications tar- trically conducting reinforcements for conducting polymer
geted as modied ller in polymeric nanocomposites and composites [18,2836]. Graphite does not bear any net
culminate with an anthology of the different processing charge and thus is different from silicate clay minerals.
methodologies explored till date. In its natural form, no reactive ion groups exist on the
In graphite, elemental carbon has the lowest energy graphene layers and as a result, it is impossible to interca-
state at ambient temperature and pressure [8,20]. The late monomers into the graphite galleries by ion exchange
graphite crystal lattice consists of stacks of parallel two- reactions as is possible for the layered silicates. How-
dimensional (2D) graphene sheets (a single carbon layer ever, graphite is readily intercalated and can host various
in the crystalline honeycomb graphite lattice is known as a atoms, molecules, metal complexes and salts between the
graphene layer or graphene sheet) with sp2 hybridized car- expanded graphene sheets to form graphite intercalation
bon atoms tightly bonded in hexagonal rings. Since the 2pz compounds (GICs). So far, GNPs are mainly obtained from
orbitals of the carbon atoms can overlap most effectively if sulfuric acid-intercalated graphite and graphene oxide
they are parallel (out-of-plane bond), the graphene sheet (GO). Broadly, three treatment methods are adopted so that
has lowest energy when it is completely at. Thus, graphite graphite is modied and these modied graphitic forms
is anisotropic due to the difference between in-plane and are termed as graphene oxide (graphite oxide), graphite
out-of-plane bonding of the carbon atoms. The elastic mod-
ulus is higher parallel to the plane than it is perpendicular
to the plane and in this respect graphite is stronger in-
plane than diamond. The orbital is distributed over the
entire graphene sheet making it thermally and electrically
conductive. The layered structure of graphite exhibits 3-
dimensional (3D) order and is shown in Fig. 3.
The adjacent graphene sheets in graphite are separated
from each other by 0.335 nm, which is half the crys-
tallographic spacing of hexagonal graphite. The adjacent
graphene sheets are held together by weak van der Waals
forces and thus the graphene sheets can easily slide with
respect to each other giving graphite its soft and lubricat-
ing nature. It is this ability of sliding of the graphene layers
which helps in the marking of paper. This also explains the
etymological origin of the word graphite from the Greek
word grapho meaning to write. Table 1 compares the
theoretical and experimental properties of graphite, CNTs Fig. 3. Layered structure of graphite showing the sp2 hybridized carbon
and VGCNF. atoms tightly bonded in hexagonal rings.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 641

Table 1
Measured and theoretical properties of graphite, CNTs and VGCNF.

Property Unit Graphitea CNTa VGCNFb

Density g cm3 2.26 0.8 for SWNT1.8 for MWNT (theoretical) 2.0
Elastic modulus TPa 1 (in-plane) 1 for SWNT 0.31 for MWNT 0.5
Strength GPa 130 50500 for SWNT 1060 for MWNT 3.0
Resistivity  cm 50 (in-plane) 550 100
Thermal conductivity W m1 K1 3000 (in-plane) 6 (z-axis) 3000 (theoretical) 1950
Thermal expansion K1 1 106 (in-plane)29 106 (z-axis) Negligible (theoretical) 1 106

Thermal stability C 450650 (in air) >700 (in air) 2800 (in vacuum) 600 (in air)
a
From Refs. [2123].
b
From Refs. [18,2427].

intercalated compounds (GICs) and expanded graphite
(EG). Recently, interest has been renewed for producing
graphenethe basic building block for all graphitic materi-
als because of its excellent mechanical, electrical, thermal
and optical properties. Until 2004, 2D crystals like graphene
were considered to be thermodynamically unstable and
hence theoretically impossible to exist in the free state
[37,38] and were passed off as mere academic materi-
als [39]. However, the discovery of free-standing graphene
in 2004 [40] changed the scenario and spurred the inter-
ests of material scientists and condensed matter physicists
[4144]. For their discovery, Geim and Novoselov received
the 2010 Nobel prize in physics.
2.1. Graphene oxide (GO)
Graphene oxide also known as graphite oxide, graphitic
oxide or graphitic acid is usually prepared by the treat-
ment of graphite akes with oxidizing agents so that polar
groups are introduced on the graphite surface thereby
widening the interlayer spacing of the graphene planes
[32]. GO rst prepared by Brodie in 1859, typically involves
the reaction of graphite akes with potassium chlorate
and fuming nitric acid [45]. Hummers and Offeman devel-
oped a faster and safer method for the preparation of GO
by reacting anhydrous sulfuric acid, sodium nitrate and
potassium permanganate, which is widely followed even
today [46]. The structure of GO which contains epoxide and
hydroxyl groups within the graphene sheets and carboxyl
and carbonyl groups at the sheet edges is shown in Fig. 4.
Unlike graphite, GO is electrically insulating. GO serves as
an important intermediate for the preparation of GNPs as
discussed later.
Fig. 4. Representation of the epoxy, hydroxyl, carboxyl and carbonyl
groups in GO.
2.2. Graphite intercalation compounds (GICs)
Graphite intercalation compounds are formed by the
insertion of atomic or molecular layers of different chem-
ical species between the layers of the graphite host lattice
[47,48]. In GICs, the graphene layers either accept elec-
trons from or donate electrons to the intercalated species.
Graphite intercalated by electron donors like alkali met-
als (e.g., potassium, sodium, etc.) are known as donor-type
GICs, whereas compounds formed by the intercalation
of molecular species acting as electron acceptors like
halogens, halide ions and acids are known as acceptor-
type GICs. The acids involved in forming GICs include
nitric acid, sulfuric acid, perchloric acid and selenic acid.
Incidentally, graphite bisulfate is the most commonly
used GIC to prepare GNPs for the fabrication of poly-
mer/graphite nanocomposites and the reaction occurring
between graphite and concentrated sulfuric acid can be
expressed as follows [49]:
n (graphite) + n H2 SO4 + n/2 [O] n [graphiteHSO4 ] + n/2 H2 O
where O is the oxidant and graphite. HSO4 stands for the
GIC. The number of graphite layers between the interca-
late layers is known as the stage and the most important
and characteristic ordering property of GICs is the staging
phenomenon. The stage number n designates the number
of graphene layers that separate adjacent intercalate lay-
ers. The stage structure of graphite is largely dependent on
the intercalation conditions and usually stage 1 to stage 5
GICs result due to chemical intercalation [50]. The staging
phenomenon is depicted in Fig. 5.
Shioyama has shown that unsaturated hydrocarbons
such as dehydrated isoprene, 1,3-butadiene and styrene
could be co-intercalated into the graphite layers of alkali
metal-GICs [5153]. Polymerization of the monomers led
to expansion of the graphite layers along the c-axis
direction. X-ray diffraction of the composites showed no
diffraction lines for the graphite or GIC, attributed to
the layers being separated and disordered due to poly-
merization. However, when acrylonitrile, 1-butene and
isobutene were used as the hydrocarbons, no expansion
of the graphite layers were observed as the polymerization
occurred on the surface of the GIC edge [52]. A schematic
diagram of GIC-initiated polymerization is shown in Fig. 6
[53].
GNPs can be prepared starting with GICs. Typically,
the process involves the heating of graphite powder with
potassium (K) under vacuum to form the GIC. Then, the GIC
642 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Fig. 5. Schematic diagram illustrating the staging phenomenon in GIC.

is reacted with ethanol (EtOH) which reacts with potassium

to form potassium ethoxide and hydrogen gas. The evolu-
tion of hydrogen gas helps in the partial exfoliation of the
graphitic layers to form GNPs. The schematic of the process
is shown in Fig. 7 [54]. However, extreme precautions are
needed since it involves handling pure alkali metals (like K),
which pose explosion hazards in the presence of moisture
and therefore calls for vacuum or dry glove box environ-
ment. The GNPs produced by this technique generally have
40 15 graphene layers.
2.3. Expanded graphite (EG)
When intercalated graphite (most commonly graphite
bisulfate is used, although in principle any GIC can be
used) is heated past a critical temperature or exposed to
microwave radiation, a large expansion (up to hundreds
Fig. 7. Preparation of GNPs from graphite powder with the intermediate
GIC step.
of times) of graphite akes occur along the c-axis than in
the in-plane direction, forming vermicular or worm-like
accordions with low density and high temperature resis-
tance, and this puffed-up product is known as exfoliated or
expanded graphite (EG) [5557]. EG is composed of stacks
of nanosheets that may vary from 100 to 400 nm [57].
The scanning electron micrograph (SEM) of EG is shown
in Fig. 8. Industrially, EG is produced by subjecting natural
graphite akes to sulfuric acid treatment followed by bru-

Fig. 6. Schematic diagram showing the GIC initiated polymerization of an unsaturated hydrocarbon.
Figure adapted with permission from Ref. [53]. Copyright 2000 Elsevier.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Fig. 8. Scanning electron micrograph of EG.
Figure reprinted with permission from Ref. [57]. Copyright 2001 Society
of Chemical Industry.
tal thermal shock. EG exhibits a layered structure similar
to layered silicates and has good afnity for organic com-
pounds and polymers [31]. Ultrasonication of EG in solvents
is usually adopted to obtain thinner GNPs (3080 nm),
which can be dispersed further by high speed shearing in
the presence of a polymer matrix.
2.4. Graphene
Although graphene has been studied for 60 years, con-
ceptually it represents a new class of material that is only
one atom thick, and hence it is gaining prominence in the
eld of materials science, nanoelectronics and condensed-
matter physics [16,17,58]. Five routes are available for the
preparation of graphene. The rst involves chemical vapor
deposition (CVD) of monolayer of graphite on transition
metal surfaces [59,60]. The second route is the microme-
chanical exfoliation of graphite and involves peeling of
the graphene from graphite using Scotch tape [40]. The
Scotch tape is then dipped in acetone to release the
graphene which are subsequently captured on a silicon
wafer with a SiO2 layer on top. The third route involves the
epitaxial growth of graphene on electrically insulating sub-
strates like silicon carbide [61]. However, the second and
third methods are unsuitable for large scale preparation of
graphene for the fabrication of polymer nanocomposites.
It appears that at present the only routes to prepare bulk
quantities of graphene and chemically modied graphene
(CMG) are from GO and GICs [17,44,58,62,63]. As shown in
643
Fig. 9. SEM of FGS.
Figure reprinted with permission from Ref. [65]. Copyright 2007 American
Chemical Society.
Fig. 4, the presence of hydroxyl and epoxide groups on the
graphitic basal planes, and carboxyl and carbonyl groups
on the edges of layers make GO water dispersible [17].
Thus, on sonication in aqueous media, GO exfoliates readily
into colloidal suspensions of single graphene oxide layers.
Chemical reduction of GO present in the colloidal sus-
pension with reducing agents like hydrazine or hydrazine
derivatives is necessary to convert the electrically insu-
lating GO layers back to conducting graphene which are
suitable for composite applications. It is pertinent to point
out that GNP is not an individual graphene sheet but com-
prises multiple graphene sheets that are stacked together.
Thus, the thickness of GNP is signicantly larger than an
individual graphene sheet [58].
The nal route by which bulk quantities of graphene can
be prepared is by thermally reducing GO. This technique
has been pioneered by researchers at Princeton University
and involves rapidly heating GO in inert (argon or nitro-
gen) environment to produce thermally reduced expanded
graphene oxide (TRGO), which is a black powder of very
low bulk density [36,58,64,65]. The heating is responsi-
ble for the exfoliation of the graphene sheets. TRGO is also
known as functionalized graphene sheets (FGS) and have a
wrinkled sheet structure due to the epoxy groups forming
chains across the graphene surface. Due to their wrinkled
nature, FGS do not collapse back to GO but remain highly
agglomerated. McAllister et al. [65] observed that after FGS
were dispersed by ultrasonication in appropriate solvents
(such as N-methylpyrrolidone, dimethylformamide, 1,2-
dichlorobenzene, nitromethane or tetrahydrofuran), 80%
of the akes were single graphene sheets. The presence
of oxygen functionalities in FGS allows it to be used as
a promising carbon nanoller in polar polymer matrices.
SEM of dry, as-produced FGS powder is shown in Fig. 9
[65]. FGS is electrically conducting while GO is electrically
insulating.
644 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

3. Methods of manufacturing polymer/graphite

nanocomposites

The manufacturing of nanocomposites involves choos-

ing a proper blending method to reach a satisfactory
dispersion of the nanollers (here, graphite and its various
forms) throughout the polymeric matrix. The three main
methods of manufacturing polymer/graphite nanocom-
posites are in situ polymerization, solution compounding
and melt blending [18,66] and the salient features of each
technique along with their disadvantages (if any) are as
discussed below.

