Progress in Polymer Science 35 (2010) 837–867

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Progress in Polymer Science

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

Polymer nanocomposites based on functionalized carbon nanotubes

Nanda Gopal Sahoo a , Sravendra Rana b , Jae Whan Cho b,∗ , Lin Li a,∗∗ , Siew Hwa Chan a
a
School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 Singapore, Singapore
b
Department of Textile Engineering, Konkuk University, Seoul 143-701, Republic of Korea

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

Article history: Carbon nanotubes (CNTs) exhibit excellent mechanical, electrical, and magnetic proper-
Received 5 August 2008 ties as well as nanometer scale diameter and high aspect ratio, which make them an ideal
Received in revised form 10 March 2010
reinforcing agent for high strength polymer composites. However, since CNTs usually form
Accepted 12 March 2010
stabilized bundles due to Van der Waals interactions, are extremely difficult to disperse
Available online 16 March 2010
and align in a polymer matrix. The biggest issues in the preparation of CNT-reinforced
composites reside in efficient dispersion of CNTs into a polymer matrix, the assessment of
Keywords:
the dispersion, and the alignment and control of the CNTs in the matrix. There are several
Nanocomposites
Carbon nanotubes methods for the dispersion of nanotubes in the polymer matrix such as solution mixing,
Mechanical properties melt mixing, electrospinning, in-situ polymerization and chemical functionalization of the
Functionalization carbon nanotubes, etc. These methods and preparation of high performance CNT-polymer
composites are described in this review. A critical comparison of various CNT functional-
ization methods is given. In particular, CNT functionalization using click chemistry and the
preparation of CNT composites employing hyperbranched polymers are stressed as poten-
tial techniques to achieve good CNT dispersion. In addition, discussions on mechanical,
thermal, electrical, electrochemical and optical properties and applications of polymer/CNT
composites are included.
© 2008 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
2. Functionalization of CNT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
2.1. Defect functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
2.2. Non-covalent functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
2.3. Covalent functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
2.4. Functionalization using click chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
3. Preparation methods of polymer/CNT nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
3.1. Solution mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
3.2. Melt mixing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
3.3. In-situ polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
4. Preparation of CNT nanocomposites using dendritic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
4.1. CNT nanocomposites via covalently functionalized CNT-dendritic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
4.2. CNT nanocomposites via non-covalently functionalized CNT-dendritic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852

∗ Corresponding author. Tel.: +82 2 450 3513; fax: +82 2 457 8895.
∗∗ Corresponding author. Tel: +65 67906285; fax: +6794 2035.
E-mail addresses: jwcho@konkuk.ac.kr (J.W. Cho), mlli@ntu.edu.sg (L. Li).

0079-6700/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2010.03.002
838 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867

5. Mechanical properties of polymer/CNT nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853

5.1. Polyurethane/CNT composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
5.2. Polyimide/CNT nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
6. Electrical conductivity of polymer/CNT nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
7. Optical properties of polymer/CNT nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
8. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
9. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859

