Progress in Polymer Science 37 (2012) 781–819

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Progress in Polymer Science

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

Modifications of carbon for polymer composites and nanocomposites

Nabarun Roy a , Rajatendu Sengupta a , Anil K. Bhowmick a,b,∗
a
Rubber Technology Centre, Indian Institute of Technology, Kharagpur 721302, India
b
Department of Chemistry, Indian Institute of Technology, Patna 800013, India

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

Article history: The various forms of carbon used in composite preparation include mainly carbon-black,
Received 26 April 2011 carbon nanotubes and nanofibers, graphite and fullerenes. This review presents a detailed
Received in revised form literature survey on the various modifications of the carbon nanostructures for nanocom-
15 December 2011
posite preparation focusing upon the works published in the last decade. The modifications
Accepted 30 December 2011
Available online 3 February 2012
of each form of carbon are considered, with a compilation of structure–property relation-
ships of carbon-based polymer nanocomposites. Modifications in both bulk and surface

Abbreviations: 1,4-PDA, 1,4-phenylenediamine; 1 H NMR, proton nuclear magnetic resonance; AFM, atomic force microscopy; AIG, alkali intercalated
graphite; A-MWNT, amine functionalized MWNT; A-PPO, amine terminated linear polypropylene oxide; ASTM, American Society for Testing and Mate-
rials; ATRA, atom transfer radical addition; ATRP, atom transfer radical polymerization; BR, polybutadiene rubber; C11 -MWNTS, undecyl-functionalized
MWNTs; CB, carbon-black; C-MWNT, carboxylated MWNT; CNF, carbon nanofibers; CNT, carbon nanotube; CPP, chlorinated polypropylene; CR, chloroprene
rubber; CRG, chemically reduced graphene; CRSG, chemically reduced sulfonated graphene; CSDPF, carbon–silica dual phase filler; CSM, chlorosulfonated
polyethylene; CVD, chemically vapor deposition; DCC, N,N -dicyclohexylcarbodiimide; DFT, density functional theory; DGEBF, diglycidyl ether of bisphenol
F; DMA, dynamic mechanical analysis; DMAc, dimethylacetamide; DMF, dimethyformamide; DPC-MWNT, diphenyl carbinol functionalized MWNT; DWNT,
double-walled nanotube; ECA, electrically conductive adhesive; EDA, ethylenediamine; EEG, electrochemically exfoliated graphite; ENR, epoxidized natural
rubber; EP, ethylene/propylene copolymer; EVA, ethylene vinyl acetate; FEF, fast extrusion furnace; FF, fine furnace; FM, flexural modulus (GPa); FS, flexural
strength (MPa); GO, graphite oxide; GMA, glycidyl methacrylate; GPCNF, CNF graphitized at 2800 ◦ C; GPCNF-M, CNF subjected to graphitization and ball
milling for 72 h; GPCNF-NA, CNF subjected to graphitization and 10% HNO3 treatment for 24 h; HAF, high abrasion furnace; HMDA, hexamethylenediamine;
HPEKs, hyperbranched poly(etherketone)s; HRTEM, high resolution TEM; iGO, isocyanate-treated GO; iPP, isotactic polypropylene; IR, isoprene rubber;
ISAF, intermediate super abrasion furnace; kGy, kilo gray; LCE, liquid-crystalline epoxy; LDPE, low density polyethylene; MAH, maleic anhydride; MEH-
PPV, poly(2-methoxy-5-(2 -ethyl-hexyloxy)-1,4-phenylene vinylene); MPF, 1-(4-methyl)-piperazinylfullerene; MW, molecular weight; MWD, molecular
weight distribution; MWNT, multiwall carbon nanotube; MWNT-PSSA, poly(styrene sulfonic acid)-modified CNTs; NBR, nitrile rubber; NMR, nuclear mag-
netic resonance; NR, natural rubber; ODA, octadecylamine; O-MWNT, oxidized MWNT; OPV, oligophenylenevinylene; PA6, polyamide 6; PA 66, polyamide
6,6; PBS, poly(P-bromostyrene); PBT, poly(butylene terephthalate); PC, polycarbonate; PCBM, [6,6]-phenyl-C61 -butyric acid methyl ester; PCL, polycapro-
lactum; PCNF, pristine CNF; PDI, polydispersity index; PDMS, polydimethylsiloxane; PEG, poly(ethylene glycol); PEGMA, poly-(ethylene glycol) methyl
ether methacrylate; PEN, poly(ethylene 2,6-naphthalate); PEDOT, poly (3,4-ethylenedioxythiophene); PEI, polyetherimide; PEO, polyethylene oxide; PET,
polyethyleneterephthalate; PHR, parts per hundred parts rubber; PLA, polylactide; PLLA, poly(l-lactide); PMMA, poly(methyl methacrylate); POSS, poly-
hedral oligomeric silsesquioxane; PP, polypropylene; PPA, poly(phenylacetylene); PPB, poly(1-phenyl-1-butyne); PPO, poly(2,6-dimethyl-1,4-phenylene
oxide); PS, polystyrene; PSF, polysulfone; PTC, positive temperature coefficient; PVAc, poly(vinyl acetate); PVDF, poly(vinylidene fluoride); PVK, poly(N-
vinyl carbazole); RAFT, reversible addition fragmentation chain transfer; RF, radio frequency; ROMP, ring-opening metathesis polymerization; SAF, super
abrasion furnace; SAN, poly (styrene-ran-acrylonitrile); SBR, styrene-butadiene rubber; SD-MWNT, silanized diphenyl carbinol functionalized MWNT;
S-MWNT, silanized MWNT; SPEI, sulfonated polyetherimide; sPP, syndiotactic polypropylene; ss-DNA, single-stranded DNA; STM, scanning tunneling
microscopy; STP, standard temperature and pressure; SWNT, single walled carbon nanotube; TC, thermal conductivity (W m−1 K−1 ); TCNEO, tetracyanoethy-
lene oxide; Td5% , temperature of 5% of the total mass degradation; TEM, transmission electron microscopy; TEMPO, 2,2,6,6-tetramethylpiperidinyl-1-oxy;
TEMPOL, (4-hydroxyl-2,2,6,6-tetramethylpiperdinyloxyl)-terminated polystyrene; Tg , glass transition temperature; TGA, thermogravimetric analysis; THF,
tetrahydrofuran; TMA, thermo-mechanical analyses; TMPTA, trimethylolpropane triacrylate; TPS, thermoplastic starch; TPU, thermoplastic polyurethane;
TRG, thermally reduced graphite oxide; UHMWPE, ultra high molecular weight polyethylene; U-MWNT, unmodified MWNT; UV, ultraviolet; VGCF, vapor-
grown carbon fibers; VGCNF, vapor-grown carbon nanofibers; XNBR, carboxylated NBR; XPS, X-ray photoelectron spectroscopy; XRD, X-ray diffraction;
YM, Young’s modulus (GPa); ˇ, field enhancement factor; c , carrier collection efficiency; e , energy conversion efficiency.
∗ Corresponding author at: Department of Chemistry, Indian Institute of Technology, Patna 800013, India. Tel.: +91 3222 283180/612 2277380;
fax: +91 3222 220312/612 2277384.
E-mail addresses: nabarunroy08@gmail.com (N. Roy), rajatsg2003@yahoo.co.in (R. Sengupta), anilkb@rtc.iitkgp.ernet.in,
director@iitp.ac.in (A.K. Bhowmick).

0079-6700/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2012.02.002
782 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Keywords: modifications have been reviewed, with comparison of their mechanical, thermal, electri-
Carbon-black cal and barrier properties. A synopsis of the applications of these advanced materials is
Carbon nanotubes presented, pointing out gaps to motivate potential research in this field.
Carbon nanofibers © 2012 Elsevier Ltd. All rights reserved.
Graphite Fullerenes

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782
2. Modifications of carbon-black, graphite, CNTs, VGCNFs and fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
2.1. Modifications of carbon-black . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
2.1.1. Introduction to carbon-black and its structural aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
2.1.2. In-process modification of carbon-blacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784
2.1.3. Post-process modification of carbon-blacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
2.2. Modifications of carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
2.2.1. Introduction to carbon nanotubes and their structural aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
2.2.2. Various types of chemical modifications of carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
2.2.3. Effect of modification of carbon nanotubes on property enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 794
2.2.4. Effect of CNT functionalization on polymer matrices of different polarity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 794
2.3. Modifications of vapor-grown carbon nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
2.3.1. Introduction to vapor grown carbon nanofibers and their structural aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
2.3.2. Tailoring of morphology of carbon nanofibers (bulk modification) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
2.3.3. Surface modification of carbon nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 798
2.4. Modified graphite/polymer nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
2.5. Modifications of fullerene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
2.5.1. Introduction to fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
2.5.2. Surface modifications of fullerene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
2.5.3. Nanocomposites with modified fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 806
3. Toxicity of modified carbon nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811

1. Introduction a polymer matrix, and several methods have been devel-

oped to improve the dispersion of carbon-black, CNTs,
Since the later half of twentieth century, advances in CNFs, graphene and fullerenes, including chemical modifi-
nanoscience and nanotechnology have been motivated cation of nanocarbons. Chemical modification can improve
by discoveries of a variety of carbon nanostructures. the dispersion of these materials in solvents, and hence
Carbon, the sixth element in the periodic table has improve physico-mechanical and thermal properties of
received immense media attention from era of the dis- nanocomposites [4,5]. This is shown by a representative
covery of fullerene buckyballs (1985) till today when image (Fig. 3) of the various forms of functionalized carbon
Andre Geim and Kostya Novoselov received the 2010 nanoparticulates/polymer nanocomposites.
Nobel prize for demonstrating the unexpected properties The field of carbon nanotechnology is dynamic, driven
of a 1-atom thick layer of graphene. Thus fullerenes, by inventive and pioneering discoveries advancing sci-
carbon nanotubes, graphenes and various other carbon entific and technological progress. This motivates the
nanostructures (shown in Fig. 1) hold their position publication of reviews to encourage innovative research in
as the strongest contenders in the development of this field. In this review, it describes modifications imple-
nanotechnology. mented on various forms of carbon nanostructures and
A survey by Noorden [2] (Fig. 2) showed that though their use in nanocomposites, with emphasis on research
innovations may be near saturation with fullerenes and work in the last decade, which saw the discovery of
carbon nanotubes, increased research may be anticipated graphene—a milestone achievement indeed. Here, we deal
for graphene in the next decade. with an array of nanostructural carbon extending from
It is well documented that a slight change in the orbital charge transfer is characterized as zero-dimensional (no
structure or macrosocpic structural forms of carbon can transfer), carbon-black and fullerene, one-dimensional car-
result in a wide range of new and fascinating proper- bon nanotube and nanofibers, two-dimensional graphene
ties. Hence, interest in the modification of carbon has to three-dimensional graphite. This study comprises of a
been intense, including modifications in the bulk or con- detailed compilation of the modifications of the various
fined to the surface. Carbon nanotubes, nanofibers and available forms of carbon and their applications as com-
various other nanostructural carbons tend to agglomer- posite materials. In this article, the main focus is on various
ate in nanocomposites, which may negate the properties modifications of nanostructured carbon-based polymer
of the individual components [3]. Thus, there is a criti- composites. However, we have also incorporated details
cal need for proper dispersion of these nanostructures in of carbon-blacks, which are aggregated nanoparticles, in
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 783

Fig. 1. Graphene as the building block of all graphitic carbon nanostructures; wrapped to form the 0-D buckyballs, rolled to form the 1-D nanotubes, and
stacked to form the 3-D graphite.
Reprinted with permission from Ref. [1] Copyright 2007 Nature Publishing Group.

Fig. 2. Survey of the research interest related to various carbon nanostructures.