3.1. In situ polymerization

The tensile and electrical properties of various poly-

mer/graphitic ller composites prepared by the in situ
polymerization method are shown in Table 2. In situ poly-
merization is an efcient method to improve the dispersion
of the graphitic llers in the polymeric matrix. Here, the
monomer (and/or oligomer) is polymerized in the pres-
ence of the ller and consequently, the in situ compounding Fig. 10. Electrical conductivity versus content of graphite for PS/expanded
technique confers stronger interactions between the rein- graphite composites.
Figure reprinted with permission from Ref. [67]. Copyright 2002 Wiley
forcing ller and the polymeric phase. Thus, composites
Periodicals, Inc.
fabricated by the in situ polymerization technique exhibit
better mechanical properties and lower percolation thresh-
old than those made by the solution compounding or melt composites having low percolation threshold. However,
blending techniques. The disadvantage of this technique the use of large amounts of solvent and the associated envi-
is that a lot of electrical energy is needed to disperse the ronmental pollution due to the removal of the solvent have
ller in the polymer matrix during processing and so this prevented the adoption of this technique on a mass scale
method may not be useful for the mass production of poly- for the fabrication of composites (Figs. 1315).
mer nanocomposites. In the PMMA matrix, the percolation threshold occurs
In in situ polymerized PMMA matrix, the percola- at 11.3 wt.% EG [91,92]. The percolation threshold value
tion threshold occurs at 3.5 wt.% (1.6 vol.%) EG [50], of FGS in PMMA is not available [103], instead the mechan-
0.31 vol.% FG [73] and 2 wt.% GO [82]. However, the ical properties have been reported and compared with
data for percolation threshold with GNP in PMMA matrix is EG. The percolation threshold is attained at 0.1 vol.% FGS
unavailable [77]. In the PS matrix, the percolation thresh- loading in PS [44], which is much lower than the value
old occurs at 1.82.2 wt.% (0.81.0 vol.%) EG [57,67], of 0.81.0 vol.% EG prepared by the in situ polymer-
12 wt.% FG [72,75] and <8.2 wt.% GIC [86]. No literature ization technique [57,67]. The mechanical properties of
exists on the use of GNP and GO in the PS matrix. These polymer nanocomposites prepared by SC technique have
values highlight the attainment of remarkable electrical
properties at very low ller loadings of different graphitic
llers, which can lead to large scale design and devel-
opment of energy materials for various applications. To
translate such success stories from the laboratory to the
application market, by rendering these advanced materi-
als usable, the onus is on materials scientists to conjointly
investigate their mechanical and dynamic mechanical
properties. Table 2 presents an outline of the scope of such
endeavors (Figs. 1012).

3.2. Solution compounding

Table 3 compares the tensile and electrical properties

of various polymer/graphite composites prepared by solu-
tion compounding. In solution compounding, the polymer
is dissolved in a solvent and a ller is dispersed in the
resulting solution. After mixing is complete, the solvent
is removed and the bulk polymer material containing the
llers is then usually molded to give shape to the com- Fig. 11. Mechanical properties of pure epoxy and expanded
posite. This technique also results in electrical conducting graphite/epoxy composites [68].
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Table 2
Tensile and electrical properties of polymer/graphite composites prepared by in situ polymerization.
Sample details Tensile properties
Expanded graphite
Poly(styrene-co-acrylonitrile)
Poly(styrene-co-methyl TS of the composites was slightly
methacrylate) higher than that of the neat
polymer. IIS (notched) was lower
for all ller loadings.
PMMA + EG blended with PVC TS of the composites were
slightly higher than that of the
neat PVC/PMMA blend.
PS + EG and TS of nanocomposites at all EG
loadings were greater than that
of neat PS.
PS + UG IIS (notched) was lower for all
ller loadings.
PS
Epoxy 21% higher UTS for 2.5 wt.% EG
and 9% higher UTS for 5 wt.% EG
loading were observed over neat
epoxy (TS = 34).
Epoxy resin and unsaturated
polyester
RPUF
PS
Electrical properties
RTC 1016 of
poly(styrene-co-methyl
methacrylate).
RTC = 101 at 5 wt.% EG loading.
RTC 1015 (neat PVC and
PMMA).
RTC = 104 at 5 wt.% EG
RTC 1016 (neat PS)
RTC = 102 at 5 wt.% EG loading.
RTC 102 at >50 wt.% UG
loading
RTC = 102 at 3 vol.% EG
PT of EG lled composites
occurred at 1.0 wt.% EG loading
in the epoxy and polyester
matrices.
RTC = 1.3 101 for a composite
comprised of stage IV KC48 with
styrene (10 wt.% graphite).
645
Comments Ref.
In-plane RTC of the composite [29]
was 117 and the
through-thickness RTC of the
composite was 83 (which is
higher than 8, the RTC of UG).
Styrene/methyl methacrylate [49]
was in the ratio 70:30 (v/v) in the
feed.
PT was attained at 1.8 wt.% EG.
5 wt.% EG loaded nanocomposite
exhibited 27% improvement
over the TS of the neat matrix (TS
25).
The greater impairment in the
impact properties at loadings
>3 wt.% was due to poor
dispersion of the EG.
PT was attained at 3.5 wt.% EG. [50]
5 wt.% EG loaded nanocomposite
exhibited 27% improvement
over the TS of the unlled
PVC/PMMA blend (TS = 12). To
reach the same RTC value of
104 , 40 wt.% UG
(20 m diameter) was required.
PT was attained at 1.8 wt.% EG. [57]
Tensile properties were reported
for EG loaded nanocomposites.
5 wt.% EG loaded nanocomposite
exhibited 27% improvement
over the TS of neat PS (TS = 30)
and this indicated that the
graphene sheets provided
reinforcement to the polymer
matrix.
PT was attained at 1.0 vol.% EG [67]
(Fig. 10).
10 and 25% improvement in Y for [68]
2.5 wt.% and 5 wt.% loaded
composites were recorded over
neat epoxy (Y = 3.0). The
composites show failure at
slightly higher strain than neat
epoxy matrix (Fig. 11).
EG and milled EG were used as [69]
nanollers.
PT of epoxy/milled EG composite
is at 5 wt.% ller and that of
polyester/milled EG composite is
at 2 wt.% ller loading.
Applications include capacitors,
sealing gaskets, etc., made by
impregnating compressed
graphite sheet with epoxy,
polyesters, etc., followed by resin
curing.
EG is an intumescent additive [70]
and holds promise as an effective
HFFR for PU foams.
ISP of styrene in different stage [71]
potassium intercalated graphites
was carried out.
RTC of control composite
(prepared by radical
polymerization of
styrene + 10 wt.% EG) = 5 103 .
GIC of stage IV or higher are
needed for high conductivity
applications.
646 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Table 2 (Continued)

Sample details Tensile properties Electrical properties Comments Ref.

Foliated graphite
PS + FG and PS + UG (7500 mesh)
PMMA + FG
PMMA + UG (7500 mesh)
PA6
PS
Graphite nanoplatelet
POBDS
PMMA + Ce(OH)3 , Pr2 O3
PETI
Unsaturated polyester
SAN
Unsaturated polyester
10 wt.% GNP loaded composite
showed 68% greater FM than
neat POBDS (FM 32).
RTC 1 at 10 wt.% FG.
RTC 0.02 at 14 wt.% UG.
RTC 1 at 4.5 vol.% FG.
RTC 102 at 8 vol.% UG.
RTC 103 at 3.2 vol.% FG.
RTC 103 at 4 wt.% (0.02
volume fraction) FG.
RTC 1016 (neat POBDS)
RTC = 103 at 5 wt.% EG loading.
PT was attained at 4 wt.% GNP.
PT was attained at 3 wt.% GNP.
EG was sonicated in solution to [72]
prepare graphite nanosheets (FG)
and had thickness of 3080 nm.
PT was attained at 1.0 wt.% FG.
PT was attained at 6.0 wt.% UG.
ISP of MMA was carried out in [73]
the presence of FG.
PT was attained at 0.31 vol.% FG.
PT was attained at 3.0 vol.% UG.
The high aspect ratio of
100500 of FG was responsible
for formation of the conducting
network within the polymer
matrix.
PA6/FG nanocomposites were [74]
prepared by ring opening anionic
polymerization of -caprolactam.
PT was attained at 0.75 vol.% FG.
The dielectric constant was [75]
7.87 104 at a volume fraction of
0.031 of FG (6 wt.%).
PT was attained at 2 wt.% FG.
EG was obtained by subjecting [76]
GIC to microwave. EG after
ultrasonication yielded GNP.
FM increased with increase in
GNP loading whereas the FS
showed very slight decrease with
increase in GNP. Potential
application areas: bipolar plate
material for fuel cell, antistatic
coatings, high temperature
conducting adhesive,
electromagnetic shielding, etc.
The composites were prepared [77]
by ISP of MMA in the presence of
GNP and Ce(OH)3 , Pr2 O3 through
reverse micelle template where
MMA was the oily phase.
PETI-5 developed by NASA [78]
Langley Research Center is used
as the matrix resin in aircrafts for
structural and electrical
applications. The samples were
prepared by ultrasonication, ball
milling and vibratory ball milling
techniques. Nanoller loading
varied from 1 to 20 wt.% in the
composites.
PT was attained at 0.64 vol.% [79]
(1.2 wt.%) GNP.
The composite exhibited a [80]
dielectric constant value of
7.84 105 at 6 wt.% GNP loading.
These composites can be used for
embedded capacitor application.
Orientation of GNP was achieved [81]
by applying dc electric eld
during curing. Optical properties
of the electric eld induced
composite lm showed
signicant improvement in
visible light transmittance
compared to those prepared
without the electric eld within
the visible wavelength range.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 647

Table 2 (Continued)

Sample details Tensile properties Electrical properties Comments Ref.

Graphene oxide
PMMA Both TS and IIS (notched) of the RTC 1016 (neat PMMA) Emulsion polymerization of [82]
composites decreased with GO RTC = 104 at 8 wt.% GO loading MMA in the presence of GO was
loading. performed.
PT was attained at 2 wt.% GO.
The impact strength behavior is
different from that shown in
PS/EG [83] and was explained on
the basis of insignicant surface
property improvement as a
result of PMMA grafting on GO.
POBDS RTC 107 (pristine GO) ISP of aromatic dithiols in the [84]
RTC = 0.51 (composite). presence of exfoliated GO.
GO acted as an oxidizing reagent
for the polymerization of
aromatic dithiols and as host of
the resulting nanocomposite, as
well.
PMMA and PMMA + MAI-GO At 6.67 parts by wt GO loading, A MAI containing a PEO segment [85]
the MAI-GO composite was intercalated between the GO
(exfoliated nanocomposite) had lamellae to induce intergallery
a RTC of 8 104 compared to polymerization of MMA and
6 105 of the GO composite thereby exfoliate GO by bulk and
(intercalated nanocomposite). suspension polymerization.
Graphite intercalated compound
PS PT attained at less than 8.2 wt.% Anionic polymerization of [86]
ller loading. styrene in THF solution
containing K-THF-GIC as the
catalyst and ller.
Dielectric constant increased
with increase in graphite loading.
Dielectric constant was 136 at a
graphite loading of 6.5 wt.%
(suitable for embedded capacitor
application).
Functionalized graphene sheets
PS 0.9 wt.% ller reinforced Covalent polymer [87]
composite showed 57.2% and functionalization of graphene
69.5% increase in Y and UTS sheets (2040 nm in diameter)
relative to neat PS lm (Y = 1.45 by diazonium addition and ATRP
and UTS = 24.44). demonstrated the effect of
functionalized graphene sheets
on non-polar polymers such as
PS.
3-step process was undertaken
for preparing PS-functionalized
graphene nanosheets (i) GO
preparation, (ii) grafting of ATRP
initiator to the reduced graphene
surface, (iii) ISP of styrene in the
presence of graphene sheets. The
reaction scheme is shown in
Fig. 12.
However, the reinforcing effect
shown by the functionalized
graphene sheets were slightly
lower than that exhibited by PS
reinforced by 0.06 wt.% f-SWNT
(where, the UTS and Y
improvements over neat PS were
82 and 78%, respectively) [88]
but higher than that shown by PS
reinforced by 1 wt.% MWNT
(where, the UTS and Y
improvements over neat PS were
25 and 3642%, respectively)
[89].
648 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Table 3
Tensile and electrical properties of polymer/graphite composites prepared by solution compounding.

Sample details Tensile properties Electrical properties Comments Ref.