1. Introduction Progress in polymer/carbon nanotube composite

Since the discovery of carbon nanotubes (CNTs) in
1991 by Iijima [1], they have received much attention for
their many potential applications, such as nanoelectronic
and photovoltaic devices [2,3], superconductors [4], elec-
tromechanical actuators [5], electrochemical capacitors
[6], nanowires [7], and nanocomposite materials [8,9]. Car-
bon nanotubes may be classified as single-walled carbon
nanotubes (SWNTs) [10,11], double-walled carbon nan-
otubes (DWNTs) [12,13] or multi-walled carbon nanotubes
(MWNTs) [1]. SWNT and DWNT comprise cylinders of one
or two (concentric), respectively, graphene sheets, whereas
MWNT consists several concentric cylindrical shells of
graphene sheets. CNTs are synthesized in a variety of ways,
such as arc discharge [10], laser ablation [14], high pres-
sure carbon monoxide (HiPCO) [15], and chemical vapor
deposition (CVD) [16,17]. CNTs exhibit excellent mechani-
cal, electrical, thermal and magnetic properties [18,19]. The
exact magnitude of these properties depends on the diam-
eter and chirality of the nanotubes and whether they are
single-walled, double-walled or multi-walled form. Typical
properties of CNTs are collected in Table 1 [20–25].
Because of these excellent properties, CNTs can be used
as ideal reinforcing agents for high performance polymer
composites. Ajayan et al. [26] reported the first polymer
nanocomposites using CNTs as a filler. The number of arti-
cles and patents in polymer composites containing CNTs
is increasing every year [27]. Various polymer matrices
are used for composites, including thermoplastics [28–30],
thermosetting resins [31,32], liquid crystalline polymers
[33,34], water-soluble polymers [35], conjugated polymers
[3], among others. The properties of polymer composites
that can be improved due to presence of CNTs include ten-
sile strength [36,37], tensile modulus [38,39], toughness
[40], glass transition temperature [41,42], thermal con-
ductivity [43,44], electrical conductivity [45,46], solvent
resistance [47], optical properties [48,49], etc.
Table 1
Typical properties of CNTs [20–25].
Property SWNT
Tensile strength (GPa) 50–500
Elastic modulus (TPa) ∼1
Elongation at break (%) 5.8
Density (g/cm3 ) 1.3–1.5
Electrical conductivity (S/m)
Thermal stability
Typical diameter 1 nm
Specific surface area
research considered here will included studies on
functionalization of CNTs their mechanical, electrical
conductivity and optical properties, and applications of
polymer/CNT composites.
2. Functionalization of CNT
Since CNTs usually agglomerate due to Van der Waals
force, they are extremely difficult to disperse and align in
a polymer matrix. Thus, a significant challenge in devel-
oping high performance polymer/CNTs composites is to
introduce the individual CNTs in a polymer matrix in order
to achieve better dispersion and alignment and strong
interfacial interactions, to improve the load transfer across
the CNT-polymer matrix interface. The functionalization of
CNT is an effective way to prevent nanotube aggregation,
which helps to better disperse and stabilize the CNTs within
a polymer matrix. There are several approaches for func-
tionalization of CNTs including defect functionalization,
covalent functionalization and non-covalent functional-
ization [50]. These functionalization methods will be
summarized here.
2.1. Defect functionalization
CNTs are purified by oxidative methods to remove
metal particles or amorphous carbon from the raw mate-
rials [51,52]. In these methods, defects are preferentially
observed at the open ends of CNTs. The purified SWNTs
contain oxidized carbon atoms in the form of –COOH group
[53,54]. In this oxidizing method, SWNTs are broken to very
short tubes (pipes) of lengths 100–300 nm [55]. Mawhin-
ney et al. [56] studied surface defect site density on SWNTs
by measuring the evolution of CO2 (g) and CO(g) on heating
to 1273 K. The results indicated that about 5% of the car-
bon atoms in the SWNTs are localized at defective sites.
Acid base titration method [57] was used to determine
that the percentage of acidic sites of purified SWNTs was
about 1–3%. However, the defective sites created at the
CNT surfaces by this method are extremely sparse, and can
DWNT MWNT
not promote good dispersion in the polymer/CNT compos-
23–63 10–60 ites. However, they can be used for covalent attachment of
– 0.3–1 organic groups by converting them into acid chlorides and
28 –
1.5 1.8–2.0
subsequently reacting with amines to give amides [58,59].
∼106 The functionalized CNTs are more soluble in organic sol-
>700 ◦ C (in air) vents than the raw CNTs. Most of the SWNT bundles
∼5 nm ∼20 nm exfoliate to give individual SWNT macromolecules [8] if the
10–20 m2 /g
reaction time of acid chloride group with amines is at ele-
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867 839

Table 2
Non-covalent functionalization of CNTs.