Reprinted with permission from Ref. [2] Copyright 2011 Nature Publishing Group.

order to highlight the various forms of modifications pos-
sible on carbon.
2. Modifications of carbon-black, graphite, CNTs,
VGCNFs and fullerenes
2.1. Modifications of carbon-black
2.1.1. Introduction to carbon-black and its structural
aspects
Carbon-black is a widely used to modify the mechanical,
electrical and optical properties of the medium in which it
is dispersed (usually polymeric matrices such as rubbers
and plastics) [6–11]. The introduction of carbon-black as
a reinforcing filler in tires in the 20th century produced a
10-fold increase in the service life of tires, and since then
carbon-black has remained the predominant reinforcing
material for use in tires as well as other rubber products.
Carbon-black comprises ∼30% of most rubber compounds.
The types of carbon-blacks usually manufactured are
furnace, thermal and acetylenecarbon-blacks. Furnace
carbon-blacks are manufactured by the partial combus-
tion of hydrocarbons in a furnace. Thermal carbon-blacks
are prepared by the thermal decomposition of natural gas,
784 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 3. Various form of functionalized carbon nanoparticles based polymer nanocomposites; R represents the functionalities introduced on the filler surface.
while the exothermal decomposition of acetylene yields
acetylene carbon-blacks. ASTM D3053-04 defines carbon-
black as an engineered material, primarily composed of
elemental carbon, obtained from the partial combustion
or thermal decomposition of hydrocarbons. Carbon-black
exists as aggregates of spheroidal primary particles gath-
ered in a aciniform morphology (shaped like a cluster of
grapes), which are composed, having uniformity of pri-
mary particle size within a given aggregate and turbostratic
disordered layering of the graphitic-like planes within pri-
mary particles. The primary aggregates of carbon-black
(also referred to as the “primary structure”) form loose
“secondary structures” of associations/agglomerations via
van der Waals forces. The secondary structures are weak
and usually do not remain when the filler is dispersed in
rubber as the secondary structure (the agglomerates) is
disrupted to leave individual aggregates in the polymer
matrix. Thus the smallest dispersible unit of carbon-black
is the primary aggregate and not the particle.
Most carbon-blacks for the rubber industry contain
98+% elemental carbon, with oxygen (0.2–0.5%), sulfur
(1–2%) and hydrogen (0.2–0.4%) constituting the majority
of the other constituents. Several studies have indicated
the existence of various functional groups such as carboxyl,
phenols, lactones, aldehydes, ketones, quinones, ethers on
the carbon-black surface [6].
The two approaches adopted for modification of
carbon-blacks are in-process modification (the addition of
components for in situ modification of carbon-black in a
reactor) and post-process modification (here the surface of
carbon-black is treated to improve properties).
2.1.2. In-process modification of carbon-blacks
In-process modifications discussed below include metal
addition, development of inversion carbon-blacks and
carbon-black–silica dual phase fillers.
2.1.2.1. Metal addition. The addition of certain alkali met-
als (e.g., potassium) and/or other metals to a carbon-black
reactor to control carbon-black “structure” and has been
explored over the past 40 years [12]. There is a close
correlation between the structure of a carbon-black and
the modulus of a rubber product compounded with that
carbon-black. Usually, highly structured carbon-blacks
yield high modulus rubber, whereas poorly structured
carbon-blacks give low modulus rubber/carbon-black com-
posites.
Various formulation choices are available for construct-
ing the tread and other portions of a tire for which
carbon-black loadings may be ∼50 PHR or even higher.
In carbon-black loaded tread compounds, the physical
properties of the carbon-black directly influence abrasion
resistance and hysteresis of the tread compound. Usually,
carbon-blacks with high surface area and small particle size
impart high abrasion resistance as well as high hysteresis
to the tread compound. For good hysteresis balance, a tire
tread compound should demonstrate low hysteresis at high
temperatures and high hysteresis at low temperatures.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 4. Surface models of ASTM grade carbon black (top) and inversion black (bottom). The right side depicts the surface models of the binding of the rubber
chains with the carbon black particles.
However, other applications, such as under-tread, side-
wall, carcass, wedge compounds of tires, engine mounts
and base compounds for industrial and automotive belts,
for which good hysteresis balance is more important than
abrasion resistance.
Notably, Mahmud et al. [13] developed elastomer
compounds having good hysteresis balance as well as abra-
sion resistance. They obtained carbon-black metal hybrids
by adding volatilizable or decomposable metal contain-
ing compounds (preferably aluminum or zinc) into the
carbon-black reactor at a point upstream of the quench
zone. Optionally, silane coupling agents such as bis(3-
triethoxysilylpropyl)tetrasulfide (Si-69 from Degussa AG,
Germany), 3-thiocyanatopropyl-triethoxy silane (Si-264
from Degussa), etc., were also used for further modification
of the metal-treated carbon-blacks. These carbon-black-
metal hybrids were incorporated in blends of solution
polymerized SBR and BR to improve the abrasion resistance
and hysteresis properties of the elastomeric compounds.
The carbon-black metal hybrids were also stated to be
suitable for other rubbers, such as NR, chlorinated rubber,
various SBR grades and polymers and copolymers of BR, CR
and IR.
2.1.2.2. Inversion carbon-blacks. Inversion carbon-blacks,
also known as nanostructure carbon-blacks, are a new
development in the manufacture of carbon-black produc-
tion [14–16]. They are produced in a furnace reactor by
contacting newly formed carbon-black nuclei with addi-
tional carbon-black oil sprayed through a second set of
oil lances positioned just downstream of the first set.
785
STM and AFM studies have shown that the nanostruc-
ture carbon-blacks have more surface roughness than
the corresponding standard ASTM carbon-blacks. Surface
models for nanostructure carbon-blacks and comparative
ASTM carbon-blacks proposed based on STM, AFM and
transversal proton NMR spectroscopy studies are shown
in Fig. 4, where the disordered cubic blocks represent
small graphite-like crystallites [15]. Due to more graphitic
edges compared to conventional carbon-blacks, polymeric
chains are conceived to be more tightly tethered on the
nanostructure carbon-black surface by means of mechan-
ical/physicochemical interactions and this hindrance in
slippage of the polymeric chains, which being the major
hysteresis mechanism in filled vulcanizates, would result
in lowering of hysteresis (e.g., tan ı at 60 ◦ C). Vogler et al.
[14,15] claimed that rubber vulcanizates loaded with nano-
structure carbon-blacks give lower rolling resistance and
comparable wet skid behavior. The nanostructure carbon-
blacks are tailor-made for use in truck tire applications for
which the key requirements are low rolling resistance and
low tread wear.
2.1.2.3. Carbon-black–silica dual phase fillers (CSDPF). The
introduction of CSDPF manufactured by a unique mul-
tistage co-fuming process by Cabot Corporation, USA
heralded a new carbon-black based technology which
reduces hysteresis in both car and truck tread compounds,
while maintaining or improving abrasion [16–18]. The
CSDPF-elastomer system reduces costs, is not abrasive and
is semiconductive. Cabot introduced two different prod-
uct categories of CSDPF – Ecoblack CRX 2XXX series, which
786 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
contain silica domains finely distributed throughout the
aggregates of the filler, and Ecoblack CRX 4XXX series
which has much higher silica coverage on the filler surface
relative than CRX 2XXX. Both types of CSDPF show higher
polymer–filler interactions and lower filler–filler inter-
actions compared to conventional carbon-blacks. Cabot
researchers have shown that CSDPF gave a lower Payne
effect than either carbon-black or silica (in the Payne effect,
the storage modulus decreases rapidly with increasing
strain amplitude to approach a lower bound for high strain
amplitude). Shanmugharaj and Bhowmick [19–21] studied
the modification of a dual phase filler by electron beam irra-
diation in the presence or absence of an acrylate monomer
such as TMPTA or a silane coupling agent such as Si-69
in an SBR matrix. The authors showed that electron beam
modification of dual phase filler in the absence of TMPTA
or Si-69 significantly improved the modulus of the SBR
vulcanizates, whereas the values of tensile strength and
elongation at break dropped. However, the presence of
TMPTA or silane slightly increased the modulus with signif-
icant improvement in tensile strength. This effect was more
pronounced at higher loading of these modified fillers in
SBR vulcanizates. Electron beam modification of the CSDPF
in the presence and absence of TMPTA or silane signifi-
cantly improved the storage modulus of the modified filler
loaded SBR composite. Electron beam irradiation affected
the primary and secondary structures of the filler that led
to higher rubber occlusion, resulting in a higher volume
fraction of filler. This was responsible for the decrease of
the tan ı at 70 ◦ C and its increase at 0 ◦ C.
2.1.3. Post-process modification of carbon-blacks
Post-process modification discussed in the following
includes surface oxidation, reaction with diazonium salts,
plasma treatment, polymer grafting and reaction with
silanes.
2.1.3.1. Surface oxidation. Oxidation is frequently used as a
post-treatment of carbon-blacks to make the surface more
hydrophilic. Such modifications, in use since 1960 have
reached a level of saturation. However, some notewor-
thy research works include those of Sutherland et al. [22]
on the effects of ozone oxidation on the tensile strength
of carbon-black (N330)-filled NR and NBR. The oxidized
carbon-blacks incorporated in a polar rubber matrix (NBR)
increased the tensile strength of the filled composite by
35%, but decreased the tensile strength (by 12%) when
incorporated in a non-polar matrix (NR). A similar study
by Bandyopadhyay et al. [23] examined the influence of
surface oxidation of carbon-black (ISAF) on its interac-
tion with NBR and XNBR. They correlated the oxidation
of the filler surface with enhanced polymer–filler inter-
action compared in comparison to that with unmodified
ISAF filler. For the oxidized carbon-black–XNBR system,
chemical bonding between the carboxyl groups of the
rubber and the reactive groups (hydroxyl, OH) on the
filler surface resulted in greater improvements in terms
of mechanical and dynamic mechanical properties over
the oxidized carbon-black–NBR system. Similar influence
(increased elastomer–filler interactions) of surface oxi-
dized carbon-blacks in various elastomer systems such as
ENR resulting in significant property improvements has
been reported [24].
The effect of oxidized carbon-black on the epoxy resin
curing process was examined by Nakahara et al. [25] by
means of DSC. The authors observed that the addition of
oxidized carbon-black accelerated the initial cure reaction
and was also effective in lowering the curing tempera-
ture without any significant alteration in the degree of
crosslinking for the epoxy-amine system. Bae et al. [26]
compared the cure behavior of LCE/CNT and LCE/carbon-
black systems by DSC. Oxidized carbon materials were used
to ensure homogeneous dispersion of the carbon fillers in
the LCE matrix. Isothermal DSC experiments revealed that
the initial rate of cure for the LCE/CNT system was higher
than that of the LCE/CB system due to bigger size of carbon-
blacks.
2.1.3.2. Reaction with diazonium salts. More than 10 years
ago, Cabot researchers patented the spontaneous reaction
of carbon-black with diazonium salts without electro-
chemical assistance [27–29]. This chemical approach led
to the grafting of a variety of organic groups on the carbon-
black surface. Moreover, the sulfide groups react with the
SBR chains on heating and thereby a coupling between the
polymer chains and the filler particles is established dur-
ing vulcanization (shown in Fig. 5). The surface modified
carbon-black (APDS-N234) was tested along with unmod-
ified carbon-black (N234) and Si-69 modified silica in a
typical passenger tire tread formulation. The conclusions
of the study were that APDS-N234 exhibited lower Payne
effect than silane modified silica and this in turn exhib-
ited lower Payne effect than N234. The tan ı values at 70 ◦ C
for APDS-N234 and Si-69 modified silica were similar and
lower than that for N234 and thus APDS modified carbon-
black was comparable to silane modified silica in terms
of hysteresis and rolling resistance, and better compared
to conventional carbon-black. Toupin and Belanger [30]
investigated the mechanism of the spontaneous chemical
functionalization of carbon-black with 4-nitrophenyl dia-
zonium cations by varying the reaction conditions and also
determined the grafting yield as a function of the reaction
conditions.
2.1.3.3. Plasma treatment. Plasma radiation is one of the
widely used techniques to tailor the surface properties of
various solid substrates and materials including fillers [31].
The principal advantages of plasma treatment of carbon-
black are: (1) the reaction takes place on the surface and
does not significantly affect the bulk, (2) it is possible to
produce a variety of plasmas to effect different modifica-
tions and (3) it reduces the surface energy of carbon-black
to make it more near to that of various elastomers such as
SBR, BR, etc., and thereby reduce the filler–filler interac-
tion [32,33]. Probst et al. [34] demonstrated the flexibility
of the plasma process for production of carbon-blacks
in a pilot reactor by using different feedstock such as
ethylene, methane, styrene, pyrolysis fuel oil and even a
renewable vegetable oil (colza oil). The authors analyzed
various carbon-blacks produced from different feedstocks
and evaluated the compound properties by incorporating
the modified carbon-blacks along with a high reinforcing
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 787

Fig. 5. Probable reaction sequence showing the coupling between APDS modified carbon black and polymer chain.

furnace carbon-black (N234) in a typical SBR recipe [28].
This manufacturing approach is more appropriately clas-
sified as in-process modification and not as post-process
modification.
Johnson reported the modification of FEF and SAF
carbon-blacks by plasma treatment and compared the
properties of the untreated and the plasma treated carbon-
blacks by incorporating into SBR [35]. Even though the
tensile strength and elongation at break improved, the
modulus values of the treated carbon-black–rubber mixes
were lower than that of the compounds containing the
untreated carbon-blacks. Akovali and Ulkem [36] reported
the modification of carbon-black (ISAF N220) by plasma
polymerization in presence of styrene and butadiene as
monomers. Under the influence of plasma, monomers such
as styrene form active monomer species which then react
with the carbon-black surface to form a film of plasma poly-
merized monomer on the substrate. Composites prepared
with plasma polymerized styrene in SBR showed improve-
ment in mechanical properties such as tensile strength and
elongation at break compared to the unmodified carbon
filled SBR compound. Park et al. [33] varied the oxygen
788 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Table 1
Methodologies for the preparation of polymer-grafted carbon black [39].