Expanded graphite
Epoxy resin
PMMA + EG and PMMA + UG
PMMA + EG and PMMA + UG
MPEO
PPE/a-PP
EVA + UG and EVA + EG
Foliated graphite
SR + FG, SR + UG (2000 mesh) and
SR + UG (8000 mesh)
Graphite nanoplatelet
PAN + GNP
TS decreased by 20% and EB
decreased by 24% compared to
control.
At 4 wt.% EG loading, TS and
100% modulus improved over
the neat EVA (TS = 5.54 and
modulus = 1.1) by 35 and 150%
while EB remained nearly same.
Y doubles with only 4 wt.% GNP
loading.
PT was attained at 0.6 vol.% EG
PT was attained at 2.0 vol.% UG.
RTC 104 (10 wt.% EG)
RTC 105 (10 wt.% UG).
RTC 1016 (neat PS), RTC
1017 (neat PPE), RTC 104
(nanocomposite)
PT 0.9, 5.3 and 7.0 vol.% for SR
lled with FG, 8000 and 2000
mesh UG, respectively.
PT was attained at 1.3 vol.% EG. [90]
PT was attained at 4.5 vol.% for [91]
PMMA/CB composites.
PT was attained at 1 wt.% EG, [92]
3.5 wt.% UG and 8 wt.% CB in
PMMA matrix.
EG is much better in forming
conductive networks than CB in
polymer matrices [91,92].
NCO grafted EG (Fig. 13) was [93]
used to prepare polymer-grafted
EG. This NCO-modied ller
holds promise as a
multi-functional additive for
improving the ame retardancy
of rigid PU foams.
Monolaments of the [94]
nanocomposites were prepared
by melt extrusion and stretching.
At 8 wt.% EG loading, TS and EB [95]
decreased compared to neat EVA.
The UG lled system, exhibited
inferior properties compared to
the EG lled system (Fig. 14a).
Dynamic mechanical properties
also exhibit similar trends
(Fig. 14b). TC = 0.24 (neat EVA).
At 4 wt.% EG loading TC increased
by 263% while the composite
with 4 wt.% UG loading showed
an increase of 100%.
George et al. [32] had earlier also
witnessed the benecial effects
of acid modied, heat treated
graphite on the mechanical
(Fig. 14c), dynamic mechanical
properties and thermal
conductivities in EVA based
nanocomposites. George et al.
[28] also undertook a
comparative study on the
inuence of carbon-based
nanollers on electrical and
dielectric properties of EVA
nanocomposites (Fig. 14d and e)
and attributed the better
performance of carbon nanober
based systems on their higher
aspect ratios.
RTV liquid silicone rubber was [96]
used as the matrix.
The SR/FG nanocomposite
exhibited a positive
piezoresistive effect under very
low pressure, namely, in the
ngerpressure range
(0.30.7 MPa). Such materials
hold promise as sensors.
Reinforced polymer composites [97]
were formed by adding 14 wt.%
GNP to a PAN solution.
Composite nanobers having
average diameters of 300 nm
were prepared by
electrospinning.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Table 3 (Continued)
Sample details Tensile properties
PAN + GNP, CPAN + GNP,
PAN + Br-GNP and
CPAN + Br-GNP
PVDF + xGNP
Functionalized graphene sheets
PMMA + EG and PMMA + FGS At 1 wt.% ller loading, Y values
of FGS lled PMMA showed
increase of 80% over neat
PMMA (Y = 2.1) while the EG
lled and SWNT lled
nanocomposites showed
increase of 47 and 50% over
neat matrix. At similar ller
loading, UTS values of FGS
system showed increase of 18%
over PMMA (UTS = 70) while EG
and SWNT systems showed
improvements of 5 and 10%,
respectively.
TPU + FGS Y of the nanocomposites
improved till 4 parts of FGS per
100 parts of TPU and thereafter
decreased to values lower than
pristine TPU (Y = 458). However,
TS and EB for the FGS loaded
samples were always lower than
neat TPU.
Electrical properties
PT for all the systems 34 wt.%
GNP.
PT was attained at 1.01 vol.%
GNP loading.
RTC of TPU 1011 . At 2 wt.%
FGS concentration, RTC became
104 which is an increase of
107 times over neat TPU.
649
Comments Ref.
RTC was particularly enhanced in [98]
conjugated PAN systems where
the value rose from 1 1010 to
2 103 (at 6 wt.% GNP
concentration).
The PT obtained here is higher
than the PT of 1 wt.% observed
in epoxy/GNP system [30] and
was related to the aspect ratio of
the GNP. Tip sonication
(performed here) resulted in
lower aspect ratios compared to
bath sonication, thereby raising
the PT.
Dielectric constant values of 200 [99]
(103 Hz) and 2700 (100 Hz) at PT
(=1.01 vol.% GNP) which were 20
and 270 times higher than that of
the PVDF matrix. PVDF/MWNT
system (PT = 8.0 vol.%) showed
dielectric constants of 600
(103 Hz) and 900 (100 Hz) [100],
PVDF/acetylene black system (PT
1.3 vol.%) showed 56 (103 and
100 Hz) [101] and PVDF/carbon
ber system (PT = 6.6 vol.%)
exhibited dielectric constant
values 30 (103 Hz) [102].
At 2.34 vol.% GNP, the dielectric
constant was 4.5 107 .
This ferroelectric polymer based
exible nanocomposites are
potential materials for
high-charge storage capacitors,
articial muscles, smart skins
for drag reduction and suitable
for EM wave absorption.
EG, FGS and unmodied SWNT [103]
were used as nanollers in this
study.
This study compares the
reinforcing ability of EG and FGS.
From the mechanical properties
perspective, FGS exhibits
superiority over EG and also
SWNT. This was ascribed to the
better interaction of FGS with the
host polymer due to its wrinkled
sheet morphology, higher
nanoscale surface roughness and
presence of pendant hydroxyl
groups which might have
interacted by means of hydrogen
bonding with the carbonyl
groups of PMMA.
The thermal properties were also
signicantly better for FGS
nanocomposites than those of
EG.
Without any chemical surface [104]
modication, FGS was nely
dispersed on the nanoscale in a
TPU matrix simply by solution
mixing.
The decrease in the TS and EB
were due to the inhibition of
molecular rearrangement and
orientation with respect to the
tensile axis during deformation
by FGS.
650
Table 3 (Continued)
Sample details
PS + graphene sheets,
ABS + graphene sheets, and
SBR + graphene sheets
Fig. 12. Schematic illustration of the fabrication of polystyrene-functionalized graphene nanosheets.
Figure Reproduced by permission of The Royal Society of Chemistry [87].
R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Tensile properties Electrical properties
PT was attained at 0.1 vol.%
ller loading.
RTC 1 (2.5 vol.% ller loading in
PS).
Comments Ref.
Isocyanate functionalized GO [44]
was incorporated into PS in DMF
followed by chemical reduction
to form PS-graphene sheet
composites with molecular level
dispersion of the graphene
layers. The presence of polymer
in the solution during the
reduction step prevented the
agglomeration of the chemically
modied graphene (CMG) sheets.
For the sake of comparison
between CMG and TRGO,
PS/TRGO nanocomposites were
also prepared and were observed
to be less homogeneous and had
higher electrical PT than the
nanocomposites containing CMG
(Fig. 15). The PT of 0.1 vol.% is
almost the same as was obtained
in PS/SWNT composites [105]
and just twice and four times
higher than those measured for
polyimide/SWNT [106,107] and
PS/PPEn-functionalized SWNT
[108] composites, respectively.
No data presented for the ABS
and SBR systems.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Fig. 13. Isocyanate modication of EG and subsequent amine modied
EG in the presence of moisture [93].
not received much study. Interfacial studies would be of
tremendous interest to delineate and manipulate the favor-
able polymergraphite interactions which facilitate stress
transfer and thus determine eventual mechanical proper-
ties. Such insights would empower engineers with the data
for a judicious choice of ller modication techniques to
develop the best performance properties required for spe-
cic applications.
3.3. Melt blending
The tensile and electrical properties of various poly-
mer/graphite composites prepared by the melt blending
(MB) technique are tabulated in Table 4. From an industrial
standpoint, melt blending is the preferred compounding
technique for the preparation of composites as it is a direct,
cost effective and environmental friendly process, since no
solvents are involved during the preparation of the com-
posite. Traditional mixing equipment such as extruder,
internal mixer, and two-roll mill can be adopted for the
melt blending operations and are usually available in most
compounding units.
In the HDPE matrix, the percolation threshold occurs
at 3 wt.% EG (1.4 vol.%) [109], 5.7 wt.% MEG [66], 6 vol.%
FG [122] and 14 wt.% GNP [129]. However, the data for
percolation threshold of melt-mixed GIC and EG in PS is
unavailable [126]; the threshold was mentioned previously
651
for in situ polymerization (ISP) and solution compound-
ing systems (SC). The observations appear to indicate that
in the case of melt blending, the percolation threshold is
attained at marginally higher levels than with ISP or SC.
Unlike the studies involving ISP and SC techniques, here,
a ne balance has often been struck between mechani-
cal and electrical properties, which could lead to faster
realization into commercial products. However, the results
illustrated above cannot be translated directly into a com-
parative report of the three processing methodologies,
primarily because exactly similar polymeric nanocom-
posites have not often been studied from this point of
view. Furthermore, the disparities in molecular weight
and other specics, such as viscosities, etc., of the poly-
mer/composites produced by each of these techniques
would tend to impair any such comprehensive effort
(Figs. 1619).
3.4. Combination of mixing techniques
Table 5 covers the tensile and electrical properties
of various polymer/graphite composites prepared by a
combination of in situ polymerization, solution com-
pounding with one or more of the following procedures:
melt blending, shear mixing, masterbatch blending, etc.
This combinatorial approach involving various techniques
becomes necessary when the system viscosity increases
rapidly with solvent decrease as in the case of epoxy
matrices. For proper ller dispersion in various polymeric
systems, this combinatorial approach has been adopted
by several authors. This is a promising approach, as it
can mitigate the problems faced in each of the indi-
vidual techniques, while harnessing the virtues of each
(Figs. 20 and 21).
4. General conclusions and remarks
The development of graphitic llers derived from nat-
ural graphite which is inexpensive and available in large
quantities (worldwide reserves estimated at 800 million
metric tons [151]), has opened up a new vista in the eld
of materials science for developing a wide range of novel
functional materials. CNTs had afforded higher Youngs
modulus and tensile strength than all the other existing
llers, but with the advent of graphene, a 2D wonder
material, the scenario has changed. Graphene, CMG and
FGS appear to be cutting edge materials with which the
electrical conductivity, stiffness and strength, barrier resis-
tance, re retardancy, thermal properties and piezoelectric
properties of polymeric nanocomposites can be tailored
according to requirement at very low carbon content.
Various processing techniques such as SC, ISP, MB, SSSP,
pan milling and masterbatch melt mixing have been used
for the preparation of graphite-based polymer nanocom-
posites and are discussed here. Finally, the benets of
combinatorial mixing techniques have been illustrated to
indicate the path ahead. Today, EG and GO have been rec-
ognized as the obvious intermediates for the preparation
of GNPs. Alternative preparative routes for obtaining GNPs
based on CVD from various organic precursors need to be
explored for the mass production of these exotic materials.
652 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Fig. 14. (a) Tensile stress versus strain plots and (b) storage modulus versus temperature plot of virgin EVA and various EVA + EG nanocomposites along
with that of EVA + 4NG (4 phr of natural unmodied graphite, represented in text as UG). Figure reprinted with permission from Ref. [95]. Copyright 2008
Springer Science + Business Media, LLC. (c) Tensile properties of EVA60 and its natural unmodied graphite (NG) and acid modied, heat treated graphite
oxide (GO) based nanocomposites. Figure reprinted with permission from Ref. [32]. Copyright 2008 Wiley Periodicals, Inc.; and effect of ller loading
on (d) AC resistivity and (e) dielectric constant of EG, MWNT and CNF based EVA nanocomposites. Inset: Network formation at percolation threshold:
EVA-10.9 vol.% EG. Figure reprinted with permission from Ref. [28]. Copyright 2010 Wiley Periodicals, Inc.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 653

Table 4
Tensile and electrical properties of polymer/graphite composites prepared by melt blending.

Sample details Tensile properties Electrical properties Comments Ref.