Polymer or surfactant Nanotube type Preparation method References

Surfactants
Cationic (CTAB) SWNT Microemulsion [332]
Cationic (CTAB) SWNT Ultrasonication [333]
Cationic (CTVB) SWNT Sonication [334]
Cationic (MATMAC) MWNT Emulsion polymerization [335,336]
Anionic (SDS) MWNT Ultrasonication [61]
Anionic (SDBS) SWNT Ultrasonication [68,70]
Anionic (SDBS) SWNT Bath sonicaton [71]
Non-ionic (Triton X-100) MWNTSWNT Ultrasonication [337,338]
Non-ionic (Triton X-305) MWNT Ultrasonication [339]

Biomacro-molecules
Proteins/DNA MWNT Immobilization [64]
Glucose (Dextran) SWNT Dialysis [340]
ˇ-1,3-glucans SWNT Electroactive interaction [341]
Chitosan SWNT Ultrasonication [342]

Polymers
Poly(4-vinyl pyridine) SWNT Sol–gel chemistry [343]
Poly(phenyl acetylene) MWNT Solution mixing [344]

Poly(m-phenylenevinylene-co-2,5-dioctoxy-p-phenylenevinylene) MWNT Solution mixing [83]

SWNT [85]

Poly(styrene)-poly(methacrylic acid) SWNT Solution mixing [90]

MWNT

vated temperature for 4 days and these SWNTs are soluble
in organic solvents.
2.2. Non-covalent functionalization
Non-covalent functionalization of nanotubes is of par-
ticular interest because it does not compromise the
physical properties of CNTs, but improves solubility
and processability. This type of functionalization mainly
involves surfactants, biomacromolecules or wrapping with
polymers (Table 2). In the search for non-destructive
purification methods, nanotubes can be transferred to the
aqueous phase in the presence of surfactants [60,61]. In this
case, the nanotubes are surrounded by the hydrophobic
components of the corresponding micelles. The interac-
tion becomes stronger when the hydrophobic part of the
amphiphilic contains an aromatic group.
CNTs can be well dispersed in water using anionic,
cationic, and non-ionic surfactants [68–71]. Anionic sur-
factants such as sodium dodecylsulfate (SDS) [72–74] and
sodium dodecylbenzene sulfonate (NaDDBS) [75,76] are
commonly used to decrease CNT aggregation in water. The
interaction between the surfactants and the CNTs depends
on the nature of the surfactants, such as its alkyl chain
length, headgroup size, and charge. SDS has a weaker inter-
action with the nanotube surface compared to that of
NaDDBS and Triton-X100 because it does not have a ben-
zene ring. Indeed ␲-stacking interaction of the benzene
rings on the surface of graphite increases the binding and
surface coverage of surfactant molecules to graphite sig-
nificantly [71]. NaDDBS disperses better than Triton-X100
because of its head group and slightly longer alkyl chain.
Fig. 1 represents the adsorption of different surfactants
onto the nanotube surfaces.
Direct non-surfactant mediated immobilization of pro-
tein and DNA on CNTs has been reported [64]. The
hydrophobic regions of the proteins are probably impor-
tant for adsorption. A controlled and specific method for
immobilizing proteins onto non-covalently functionalized
SWNTs has been developed [62]. The mechanism of protein
immobilization on nanotubes involves the nueleophilic
substitution of N-hydroxysuccinimide by an amine group
on the protein. In this case, non-covalent functionaliza-
tion is accomplished by the interaction of delocalized
␲-bonds on the CNTs wall due to sp2 hybridization with
␲-bonds of polymer molecules of the matrix [62,63]. CNTs