Particulars Categories

Grafting onto carbon black Grafting from carbon black (Category 2) Reaction of carbon black with
(Category 1) functional polymers (Category 3)

Brief description Deactivation of growing polymer
radical by chain termination and
chain transfer with functional
groups on CB surface
Remarks Low grafting yield due to
preferential formation of ungrafted
polymer.
Graft polymerizations initiated by
reactive groups introduced onto CB
surface
Highest grafting yield but difficult to
control the molecular weight and the
number of grafted polymer chains.
Reaction of functional polymers with
the reactive functional groups on CB
surface
Both molecular weight and number of
grafted polymer chains can be easily
controlled. The grafted polymer has a
well defined structure.

plasma treatment time from 0 to 30 min, reporting an
optimum treatment time of 20 min. They observed that
the tearing energy of the NBR composites reinforced with
plasma treated carbon-blacks was higher than that of NBR
composites reinforced with the untreated carbon-blacks
(N220). The tensile strength as well as the ultimate elonga-
tion increased with the plasma treatment time (optimum
at 20 min). The authors explained the trend on the basis
of better wettability of the oxygen plasma treated carbon-
blacks in the polar NBR matrix.
2.1.3.4. Polymer grafting and reaction with silanes. Grafting
of polymers on the carbon-black surface is another mod-
ification technique by which the filler–filler interaction
can be reduced (which in turn is expected to enhance the
filler–polymer interaction) and thus should result in bet-
ter dispersion of the carbon-black in the polymer matrix.
Aboytes and Iannicelli [37] reported the modification of
SAF, HAF, ISAF, FEF and FF carbon-blacks with benzene
suitable for use as high temperature greases, inks and
molded items such as battery plates. Vidal et al. [38] dis-
closed a process for grafting polymers on carbon-black
through a transfer reaction free radical mechanism, and
thereby grafted PS, PVAc, PP, PMMA, etc., on a carbon-
black surface. They reported increased dispersibility of the
grafted carbon-blacks, leading to improved efficiency as a
pigment, UV filter, filler and antioxidant. Tsubokawa [39]
generalized the preparation methodologies of polymer-
grafted carbon-black under three categories summarized in
Table 1. The author reviewed the work on polymer grafting
on carbon-black up to 1991.
Tsubokawa et al. [40] reported the grafting of polymers
onto carbon-black surface by the direct condensation reac-
tion of surface carboxyl groups with functional polymers
having hydroxyl or amino groups, in the presence of N,N -
dicyclohexylcarbodiimide (DCC) as a condensing agent at
ambient temperature (Fig. 6). The authors observed that
in the absence of DCC, no grafting occurred to the carbon-
black surface.
Lin et al. [41] grafted polymers on carbon-blacks by a
very simple and easy impregnation method without using
any coupling agent. The authors oxidized carbon-black by
nitric acid and then impregnated the oxidized carbon-
blacks with polymers such as PEG to obtain the polymer
grafted carbon-blacks. Tsubokawa’s group reported the
grafting of PS with controlled MW and narrow MWD
to carbon-black surface [42], as well as the grafting of
dendrimers [43]. The grafting of polymers with con-
trolled MW and narrow MWD onto carbon-black is of
primary importance for the preparation of high perfor-
mance carbon-black/polymer nanocomposites.
Jia and Zhang [44] had worked previously in a sim-
ilar direction and studied the effect of MAH modified
carbon-black prepared by solid state grafting in situ on the
adhesion between Nylon 66 cords and NR. MAH-modified
carbon-black containing vulcanizate had higher tensile
strength, modulus and elongation at break compared to the
vulcanizate containing untreated carbon-black.
Hou et al. [45] established covalent bonding between
CB and LDPE through in situ grafting of monomers such
as acrylic acid, butyl acrylate and maleic anhydride with
dicumyl peroxide as initiator during melt compounding.
When compared with the untreated CB-filled LDPE com-
posites, the composites manufactured through in situ melt
grafting exhibited reduced room temperature resistivities
and greatly increased PTC intensities, along with enhanced
performance reproducibility. The PTC phenomenon is char-
acterized by a drastic increase in volume resistivity as the

Fig. 6. The direct condensation reaction of surface carboxyl groups with functional polymers having hydroxyl or amino groups in the presence of DCC as
condensing agent [40].
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
temperature approaches the melting point of the matrix
polymer [46].
Ganguly et al. [47] used resorcinol as a surface modi-
fier for carbon-black (thereby generating excess hydroxyl
groups on the carbon-black surface), and improved the
thermomechanical and dynamic mechanical properties of
NR filled with the modified carbon-blacks. The principle of
using a coupling agent to react with the functional moieties
present on the carbon-black surface was adopted by sev-
eral researchers to improve filler dispersion in the rubber
matrix and thereby improve vulcanizate properties [48].
With the discovery of various types of novel carbon
nanoparticulates, the spotlight of research has shifted from
carbon-black. However, research has revived this field by
executing novel methods of modification of carbon-black,
for example, through click chemistry, raft polymerization
and other new modes of filler modification and hence
investigate the effect of chemical modification on the
property-improvement of the composites.
2.2. Modifications of carbon nanotubes (CNTs)
2.2.1. Introduction to carbon nanotubes and their
structural aspects
Since the discovery of multi-walled carbon nanotubes,
MWNTs), in 1991 [49] these exotic materials have been the
focus of extensive global research to exploit the remark-
able physical and mechanical properties of this new form
of carbon [50–63]. With unique electronic properties, ther-
mal conductivity higher than diamond, and mechanical
properties for which the stiffness, strength and resilience
exceeds any other current material, CNTs hold promise for
the development of fundamentally new material systems.
A carbon nanotube is a graphene sheet rolled into a cylin-
der typically several nanometers in diameter and the ends
are capped with half fullerene balls [51,52,64]. This is, in
fact, the minimum energy conformation of a graphite layer
of finite size. The properties of the nanotubes depend on
the arrangement of the graphene sheets (how the sheets
are “rolled”), the diameter and length of the tubes and the
nanostructure. The MWNTs comprise of a coaxial assembly
of several SWNTs (“Russian doll” structure), separated from
one another by ∼0.34 nm, which is slightly more than the
interlayer distance in single-crystal graphite [51]. Another
form of nanotubes is the double-walled carbon nanotubes
(DWNTs), which consist of two graphene layers only [62].
DWNTs are model systems for research as they are at the
frontier between SWNTs and MWNTs [65]. The remarkable
feature to be noticed in DWNTs is that on functionaliza-
tion the outer wall would be solely involved (this is in
contrast to SWNTs), while the inner tube would remain
intact thereby providing both good mechanical properties
as well as retention of electronic properties. This special
feature of DWNTs may be exploited fruitfully when they
are integrated into composites. Some of the potential appli-
cation areas of CNTs are as catalysts, electron field emitters,
electromagnetic wave absorbers and shielding agents,
Lithium-battery anodes, hydrogen storage materials, fillers
in nanotube-based composites (including conducting com-
posites), nanoprobes (for nanolithography, drug delivery,
sensors, etc.) and supercapacitors [51,52,66].
789
Several reviews based on chemical modification of car-
bon nanotubes for polymer nanocomposites have appeared
[67–71]. In spite of these, the wide-ranging research which
is in progress with this new generation material encourages
more reviews to be written on the ongoing investigations
in this field.
2.2.2. Various types of chemical modifications of carbon
nanotubes
The modifications of CNTs are basically divided into
two categories: (1) involvement of the ␲-conjugated skele-
ton of CNTs in chemical reaction with various reagents,
thereby introducing chemical groups on the surface and
(2) adsorption of various molecules through non-covalent
interaction. Modification of CNTs fosters integration of
these materials into various organic, inorganic and bio-
logical systems and hence enables exploring its excellent
properties.
Due to the inherent stability of CNTs, covalent function-
alization by disruption of the ␲-conjugation is attainable
only upon imposition of harsh conditions. Various types
of chemical modifications have been performed on car-
bon nanotubes (Fig. 7). The literature mentioned earlier
[67–71] exemplifies the different types of conventional
modifications shown in Fig. 7. Apart from these examples,
some work needs special attention. For example, the
unsaturated backbone of the CNTs was modified through
hydrogenation by Birch reduction [72] and computational
methods were employed to estimate the binding energy
between C and H atoms [73]. Morphological analysis
through TEM studies suggested corrugation and disor-
derness of the CNT walls due to hydrogenation. Other
methods involved functionalization with atomic hydrogen
using glow discharge or proton bombardment [74–76].
Cycloaddition to CNT can be carried out by various
means and using different reagents. A unique way of sur-
face modification involves carbene [2 + 1] cycloaddition
using chloroform/sodium hydroxide mixture or phenyl
(bromodichloro methyl)mercury reagent [77–80]. Besides
this, nucleophilic addition of carbenes had been pursued
via zwitterionic 1:1 adducts [81,82]. Recent advances in
such modifications involve chemical modification of CNTs
with gold nanoparticle functionalized carbene through a
photoinitiated carbene addition reaction [83]. Nitrenes also
undergo [2 + 1] cycloaddition reactions, where the first
step involves the generation of a nitrene intermediate
by thermal decomposition of the organic azides and the
second step results in sidewall addition of the nitrene
to CNT [84,85]. Other routes for cycloaddition reactions
involve photochemical reactions with azides [86,87], ylides
[88,89] nitrile imines (1,3-dipolar cycloaddition reaction)
[90,91], 1,8-diazobicyclo[5,4,0]-undecene (DBU) [92,93]
and o-quinodimethane (Diels–Alder cycloaddition) [94].
2.2.2.1. Modifications of single walled carbon nanotube for
nanocomposites. Single-walled carbon nanotubes (SWNTs)
were discovered independently in 1993 by Iijima and
Ichihashi of NEC [95] and Bethune and his group at the
IBM Almaden Laboratory [96]. Subsequently, researchers
strived to explore these versatile materials in enhancing
properties of various polymers through nanocomposite
790 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 7. The various covalent functional modifications possible with carbon nanotubes.
preparation. Some advanced laboratories functionalized
these materials through series of chemical reactions at the
beginning of this century. Peng et al. [97] introduced 2-
carboxyethyl or 3-carboxypropyl groups on to the SWNT
surface followed by conversion to amides via acyl chloride
intermediate. These superior materials were suitable for
drug delivery and biosensor applications.
A number of studies have investigated the prepara-
tion of nanocomposites with functionalized SWNTs. In
the first successful fluorination of SWNTs Khabashesku
et al. [98] prepared functionalized nanotubes through
direct fluorination. Rangari et al. [99] studied the effect
of fluorination of nanotubes on property-improvement of
nylon-6 composites. They aligned pristine and fluorinated
CNTs in nylon-6 matrix by a single-screw extrusion tech-
nique. Composites prepared with 1 wt% of pristine CNT
and 0.5 wt% of fluorinated CNT showed a 230% increase
in tensile strength. In addition, the composite with func-
tionalized CNT showed higher elongation at break, as well
as a tensile modulus compared with the pristine CNT
(1 wt%)/nylon-6 composite. It was observed that lower
amount of fluorinated CNT was more effective in rein-
forcing the matrix. There is covalent bonding between the
modified CNT and the matrix. However, the by-product
HF is detrimental towards nylon-6 matrix, reflected in the
reduced mechanical properties with an increasing amount
of functionalized CNT. The improvement in properties is
also partly contributed by the increase in crystallinity of the
matrix in presence of nanotubes, since the latter act as sites
for nucleation. The F atoms in the fluorinated nanotubes
are the active reaction sites for reaction with Grignard
reagent whereby the F atom is replaced by alkyl group.
This facilitates better dispersion of the fillers in various
organic solvents. The fluoro group can undergo nucle-
ophilic substitution with various amines and thiols, which
improve their dispersion in highly polar solvents including
water [100]. Few current investigations help us to under-
stand the role of the functionalized SWNTs as reinforcing
materials in various polymeric systems and hence should
not be left unmentioned. Zhu et al. [101] prepared epoxy
nanocomposites with SWNTs functionalized by oxidation
followed by fluorination. Just 1 wt% of the functionalized
nanotubes resulted in a 30% increase in tensile modulus and
18% increase in tensile strength. The functionalized filler
underwent chemical bonding with the polymer, thereby
resulting in improved dispersion and subsequent property
improvement. Phenyl and undecyl groups were introduced
on the sidewalls of SWNTs by Peng et al. [102] through reac-
tion of pristine and fluorinated nanotubes with relevant
peroxides.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 791