Expanded graphite
HDPE + UG and HDPE + EG
NBR + UG, NBR + subUG,
NBR + spherUG and NBR + EG
PPCP
HDPE + MEG and HDPE + UG
(2000 mesh)
At 3 wt.% ller loading, tensile
modulus improved by 17% (EG)
and 10% (UG) over neat HDPE.
At a similar ller loading, the TS
improvement was meager, viz.,
4% (EG) and 7% (UG)
compared to neat HDPE
(TS = 18.0).
With each type of ller, the 100%
modulus, 300% modulus and
even TS increased with increase
in ller content. EB also
increased to some extent with
increase in ller loading.
TS of the composites were higher
than neat HDPE at all EG
loadings. But, the TS increased
with increasing ller content up
to 4 wt.% and fell subsequently.
Notched IIS of the composites
were lower than the neat HDPE
at all EG loadings.
RTC 1016 (neat HDPE). The PT value of 3 wt.% for EG [109]
At 10 wt.% ller loading, composite was higher than that
RTC 103 and 104 for observed in other polymer systems
EG and UG composites. lled with EG, viz., 1.5 wt.%
PT was attained at 3 wt.% (0.75 vol.%) in PA6 [110], 1 wt.% in PS
(EG composite) and PT [72], 2.4 wt.% (1.3 vol.%) in epoxy [90]
was attained at 5 wt.% in and 1 wt.% in PMMA [93] but lower
the UG composite. than CB lled composites, viz.,
8.0 wt.% in PMMA [111], 6.2 wt.% in
PP [111] and 9 wt.% in PA6 [112].
It proved that the dispersion of the
graphitic sheets was better using ISP
or solution blending compared to
direct melt mixing.
The EB was substantially lower for
the lled composites.
Regular micrometer graphite (UG), [113]
submicrometer size graphite
(subUG), spherical graphite
(spherUG) and EG were used at 10,
20, 30, 40 and 60 phr ller loading by
mixing in a two-roll mill.
The permanent tensile set increased
with increase in ller loading.
EG at 40 phr loading showed an
improvement of 83% in TS over
neat NBR (TS = 3.0). However, this
increment is much lower compared
to that shown by UG and subUG
(170%) but higher than that shown
by spherUG (57%) at similar
loading. The mechanical properties
were determined by the size and
shape of the llers.
The wear and friction properties of
the composites were also studied.
At ller loadings of 8, 12 and 20 wt.%, [114]
the TC of the composites improved in
comparison to the base polymer.
However, the TC value of 0.5 at EG
loading of 20 wt.% was much lower
than that attained with the SC
technique in other polymer matrices
[14,95,115].
RTC 1016 (neat HDPE). MEG (modied EG) was prepared by [66]
PT was attained at modifying EG with UPR. UPR
5.7 wt.% (EG) and PT was monomer, hardener and EG in
attained at 22.2 wt.% appropriate ratios were mixed and
(UG). hardened by heating. The hardened
mixture containing 20 wt.% EG was
powdered to give MEG, which was
melt mixed with HDPE in an
extruder.
TS improvement of 15% over neat
HDPE (TS 22) occurred at 4 wt.% EG.
The reduction in the notched IIS
values for the composites may be
due to the poor afnity between the
polar graphite and non-polar matrix.
PT value of 5.7 wt.% for MEG in this
work was higher than 3 wt.% for EG
[109] and this may be due to the
reduced aspect ratio of the MEG as a
result of comminution.
654 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Table 4 (Continued)
Sample details Tensile properties
HDPE TS was enhanced at all EG
loadings for the masterbatch
process compared to direct melt
extrusion. At 20 wt.% EG loading,
PE/EG and PS/EG prepared by
MBFP showed tensile
improvements of 10 and 5%
over the composite prepared by
direct MB.
For EG loadings >5 wt.%, the
direct MB composite showed
higher tensile modulus than that
prepared by MBFP.
MA-g-PP
TPV/PP-g-MA + UG,
TPV/PP-g-MA + GIC,
TPV/PP-g-MA + EG and
TPV + EG
Electrical properties
PT (PE/EG by MBFP) at
16 wt.% EG, PT (PS/EG by
MBFP) at 18 wt.% EG and PT
(direct MB) at 20 wt.% EG.
However, the RTC at
28 wt.% EG (direct MB) was
102 which was higher
than the RTC values of
103 104 at 30 wt.% EG by nally diluted with HDPE by melt
the masterbatch process.
PT was attained at 0.4 wt.%
EG loading.
PT of TPV/PP-g-MA/EG at
6 wt.% while TPV/EG
prepared by direct MB
showed little change in RTC
up to 10 wt.% EG loading. At
15 wt.% EG loading, TPV/EG
by the masterbatch
technique showed RTC
5 104 while that by
direct MB showed RTC
1012 (proving the efcacy
of MMB technique over
direct MB [119]).
Comments Ref.
A new processing method, viz., the [116]
masterbatch lling process (MBFP)
was used in this work. Two highly
lled PE/EG and PS/EG masterbatches
(60 wt.% EG) were rst prepared by
intensive rolling process (two roll
milling in presence of PE wax
followed by melt extrusion) and was
extrusion. For comparison, HDPE and
EG were also prepared by the direct
MB method.
The difference in the conductive
behavior between masterbatch
process and direct MB process is due
to the encapsulation of EG sheets by
PE and PS, which inhibits the effective
contact between adjacent EG
particles.
Tensile modulus trends indicate the
lower interfacial interaction between
polymer and EG by MBFP (due to an
increase in PE wax with increase of
masterbatch contents) compared to
the non-masterbatch technique.
Impact strength at all ller loadings
for both the process techniques was
lower than that of neat HDPE.
Piezoresistive properties of EG [117]
reinforced PP modied by MA were
investigated. At a compressive stress
less than 10 MPa, the electrical
resistivity decreased rapidly with an
increase in compressive stress and
attained a steady state value in the
1030 MPa range. The electrical
resistivity increased slightly when the
compressive stress increased beyond
30 MPa. This behavior was due to the
formation of conductive paths and
the degeneration of such a network
arising from the reorientation and
rupture of the graphite platelets in the
matrix due to the generation of shear
forces as a result of large compressive
stresses. The piezoelectric property
can be utilized in passive sensing
materials for MEMS.
PP-g-MA was mixed separately with [118]
UG, GIC and EG to prepare the
respective masterbatches. In all the
masterbatches, the weight ratio of
PP-g-MA to ller was kept at 3:1. The
prepared masterbatches were ground
into powder and then mixed with TPV
(based on PP/EPDM) in various ratios
to obtain nanocomposites containing
different ller loadings. For
comparative purposes,
nanocomposites were also prepared
by direct melt mixing of TPV with EG.
PP-g-MA acts as the interfacial
compatibilizer between TPV and the
active functional groups existing on
the EG surface, leading to better
exfoliation of the graphite nanolayers.
The PT values for TPV/PP-g-MA/GIC
and TPV/PP-g-MA/UG occurred at
>20 wt.% ller loading.

Table 4 (Continued)
Sample details
EVA
PET and PET + epoxy-EG
Foliated graphite and natural unmodied graphite
HDPE + FG, HDPE + UG (7500
mesh) and HDPE + UG (2000
mesh)
R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Tensile properties Electrical properties
PT of PET/epoxy-EG was lower
(1.86 vol.% ller) than that of
PET/EG nanocomposites
(3.39 vol.% ller loading).
PT values were 6, 17 and
19 vol.% for composites lled
with FG, 7500 and 2000 mesh
UG, respectively.
655
Comments Ref.
EVA was melt compounded with [120]
EG, MWNTs, VGCNFs, metallized
VGCNFs, Ni nanostrands, boron
nitride and Al powder.
Electrostatic (chemisorbed)
modication of MWNT and EG
was accomplished with
1-dodecylbromide treatment and
covalent modication of MWNT
and EG was accomplished with
1-dodecylamine treatment. TC
measurements were performed
for both aligned (prepared by
extrusion) and unaligned
(prepared by compression
molding) samples.
Electrostatic modication of
MWNTs led to signicant
improvement in TC compared to
composites containing
unmodied MWNTs, but this
behavior was not observed for the
electrostatically modied EG
sample.
40 wt.% EG lled EVA showed the
highest TC value of 5.554 (in the
direction of ller alignment)
among all the ller combinations
and ller loadings tested.
However, 20 and 30 wt.% loading
levels of EG and 30 wt.% Al powder
exhibited excellent exibility,
high TC and proved to be cost
effective. So the use of Al powder
and EG to improve the TC of the
cooling tubes of the LCVG
subcomponents may lead to
advanced spacesuit designs that
would enable longer
extravehicular excursions by
future astronauts.
Epoxy-EG was prepared by [121]
solution blending of EG and epoxy
resin. EG and epoxy-EG were melt
blended to form the conductive
composites.
The possible interactions between
the epoxy group and the
functional groups on the EG
surface meant that the epoxy
resin had a greater exfoliation
effect on EG resulting in a much
lower PT value. However, PT value
shown by the PET/epoxy-EG was
higher than the value of 1.3 vol.%
noticed in epoxy/EG system [90],
which was prepared by SC.
FG was prepared by [122]
ultrasonicating EG.
HDPE/FG nanocomposites
prepared in a two-roll mill
exhibited both negative and
positive pressure coefcient of
resistivity (piezoresistive
behavior).
The PPCR (positive pressure
coefcient of resistivity) of the FG
nanocomposites was much
stronger than that of HDPE lled
with UG particles.
656 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Table 4 (Continued)
Sample details Tensile properties
PP + UG and PVDF + UG FM increased by 686% and
764% for PP and PVDF
composites compared to the neat
PP (FM = 1.45) and PVDF
(FM = 1.54) matrices.
PP + UG Relative to neat PP (Y = 910, yield
strength = 28 and EB = 810), the
SSSP-made nanocomposite
showed 100% increase in Y,
60% increase in yield strength
and only 30% reduction in EB,
while the extruded hybrid
exhibited 4045% increase in Y
and a 100 fold reduction in EB
(extreme brittle behavior). Both
PP-UG systems showed 72%
reduction in impact strength
relative to neat PP but, the
SSSP-processed nanocomposite
had 45% higher impact strength
than that of the extruded hybrid.
(Fig. 16)
Graphite nanoplatelet
AS + GNP, HDPE + GNP and
HDPE + UG (7500 mesh)
Electrical properties
RTC of PP composite was 71
and that for PVDF was 44.
PT values for AS/GNP and
HDPE/GNP nanocomposites
were at 9 and 14 wt.% GNP
loading. PT for HDPE/UG was
at 34 wt.% ller loading.
Comments Ref.
Composite containing 70 vol.% of UG [123]
were melt blended in a kneader and
targeted as bipolar plate of PEFC.
FS were 48.6 and 62.6 for the PP
composite and PVDF composite.
SSSP is a continuous, one-step [33]
process for converting pelletized or
aked polymeric feedstock (may be
single polymer type or blend, virgin
or recycled) with or without ller
into powder by means of high
pressures and high shear stresses
[124,125]. The processing
temperatures used in SSSP for
plastics are below the melting
transition for semicrystalline
polymers and below the glass
transition for amorphous polymers.
The powder is further processed by
injection molding, compression
molding, extrusion, etc. for shaping
purpose.
Here, PP pellets and UG (3 wt.%) were
manually blended and then
subjected to SSSP and nally
compression molded. For
comparison, composite material
with similar ller content was
fabricated by melt extrusion.
Reduction in impact strength is
normally the norm when a rigid ller
is added to a relatively tough
polymer.
Such enhancement in Y was
comparable to that attained in the
PAN-GNP system [97], but was not
observed in other polymergraphite
systems [68,109,126].
The increase in the yield strength
and Y values were 1429% and
1136% for PP/MWNT (3 wt.%
loading) over neat PP [127], which
were obviously lower than that
attained by the SSSP-processed
nanocomposite. However, nearly
similar improvement in Y (113%) was
noticed in CNT-MA-PP system at a
similar ller loading of 3 wt.% [128].
GNPs were prepared by [129]
ultrasonicating EG in aqueous
alcoholic solution. GNP or UG were
dispersed in 20 wt.% AS resin in
solvent by ultrasonication and
precipitated out to prepare
masterbatch. The masterbatches
were then melt extruded with AS or
HDPE to prepare specimens.
The miscibility of HDPE with AS resin
was poor due to its non-polar nature.
Thus, although the GNPs were well
coated by AS resin, the dispersion of
GNPs in HDPE was not as good as
that in the AS matrix leading to
higher PT values.
GNPs with elongated geometry had
great advantage in forming
conducting networks in the polymer
matrix and thus lead to lower PT
compared to UG.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Table 4 (Continued)
Sample details Tensile properties
PP + xGNP KB and xGNP-1 exhibited the
greatest FS improvement up to a
loading of 5 vol.% followed by
VGCNF, PAN-CF and xGNP-15.
But in the 1020 vol.% ller
loading level, FS improvement
was greatest with PAN-CF
(125%) followed by VGCNF
(82%), xGNP-1 (70%) and
xGNP-15 (30%). ODA-MMT in
PP showed the lowest FS than
the other llers at all loadings
due to lack of compatibilization
between the clay and the PP
matrix. In case of FM, xGNP-1
showed the best reinforcing
action by increasing the modulus
700% at 20 vol.% loading,
followed by PAN-CF (470%),
VGCNF (400%), xGNP-15
(320%) and ODA-MMT (100%).
PPS + EG and PPS + GNP FS of both PPS/GNP and PPS/EG
were lower than that of pure PPS
at all ller loadings from 1 to
10 wt.%. This was due to the poor
interaction between the ller and
the matrix and also due to the
presence of ller agglomerations
in the polymer matrix.
Electrical properties
- EG was ultrasonicated to obtain
PT values were 1 and 2 wt.% for
PPS/GNP and PPS/EG
nanocomposites.
RTC for both PPS/GNP and PPS/EG
nanocomposites at 10 wt.% ller
loading were 102 and 103 .
657
Comments Ref.
[130]
individual GNPs which were
<10 nm thick and 15 (m
diameter (xGNP-15). The
diameter was brought down to
<1 (m but the thickness remained
same (xGNP-1) using a vibratory
mill. These xGNP/PP
nanocomposites were compared
with PAN-CF, VGCNF, KB and
ODA-MMT. Filler loadings up to
20 vol.% were used excepting the
KB/PP system, where the
maximum ller loading was
5 vol.% (due to extrusion related
problems).
xGNP-1 showed better FM and
IIS improvements compared to
xGNP-15 in PP due to its more
homogeneous dispersion, less
agglomeration and retention of
its platelet morphology in the PP
matrix. The FS of both xGNP-1
and xGNP-15 reinforced PP
nanocomposites at higher
loadings (1020 vol.%) were
lower possibly due to dispersion
difculty at higher loadings in
the PP matrix.
The IIS of various PP composites
up to 10 vol.% ller loading was
studied. The highest impact
properties were obtained with
xGNP-1 at an optimum
concentration of 3 vol.% where
the IIS of PP was increased by a
factor of two. However, KB at
5 vol.% loading reduced the IIS of
neat PP by 50%.
PPS due to its low melt viscosity [131]
can easily ow into the pores of
EG (better intercalation)
resulting in the formation of
better ller networks compared
to HDPE/EG [119] and PS/EG
[132] nanocomposites prepared
by direct MB since the melt
viscosities of HDPE and PS are
higher than PPS. The PT values
were higher in these systems,
viz., 4.68 vol.% (10.3 wt.%) EG
[119] and >20 wt.% EG [132].
The FM variation with increasing
ller loading showed a similar
trend as the variation of FS for
PPS/EG system. In the PPS/GNP
system, the FM increased slightly
with increasing GNP content
followed by a dramatic increase
when the ller loading was
higher than 6 wt.%. At 10 wt.%
GNP content, the FM
improvement was 30% over
neat PPS.
The PPS/GNP nanocomposites
exhibited better FS and FM than
PPS/EG nanocomposites due to
better dispersion of the GNPs
compared to EG in the PPS
matrix.
658
Table 4 (Continued)
Sample details
Fluoroelastomer + xGNP
Graphite intercalated compound
(i) PS + UG, PS + GIC and PS + EG
(ii) ABS + UG, ABS + GIC and
ABS + EG
(iii) HIPS + UG, HIPS + GIC and
HIPS + EG
PA6 + UG, PA6 + GIC and PA6 + EG
Graphene oxide
PP + UG and GO
Functionalized graphene sheets
PAS + graphene nanosheets
R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
Tensile properties
PT was attained at 2.53.5 phr
TS and EB for all the graphite
polymer nanocomposites were
lower than neat PS.
In the PS system, Y for the GIC
lled specimens were lower than
that of neat PS (Y = 3.0) while
those lled with UG and EG were
similar to neat PS.
All the lled systems exhibited
lower TS and EB at all loadings.
The deterioration in properties
was lower for UG and EG lled
systems compared to the GIC
lled composites as they liberate
sulfuric acid with concomitant
degradation of PA6.
RTC of SGN = 0.69 indicating its
Electrical properties
xGNP-15 [130] was used as the
ller loading.
UG, EG and four grades of GIC as
Nanocomposites were prepared
conductive nature in contrast to
the electrically insulating GO.
RTC of PAS/graphite
nanocomposite was not
reported.
Comments Ref.
[133]
reinforcing ller in this study.
Samples were prepared by
two-roll mixing at 80 C followed
by compression molding.
Four GICs (based on sulfuric acid [126]
as the intercalant) were used in
this study. The GICs were graded
on the basis of onset temperature
for the release of the sulfuric acid
and the nature (acidic, basic or
neutral) of the graphitic surface.
All the graphite llers were of 80
mesh particle size.
In the HIPS system, UG and EG
have Y comparable to that of HIPS
(Y = 2.4). However, except for one
of the GICs at 3 and 5 wt.%
loading, all the other GICs have
similar Y as that of neat HIPS.
In the ABS system (Y = 2.4), all the
nanocomposites showed similar Y
as that of neat ABS only at low
(1 wt.%) ller loading but at higher
loadings, the Y values were lower.
[134]
described in [126] were used in
this study.
Y also did not change much with
the lled systems (Y = 1.4 for neat
polymer). On annealing, the Y
values signicantly decreased for
the lled systems and could be
ascribed due to the acid
instability of the polyamides.
[135]
using a Gelimat, a high speed
thermo-kinetic mixer with
different levels of UG and GO
using MA-g-PP as interface
modiers. Filler dispersion
promoted the nucleation of (
crystallites in PP.
The nanocomposites showed
higher thermal stability than neat
PP.
A novel MB method to fabricate [34]
polymer/graphite
nanocomposites in two stages: (i)
GO was sonicated to prepare GO
slurry in basic solution which
then underwent redox reaction
with polysulde ions to obtain
sulfur/graphite nanocomposite
(SGN). (ii) SGN is used as ller and
melt mixed with cyclic oligomer
of PAS at 180 C to obtain
PAS/graphene nanosheet
composite. The reaction scheme is
shown in Fig. 17.
The SGN holds promise for
applications like electrode
material in lithium batteries
[136,137], vulcanization agent for
fabrication of conductive polymer
nanocomposites [138140] and as
effective mercury sorbents
[141,142].
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 659

Table 4 (Continued)

Sample details Tensile properties Electrical properties Comments Ref.

PEN + UG and PEN + FGS
SAN + FGS, PC + FGS, iPP + FGS and
PA6 + FGS
Y and EB of the neat and lled
systems are compared in Fig. 18a
and b. It is obvious that in all the
thermoplastic systems, FGS lled
nanocomposites showed much
better Y values but the EB values
were inferior to the CCB and
MWNT lled samples.
PT varied from 0.030 to
0.036 vol.% for PEN/UG
nanocomposites and from 0.003
to 0.006 vol.% for PEN/FGS
nanocomposites. The PT values
varied due to different sample
preparation conditions.
PT in iPP were at <5 wt.% FGS,
<10 wt.% CCB and <5 wt.% MWNT
loading, respectively. In SAN, FGS
and CCB had PT was attained at
4 wt.% while MWNT needed
12 wt.% loading. In PC all the
three llers showed PT was
attained at 2.5 wt.% loading.
FGS were prepared by thermally [35]
exfoliating GO.
The thermal expansion of PEN
was suppressed by 15% by the
incorporation of 3 wt.% UG or
FGS.
PEN/FGS nanocomposites hold
promise as mechanically robust
recording tapes.
FGS, MWNT and CCB were used [36]
as llers.
Since FGS had very low bulk
density, SC (SAN, PC, iPP) and
FGS coating of PA6 powder were
employed to premix FGS with
the polymers. The premixed
compounds were dried prior to
melt compounding.
RTC of neat PC and iPP 1018 .
RTC of neat SAN and PA6 1016 .
The RTC of the llers in SAN, PC,
iPP and PA6 are compared in
Fig. 19.
At comparable ller loadings in
SAN, PC and PP matrices, FGS
lled systems showed lower RTC
than CCB lled systems. But in
PA6, their conductivities were
comparable.

Fig. 16. Mechanical testing results of neat PP and PP-graphite hybrid sam-
Fig. 15. Electrical conductivity of the polystyrenegraphene compos-
ples, YM: Youngs Modulus, EB: Elongation at break, A.E.: Absorbed Energy
ites as a function of ller volume fraction. Right inset, log  c plotted
per Thickness [33].
against log( c ), where c is the percolation threshold. Solid lines
in both graphs are calculated conductivities based on the tting (inset:
loglog plot) of the experimental data to the effective conductivity equa-
tion described in the text. Left inset: top and middle diagrams show the
four-probe setup for in-plane and transverse measurements, respectively;
bottom diagram, one of the computed distributions of the current density
(contour lines) with local directions and magnitude (shown by arrows) in
a specimen for the following conditionsthe sample thickness is twice the
electrode width and the gap between them, and the in-plane resistivity is
10 times lower than the transverse resistivity.
Figure reprinted with permission from Ref. [44]. Copyright 2006 Nature
Publishing Group.
660 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Table 5
Tensile and electrical properties of polymer/graphite composites prepared by combinatorial techniques.

Sample details Tensile properties Electrical properties Preparation/ Comments Ref.

processing

Expanded graphite
PMMA + UG, PMMA + EG At 5 wt.% ller loading,
and PMMA + GNP RTC of GNP, EG and UG
lled composites were
101 , 104 and 105 .
Epoxy FM of the small ake RTC of neat epoxy 109 .
lled (20 wt.%) At 20 wt.% EG loading,
composites was 60% the RTC of the large,
higher than the neat medium and small ake
epoxy (FM = 2.4). FS of lled systems were 0.5,
the large ake lled 0.1 and 0.03.
(0.1 wt.%) composites
was 87% higher than neat
epoxy (FS = 92).
MA-g-PP At 3.90 vol.% EG, RTC of
composites prepared by
SC was 6 orders of
magnitude higher than
that prepared by MB
NBR 195% increase in TS and RTC = 0.3 for 10 phr EG
945% increase in 100% lled composite. No
modulus for 10 phr EG conductivity data
lled sample prepared by presented for 10 phr EG
LC over control (TS = 4 lled composite
and 100% modulus = 1.1). prepared by melt
blending technique.
SC and shear Surface area of the UG, EG [19]
mixing and GNP were >1, 20 and
29 m2 /g, respectively. The
GNPs had thicknesses of
10 nm.
GNPs had the highest aspect
ratio and higher surface
roughness than UG and EG
and thus were better
dispersed in the matrix
leading to better electrical
conductivity than EG and UG
systems.
SC and shear EG akes of three different [31]
mixing particle sizeslarge (50
mesh), medium (100 mesh)
and small (150 mesh) were
used in this study. SEM
illustrated the expansion of
exfoliated graphite
nanoparticles created a
porous microstructure
(Fig. 20). FS for all three
graphite sizes showed their
largest increase in strength
with minimal graphite
content. After 4 wt.% EG
loading, the FS continuously
decreased with increasing
ller loading. At 20 wt.%
graphite loading, all the
three EG lled polymers
showed 2000% increase in
TC over neat epoxy
(TC = 0.219). The electrical
and thermal conductivities of
EG lled composites were
higher than VGCNF based
polymer composites.
SC and MB PT (of composites prepared [143]
by SC) was attained at
0.67 vol.% EG.
PT (of composites prepared
by MB) was at 2.96 vol.% EG.
RTC of composites prepared
by MB was 6.85 109 .
SC (latex At 10 phr EG loading, sample [144]
compounding) prepared by LC showed
and MB 103% increase in TS and
539% increase in 100%
modulus over sample
prepared by melt blending.
At the same ller loading of
10 phr, EG based
nanocomposites prepared by
LC exhibited the highest
reinforcing efciency
compared to composites
lled with carbon black and
silica. Composites (with
10 wt.% EG) prepared by LC
showed lower wear rates and
higher TC (30%) than those
prepared by direct MB. TC
improved by 58% for
10 wt.% EG composite
prepared by LC over neat
NBR (TC = 0.19).
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 661

Table 5 (Continued)

Sample details Tensile properties Electrical properties Preparation/ Comments Ref.

processing

PA6 FM was slightly RTC 1015 (neat Method A: ISP PT was attained at [110]
higher at all graphite PA6) Method B: ISP + high 0.75 vol.% EG
loadings. RTC = 103 at 3 vol.% shear colloidal mill (Method A), PT
FS decreased after EG (Method A) was attained at
0.5 vol.% EG loading. RTC = 104 at 4 vol.% 2.7 vol.% EG
IIS (notched) was EG (Method B) (Method B). Aspect
lower for all ller ratio (of EG) 3000
loadings. (Method A) and
1500 (Method B).
Tensile properties
were measured for
nanocomposites
prepared by
Method A only.
Interfacial
adhesion between
the ller and
matrix was not
strong enough to
withstand large
mechanical forces
resulting in lower
IIS.
PS IIS (notched) of RTC 1016 (neat PS) ISP and solution Cationic grafting [83]
EG-g-PS/PS RTC = 102 at blending polymerization of
composites was 13.4 wt.% EG loading styrene initiated
higher than that for by CO+ ClO4
pure PS due to the group on EG
homogeneous surface.
distribution of PT was attained at
EG-g-PS particles in 2.6 wt.% EG.
the matrix. 5 wt.% EG loaded
composite showed
24% increase in
IIS (notched) over
the unlled matrix
(IIS 6.2).
PE and PE/MA-g-PE PT in terms of MB, SC and MMB PE/EG prepared by [119]
ller vol.% by direct MB was the
adopting the control (EG-C).
different techniques PE/MA-g-PE/EG
were 5.35 (EG-C), was also prepared
2.19 (EG-SC), 3.81 by the SC
(EG-MMB) and 4.68 technique (EG-SC).
(EG-MB). For the SC, MA-g-PE and EG
MMB and direct MB masterbatch was
composites, the prepared by SC
weight ratio of which was
MA-g-PE to EG was subsequently melt
1.5. mixed with PE to
obtain MMB
(EG-MMB). PE,
MA-g-PE and EG
were directly MB
and was
designated as
EG-MB. SC gives
the lowest PT
value compared to
the MB techniques.
The MMB
technique provides
better
delamination of EG
and dispersion
than direct MB
technique and
hence depicted
lower PT value.
662 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Table 5 (Continued)