Zhu et al. [103] used the same epoxy matrix to prepare

nanocomposites but, in this case, SWNTs were func-
tionalized by reaction between terminal diamines and
alkylcarboxyl functionalities on the nanotube surface. A
30–70% improvement in strength and modulus was found
with 1–4 wt% filler incorporation.
Nanocomposites have been prepared with variety of
functionalized SWNTs to widen the range of application.
Several conventional functionalizations, such as function-
alization with various benzenediazonium salts through
electrochemical reduction [104] or by in situ synthesis of
the diazonium species in presence of the SWNTs [105],
through free radical chemistry [106], nitrene chemistry
[107] and carbene chemistry [108] have been successfully
used in the functionalization of SWNTs with alkyl, aziri-
dene and cyclopropane groups, respectively. Besides these
methodologies, many typical organic reactions have been
used as tools in functionalizing SWNTs. For instance, the
Billups reaction, which involves metal-based reduction,
was carried out to introduce alkyl and aryl addendum on
the nanotube surface [109], while pyrrolidene was attached Fig. 8. Comparison of permittivity of various composites as a function of
to the SWNT surface by Prato reaction exploring the ylide raw to functionalized SWNT ratio [112].
chemistry [110]. However, nanotube research is acquir-
ing newer dimensions with time. In fact, modifications are
being carried out through unconventional techniques and
the resulting nanocomposites find applications in various
non-traditional applications. Functionalized SWNT-based
composites may be used in supercapacitor applications
where it may find a role as the electrode of the super-
capacitor. Nanocomposites were prepared with SWNTs
coated with poly (3,4-ethylenedioxythiophene) (PEDOT).
The resulting composite showed a much higher specific
capacitance than PEDOT alone, up to 200 F/g, with a very
rapid charge/discharge ability [111]. Materials suitable
for radio frequency applications with tunable permittivity
were designed and fabricated by Higginbotham et al. [112]
The group generated polymer composite materials using
tert-butyl aniline functionalized SWNT and silicone elas-
tomer. The permittivity was determined for composites
prepared with varying amounts of raw and functionalized
SWNT. Fig. 8 shows how the permittivity depends on the
SWNT ratio, facilitating tuning for specific requirements.
Fig. 9. Comparison of compressive mechanical properties of pristine and
Recent advances include the use of polymer grafted
functionalized SWNT/PPF composites [118].
SWNT/biomolecular nanocomposites in therapeutic
devices. The biomolecular substrates used range from DNA
to antibodies [113–116]. Recently, Zhang and Henthorn reaction improved dispersion of the filler in the biopoly-
[117] functionalized SWNTs with copolymer having poly- mer, thereby improving its physico-mechanical properties.
(ethylene glycol) methyl ether methacrylate (PEGMA) Figs. 9 and 10 show the compressive and flexural
and glycidyl methacrylate (GMA) repeating units through mechanical properties of the crosslinked PPF and its
UV light mediated “graft from” copolymerization. This nanocomposites with pristine and functionalized SWNT.
favored aqueous dispersibility and enzyme loading for the Functionalized SWNT showed prominent improvement in
nanocomposites. A 1:1 PEGMA:GMA composition resulted these properties. However, electrical conductivity did not
in nanocomposites with optimal aqueous dispersibility show any appreciable change upon functionalization [118].
and the highest enzyme loading. Nanotechnology has Many research groups have suggested novel schemes
spread through every walk of science and technology. In to functionalize SWNTs. Examples include nanocompos-
fact, current progress in bone tissue engineering involves ites prepared with SWNT functionalized with amine
the synthesis of injectable nanocomposites prepared from terminated polyimide with strong photoluminescence
functionalized SWNT and a biodegradable polymer, such as [119], poly(N-vinyl carbazole) (PVK) functionalized SWNT
poly(propylene fumarate) (PPF). These advanced injectable nanocomposites capable of improved charge dissipa-
materials were used to form scaffolds. It was found tion when illuminated [120] and nanocomposites pre-
that functionalization of SWNT through diazotization pared with carboxylic acid-terminated hyperbranched
792 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 10. Comparison of flexural mechanical properties of pristine and
functionalized SWNT/PPF composites [118].
poly(etherketone) (HPB-PEK) with improved solubility
[121]. However, an unresolved aspect is the effect of these
types of functionalization upon the physico-mechanical
properties of these novel nanocomposites.
2.2.2.2. Modifications of double-walled carbon nanotube
for nanocomposites. Though DWNTs exhibit some unique
physico-mechanical differences from either SWNTs
or MWNTs, few studies have pursued functionalizing
them and using them in nanocomposite preparation,
some of which are reviewed in the following. Terenzi
et al. [122] studied the chemorheological behavior
of N-methyldiethanolamine grafted carboxy-modified
DWNT/epoxy nanocomposites. It had been observed
from the calorimetric test that the functionalized DWNT
catalyze the curing reaction by shifting the cure reac-
tion peak towards shorter times. A novel approach was
adopted by Datsyuk et al. [123] in functionalizing DWNT
with various short polymeric chains through in situ
nitroxide mediated polymerization (NMP) of different
types of monomers. Diblock polymeric chains were
introduced on the nanotube surface in which the first
block consisted of PS (hydrophobic) or PAA (polyacrylic
acid) (hydrophilic), while the second block consisted
of PMA (polymethylacrylate). TGA studies showed that
while PS based nanocomposites decomposed at 440 ◦ C,
nanocomposites with PAA showed complete degradation
at 575 ◦ C. In addition, DWNT functionalized with PAA
showed an electrical conductivity of 0.3 S cm−1 and a low
percolation threshold of 2 wt%. Despite these examples,
the behavior of DWNTs as nanofillers and the effect of its
functionalization in nanocomposite preparation requires
additional systematic study.
2.2.2.3. Modifications of multiwalled carbon nanotube for
nanocomposites. From the time of its discovery MWNT
is the one among all the forms of carbon nanostruc-
tures which has been subjected to extensive modification
through various chemical reactions. In addition, it has been
used to produce nanocomposites with various polymer sys-
tems to yield materials with improved properties.
The various modifications include those discussed in
Section 2.2.2. For example, Giambastiani et al. [124] car-
ried out cycloaddition reactions with cyclic nitrones and
prepared highly soluble materials (Fig. 11), investigating
the role of the various carbons in the CNT structure in the
cycloaddition reaction through DFT calculations.
Recently, Syrgiannis et al. [125] reported a method of
tuning the alkyl functionalities on the nanotube surface.
Some of the alkyl groups attached to the CNT surface
were removed by treatment with lithium or sodium in liq-
uid ammonia. These were then replaced by different alkyl
groups (Fig. 12).
Besides these, some other forms of modifications
include bulk modification and modification of MWNT sur-
face by grafting polymer chains.
Manipulating morphology of CNTs: Bulk modification: The
purification and morphological change of SWNTs have
been effected by treatment in the temperature range
1400–2400 ◦ C in Krypton atmosphere. Thermal treatment
of a SWNT at 2400 ◦ C results in conversion to an MWNT
consisting of 2–20 carbon layers [127]. In another study,
He et al. [128] produced bamboo-shaped CNTs by decom-
position of methane over a Ni/Al catalyst at 600 ◦ C. The
initial stages showed carbon-coated nickel nanoparticles,
the diameter of which increased with time, resulting in
carbon clusters. These clusters were seeds of CNT growth,
ultimately resulting in the production of MWNTs 100 and
1000 nm in length with different diameters. Prominent
growth of MWNTs was observed after reaction for 60 min.
The nanotubes were cylindrical or conical depending on the
shape of quasi-sphere or quasi-cone catalytic particles. Cao
et al. [129] showed that morphology of the nanotubes can
be varied by using different growth substrate by pyrolysis
of ferrocene/melamine mixture. While growth of MWNTs
on a silica wafer produced nanotubes with a uniform diam-
eter of 25 nm, a rough polycrystalline ceramic surface
led to nanotube production with diameters ranging from
10 to 90 nm. Thus, substrate surface morphology has an
important role to play in nanotube preparation. However,
no literature is available on the preparation of polymer
nanocomposites with thermally treated MWNT. Thus, the
effect of heat treatment of MWNT on the properties of the
nanocomposites is a target for further investigation.
Grafting of polymer chains to MWNT: As mentioned ear-
lier in Section 2.2.2, once the unreactive surface of the
MWNT is functionalized by various chemically reactive
groups, the next step involves grafting of polymer chains
on the functionalized nanotube surface. There are two
types of grafting methods viz., “grafting to” and “grafting
from”. The “grafting to” method involves attachment of
a preformed polymer chain to the surface of pristine or
functionalized MWNTs, while the “grafting from” method
facilitates growth of the polymer chains from the sur-
face of the functionalized MWNTs by reaction between the
surface functionalities of the nanotube with the relevant
monomers.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 793

Fig. 11. Optimized structure for cycloaddition of nitrone to CNT.

Reprinted with permission from Ref. [124] Copyright 2011 American Chemical Society.

Fig. 12. Defunctionalization and refunctionalization of alkyl groups on CNT surface.

Reprinted with permission from Ref. [126] Copyright 2010 Nature Publishing Group.

The reactions involved in the first mechanism are pri-
marily condensation reactions such as ester [130] and
amide formation reaction [131,132], through radical reac-
tion [133,134], nucleophilic addition reactions [135,136],
and condensation [137,138] whereas the reactions in
the second type of grafting are atom transfer radi-
cal polymerization (ATRP) [139,140], nitroxide mediated
polymerization (NMP) [141,142], free radical polymeriza-
tion [143,144], reversible addition fragmentation chain
transfer (RAFT) [145,146], cationic and anionic poly-
merization [147,148], and ring opening polymerization
[149]. Clark and Krishnamoorti who significantly improved
dispersion of MWNTs in various solvents by functional-
izing them through the Birch alkylation procedure. They
interpreted the solubility results via Hansen solubility
parameters and a three-component surface energy analy-
sis. Solubility increased by 50–100% in o-dichlorobenzene
while it decreased for N,N-dimethylformamide and N-
methyl-2-pyrrolidinone [150]. In another case, MWCNTs
were successfully grafted with polystyrene, poly(␧-
caprolactone) and their block co-polymers by reaction with
alkoxy-amine terminated precursors. TEMPO terminated
polymer molecules were generated by polymerization
of monomers by various methods, such as controlled
radical polymerization and ring opening polymerization.
Polymer grafted nanotubes show huge improvement in
dispersion in THF compared to pristine MWNT [151]. Xu
et al. [152] synthesized a novel nanocomposite based
on sulfonated polyaniline and phenylamine functional-
ized MWNT through a mixed mechanism, obtaining a
highly water soluble nanocomposites. The nanocomposites
exhibit improved thermal stability, attributed to a chemical
reaction between the filler functional groups and the poly-
mer. This, undoubtedly, implies better dispersion in various
794 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
polar and non-polar matrices, with resulting improvement
in the properties of the resultant nanocomposites.
2.2.3. Effect of modification of carbon nanotubes on
property enhancement
Recent examples include grafting of n-hexa decylamine
with acyl chloride functionalized MWNTs by Liu et al. [153].
Polyamide 6 (PA6) nanocomposites prepared with func-
tionalized MWNT showed around 30% increase in Young’s
modulus, while it was only 24% for pristine MWNT based
nanocomposites.
In a similar way, Liu et al. [154] demonstrated enhanced
properties for a dispersion of MWNTs enhanced by
grafting PPO. Brominated PPO was grafted onto the nan-
otube surface by ATRP. The resulting nanocomposites
showed improved tensile strength though there was not
much change in Young’s modulus. Electrical conductiv-
ity increased from 10−13 S cm−1 for the PPO matrix to
10−8 S cm−1 with a frequency independent plateau region
for the nanocomposites.
A significant improvement in mechanical properties
(tensile strength and modulus) of PLLA was observed by
Chen et al. by incorporating PLLA grafted CNTs. Graft-
ing was effected by reaction of the COCl groups on the
nanotube surface with l-lactide by ring opening polymer-
ization [155,156].
Other modes of chemical modification of MWNTs
have also had an impact on property-improvement of
various polymer nanocomposites. For example, amine
modification has been carried out on CNTs to impart
excellent properties to the nanocomposites. MWNTs were
modified with HNO3 /H2 SO4 (2:3), followed by function-
alization using a EDA/DCC/THF solution with a weight
ratio of EDA:DCC:MWNT::20:20:1. These were added to
polyamic acid which was further heated to 300 ◦ C to pro-
duce modified CNT/polyimide nanocomposites. The amine
modified nanocomposites showed a decrease in volume
resistivity from 1.28 × 1015 /cm2 for virgin polyimide to
1.73 × 107 /cm2 for 6.98 wt% amine modified MWNT con-
tent. The tensile strength for the nanocomposites increased
from 102 MPa for neat polymer to 124 MPa for the amine
modified CNT based nanocomposites and Tg increased from
281 ◦ C to 289 ◦ C [157]. In order to improve the degree
of dispersion of the CNTs in PDMS matrix, Chua et al.
[158] functionalized nanotubes with diphenyl carbinol fol-
lowed by reaction with 3-aminopropyltriethoxysilane. The
nanocomposites prepared with the functionalized CNTs
showed better dispersion of the nanofillers, and as a conse-
quence resulted in property-improvement. While thermal
conductivity for unmodified MWNT based nanocompos-
ite (0.5 vol%) increased by 40% compared to the neat
matrix, the increase was up to 59% for amino silane
modified MWNT based nanocomposites with the same
filler concentration. DMA also showed improvement for
nanocomposites with aminosilane modified MWNT based
nanocomposites. Interfacial bonding is responsible for
property improvement and the increases by CNT function-
alization mentioned above. This was proved by Lee et al.
[159] who functionalized CNTs by aminosilane in order
to study the effect of filler surface functionalization on
various properties. Aminosilane functionalized CNT based
nanocomposites showed approximately 6% improvement
in tensile strength and 37% increase in fracture strength
as compared to unmodified CNT based system. However,
sea water treated samples showed reduction in prop-
erty improvement due to weakened interfacial bonding
as a result of matrix swelling. On the other hand, Chen
et al. [160] employed ionic bonding in order to graft
A-PPO molecules of different molecular weight to the oxi-
dized nanotubes in the preparation of nanocomposites
with epoxy elastomer. Significant increase in Tg and stor-
age modulus values was observed for A-PPO of lower
molecular weight than those of higher molecular weight.
Thus, the nature of the interphase can be manipulated
by the nature of the grafts and their interaction with the
matrix phase. According to Valentini et al. [161], who
functionalized the CNTs with amine groups, the electri-
cal properties of the amine modified CNTs improve on
filler functionalization. They found significant improve-
ment in the electrical conductivity on incorporation of
these functionalized nanotubes in the epoxy matrix. A new
technique for amination of MWNTs was undertaken by
Lee et al. [162] in which MWNTs were subjected to flu-
orination by CF4 plasma treatment, followed by reaction
with ODA. The ODA modified MWNT/PP nanocomposites
showed enhanced electrical and rheological properties.
While pristine MWNT/PP nanocomposites showed perco-
lation at 3–5 wt% filler loading, ODA modified MWNT/PP
nanocomposites attained the percolation threshold at just
1–2 wt% of nanotube loading. Basiuk et al. [163] attempted
direct solvent-free amination of MWNTs with ODA as a
positive approach towards environmental issues. Follow-
ing this procedure, Sengupta et al. [164] reacted HMDA
and MWNT to obtain aminated MWNTs subsequently used
in a PA66 matrix to prepare nanocomposites. The amine
functionalized nanocomposites exhibited higher maxi-
mum tensile stress (∼43%) and Young’s modulus (∼32%)
compared to the neat PA66 matrix. George et al. [165]
used HMDA modified MWNTs in EVA matrix and reported
enhancements in tensile strength and modulus over neat
EVA.
A few representative modifications of all forms of CNT
are collected in Table 2 along with the relevant properties
and applications.
2.2.4. Effect of CNT functionalization on polymer
matrices of different polarity
The properties of various polar and non-polar host
polymers depend on the chemical modifications of the
nanotubes. A few studies in which carbon nanotube based
composites have been prepared with several thermoplas-
tics are available in the literature. For example, Homenick
et al. [176] grafted polystyrene chains with molecular
weights ranging from 2900 to 105,000 g mol−1 onto SWNT
via nitroxide mediated radical polymerization and investi-
gated the solubility of the composites in THF. The polymer
with intermediate molecular weight and relatively high
molecular density gave maximum solubility. In another
work, incorporation of just 0.50 wt% of CPP-grafted MWNTs
in a PS matrix showed an increase of 100% in both the
tensile strength and the tensile modulus [177]. Toughness
is an important criterion in nanocomposite applications.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 795

Table 2
Representative modifications of CNT with the relevant properties and applications.

Materials Reaction Products Properties/applications Reference

Aniline, chlorosulfonic acid, In situ polymerization Sulfonated polyaniline Potential application areas include [166]
MWNTs of aniline followed by (SPAN)/MWNTs light-emitting diodes, photovoltaic
sulfonation with nanocomposites and electrochromic devices and
chlorosulfonic acid and chemical sensors.
hydrolysis by water.
3-Aminophenylboronic acid, DNA In situ polymerization Poly-(anilineboronic The authors suggest production of [167]
and SWNTs acid)/ss-DNA/SWNT advanced nanocomposite materials
nanocomposites with greatly improved performance.
HPEKs, MWNTs In situ polymerization HPEK-g-MWNT Due to the presence of large number [168]
nanocomposites of surface carboxylic acid groups in
HPEK-g-CNT nanocomposites, it
appears to be a potential candidate as
a reinforcing additive in advanced
composites.
CMWNT, TPS Prepared by solution CMWNT/TPS CMWNTs improved the thermal [169]
casting nanocomposite stability of TPS matrix. PT occurred at
1.5 wt% CMWNT. At 1.5 wt% CMWNT
content, the TS was 7.7 MPa compared
to 4.5 MPa for the neat TPS. Higher
CMWNT contents deteriorated the
mechanical properties of the
CMWNT/TPS composites.
U-MWNT O-MWNT, S-MWNT, Solution mixing U-MWNT/epoxy, The TS of dry S-MWNT/epoxy [159]
epoxy O-MWNT/epoxy, nanocomposites improved by ∼6%
S-MWNT/epoxy and fracture strengths were 37%
nanocomposites greater than those of U-MWNT/epoxy
nanocomposites (TS ∼ 56 MPa and
fracture load ∼ 847 N). Compared to
dry nanocomposites, sea water
absorption decreased the TS and
elastic modulus for each surface
modification. The fracture behavior of
the three types of nanocomposites
showed a similar trend as the tensile
results.
DPC-MWNT, SD-MWNT, PDMS, Solution mixing DPC-MWNT/PDMS, TC of SD-MWNT/PDMS higher than [158]
3-aminopropyltriethoxysilane SD-MWNT/PDMS neat PDMS due to better interfacial
nanocomposites interaction between the MWNTs and
PDMS matrix. However, the electrical
conductivity of the nanocomposites
decreased due to the wrapping of the
MWNTs with non-electrical
conducting organic materials. Better
dynamic mechanical properties were
exhibited by the composite containing
SD-MWNT compared to those
containing DPC-MWNT.
A-MWNT, epoxy Shear mixing A-MWNT/epoxy The FS increased with increase in [170]
nanocomposites A-MWNT loading (maximum loading
was 1 wt%) and at 1 wt% A-MWNT
loading, FS approximately doubled
while the FM slightly changed.
MWNT-PSSA, chitosan Ionic linking MWNT-PSSA/chitosan The nanocomposites were superior to [171]
the neat chitosan polymer in terms of
thermal, mechanical and electrical
conductivity properties and thus find
potential use in separation
membranes and sensor electrodes.
The presence of PSSA chains on the
MWNT surfaces improves the
interfacial compatibility between
chitosan and MWNTs.
C-MWNT, PEN Melt compounding MWNT/PEN and The TS and TM of the PEN [172]
C-MWNT/PEN nanocomposites significantly
nanocomposites improved with the introduction of
very small quantity of MWNT and
C-MWNT. However, the EB of the
nanocomposites were much lower
than that of the neat PEN matrix.
796 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Table 2 (Continued )
Materials Reaction
MWNT and DWNT with 3-roll milling
(MWNT-NH2 and DWNT-NH2 )
and without amine functional
groups, vinyl ester/polyester
hybrid
C11 -MWNTs, iPP and sPP, In situ polymerization
isospecific C2-symmetry
metallocene catalyst
rac-Me2 Si(2-Me-4-PhInd)2 ZrCl2
Plasma treated MWNT, maleic Shear mixing followed
anhydride (MAH), epoxy by sonication
PMMA filled with pristine MWNT (1 wt%) showed a mod-
erate increase of 170% in toughness [178], whereas PMMA
grafted MWNT [143,179] showed an increase of 1200%
for the nanocomposite prepared with 0.15 wt% of the
grafted nanofiller [143]. The compatibility of the filler is
significantly improved by grafting the filler with the same
polymer as the matrix when a nanocomposite is prepared.
For example, SWNT grafted with PVA gave a 20 and 40%
increase in tensile strength and modulus respectively,
while incorporation of the unmodified SWNT gave only
−5 and 35% increase in the respective parameters [180].
A PU matrix was combined with functionalized MWNTs in
several nanocomposite preparations. While incorporation
of pristine MWNT resulted in deterioration of tensile
strength [181], alkoxysilane modified (0.5 wt%) [182], oxi-
dized (1.5 wt%) [183] and amine modified MWNT (4 wt%)
[184] based nanocomposites showed 60, 30 and 270%
increase in tensile strength, respectively. In situ conden-
sation between PU and an amido-functionalized MWNT
has also been successfully carried out by Chen et al. [185],
with maximum increase of 900 and 741%, respectively,
Products Properties/applications Reference
MWNT/vinyl Nanocomposites containing MWNTs [173]
ester/polyester hybrid, and MWNT-NH2 resulted in higher
DWNT/vinyl tensile modulus, fracture toughness
ester/polyester hybrid and fracture energy values compared
(MWNT-NH2 and to nanocomposites containing DWNT
DWNT-NH2 )/vinyl or DWNT-NH2 . Moreover, in polyester
ester/polyester hybrid or vinyl-ester resins, the reinforcing
nanocomposites ability of DWNT and DWNT-NH2 was
observed to be lower compared to
MWNT and MWNT-NH2 .
MWNT/PP and YM of iPP increased by ∼22% from [174]
C11 -MWNTs/PP ∼12 to ∼14.7 GPa and YM of sPP grew
nanocomposites by ∼34% from ∼3.8 to 5.1 GPa at
0.1 wt% filler loading. The ultimate
tensile stress of MWNT/iPP and
C11 -MWNT/iPP nanocomposites was
nearly independent of nanotube
loading and remained at ∼31 MPa. For
the sPP based composites, minor
strengthening (∼7–8%) also took place
at low filler loading (0.1–0.5 wt%) but
higher filler loadings led to significant
decrease in the ultimate tensile stress.
This behavior was explained on the
basis of filler aggregates acting as
stress concentrators in the sPP based
nanocomposites.
MWNT-MAH/epoxy At just 1 wt% MWNT-MAH loading, [175]
nanocomposites TM increased 100% compared to a 42%
increase for the unmodified MWNTs.
For the MWNT-MAH system, TS
increased with increase in
MWNT-MAH loading. The average
tensile strength was 50% higher than
pristine epoxy with the addition of
1.0 wt% MWNT-MAH. At 1.0 wt%
MWNT-MAH content, the
nanocomposite exhibited ∼43% EB,
which was an increase of ∼380% over
the neat epoxy matrix. PT occurred at
∼0.1–0.2 wt% MWNT-MAH compared
to ∼0.5–0.6 wt% of unmodified
MWNTs.
in tensile strength and elongation at break at 1 wt% filler
loading. Polymer–filler interactions are ultimately mani-
fested in the properties of the nanocomposites, resulting
in a shift in the tan ı peak corresponding to Tg towards
higher temperature. This is observed with nanocomposites
prepared with epoxy matrix and MWNT. While a pristine
nanotube filled sample (0.75 wt%) showed a shift of 16 ◦ C,
a shift of 19 ◦ C was observed for nanocomposite prepared
with same amount of amino functionalized nanotubes
[186]. A study by Wladyka-Przybylaka et al. [187] intro-
duced various functionalities on MWNT, such as carboxyl,
amide, hydroxyl, amino and carboxyammonium. These
functionalized MWNTs were incorporated in an epoxy
system and various properties were studied. Among all the
modifications, the carboxyammonium modified MWNT
filled nanocomposite gave the highest tensile strength.
However, samples with aminated and carboxylated
nanotubes resulted in the highest hardness. In addition,
volume resistivity was highest for carboxylated CNTs.
Electrically conductive adhesives (ECAs) were prepared
using surface modified MWNT/epoxy nanocomposites.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 13. Plot of tensile strength and tensile modulus of polymer-grafted
MWNT/PVDF nanocomposites [189].
Pristine, acid treated and m-phenylenediamine treated
MWNT/diglycidyl ether of bisphenol F (DGEBF) epoxy
resin based nanocomposites showed pull strengths of
8.4, 10.6 and 11.3 N, respectively, thereby exhibiting their
effectiveness as superior quality adhesives [188].
Chang et al. [189] grafted various polymers to
MWNTs, including poly(vinylidene fluoride) (PVDF),
poly(2,6-dimethylphenylene oxide), polysulfone (PSF) and
poly(phthalazinone ether ketone) through ozone mediated
functionalization, and PVDF based nanocomposites were
prepared with these surface modified nanotubes. The
comparison of tensile properties shown in Fig. 13 reveals
that tensile strength and tensile modulus is highest for
PVDF grafted sample. Electrical conductivity was highest
for the MWNT-PVDF/PVDF nanocomposite. While for
PVDF and MWNT-PSF/PVDF it was 6.8 ± 0.2 × 10−14 S cm−1
and 7.2 ± 0.3 × 10−9 S cm−1 , respectively, it increased to
1.9 ± 0.2 × 10−8 S cm−1 at 1 PHR filler loading. According
to O’Bryan et al. [190], the percolation threshold of PVDF
nanocomposites with functionalized MWNT decreased
from 0.49 to 0.25 wt%, with a subsequent increase in
conductivity upon functionalizing MWNT with hydroxyl
797
groups. An efficient mainspring for a miniature device
should possess a high Young’s modulus. Jia et al. [191]
aimed at improving this parameter of mainsprings by
co-electrodeposition of a modified MWNT/chitosan
composite coating. Carboxylated MWNT based nanocom-
posites showed increased modulus due to covalent linking
between the COOH group of the filler and NH2 and OH
groups of the polymer.
2.3. Modifications of vapor-grown carbon nanofibers
2.3.1. Introduction to vapor grown carbon nanofibers
and their structural aspects
Vapor grown carbon nanofibers (VGCNFs) typically
have diameters in the range 60–200 nm and hundreds
of microns in length bridging the gap between those of
commercial carbon fibers (∼7–10 ␮m diameter) and either
SWNTs (∼1 nm) or MWNTs (2–50 nm) [192]. Unlike SWNTs
or MWNTs, VGCNFs have attracted the research attention
owing to their relatively low cost and commercial availabil-
ity; they are produced by the CVD process in high volumes
at low cost using carbon containing gases as feedstock, over
a metal or metal alloy surface as a catalyst [193].
Pyrograf I TM and Pyrograf III TM manufactured by
Pyrograf Products Inc., Cedarville, Ohio, USA are typical
examples of VGCFs and VGCNFs, respectively. VGCNFs have
hollow cores with single or double graphitic layers. The
graphite planes are parallel and/or oriented at an angle
with the nanofiber axis. However, both the single layer
VGCNF and the inside layer of the double layer VGCNF show
truncated cone morphology. In a single layer VGCNF, the
graphite layers are oriented at ∼15–17◦ to the fiber axis.
Further, Uchida et al. [194] observed folds of 3–5 graphite
sheets at the inner and outer surfaces of the single layer
VGCNF, with a separation between the folds of ∼60 nm.
Such folds might affect the mechanical properties of the
CNFs, especially if they occur on the outer surface of the
VGCNF. In a double layer VGCNF, the graphite sheets in the
outer layer are oriented parallel to the nanofiber axis. How-
ever, the angle of the inner graphite sheets in the double
layer morphology varies between 4◦ and 36◦ . It is known
that the graphite modulus drops significantly with graphite
sheet axis orientation away from the fiber axis [194], and
that the fiber diameter is also known to affect the tensile
properties of the CNFs [195].
Other complicated morphologies of CNFs such as
disordered bamboo-like structure [196], graphitized cup-
stacked structures [197] and nested conical shell structure
[198] have also been observed. Further, the structure may
depend on the catalyst used for nanofiber synthesis, as
observed by Ominami et al. [199].
The modes of modification of carbon nanofibers are sim-
ilar to those of CNTs and involve bulk modification and
surface modification through chemical reactions.
2.3.2. Tailoring of morphology of carbon nanofibers (bulk
modification)
Research on carbon nanofibers (CNFs) has developed
a wide-ranging variation in the morphology of CNFs by
manipulating reaction conditions and nature of catalyst.
Fig. 14 is a compilation of the various bulk modifications
798 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Fig. 14. Chronological events from discovery of transition metal catalyzed VGCNF synthesis to bulk modification of the nanofibers till date [197,200–211].