Sample details Tensile properties Electrical properties Preparation/ Comments Ref.

processing

Natural unmodied graphite

POM + UG and The TS, EB and NCIS of MB, ISP, SC and solid UG and nano-UG used in this [145]
POM + nano-UG the composite lled with state pan milling study had average diameter
nano-UG were higher intercalation (SMI) 4 (m and 200 nm, respectively.
than that of the The graphitic llers were
composite lled with UG surface modied using
possibly due to the various titanate coupling
relatively small particle agents to improve the
size of the nano-UG. At compatibility between the
10 wt.% nano-UG loading, ller and the POM matrix.
the TS improved by a POM/graphite composites
meager 5.7% (TS of neat were prepared by four
POM was 60.16) while EB techniques: (i) direct MB, (ii)
reduced drastically by ISP of the monomers
90% (EB of POM was 40) 1,3,5-trioxane and
and NCIS dropped by 1,3-dioxolane mixed with
6% (NCIS of POM was ller in presence of catalyst at
7.01). However, by the 65 C. This was then
addition of alcohol amino compounded and melt
titanate coupling agents, processed with POM, (iii) SC
the toughness of the of POM powder and ller in
composites were slightly benzyl alcohol, which was
improved but the then precipitated, washed
improvements in TS and dried. Then, this was
were not appreciable and compounded and melt
the NCIS also remained blended with POM, (iv) POM
lower than neat POM. powder and ller were mixed
and grinded in a pan mill and
nally compounded and melt
mixed with POM. This process
is termed as SMI.
The TC and TD of the
composites lled with UG
were higher than that of the
composites lled with
nano-UG and this behavior
was explained on the basis of
larger aspect ratios of UG
leading to more conductive
paths. TC increased from 0.36
(for neat POM) to 1.15 (for
30 wt.% UG) and to 1.05 (for
30 wt.% nano-UG).
The alcohol amino coupling
agents had little or no
inuence on the TC of the
nano-UG containing
composites but the TD values
were improved by
140170% over neat POM
(TD = 0.19) and 1020% over
POM/10 wt.% nano-UG
(TD = 0.42). Comparison of the
MB, ISP, SC and SMI revealed
that composites prepared
using SC had relatively higher
thermal conductive
properties while the
mechanical properties were
relatively higher for the
composites prepared by SMI
(pan milling) method. These
trends were explained on the
basis of decreased size, more
narrow size distribution,
thinner overlapped sheets
and better ller dispersion in
case of composites prepared
by ISP, SC and SMI than that
prepared by MB method.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 663

Table 5 (Continued)

Sample details Tensile properties Electrical properties Preparation/ Comments Ref.

processing

Graphite nanoplatelet
Epoxy FM increased with PT of the nanocomposites SC and shear mixing UV/O3 treatment [14]
increasing GNP content with and without UV/O3 increased the
for the both treated and treatment were 1 wt.% oxygen-containing
untreated GNPs. The (0.5 vol.%), which is much functional groups (like
increase was 17% and lower than the PT values hydroxyl, ether, carboxyl
8% for the treated and reported in Refs. [50] and and carbonyl) on the GNP
untreated GNPs (at [68] and comparable surface, which facilitated
2 wt.% loading) compared with that reported in interfacial adhesion with
to neat epoxy (FM 3.1). Refs. [72] and [92]. the epoxy matrix.
FS decreased with TC of the
increase in GNP loading. nanocomposites was
The decrease was lower insensitive to UV/O3
with the treated GNPs treatment of the GNPs. At
compared to the 2 wt.% ller loading in
untreated ones. epoxy matrix, GNPs were
more efcient in
improving the TC
compared to CB.
At 2 wt.% GNP loading, TC
was 1.0 whereas that for
2 wt.% CB was 0.4 (TC of
neat epoxy was 0.2).
A recent review article
[146] has dealt with
some other forms of
surface modication of
graphene, especially of
chemical nature, and
discussed their effect on
inclusion in some
common polymer
matrices.
Epoxy + GNP, RTC of GNP composite SC and shear mixing SWNT and GNP were [115]
Epoxy + SWNT and was around two orders of combined to prepare a
Epoxy + hybrid magnitude higher than series of hybrid graphitic
GNPX SWNT10 X that of SWNT composite nanollers.
(RTC 0.003) at a ller The RTC of the hybrid
loading of 10 wt.%. GNP-SWNT composite
was lower than that of
the GNP composite at the
same ller loading of
10 wt.%.
At 10 wt.% ller loading,
the TCSWNT = 0.85 and
TCGNP = 1.49
TChybrid = 1.75 at a GNP:
SWNT ller ratio of 3:1.
Such high TC value
composites have
potential as advanced
thermal interface
materials.
Epoxy PT was attained at SC and shear mixing At 0.5 vol.% GNP loading, [147]
0.5 vol.% GNP loading the nanocomposite
exhibited strong PTC and
NTC effects. Such
materials with properties
of temperature
dependency of
conductivity are
promising materials for
applications in
self-regulating heaters;
self-resetting
overcurrent protectors
and sensors.
664 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Table 5 (Continued)

Sample details Tensile properties Electrical properties Preparation/processing Comments Ref.

Epoxy (GNP were Y of GNP nanocomposite SC and shear mixing (the This study showed [58]
obtained from FGS) was 31% greater than sample preparation that at a nanoller
pristine epoxy as technique is shown in weight fraction of
compared to 3% Fig. 21) 0.1 0.002%, GNP
increase for SWNT, lled
whereas MWNT nanocomposites
incorporation caused a out-perform CNT
slight decrease compared lled epoxy
to pristine epoxy nanocomposites in
(Y = 2.85). TS of the GNP terms of mechanical
nanocomposite was properties.
40% higher than The KIc of the GNP
baseline epoxy nanocomposite
(TS = 55.75) compared to showed 54%
14 and 11% increase over neat
improvement for MWNT epoxy (KIc = 0.96)
and SWNT compared to 20 and
nanocomposites, 15% improvement for
respectively. MWNT and SWNT
nanocomposites,
respectively. On a
comparative basis, a
78-fold higher ller
loading of SiO2
nano-particles in
epoxy matrix raise
the fracture
toughness of neat
epoxy by 54% [148]
and 50- to 100-fold
higher ller loading
of nanoclays in
various epoxy
matrices is required
to achieve a 60%
increase in fracture
toughness [149]. GIc
improved by 46, 66
and 126% for the
SWNT, MWNT and
GNP lled
nanocomposites
compared to neat
epoxy (GIc 251).
GNP lled
nanocomposite
showed signicant
lowering in the crack
growth rate over the
full range of stress
intensity factor
amplitudes
compared to baseline
epoxy and the
MWNT and SWNT
lled
nanocomposites.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 665

Table 5 (Continued)

Sample details Tensile properties Electrical properties Preparation/processing Comments Ref.

TPU Tensile modulus SC followed by MB TPU containing [150]

increased with increase 5.6 vol.% GNP was
in GNP loading. TS and EB prepared by SC and
at all GNP loadings were was used as the
lower than that of the masterbatch for
neat TPU. further melt mixing
with TPU pellets. At
3.9 vol.% GNP loading
(maximum ller
concentration used
here), the tensile
modulus was 280%
higher than that of
the neat TPU.
GNPs are potential
intumescent ame
retardants and
improved the ame
retardancy of the
TPU matrix.

Fig. 17. Synthetic route to the fabrication of poly(arylene sulde)/graphite nanocomposites.

Figure reprinted with permission from Ref. [34]. Copyright 2008 Macromolecules.
666 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670

Fig. 19. Comparison of the electrical conductivity of the lled nanocom-

posites [36].

Fig. 18. Comparison of (a) Youngs modulus and (b) elongation at break
of the thermoplastic nanocomposites prepared by the addition of TRGO,
CCB and MWNT [36].

Fig. 20. High magnication SEM micrograph of exfoliated graphite

nanoparticle.
Figure reprinted with permission from Ref. [31]. Copyright 2007 Elsevier.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670 667

Fig. 21. Preparation of the test specimens starting with GNP dispersion in the epoxy matrix by ultrasonication, solution blending and high speed shear
mixing.
Figure reprinted with permission from Ref. [58]. Copyright 2009 American Chemical Society.