carried out on this form of carbonaceous nanofiller. In one
of the modifications, Ren and Cheng [205] used methane
as the carbon source and ferrocene as the precursor for the
catalyst. In this method, herringbone-type nanofibers with
very small diameter and a large hollow core were success-
fully prepared. The advantage of this method is catalyst-
free nanofibers are obtained by virtue of acid treatment
and sonication. Fig. 15(i) shows the herringbone nanofibers
with and without catalyst. In another case, Qin et al. [211]
synthesized helical VGCNF with a symmetric growth mode
by decomposition of acetylene with copper nanocrystals as
catalyst which was obtained by thermal decomposition of
copper tartrate. This is shown in Fig. 15(ii).
2.3.3. Surface modification of carbon nanofibers
2.3.3.1. Surface modification by high temperature graphitiza-
tion. Carbon nanofibers can be categorized by differences
in the orientation of graphitic layers with respect to fiber
axis: platelet (alignment perpendicular to the fiber axis),
tubular (layers aligned parallel to the axis), and herring-
bone (alignment at definite angles to the fiber axis). This
is revealed from the XRD profiles of the nanofibers [212]
graphitized by heat treatment above 2400 ◦ C. Moreover,
TEM analysis shows some more ordered arrangement
of the layers. High temperature graphitization facilitates
loop formation by closing the free ends of the platelets
[213,214]. Lim et al. [215] subjected the nanofibers to high
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 799

Fig. 15. (i) HRTEM image of a herringbone-type carbon nanofiber. (a) With an ellipsoid catalyst located at its tip and (b) without a catalyst (reprinted with
permission from Ref. [205], Copyright 2003 Elsevier). (ii) TEM images two helical fibers with irregular tips (A) with different morphologies and (B) with
same morphologies. (C–H) Other irregular tips with dissimilar morphologies (scale bar = 200 nm).
Reprinted with permission from Ref. [211], Copyright 2004 Elsevier.

temperature graphitization followed by mechanical and Heat treatment results in loop formation through fold-
chemical treatments. The results of the XRD analysis of the ing of planar hexagons at their edges (Fig. 16). Loop
pristine CNF and those subjected to heat, mechanical and formation is not arbitrary, but rather is based on the reg-
chemical treatments are compiled in Table 3. ularity in the various substructures of CNF. There is no

Table 3
Preparation conditions and some physical properties of platelet CNFs used in this study.

Samples XRD propertiesa Surface area (m2 /g)

d0 0 2 (nm) Lc (0 0 2) (nm)

Pristine CNF (PCNF) 0.3363 28 91

CNF graphitized at 2800 ◦ C (GPCNF) 0.3363 32 32
CNF subjected to graphitization and ball-milling for 72 h (GPCNF-M) 0.3360 40 45
CNF subjected to graphitization and 10% HNO3 treatment for 24 h (GPCNF-NA) 0.3356 137 66

Table reprinted with permission from Ref. [215], Copyright 2004 American Chemical Society.
a
d0 0 2 = interlayer spacing; Lc = the height of layered stackings.
800 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 16. HR-TEM images of (a) PCNF, (b) GPCNF, (c) GPCNF-M, and (d) GPCNF-NA.
Reprinted with permission from Ref. [215], Copyright 2004 American Chemical Society.
significant change in crystallite size owing to high temper-
ature graphitization owing to restriction imposed by the
decrease in interlayer spacing due to loop formation. The
interlayer spacing decreases significantly due to mechani-
cal distortion of the loops chemically removed due to local
strain and the resultant high reactivity in those regions.
It has been observed on heat treatment at 2800 ◦ C
VGCNFs undergo a structural modification, whereby the
conically nested graphene planes recrystallize into conical
crystallites in a discontinuous form. In spite of an inher-
ent increase in the crystallinity of the nanofibers, they fail
to impart optimum improvements in physico-mechanical
and electrical properties of the nanocomposites, with a
decrease in the longitudinal strength and electrical con-
ductivity of the heat-treated nanofibers. In order to prepare
composites with good electrical properties and mechanical
strength, the nanofibers were heat-treated at an optimum
temperature of 1500 ◦ C, to produce graphitization of the
external carbon layer along the nanofiber axis to the max-
imum extent [216]. However, this optimum temperature
may vary depending on the precise application.
2.3.3.2. Grafting of polymer chains on VGCNF. One criterion
for polymer nanocomposites to exhibit superior properties
is the proper dispersion of the nanofillers in the poly-
mer matrix. Due to their inherent strong van der Waals
attraction CNFs tend to agglomerate, resulting in improper
dispersion. Grafting polymer chain on the carbon nanofiber
surface significantly improves the extent of dispersion of
the nanofibers in the polymer matrices. VGCNFs possess
a significant fraction of surface H atoms attributed to sp3
C H and sp2 C H defects. Baek et al. [217] character-
ized this from the FTIR spectrum of VGCNF. Appearance
of the bands around 2900 cm−1 was due to C H stretch-
ing of the sp2 and sp3 carbon atoms due to the presence
of defects at the sidewalls and open ends of VGCNF.
These defects, in fact, provided the reactive sites for elec-
trophilic substitution reaction. The same group established
the viability of the surface functionalization of VGCNF
by Friedel-Crafts acylation with trimethylphenoxybenzoic
acid in PPA [217]. This was followed by in situ poly-
merization of 3-phenoxybenzoic acid on the surface of
the functionalized VGCNF. The resulting nanocomposites
showed improvement in oxidative thermal stability as well
as shift in Tg towards high temperature. For ∼10 wt% of CNF
in the polymer grafted system, DSC showed an increase
of Tg from 136.6 ◦ C to 143.7 ◦ C. Moreover, TGA showed an
increase in Td5% from 414 ◦ C to 430 ◦ C for 10 wt% in air.
Arlen et al. [218] functionalized CNFs by introducing aro-
matic amine groups on the filler surface via Friedel-Crafts
acylation reaction with 4-(3-aminophenoxy) benzoic acid,
followed by grafting of polyimide chains. Surface function-
alized CNF based nanocomposites showed three orders of
reduced dc conductivity compared to pristine CNF based
nanocomposites. This reduced conducting nature of the
nanocomposites originated from the restricted CNF–CNF
interaction induced by the surface grafted polymer chains.
2.3.3.3. Plasma treatment of VGCNFs. VGCNFs grown from
vapor phase are promising candidates as reinforcing fillers
provided proper dispersion is achieved. Plasma treatment
introduces nitrogen and oxygen containing functional
groups on the surfaces, thereby increasing the surface
energy, which facilitates good dispersion of the nanofibers
in the polymer matrix and hence improves various proper-
ties of the nanocomposites due to stronger polymer–filler
interface formation. Heintze et al. [219] carried out the
plasma treatment of VGCNF in two different reactors,
varying the means of fluidizing of VGCNF: vibrating bed
reactor (mechanical vibration) and fluidized bed reactor
(gas stream). Ar O2 and Ar CO2 were each used gas mix-
tures, both in the ratio of 1:1, in the pressure range of
0.1–40 mbar. The plasma power was 80 and 150 W and the
treatment time was varied from 5 to 40 min. In both the
cases, surface energy was found to increase after a treat-
ment time of 5 min, followed by slight decrease at 40 min.
On the other hand, Bruser et al. [220] tried to manipulate
the surface wettability of VGCNF by treatment in RF plasma.
VGCNFs were subjected to surface modification by treat-
ment with nitrogen and oxygen containing plasma gases.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 17. HRTEM images of interfaces of (a) coated CNF with PS and (b)
uncoated CNF with PS.
Reprinted with permission from Ref. [222], Copyright 1969 American
Institute of Physics.
It was found that water contact angle decreased on sub-
jecting the nanofibers to plasma treatment in ammonia,
O2 , CO2 , H2 O and formic acid. Moreover, this contact angle
is dependent on the process pressure. Increasing effective-
ness of different plasma gases was in the following order:
HCOOH < H2 O < CO2 < O2 . XPS analysis showed that O2 and
CO2 were more effective in increasing the concentration
of carboxylic acid and carbonyl groups of the nanofiber
surface than H2 O and formic acid.
He et al. [221] deposited an ultrathin 5 nm thick polymer
film on the surface of CNFs by plasma polymerization and
then incorporated these surface modified CNFs into poly-
carbonate matrix for reinforcement. They found that CNF
surface modification by plasma polymerization facilitated
better dispersion of the nanofibers compared to pristine
CNF, reflected in the mechanical properties of the com-
posites. For 1% filler loading, tensile strength and Young’s
modulus increased on increasing the ultrasonication time
0.5–2 h, but decreased on further ultrasonication. Thus, the
ultrasonication time had to be optimized to obtain full-
fledged improvement in the mechanical properties of the
nanocomposites. Similarly, Shi et al. [222] deposited an
ultrathin PS film (∼3 nm) on nanofiber surface and incorpo-
rated those in polystyrene matrix. Fig. 17 shows the HRTEM
image of a PS coated CNF based nanocomposite. While
the nanocomposites with uncoated CNF showed gradual
decrease in strength and modulus with increasing filler
loading, there was an increase up to 3 wt% filler loading
for nanocomposites with coated CNF. This difference in
strength of the nanocomposites was explained on the basis
of difference in state of dispersion of the nanofibers in the
polystyrene matrix.
801
In order to study the effect of plasma treatment of
CNF on field emission characteristics, Kimura et al. [223]
subjected CNF synthesized on an iron-evaporated Si sub-
strate by microwave plasma chemical vapor deposition
to N2 plasma treatment. The turn-on electric field was
decreased by the plasma treatment, along with improve-
ment in the stability of the electron emission current. CNFs
were treated with argon plasma in order to understand the
effect of plasma damage on field emission characteristics.
For low values of the field enhancement factor ␤ of the CNF,
the ␤ value remained almost same after Ar plasma treat-
ment. However, in the ␤ region above 1500, ␤ of the CNF
reduced after Ar plasma treatment. This suggests rupture
of the fine structure of the CNF on plasma treatment.
2.3.3.4. Other chemical modifications. The literature reveals
an abundant record of different chemical modifications
of CNFs and nanocomposites that have been synthesized
and characterized. These include oxidation, amination,
silanation, etc. Oxidation of VGCNF with HNO3 or (1:1,
HNO3 /H2 SO4 mixture) is generally effected prior to any
kind of chemical modification. Upon oxidation, oxygen
containing functionalities such as carboxyl, lactone, phe-
nol and carbonyl/quinone become predominant and the
oxygen content increases up to six times. According to
Sebastián et al. [224], oxidation does not significantly affect
the textural characteristics of the nanofibers except under
harsh treatment conditions. However, with 5% increase in
oxygen content, there was a tremendous fall in electronic
conductivity. For example, for one type of VGCNF, CNF1
(obtained at a temperature of 700 ◦ C under a flow of 4 L
(STP) g−1 cat h−1 of methane), the conductivity decreased
from 213 to 106 S m−1 for 1:1 HNO3 /H2 SO4 mixture at room
temperature and 20 S m−1 for HNO3 /H2 SO4 mixture under
boiling conditions. This was due to morphological destruc-
tion on imposing harsh reaction conditions.
There are numerous reports in the literature on the
surface modification of carbon nanofibers that explore
covalent or non-covalent type of interaction. Covalent
binding of small groups on the nanofiber surface facilitates
better wetting with the polymer and hence improves dis-
persion. With the same objective, Li and Coleman [225]
functionalized oxidized CNFs with a polyimide oligomer.
This work was pursued to enhance the length of the sur-
face functional groups, to increase compatibility of the
dispersed and continuous phases and to promote entangle-
ment between the surface bound oligomeric chains and the
polymer matrix. The oxidized nanofibers were covalently
attached to 1,4-PDA by two reaction pathways. The first
was direct reaction of the diamine in DMAc solution, while
the second exploited the acylation–amidation reaction. The
PDA modified nanofibers were subsequently reacted with
dianhydride end capped polyimide oligomer through an
imidation reaction. This affected the surface property of
CNFs as was evident from the suspension test in DMAc.
In the context of nanocomposite formation, Wang et al.
[226] pointed out the advantage of functionalization of
nanofibers in nanocomposite formation. They observed
that more VGCNF could be incorporated in the epoxy
matrix by functionalizing the surface of the nanofibers
with functionalities similar to the matrix. They successfully
802 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Fig. 18. (i) (a) Modulus and (b) strength of VGCNF/epoxy nanocomposites versus VGCNF contents (reprinted with permission from Ref. [226] Copyright
2010 Elsevier). (ii) TGA thermograms of functionalized VGCNF epoxy/at heating rate of 10 ◦ C/min (a) in air and (b) in nitrogen.
Reprinted with permission from Ref. [226] Copyright 2010 Elsevier.
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819 803

Fig. 19. Stress–strain curves of melt-pressed UHMWPE, oxidized

CNF/UHMWPE, and surface modified CNF/UHMWPE (with 0.2 wt% and
5 wt% modified CNF) films.
Reprinted with permission from Ref. [227], Copyright 2005 American
Chemical Society.

functionalized VGCNFs with 4-(3-aminophenoxy)benzoic

acid by Friedel Crafts acylation. This was followed by reac-
tion with epichlorohydrin and sodium hydroxide solution
which resulted in formation of N,N-diglycidyl-modified
VGCNF. Nanocomposites with functionalized CNF showed
improved mechanical (Fig. 18(i)) and thermal properties
(Fig. 18(ii)) compared to those prepared with pristine CNF.
A similar approach was adopted by Chen et al. [227].
Octadecylamine was grafted on the CNF surface via oxida-
tion with potassium chlorate-sulfuric acid solution. Though
the modified CNF/UHMWPE nanocomposites showed simi-
lar initial moduli, the modifications with 0.2 wt% UHMWPE
produced more than 10-fold increase in elongation at
break. In fact, 0.2 wt% amine grafted CNF based nanocom-
posites showed maximum improvement in tensile strength
and the toughness value was 16 times that of the unfilled
film (Fig. 19).
George and Bhowmick [228] subjected the CNFs to acid,
amine and silane treatments, as well as electron beam radi-
ation, and prepared EVA matrix based nanocomposites.
The results, shown in Fig. 20 gave a maximum improve-
ment in properties for silane treated and gamma-irradiated
CNF based nanocomposites. This was due to better dis-
persion of the fillers due to surface modification. In situ
polymerization of PDMS by anionic ring opening poly-
merization of octamethylcyclotetrasiloxane in presence of
amine modified CNF was carried out in our laboratory.
While improvements in tensile strength and tensile mod-
ulus were 370% and 515%, respectively, for 8 PHR amine
modified CNF loaded samples, these were, respectively,
132% and 105% for in situ prepared nanocomposites with
unmodified CNF at same filler loading. This was due to bet-
ter dispersion of the filler in the polymer matrix by amine
functionalization [229]. Xu et al. [230] employed free radi-
cal reactions to graft three different types of polymers by ␥
irradiation. While epoxy resin and chloro-epoxy propane
reacted with the nanofibers via co-irradiation grafting
(with the CNFs were immersed in the monomer followed
Fig. 20. Effect of (a) filler loading, (b) EB irradiation dose, and (c) gamma
irradiation dose on the mechanical properties of nanocomposites.
Reprinted with permission from Ref. [228] Copyright 2008 Springer.
by irradiation), acrylic acid was grafted by pre-irradiation
grafting method (with the nanofibers were subjected to
irradiation in vacuum prior to immersion in monomer). The
resulting nanocomposites exhibited improved physico-
mechanical properties owing to better interfacial adhesion.
There was a 17.5% increase in tensile strength for the
nanocomposites with treated CNF as compared to those
prepared with pristine CNF. A detailed investigation and
comparison of the effect of various types of CNF func-
tionalization upon different polar and non-polar polymer
matrices is summarized in Table 4.
In the recent years, novel surface modifications of CNFs
have been pursued by various groups. For example, Ghis-
landi et al. [244] carried out ATRP on the surface of
chemically functionalized VGCNFs to prepare poly(tert-
butyl acrylate)/CNF nanocomposites. The nanocomposites
showed improved thermal properties and solubility in
organic solvents. On the other hand, Mapkar et al.
[245] prepared highly thermally stable nanocomposites
by exploring carbodiimide chemistry. CNF was function-
alized with various organic amines such as aminopropyl
 804
Table 4
Preparation and properties of functionalized carbon nanofibers/polymer nanocomposites.

Matrix CNF Technique Loading Tensile strength Tensile modulus Electrical Electrical Maximum Storage Reference
(wt%) increment (%) increment (%) resistivity conductivity weight loss modulus
( cm) (S cm−1 ) temperature increment (%)
(◦ C)
PEI Pristine Melt mixing 1 10 45 [231]
PEI Oxidized Melt mixing 1 −1.6 26 [231]
PEI Pristine Melt mixing 3 7.18 × 1010 [231]
PEI Oxidized Melt mixing 3 109 [231]
Epoxy Pristine Solution mixing 1 70 [232]
Epoxy Oxidized Melt mixing 0.1 17 (flexural strength) 23 (flexural modulus) 17 [233]
Epoxy Amine functionalized Solution mixing 1 100 [232]
Epoxy – Melt mixing 6.71 × 10−15 [234]
Epoxy Pristine Melt mixing 3 45 3.44 × 10−4 [234]
Epoxy Amine functionalized Melt mixing 3 61 2.69 × 10−3 [234]
Epoxy Pristine Solvent mixing, high 0.5 74 [235]

N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

shear mixing
Epoxy Oxidized Solvent mixing, high 0.5 57 [235]
shear mixing
Epoxy Amine functionalized Solvent mixing, high 0.5 104 [235]
shear mixing
Epoxy Amine functionalized Mechanical mixing 12.8 260 3.19 × 10−2 [236]
s-PS Pristine Melt mixing 3.1 109 394 15 [237]
s-PS Oxidized Melt mixing 3.1 5.76 × 108 404 20 [237]
PLA Pristine Melt mixing 7 3.98 (flexural strength) 35.4 (flexural modulus) [238]
PLA PLA grafted Melt mixing 3 7.03 (flexural strength) 25.4 (flexural modulus) [238]
PP Pristine Melt mixing 5 7.25 × 1016 [239]
PP Nitric acid (11.2 N) Melt mixing 5 1.12 × 108 [239]
treated
PET Pristine Ball milling followed 5 −23 10 [240]
by melt mixing
PET Heat treated at 3000 ◦ C Ball milling followed 5 −2 10 [240]
by melt mixing
PP Pristine Extrusion 5 15 40 1.0 × 1010 [241]
PP Oxidized followed by Extrusion 5 10 53 5.5 × 1010 [241]
Diels–Alder adduct
formation with
1,3-butadiene
PP Adduct via 1,3-dipolar Extrusion 5 11 29 1.2 × 1011 [241]
cycloaddition
PP+PP-g-MAH Pristine Extrusion 5 12 41 1.0 × 1010 [241]
PP+PP-g-MAH Oxidized followed by Extrusion 5 10 55 2.5 × 1010 [241]
Diels–Alder adduct
formation with
1,3-butadiene
PP+PP-g-MAH Adduct via 1,3-dipolar Extrusion 5 7 33 1.1 × 1010 [241]
cycloaddition
PDMS Pristine In situ 1 10−10 [242]
polymerization
PDMS Amine modified In situ 1 10−8 [242]
polymerization
PA6 Pristine 3 8 3 [243]
PA6 1,3-Dipolar adduct of N- 1,3-Dipolar 3 50–75 15 [243]
benzyloxycarbonylglycine cycloaddition
and paraformaldehyde
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 21. Various modifications of graphite [249–268].
terminated polydimethylsiloxane. These and several other
modifications have been carried out with CNF includ-
ing the grafting of PS chains on the nanofiber surface
through a methacylate moiety [246] and the introduction
of hyperbranched polymer chains on the oxidized surface
of CNFs through cationic polymerization of glycidol [247].
However, the physico-mechanical properties of these new
generation materials need to be explored.
2.4. Modified graphite/polymer nanocomposites
Since we reviewed the polymer graphene nanocompos-
ites in a previous publication [248], they are not included
here. Various forms of graphite available are categorized as
(a) exfoliated graphite, (b) graphite oxide (GO), (c) chem-
ically reduced graphene (CRG), and (d) thermally reduced
graphite oxide (TRG). The various forms of modifications of
graphite are shown in Fig. 21.
Some typical modifications along with their uses in
nanocomposite preparation are shown in Table 5.
2.5. Modifications of fullerene
2.5.1. Introduction to fullerenes
Kroto et al. discovered Buckminsterfullerene C60 at Rice
University in 1985 [282]. Though disputed, reports are
there of meteorite samples containing fullerenes [283].
Mass spectroscopy reveals that cyclodehydrogenation of
polyarene results in the formation of C60 [284]. Subse-
quently, many successful attempts have been made by var-
ious research groups to synthesize [36]fullerene [285] and
[60]fullerene [286] in the gas phase. Since then researchers
have strived to elaborate the intricacy of fullerene
structure and its properties. Structurally, fullerene is
rigid with 12 pentagons and 20 hexagons constituting
805
a single C60 molecule with a hybridization of sp2 for all
the C atoms and a C C bond length of 1.46 angstrom
[287,288]. It follows the Euler theorem of spherical net-
work closure where the pentagons are responsible for the
formation of curvature in the fullerene structure [289]. In
terms of stability, the first member is C60 . Next comes the
higher homologue C70 followed by C76 , C78 , C80 , C82 , C84 ,
etc. [290]. In terms of addition reactions, it shows some
similarity to olefins. Though structural analysis reveals
high stability, yet fullerene was found to be very reactive
and hence this led the beginning of a new chemistry which
is still being explored. With the availability of C60 and C70
in macroscopic quantity, characterization of the fullerene
soot revealed chirality of fullerenes. For instance, C76 was
found to be D2 symmetric [291] while D3 symmetry was
observed in C78 [292]. With time, production of fullerene
has increased with the aid of innovative technology.
Recently, a Japanese company is capable of producing tons
of fullerenes by burning toluene [293].
2.5.2. Surface modifications of fullerene
The literature describes a variety of chemical methods to
produce novel composite materials with unusual proper-
ties by attaching polymeric moieties to fullerene. These are
pursued in order to impart excellent properties of fullerene
(mechanical, thermal and electrical) to the polymer matri-
ces in nanocomposites. The modification of fullerenes
through chemical reactions may produce fullerene con-
taining main chain polymers, side chain polymers and
polymers with different molecular architectures, some of
which are schematically represented in Figs. 22–25.
Side chain fullerene polymer synthesis was initiated
by Shi et al. [294] in the preparation of fullerene con-
taining the polyurethane or polyester by polycondensation
806 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Table 5
Preparation and properties of various modified graphite based nanocomposites.

Nanocomposite Filler volume (%) Mode of Properties Reference

preparation

GO/PVA 2.5 Solution mixing Tensile modulus measured gives 128% increase. [269]
GO/PVA Solution casting Tensile modulus Tensile strength
increase (%) increase (%)
0.49 62 76 [270]
GO/PCL 2.4 Solution casting 108 36 [271]
TRG/NR 1.2 Solution/melt Modulus increase% [272]
750
Silicone foam 0.12 In situ 200 [273]
polymerization
Acid functionalized TRG/PVA 0.4 Solution mixing 35 [274]
CRSG/TPU 0.5 Solution mixing 120 [275]
AIG/PAN 2.1 Electrospinning, 100 [276]
solution mixing
Nanocomposite Mode of preparation Electrical percolation threshold (vol%) Reference

TRG/PC Melt compounding 0.6 [277]

GO/PMMA In situ polymerization 1.6 [278]
TRG/PEN Melt mixing 0.5 [279]
TRG/PVDF Solution blending 1.6 [280]

Nanocomposite Mode of preparation Graphene (vol%) Permeable to Relative permeability reduction (%) Reference

TRG/TPU Melt mixing 1.6 Nitrogen 52 [281]