Acknowledgements
[13] Yasuda E, Inagaki M. Introduction. In: Yasuda E, Inagaki M, Kaneko
K, Endo M, Oya A, Tanabe Y, editors. Carbon alloysnovel concepts
This study was sponsored by Indo-Australia Strategic to develop carbon science and technology. Oxford: Elsevier Science
Research Fund, DST, New Delhi and supported by the Com- Ltd.; 2003. p. 311.
[14] Li J, Sham ML, Kim J-K, Marom G. Morphology and properties of
monwealth of Australia under the Australia-India Strategic UV/ozone treated graphite nanoplatelet/epoxy nanocomposites.
Research Fund. Compos Sci Technol 2007;67:296305.
[15] Ganguly A, George JJ, Kar S, Bandyopadhyay A, Bhowmick AK.
Rubber nanocomposites based on miscellaneous nanollers. In:
References Bhowmick AK, editor. Current topics in elastomers research. Boca
Raton: CRC Press; 2008. p. 8999.
[16] Geim AK, Novoselov KS. The rise of graphene. Nat Mater
[1] Kroto HW. The stability of the fullerenes C-24, C-28, C-32, C-36,
2007;6:18391.
C-50, C-60 and C-70. Nature 1987;329:52931.
[17] Park S, Ruoff RS. Chemical methods for the production of graphenes.
[2] Dresselhaus MS, Dresselhaus G, Eklund PC. Science of fullerenes
Nat Nanotech 2009;4:21724.
and carbon nanotubes. San Diego: Academic Press; 1996. p. 1559.
[18] Jang BZ, Zhamu A. Processing of nanographene platelets (NGPs) and
[3] Ugarte D. Curling and closure of graphitic networks under electron-
NGP nanocomposites: a review. J Mater Sci 2008;43:5092101.
beam irradiation. Nature 1992;359:7079.
[19] Ramanathan T, Stankovich S, Dikin DA, Liu H, Shen H, Nguyen ST,
[4] Rodriguez NM. A review of catalytically grown carbon nanobers.
Brinson LC. Graphitic nanollers in PMMA nanocompositesan
J Mater Res 1993;8:323350.
investigation of particle size and dispersion and their inu-
[5] Tibbetts GG, Lake ML, Strong KL, Rice BP. A review of the fabri-
ence on nanocomposite properties. J Polym Sci B Polym Phys
cation and properties of vapor-grown carbon nanober/polymer
2007;45:2097112.
composites. Compos Sci Technol 2007;67:170918.
[20] Kelly BT. Physics of graphite. London: Applied Science Publishers;
[6] Ajayan PM. Nanotubes from carbon. Chem Rev 1999;99:178799.
1981. p. 133.
[7] Dresselhaus MS, Avouris P. Introduction to carbon materials
[21] Xie X-L, Mai Y-W, Zhou X-P. Dispersion and alignment of car-
research. In: Dresselhaus MS, Dresselhaus G, Avouris P, editors.
bon nanotubes in polymer matrix: a review. Mater Sci Eng R
Carbon nanotubes: synthesis, structure, properties and application.
2005;49:89112.
Berlin: Springer; 2001. p. 19.
[22] Coleman JN, Khan U, Gunko YK. Mechanical reinforcement of poly-
[8] Han J, Structures. Properties of carbon nanotubes. In: Meyyappan
mers using carbon nanotubes. Adv Mater 2006;18:689706.
M, editor. Carbon nanotubes: science and applications. Boca Raton:
[23] Schadler LS. Polymer-based and polymer-lled nanocomposites.
CRC Press; 2005. p. 124.
In: Ajayan PM, Schadler LS, Braun PV, editors. Nanocomposite sci-
[9] Kroto HW, Heath JR, OBrien SC, Curl RE, Smalley RE. C60: Buckmin-
ence and technology. Weinheim: Wiley-VCH; 2003. p. 77144.
sterfullerene. Nature 1985;318:1623.
[24] Breuer O, Sundararaj U. Big returns from small bers: a
[10] Iijima S. Helical microtubules of graphitic carbon. Nature
review of polymer/carbon nanotube composites. Polym Compos
1991;354:568.
2004;25:63045.
[11] Pierson HO. Handbook of carbon, graphite, diamond and
[25] Al-Saleh MH, Sundararaj U. A review of vapor grown carbon
fullerenesproperties, processing and applications. Park Ridge:
nanober/polymer conductive composites. Carbon 2009;47:222.
Noyes Publications; 1993. p. 110.
[26] Chatterjee A, Deopura BL. Thermal stability of polypropy-
[12] McEnaney B. Structure and bonding in carbon materials. In:
lene/carbon nanober composite. J Appl Polym Sci
Burchell TD, editor. Carbon materials for advanced technologies.
2006;100:35748.
Oxford: Elsevier Science Ltd; 1999. p. 133.
668 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
[27] Endo M, Kim YA, Hayashi T, Nishimura K, Matusita T, Miyashita
K, Dresselhaus MS. Vapor-grown carbon bers (VGCFs)basic
properties and their battery applications. Carbon 2001;39:
128797.
[28] George JJ, Bhadra S, Bhowmick AK. Inuence of carbon-based
nanollers on the electrical and dielectric properties of ethylene
vinyl acetate nanocomposites. Polym Compos 2010;31:21825.
[29] Zheng G, Wu J, Wang W, Pan C. Characterizations of expanded
graphite/polymer composites prepared by in situ polymerization.
Carbon 2004;42:283947.
[30] Li J, Vaisman L, Marom G, Kim J-K. Br treated graphite nanoplatelets
for improved electrical conductivity of polymer composites. Carbon
2007;45:74450.
[31] Debelak B, Lafdi K. Use of exfoliated graphite ller to enhance poly-
mer physical properties. Carbon 2007;45:172734.
[32] George JJ, Bandyopadhyay A, Bhowmick AK. New generation lay-
ered nanocomposites derived from ethylene-co-vinyl acetate and
naturally occurring graphite. J Appl Polym Sci 2008;108:160316.
[33] Wakabayashi K, Pierre C, Dikin DA, Ruoff RS, Ramanathan T, Brin-
son LC, Torkelson JM. Polymergraphite nanocomposites: effective
dispersion and major property enhancement via solid-state shear
pulverization. Macromolecules 2008;41:19058.
[34] Du X, Yu Z-Z, Dasari A, Ma J, Mo M, Meng Y, Mai Y-W. New method
to prepare graphite nanocomposites. Chem Mater 2008;20:
20668.
[35] Kim H, Macosko CW. Morphology and properties of
polyester/exfoliated graphite nanocomposites. Macromolecules
2008;41:331727.
[36] Steurer P, Wissert R, Thomann R, Mulhaupt R. Function-
alized graphenes and thermoplastic nanocomposites based
upon expanded graphite oxide. Macromol Rapid Commun
2009;30:31627.
[37] Peierls RE. Quelques proprietes typiques des corpses solides. Ann
Inst Henri Poincare 1935;5:177222.
[38] Landau LD. Zur theorie der phasenumwandlungen II. Phys Z Sow-
jetunion 1937;11:2635.
[39] Fradkin E. Critical behavior of disordered degenerate semiconduc-
tors. Phys Rev B 1986;33:32638.
[40] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos
SV, Grigorieva IV, Firsov AA. Electric eld effect in atomically thin
carbon lms. Science 2004;306:6669.
[41] Novoselov KS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov
SV, Geim AK. Two-dimensional atomic crystals. Proc Natl Acad Sci
U S A 2005;102:104513.
[42] Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grig-
orieva IV, Dubonos SV, Firsov AA. Two-dimensional gas of massless
Dirac fermions in graphene. Nature 2005;438:197200.
[43] Zhang Y, Tan Y-W, Stormer HL, Kim P. Experimental observation
of the quantum Hall effect and Berrys phase in graphene. Nature
2005;438:2014.
[44] Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ,
Stach EA, Piner RD, Nguyen ST, Ruoff RS. Graphene-based composite
materials. Nature 2006;442:2826.
[45] Brodie BC. On the atomic weight of graphite. Phil Trans R Soc Lond
Ser A 1859;149:24959.
[46] Hummers WS, Offeman RE. Preparation of graphitic oxide. J Am
Chem Soc 1958;80:13391339.
[47] Boehm H-P, Setton R, Stumpp E. Nomenclature and termi-
nology of graphite intercalation compounds. Pure Appl Chem
1994;66:1893901.
[48] Dresselhaus MS, Dresselhaus G. Intercalation compounds of
graphite. Adv Phys 2002;51:1186.
[49] Chen G-H, Wu D-J, Weng W-G, Yan W-L. Preparation of
polymer/graphite conducting nanocomposite by intercalation
polymerization. J Appl Polym Sci 2001;82:250613.
[50] Chen G-H, Wu D-J, Weng W-G, Yan W-L. Dispersion of graphite
nanosheets in a polymer matrix and the conducting properties of
the nanocomposites. Polym Eng Sci 2001;41:214854.
[51] Shioyama H. Polymerization of isoprene and styrene in the inter-
layer spacing of graphite. Carbon 1997;35:16645.
[52] Shioyama H, Tatsumi K, Iwashita N, Fujita K, Sawada Y. On the inter-
action between the potassium-GIC and unsaturated hydrocarbons.
Synth Met 1998;96:22933.
[53] Shioyama H. The interactions of two chemical species in the inter-
layer spacing of graphite. Synth Met 2000;114:115.
[54] Viculis LM, Mack JJ, Kaner RB. A chemical route to carbon nano-
scrolls. Science 2003;299:1361.
[55] Stevens RE, Ross S, Wesson SP. Exfoliated graphite from the inter-
calate with ferric chloride. Carbon 1973;11:52530.
[56] Yoshida A, Hishiyama Y, Inagaki M. Exfoliated graphite from various
intercalation compounds. Carbon 1991;29:122731.
[57] Chen G-H, Wu D-J, Weng W-G, He B, Yan W. Preparation of
polystyrenegraphite conducting nanocomposites via intercala-
tion polymerization. Polym Int 2001;50:9805.
[58] Raee MA, Raee J, Wang Z, Song H, Yu Z-Z, Koratkar N. Enhanced
mechanical properties of nanocomposites at low graphene content.
ACS Nano 2009;3:388490.
[59] Eizenberg M, Blakely JM. Carbon monolayer phase condensation on
Ni (1 1 1). Surf Sci 1979;82:22836.
[60] Aizawa T, Souda R, Otani S, Ishizawa Y, Oshima C. Anomalous bond
of monolayer graphite on transition-metal carbide surfaces. Phys
Rev Lett 1990;64:76871.
[61] Berger C, Song Z, Li X, Wu X, Brown N, Naud C, Mayou D, Li T, Hass J,
Marchenkov AN, Conrad EH, First PN, de Heer WA. Electronic con-
nement and coherence in patterned epitaxial graphene. Science
2006;312:11916.
[62] Stankovich S, Dikin DA, Piner RD, Kohlhaas KA, Kleinhammes A,
Jia Y, Wu Y, Nguyen ST, Ruoff RS. Synthesis of graphene-based
nanosheets via chemical reduction of exfoliated graphite oxide.
Carbon 2007;45:155865.
[63] Gilje S, Han S, Wang M, Wang KL, Kaner RB. A chemical route to
graphene for device applications. Nano Lett 2007;7:33948.
[64] Schniepp HC, Li J-L, McAllister MJ, Sai H, Herrera-Alonso M, Adam-
son DH, Prudhomme RK, Car R, Saville DA, Aksay IA. Functionalized
single graphene sheets derived from splitting graphite oxide. J Phys
Chem B 2006;110:85359.
[65] McAllister MJ, Li J-L, Adamson DH, Schniepp HC, Abdala AA, Liu
J, Herrera-Alonso M, Milius DL, Car R, Prudhomme RK, Aksay IA.
Single sheet functionalized graphene by oxidation and thermal
expansion of graphite. Chem Mater 2007;19:4396404.
[66] She Y, Chen G, Wu D. Fabrication of polyethylene/graphite
nanocomposite from modied expanded graphite. Polym Int
2007;56:67985.
[67] Zou J-F, Yu Z-Z, Pan Y-X, Fang X-P, Ou Y-C. Conductive mechanism
of polymer/graphite conducting composites with low percolation
threshold. J Polym Sci B Polym Phys 2002;40:95463.
[68] Yasmin A, Daniel IM. Mechanical and thermal properties of graphite
platelet/epoxy composites. Polymer 2004;45:82119.
[69] Jia W, Tchoudakov R, Narkis M, Siegmann A. Performance of
expanded graphite and expanded milled-graphite llers in ther-
mosetting resins. Polym Compos 2005;26:52633.
[70] Shi L, Li Z-M, Xie B-H, Wang J-H, Tian C-R, Yang M-B. Flame
retardancy of different-sized expandable graphite particles for
high-density rigid polyurethane foams. Polym Int 2006;55:
86271.
[71] Kim H, Hahn HT, Viculis LM, Gilje S, Kaner RB. Electrical conduc-
tivity of graphite/polystyrene composites made from potassium
intercalated graphite. Carbon 2007;45:157882.
[72] Chen G, Wu C, Weng W, Wu D, Yan W. Preparation
of polystyrene/graphite nanosheet composite. Polymer
2003;44:17814.
[73] Chen G, Weng W, Wu D, Wu C. PMMA/graphite nanosheets com-
posite and its conducting properties. Eur Polym J 2003;39:232935.
[74] Weng W, Chen G, Wu D, Chen X, Lu J, Wang P. Fabrication
and characterization of nylon 6/foliated graphite electrically con-
ducting nanocomposite. J Polym Sci B Polym Phys 2004;42:
284456.
[75] Srivastava NK, Mehra RM. Study of structural, electrical and
dielectric properties of polystyrene/foliated graphite nanocom-
posites developed via in situ polymerization. J Appl Polym Sci
2008;109:39919.
[76] Du XS, Xiao M, Meng YZ, Hay AS. Synthesis and properties of
poly(4,4 -oxybis (benzene) disulde)/graphite nanocomposites via
in situ ring-opening polymerization of macrocyclic oligomers. Poly-
mer 2004;45:67138.
[77] Mo Z, Sun Y, Chen H, Zhang P, Zuo D, Liu Y, Li H. Preparation and
characterization of a PMMA/Ce(OH)3 , Pr2 O3 /graphite nanosheet
composite. Polymer 2005;46:126706.
[78] Cho D, Lee S, Yang G, Fukushima H, Drzal LT. Dynamic mechani-
cal and thermal properties of phenylethynyl-terminated polyimide
composites reinforced with expanded graphite nanoplatelets.
Macromol Mater Eng 2005;290:17987.
[79] Lu W, Lin H, Wu D, Chen G. Unsaturated polyester resin/graphite
nanosheet conducting composites with a low percolation thresh-
old. Polymer 2006;47:44404.
[80] Panwar V, Mehra RM. Study of electrical and dielectric properties
of styrene-acrylonitrile/graphite sheets composites. Eur Polym J
2008;44:236775.
 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
[81] Wang H, Zhang H, Zhao W, Zhang W, Chen G. Preparation of
polymer/oriented graphite nanosheet composite by electric eld-
inducement. Compos Sci Technol 2008;68:23843.
[82] Wang W-P, Pan C-Y. Preparation and characteriza-
tion of poly(methyl methacrylate)-intercalated graphite
oxide/poly(methyl methacrylate) nanocomposite. Polym Eng
Sci 2004;44:23359.
[83] Wang W-P, Pan C-Y. Preparation and characterization of
polystyrene/graphite composite prepared by cationic grafting poly-
merization. Polymer 2004;45:398795.
[84] Du XS, Xiao M, Meng YZ, Hay AS. Novel synthesis of conduc-
tive poly(arylene disulde)/graphite nanocomposite. Synth Met
2004;143:12932.
[85] Jang JY, Kim MS, Jeong HM, Shin CM. Graphite oxide/poly(methyl
methacrylate) nanocomposites prepared by a novel method utiliz-
ing macroazoinitiator. Compos Sci Technol 2009;69:18691.
[86] Xiao M, Sun L, Liu J, Li Y, Gong K. Synthesis and properties of
polystyrene/graphite nanocomposites. Polymer 2002;43:22458.
[87] Fang M, Wang K, Lu H, Yang Y, Nutt S. Covalent polymer func-
tionalization of graphene nanosheets and mechanical properties
of composites. J Mater Chem 2009;19:7098105.
[88] Xie L, Xu F, Qiu F, Lu H, Yang Y. Single-walled carbon nanotubes
functionalized with high bonding density of polymer layers and
enhanced mechanical properties of composites. Macromolecules
2007;40:3296305.
[89] Qian D, Dickey EC, Andrews R, Rantell T. Load transfer and defor-
mation mechanisms in carbon nanotubepolystyrene composites.
Appl Phys Lett 2000;76:286870.
[90] Celzard A, McRae E, Mareche JF, Furdin G, Dufort M, Deleuze C.
Composites based on micron-sized exfoliated graphite particles:
electrical conduction, critical exponents and anisotropy. J Phys
Chem Solids 1996;57:7158.
[91] Zheng W, Wong S-C, Sue H-J. Transport behavior of
PMMA/expanded graphite nanocomposites. Polymer
2002;43:676773.
[92] Zheng W, Wong S-C. Electrical conductivity and dielectric proper-
ties of PMMA/expanded graphite composites. Compos Sci Technol
2003;63:22535.
[93] Wang W-P, Pan C-Y. Synthesis and characterizations of
poly(ethylene oxide) methyl ether grafted on the expanded
graphite with isocyanate groups. Eur Polym J 2004;40:5438.
[94] Celik C, Warner SB. Analysis of the structure and properties
of expanded graphite-lled poly(phenylene ether)/atactic
polystyrene nanocomposite bers. J Appl Polym Sci
2007;103:64552.
[95] George JJ, Bhowmick AK. Ethylene vinyl acetate/expanded graphite
nanocomposites by solution intercalation: preparation, character-
ization and properties. J Mater Sci 2008;43:7028.
[96] Chen L, Chen G, Lu L. Piezoresistive behavior study on nger-
sensing silicone rubber/graphite nanosheet nanocomposites. Adv
Funct Mater 2007;17:898904.
[97] Mack JJ, Viculis LM, Ali A, Luoh R, Yang G, Hahn HT, Ko FK, Kaner
RB. Graphite nanoplatelet reinforcement of electrospun polyacry-
lonitrile nanobers. Adv Mater 2005;17:7780.
[98] Green M, Marom G, Li J, Kim J-K. The electrical conductivity of
graphite nanoplatelet lled conjugated polyacrylonitrile. Macro-
mol Rapid Commun 2008;29:12548.
[99] He F, Lau S, Chan HL, Fan J. High dielectric permittivity
and low percolation threshold in nanocomposites based on
poly(vinylidene uoride) and exfoliated graphite nanoplates. Adv
Mater 2009;21:7105.
[100] Dang Z-M, Wang L, Yin Y, Zhang Q, Lei Q-Q. Giant dielectric permit-
tivities in functionalized carbon nanotube/electroactivepolymer
nanocomposites. Adv Mater 2007;19:8527.
[101] Chen Q, Du P, Jin L, Weng W, Han G. Percolative conductor/polymer
composite lms with signicant dielectric properties. Appl Phys
Lett 2007;91:022912.
[102] Dang Z-M, Wu J-P, Xu H-P, Yao S-H, Jiang M-J, Bai J. Dielectric
properties of upright carbon ber lled poly(vinylidene uoride)
composite with low percolation threshold and weak temperature
dependence. Appl Phys Lett 2007;91:072912.
[103] Ramanathan T, Abdala AA, Stankovich S, Dikin DA, Herrera-Alonso
M, Piner RD, Adamson DH, Schniepp HC, Chen X, Ruoff RS, Nguyen
ST, Aksay IA, PrudHomme RK, Brinson LC. Functionalized graphene
sheets for polymer nanocomposites. Nat Nanotech 2008;3:32731.
[104] Nguyen DA, Lee YR, Raghu AV, Jeong HM, Shin CM, Kim
BK. Morphological and physical properties of a thermoplas-
tic polyurethane reinforced with functionalized graphene sheet.
Polym Int 2009;58:4127.
669
[105] Grossiord N, Loos J, Koning CE. Strategies for dispersing carbon
nanotubes in highly viscous polymers. J Mater Chem 2005;15:
234952.
[106] Ounaies Z, Park C, Wise KE, Siochi EJ, Harrison JS. Electrical
properties of single wall carbon nanotube reinforced polyimide
composites. Compos Sci Technol 2003;63:163746.
[107] McLachlan DS, Chiteme C, Park C, Wise KE, Lowther SE, Lillehei PT,
Siochi EJ, Harrison JS. AC and DC percolative conductivity of single
wall carbon nanotube polymer composites. J Polym Sci B Polym
Phys 2005;43:327387.
[108] Ramasubramaniam R, Chen J, Liu H. Homogeneous carbon nan-
otube/polymer composites for electrical applications. Appl Phys
Lett 2003;83:292830.
[109] Zheng W, Lu X, Wong S-C. Electrical and mechanical properties
of expanded graphite-reinforced high density polyethylene. J Appl
Polym Sci 2004;91:27818.
[110] Pan Y-X, Yu Z-Z, Ou Y-C, Hu G-H. A new process of fabri-
cating electrically conducting nylon 6/graphite nanocomposites
via intercalation polymerization. J Polym Sci B Polym Phys
2000;38:162633.
[111] Zois H, Apekis L, Omastova M. Electrical properties and percolation
phenomena in carbon black lled polymer composites. In: Pro-
ceedings of the 10th International Symposium of Electrets (ISE 10).
Piscataway: Institute of Electrical and Electronics Engineers, Inc.;
1999. p. 52932.
[112] Pinto G, Lopez-Gonzalez C, Jimenez-Martin A. Polymer composites
prepared by compression molding of a mixture of carbon black and
nylon 6 powder. Polym Compos 1999;20:8048.
[113] Yang J, Tian M, Jia Q-X, Zhang L-Q, Li X-L. Inuence of graphite
particle size and shape on the properties of NBR. J Appl Polym Sci
2006;102:400715.
[114] Causin V, Marega C, Marigo A, Ferrara G, Ferraro A. Morpholog-
ical and structural characterization of polypropylene/conductive
graphite nanocomposites. Eur Polym J 2006;42:315361.
[115] Yu A, Ramesh P, Sun X, Bekyarova E, Itkis ME, Haddon RC. Enhanced
thermal conductivity in a hybrid graphite nanoplateletcarbon
nanotube ller for epoxy composites. Adv Mater 2008;20:47404.
[116] Li Y-C, Chen G. HDPE/expanded graphite nanocomposites prepared
via masterbatch process. Polym Eng Sci 2007;47:8828.
[117] Qu S, Wong S-C. Piezoresistive behavior of polymer reinforced by
expanded graphite. Compos Sci Technol 2007;67:2317.
[118] Katbab AA, Hrymak AN, Kasmadjian K. Preparation of interfa-
cially compatibilized PP-EPDM thermoplastic vulcanizate/graphite
nanocomposites: effects of graphite microstructure upon morphol-
ogy, electrical conductivity and melt rheology. J Appl Polym Sci
2008;107:342533.
[119] Shen J-W, Huang W-Y, Zuo S-W, Hou J. Polyethylene/grafted
polyethylene/graphite nanocomposites: preparation, structure and
electrical properties. J Appl Polym Sci 2005;97:519.
[120] Ghose S, Watson KA, Working DC, Connell JW, Smith JG, Sun
YP. Thermal conductivity of ethylene vinyl acetate copoly-
mer/nanoller blends. Compos Sci Technol 2008;68:184353.
[121] Zhang M, Li D-J, Wu D-F, Yan C-H, Lu P, Qiu G-M. Poly(ethylene
terephthalate)/expanded graphite conductive composites: struc-
ture, properties and transport behavior. J Appl Polym Sci
2008;109:14829.
[122] Lu J, Weng W, Chen X, Wu D, Wu C, Chen G. Piezoresistive materials
from directed shear-induced assembly of graphite nanosheets in
polyethylene. Adv Funct Mater 2005;15:135863.
[123] Arai T, Tominaga Y, Asai S, Sumita M. A study on correlation
between physical properties and interfacial characteristics in
highly loaded graphitepolymer composites. J Polym Sci B Polym
Phys 2005;43:256877.
[124] Furgiuele N, Lebovitz AH, Khait K, Torkelson JM. Efcient mix-
ing of polymer blends of extreme viscosity ratio: elimination of
phase inversion via solid-state shear pulverization. Polym Eng Sci
2000;40:144757.
[125] Furgiuele N, Lebovitz AH, Khait K, Torkelson JM. Novel strategy for
polymer blend compatibilization: solid-state shear pulverization.
Macromolecules 2000;33:2258.
[126] Uhl FM, Yao Q, Wilkie CA. Formation of nanocomposites of styrene
and its copolymers using graphite as the nanomaterial. Polym Adv
Technol 2005;16:53340.
[127] Xia H, Wang Q, Li K, Hu G-H. Preparation of polypropylene/carbon
nanotube composite powder with a solid-state mechanochemical
pulverization process. J Appl Polym Sci 2004;93:37886.
[128] Li W-H, Chen X-H, Yang Z, Xu L-S. Structure and properties
of polypropylene-wrapped carbon nanotubes composite. J Appl
Polym Sci 2009;113:380914.
670 R. Sengupta et al. / Progress in Polymer Science 36 (2011) 638670
[129] Chen G, Chen X, Wang H, Wu D. Dispersion of graphite nanosheets
in polymer resins via masterbatch technique. J Appl Polym Sci
2007;103:34705. [142]
[130] Kalaitzidou K, Fukushima H, Drzal LT. Mechanical prop-
erties and morphological characterization of exfoliated
graphitepolypropylene nanocomposites. Composites A [143]
2007;38:167582.
[131] Zhao YF, Xiao M, Wang SJ, Ge XC, Meng YZ. Preparation
and properties of electrically conductive PPS/expanded graphite [144]
nanocomposites. Compos Sci Technol 2007;67:252834.
[132] Xiao P, Xiao M, Gong K. Preparation of exfoliated
graphite/polystyrene composite by polymerization-lling
technique. Polymer 2001;42:48136. [145]
[133] Xu D, Sridhar V, Mahapatra SP, Kim JK. Dielectric properties of
exfoliated graphite reinforced uoroelastomer composites. J Appl [146]
Polym Sci 2009;111:135868.
[134] Uhl FM, Yao Q, Nakajima H, Manias E, Wilkie CA. Expand-
able graphite/polyamide-6 nanocomposites. Polym Degrad Stab [147]
2005;89:7084.
[135] Gopakumar TG, Page DJYS. Polypropylene/graphite nanocompos-
ites by thermo-kinetic mixing. Polym Eng Sci 2004;44:11629. [148]
[136] Marmorstein D, Yu TH, Striebel KA, McLarnon FR, Hou J, Cairns
EJ. Electrochemical performance of lithium/sulfur cells with three
different polymer electrolytes. J Power Sources 2000;89:21926. [149]
[137] Noel M, Suryanarayanan V. Role of carbon host lattices in
Li-ion intercalation/de-intercalation processes. J Power Sources
2002;111:193209. [150]
[138] Gubbels F, Blacher S, Vanlathem E, Jerome R, Deltour R, Brouers F,
Teyssie PH. Design of electrical conductive composites: key role of
the morphology on the electrical properties of carbon black lled
polymer blends. Macromolecules 1995;28:155966. [151]
[139] Huang J-C. Carbon black lled conducting polymers and polymer
blends. Adv Polym Tech 2002;21:299313.
[140] Kluppel M. The role of disorder in ller reinforcement of elastomers
on various length scales. Adv Polym Sci 2003;164:186.
[141] Liu W, Vidic RD, Brown TD. Optimization of sulfur impregna-
tion protocol for xed-bed application of activated carbon-based
sorbents for gas-phase mercury removal. Environ Sci Technol
1998;32:5318.
Feng W, Borguet E, Vidic RD. Sulfurization of a carbon surface for
vapor phase mercury removal. II. Sulfur forms and mercury uptake.
Carbon 2006;44:29983004.
Shen J-W, Chen X-M, Huang W-Y. Structure and electrical proper-
ties of grafted polypropylene/graphite nanocomposites prepared
by solution intercalation. J Appl Polym Sci 2003;88:18649.
Yang J, Tian M, Jia Q-X, Shi J-H, Zhang L-Q, Lim S-H, Yu Z-Z,
Mai Y-W. Improved mechanical and functional properties of elas-
tomer/graphite nanocomposites prepared by latex compounding.
Acta Mater 2007;55:637282.
Zhao X, Ye L. Study on the thermal conductive polyoxymethy-
lene/graphite composites. J Appl Polym Sci 2009;111:75967.
Kuila T, Bhadra S, Yao D, Kim NH, Bose S, Lee JH. Recent advances
in graphene based polymer composites. Prog Polym Sci 2010,
doi:10.1016/j.progpolymsci.2010.07.005.
Zheng C, Fan Z, Wei T, Luo G. Temperature dependence of the
conductivity behavior of graphite nanoplatelet-lled epoxy resin
composites. J Appl Polym Sci 2009;113:15159.
Blackman BRK, Kinloch AJ, SohnLee J, Taylor AC, Agarwal R,
Schueneman G, Sprenger S. The fracture and fatigue behavior of
nano-modied epoxy polymers. J Mater Sci 2007;42:704951.
Becker O, Varley R, Simon G. Morphology, thermal relaxations and
mechanical properties of layered silicate nanocomposites based
upon high-functionality epoxy resins. Polymer 2002;43:436573.
Quan H, Zhang B-Q, Zhao Q, Yuen RKK, Li RKY. Facile preparation
and thermal degradation studies of graphite nanoplatelets (GNPs)
lled thermoplastic polyurethane (TPU) nanocomposites. Compos-
ites A 2009;40:150613.
Olson DW. Graphite (natural). USGS Mineral Commodity Summary.
Reston VA: US Geological Survey; 2008. p. 7475. Also available at
http://minerals.usgs.gov/minerals/pubs/commodity/graphite/mcs-
2008-graph.pdf.