Solution casting 1.6 81
In situ polymerization 1.5 71
iGO/TPU Solution mixing 1.6 94–99
GO/TPU In situ polymerization 1.5 62

reaction shown in Fig. 22. This was followed by the syn-
thesis of various side chain based fullerene polymers
by different groups through manipulation of the reac-
tion conditions and reagents to functionalize fullerenes
[295–297]. For example, some utilized reactions with
amino terminated polymer and nitrogen bridging through
azidomethyl units by Hawker’s method [298–303]. Side
chain polymers were also obtained by polymerization
of fullerene containing methacrylate monomers [304].
Fullerenated polymers have been prepared by cycload-
dition of C60 and benzocyclobutenone containing PS
copolymer and PDMS grafted with C60 were successfully
synthesized and characterized [305,306]. Chemically func-
tionalized fullerenes were grafted to polymeric moieties
through cycloaddition reaction in the presence of a Lewis
acid catalyst (fullerenated polycarbonates) [307,308], as
shown in the scheme of Fig. 24. Likewise, attachment
of fullerenes to polythiophenes by the same principle
provided a polymer with enhanced processability for
polymeric photodiodes [309]. Polymeric carbanions have
also been prepared to react with fullerene to generate
side chain fullerene based polymer composites. Based
on organometallic reactions, fullerenated polystyrene,
poly(bromostyrene) and poly(vinylbenzylchloride) were
synthesized and microstructures of the polymers were
determined by the geometry of the fullerene group which,
in turn, resulted in abrupt changes in properties of the
nanocomposites [310–312]. In another case, C60 moieties
were successfully attached to the 1,4-polydienes through
carbanionic intermediate as evident from Fig. 25 [313,314].
A structurally distinct class of polymers, namely the
main chain fullerene based polymers have been obtained
primarily by free radical polymerization [315], cycload-
dition [316] and polycondensation reaction [317]. Free
radical nitroxyl-mediated polymerization of PS-TEMPO
with C60 resulted in a well-defined nanocomposite with
narrow polydispersity [315]. Main chain fullerene polymer
formation through cycloaddition is exemplified by reac-
tion of fullerene with bis-anthracene [316]. The scheme
in Fig. 23 shows functionalized fullerenes incorporated in
PDMS main chain. The resulting nanocomposites showed
high thermal stability and good film forming property
[306].
Radical polymerization of a group of reactive monomers
in the presence of fullerene often ends up in star-shaped
fullerene polymers. A star-shaped fullerene containing
polymer was synthesized by radical polymerization of
styrene with fullerene in the presence of a radical generator
[318]. Similar star-shaped polymers have been synthesized
by polycondensation reaction, e.g., polycondensation of
fullerenol with polyurethane [319] and by grafting living
anionic polymers to fullerene [320].
Besides these, fullerene chemistry also shows a dis-
tinctly unique class of polymers known as fullerene
endcapped polymers. The literature reveals that fullerene
endcapped polystyrenes [321,322], PPB [323], TEMPOL ter-
minated PS [324], PMMA [325], OPV [326], PEOs [327,328],
oligothienylenevinylenes [329], with well-defined molec-
ular weight and narrow molecular weight distribution have
been prepared by various methods.
2.5.3. Nanocomposites with modified fullerenes
Due to its limited availability, applications based on the
extraordinary properties of exquisite fullerene remain par-
tially explored. However, this limitation can be overcome
by the preparation of nanocomposites with fullerene as one
of the components since the hybrid materials exhibit simi-
lar properties to those of fullerene. In fact, several matrices
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 22. Polyester and polyurethane derivatives of C60 .
have been used to prepare nanocomposites, including
polyethylene [305], polystyrene [330], acrylic [331–334] or
vinyl polymers [335], polyimide [336,337], etc. However,
very few investigations have been carried out on modified
fullerene based nanocomposites.
Woźniak-Braszak et al. [338] prepared decylamine-C60
and tetracyanoethylene-C60 by cycloaddition reaction
with n-decylamine (DA) or tetracyanoethylene oxide
(TCNEO). Nanocomposites were synthesized following the
principles of the Olah method using a AlCl3 catalyst. While
virgin PBT showed a Tg of 326 K in DSC studies, a shifts in
Tg were observed for both the nanocomposites (Tg = 334 K
for PBT/DA/C60 0.1 wt% and Tg = 337 K for PBT/TCNEO/C60
0.1 wt%). Moreover, the percentage crystallinity of the
PBT/DA/C60 nanocomposites was higher than that with
TCNEO/C60 . Solid state 1 H NMR showed longer correlation
times and higher activation times for molecular motion,
suggesting slower and restricted motion of the molecular
chains in the nanocomposites. Proton spin-diffusion data
indicated that the domain size of the mobile phase at
303 K was larger for PBT/DA/C60 nanocomposites than
for PBT/TCNEO/C60 . Fullerenated polycarbonates were
prepared by direct reaction of TCNEO-C60 with PCs by
using AlCl3 catalyst. These nanocomposites showed high
807
thermal stability, with no weight loss below 350 ◦ C in
nitrogen atmosphere. The 30–40 ◦ C of Tg to lower tem-
perature side than PCs owing to chain cleavage during
reaction. Moreover the nanocomposites exhibit better
optical properties than the virgin polymer [307,308].
Polymer nanocomposites with functionalized
fullerenes find use in polymer photodiodes. For example,
Ferraris et al. [303] and Zhang et al. [309] designed meth-
ods to attach fullerenes to polythiophene derivatives to
facilitate good processing characteristics for polymeric
photodiodes. Wakai et al. [339] grafted PEO chains to
fullerenes by reaction with a macroazoinitiator with a
poly(ethyleneoxide) unit (azo-PEO). The thermal decom-
position temperature Td increased by more than 100 ◦ C
compared to the azo-PEO. The grafting process facilitated
improved solubility of fullerene in different solvents such
as water, methanol and THF. In another case, Ouyang et al.
[340] hydroxylated fullerene to fullerenol with 11 hydroxyl
groups attached to the C60 core. Fullerenol/PDMS-di-NH2
nanocomposites were prepared by solution casting. The
two depolymerizing peaks at 424 ◦ C and 589 ◦ C for virgin
PDMS increased to 574 ◦ C and 640 ◦ C for the nanocompos-
ites with ( OH/ NH2 ) molar ratios 0.75:1, 1:1 and 2:1. DSC
studies showed a shift of the Tg for the nanocomposites
808 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Fig. 23. Synthesis of polysilicones modified with C60 units.

from ∼−121 ◦ C (neat) to ∼−119 ◦ C, ∼−118 ◦ C, and −117 ◦ C
for mole ratios (1:1), (2:1) and (4:1), respectively. In TMA
studies, the thermal penetration increased from −41 ◦ C for
PDMS-di-NH2 to 0 ◦ C and 41 ◦ C for OH/NH2 molar ratio of
0.75:1 and 1:1, respectively. In addition, a high fraction
of nanofiller in the nanocomposite led to an increase in
permittivity with a simultaneous decrease in loss factor.
In viscoelastic studies, G > G for frequencies above 1 rad/s
was observed for compositions with lower fullerenol
content, whereas G exceeded G for frequencies below
50 rad/s for higher filler showing that elastic response
dominated over viscous response at high filler concentra-
tion. However, the storage modulus increased more than
ten-fold with increasing nanofiller concentration.
Functionalized fullerene-based polymer nanocompos-
ites exhibit enhanced properties of photoconductivity,
fluorescence and chemiluminescence. Li et al. [341] syn-
thesized 1,2-(1 ,1 ,2 ,2 -tetracyanomethanoxymethano)
[60]fullerene by reaction of fullerene with TCNEO. It
displayed stronger electron accepting ability than pristine

Fig. 24. Synthesis of polycarbonates with a fullerene derivative.

 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 25. Grafting reaction of fullerene to the polydiene backbone.
fullerene. The photoconductivity of this fullerene deriva-
tive based PVK nanocomposite was higher than unmodified
fullerene based PVK nanocomposites. Kasai et al. [342],
on the other hand, synthesized fluoroalkyl endcapped co-
oligomers having fullerene in the main chain by reacting
fluoroalkanoyl peroxides with fullerenes and various other
monomers, such as acrylic acid, N,N-dimethylacrylamide
polymerizable through radical pathway. These materials
showed fluorescence similar to fullerene, and led to
an increase in chemiluminescence intensity compared
to the fluorinated acrylic homoligomers. Yoshino et al.
[343] attached fullerene to the conjugated poly(2,5-
dialkoxy-p-phenylene vinylene) and thereby produced
new photoconductive materials which facilitated associ-
ation of the donor and acceptor counterpart. Chen et al.
[311] found that attaching C60 to the PBS chain using
carbanions on the polymer chain (Fig. 26) resulted in an
increase in Tg from ∼83 ◦ C (PBS) to 134 ◦ C owing to the
restriction imposed upon the PBS macromolecular chains
due to steric effect of the C60 unit. However, thermal stabil-
ity did not change much for the nanocomposites. Thermal
stability improved dramatically for C60 /PS prepared by the
same procedure (∼433 ◦ C for C60 /polystyrene compared
809
to ∼417 ◦ C for neat PS) [310]. In a similar way, the same
group prepared C70 /poly(N-vinylcarbazole) by covalently
linking C70 to the macromolecular unit. The temperature
for the onset of degradation increased from ∼449 ◦ C for
the polymer to ∼459 ◦ C for the C70 based nanocomposite
[312].
Dai et al. [313] investigated the lithiation of polydi-
enes followed by attachment to fullerene. DSC studies of
these fullerene modified polydienes showed increased Tg
by 10 ◦ C for C60 grafted cis-1,4-polybutadienes and by 75 ◦ C
for cis-1,4-polyisoprene. Improvement in thermal stability
of the fullerene modified polydienes was noteworthy.
Grafted fullerene based nanocomposites are suitable
for advanced applications such as photovoltaic cells and
laser applications. In this connection, some novel pieces
of work include those of Yu et al. [344] and Tang et al.
[323]. Yu et al. [344] prepared nanocomposite films from
MEH-PPV and fullerene or its derivatives and fabricated
them in polymer photovoltaic cells with improved carrier
collection efficiency (c ) and energy conversion efficiency
(e ). Thus, a c of about 29% of electrons per photon and
e of about 2.9% was found for the composite films, both
much better than the devices with unfilled MEH-PPV. An
 810
Table 6
Preparation and properties of functionalized fullerene based polymer nanocomposites.

Polymer moiety Nanoparticulate PDI Mode of Temperature of Glass transition Reference

formation/reagents maximum degradation temperature (◦ C)
used (◦ C)

Four armed PS moiety with bromine functionality – 1.18 ∼400 100.5 [345]
Four armed PS moiety with bromine functionality Fullerene 1.48 ATRA ∼400 103.3 [345]
Four armed PMMA moiety with bromine functionality – 1.35 ∼330 120.7 [345]

N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819

Four armed PMMA moiety with bromine functionality Fullerene 1.38 ATRA ∼300 122.9 [345]
SPEI – 280 [346]
SPEI Polyhydroxylated fullerene 380 [346]
Maleimide–thiophene copolymers – 1.93 303 86 [347]
Maleimide–thiophene copolymers PCBM 1.88 335 96 [347]
PCL POSS 1.2 Ring opening <350 [348]
polymerization
PCL POSS, fullerene – Ring opening ∼400 [348]
polymerization
followed by reaction
with chlorobutyryl
chloride and pyridine
in dry
dichloromethane;
sodium azide and
tetrabutylammonium
iodide in dry DMF;
fullerene in
chlorobenzene
iPP – 313 [349]
iPP Fullerene Free radical 428 [349]
polymerization
Polysulfone – 3.8 550 189 [350]
Polysulfone Fullerene 4.7 Electrophilic 559 187 [350]
substitution, AlCl3
catalyst
Polysulfone Fullerene 4.4 Mechanical mixing 557 187 [350]
Polydimethylsiloxane with (3-carboxypropyl)methylsiloxane unit – Solution mixing −66 [351]
Polydimethylsiloxane with (3-carboxypropyl)methylsiloxane unit MPF Solution mixing −64 [351]
 N. Roy et al. / Progress in Polymer Science 37 (2012) 781–819
Fig. 26. Synthesis of fullerene grafted polystyrenes. Here A = Br, B = C60
[311]; A = H, B = C60 [310].
efficient initiator for phenylalkyne polymerization was
synthesized by addition of C60 to WCl6 Ph4 Sn, to give
up to 99.5% yield of a high molecular weight polymer
with a broad PDI (larger than 2.2). Multiple addition of
poly(1-phenyl-1-butyne) (PPB) chains to the C60 cage
leads to much higher molecular weight of the polymer
than that obtained by normal polymerization. These star
shaped polymers emit blue light, thereby effectively atten-
uating the power of a pulsed laser beam [323]. A detailed
analysis of various nanocomposites prepared using mod-
ified fullerene and various polar and non-polar polymer
matrices and their properties are compiled in Table 6. The
information in the table shows that not much work has
been done on functionalized fullerene/polymer nanocom-
posites. Moreover, the work reported does not give any
detailed characterization of the physico-mechanical
properties of the nanocomposites. Current trends in
fullerene chemistry involve nanocomposite preparation
by attaching novel polymer moieties through advanced
polymerization mechanism. These include the synthesis of
C60 attached to dendrionized norbornene derivatives with
reactive surface azide groups via ring-opening metathesis
polymerization (ROMP) [352], the esterification reaction
between dendritic alcohol and fullerene modified with
acyl chloride [353], and the attachment of fullerenes with
a) polymer of 1,3-cyclohexadiene through living anionic
811
polymerization [354] or b) amphiphilic coil-rod-coil tri-
block copolymer poly(2-vinylpyridine)-b-poly(n-hexyl
isocyanate)-b-poly(2-vinylpyridine) [355]. Besides these,
click chemistry has been used to synthesize exquisite
nanocomposite materials consisting of fullerene attached
to various reactive homo and co-polymers [356,357]. How-
ever, the mechanical and dynamic mechanical properties
of these elegant nanomaterials remain unexplored.
3. Toxicity of modified carbon nanomaterials
A cytotoxicity study of nanostructured carbon mate-
rials by Magrez et al. [358] revealed that CNTs are less
toxic than CNFs and carbon nanoparticles. At low con-
centration, the number of feasible cells reduced in the
order: CB > CNFs > CNTs. However, surface oxidation of
CNTs enhances the toxicity level leading to cell death.
4. Conclusions
Though various modifications have been carried out on
nanostructured carbon materials, their use in nanocom-
posites is a continuing demand for the advancing rubber
and plastic manufacturing industries. For instance, sev-
eral modifications of fullerenes have been carried out
for past few decades, but their incorporation in prop-
erty enhancement of nanocomposites has not yet been
achieved. Moreover, despite the awareness of DWNTs as
potential candidates for nanocomposite preparation, their
extensive use in the surface modified form is still to be
pursued. This gap needs to be bridged. However, it can
be anticipated that the availability of graphene will divert
attention on relevant applications in the future. Last but
not the least is the cost. In comparison to carbon-black, car-
bon nanotubes and graphenes are much costlier. This is the
biggest hurdle in the path of advancement of nanoscience
and nanotechnology. However, production scale-up will
soon put an end to this problem.
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