Fig. 1. Schematic representation of how surfactants may adsorb onto the nanotube surface. Reprinted with permission from Ref. [71]. Copyright 2003,
American Chemical Society, USA.
840 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 2. A bundled pair of copolymer encapsulated SWNTs from unpurified material (a) and purified encapsulated SWNTs (b). Reprinted with permission
from Ref. [87]. Copyright 2003, American Chemical Society, USA.
can be successfully solubilized in organic [65] or aqueous
[66] solvents after non-covalent functionalization, partly
attributed to the much better coverage of functional groups
[67].
The dispersion of CNT in both water [77,78] and organic
solvents [79] may be enhanced by the physical associ-
ation of polymers with CNT. This can be explained by
the ‘wrapping’ mechanism [78] that attributed to spe-
cific interactions between the polymer and the CNTs.
Polymers can wrap around CNTs, forming supramolec-
ular complexes [80–82]. In these cases, ␲-stacking
interactions between the polymer and the nanotube sur-
face are responsible for the close association of the
structures. Blau and co-workers [83–86] prepared a
nanotube-polymer hybrid by suspended SWNTs in organic
solvents poly(p-phenylenevinylene-co-2,5-dioctyloxy-m-
phenylenevinylene) to wrap the copolymer around the
nanotubes. The electrical properties of these hybrids were
improved relative to those of the individual components. A
non-covalent method has been used to modify SWNTs by
encapsulating SWNTs within crosslinked and amphiphilic
poly(styrene)-block-poly(acrylic acid) copolymer micelles
(Fig. 2) [87]. This encapsulation significantly enhanced
the dispersion of SWNTs in a wide variety of polar and
non-polar solvents and polymer matrices because the
copolymer shell was permanently fixed. Thus, encapsu-
lated SWNTs may be stabilized with respect to typical
polymer processing and recovery from the polymer matrix.
Non-wrapping approaches have also been used for dis-
persion and solubility of CNT in different media [88,89]. In
these cases, copolymers of various different structures and
compositions act efficiently as stabilizers, and may be tai-
lored so as to disperse the tubes in a variety of solvents.
Nativ-Roth et al. [90] suggested that the block copolymers
adsorbed to the nanotubes by a non-wrapping mecha-
nism, and the solvophilic blocks act as a steric barrier that
leads to the formation of stable dispersions of individual
SWNTs and MWNTs above a threshold concentration of
the polymer. The strong ␲–␲ interaction between polymer
backbone and nanotube surface led to soluble SWNTs. The
main potential disadvantage of non-covalent attachment
is that the forces between the wrapping molecule and the
nanotube might be weak, thus as a filler in a composite the
efficiency of the load transfer might be low.
2.3. Covalent functionalization
Because of the ␲-orbitals of the sp2 -hybridized C atoms,
CNTs are more reactive than those with a flat graphene
sheet, they have an enhanced tendency to covalently attach
with chemical species [91]. In the case of covalent function-
alization, the translational symmetry of CNTs is disrupted
by changing sp2 carbon atoms to sp3 carbon atoms, and
the properties of CNT, such as electronic and transport
are influenced [92]. But this functionalization of CNT can
improve solubility as well as dispersion in solvents and
polymer. Covalent functionalization can be accomplished
by either modification of surface-bound carboxylic acid
groups on the nanotubes or by direct reagents to the side
walls of nanotubes (Table 3). Generally, functional groups
such as –COOH or –OH are created on the CNTs during
the oxidation by oxygen, air, concentrated sulfuric acid,
nitric acid, aqueous hydrogen peroxide, and acid mixture
[55,93]. The surface of the acid treated MWNTs indicates
the presence of some defects in the carbon–carbon bonding
associated with the formation of carboxylic acid groups on
the surface, while the raw MWNTs show uniform surfaces
and a clear diffraction pattern because of their perfect lat-
tice structure of carbon–carbon bonds (Fig. 3) [94–96]. The
number of –COOH groups on the surface of CNT depends
on acid treatment temperature and time, increasing with
increasing temperature [95]. The extent of the induced
–COOH and –OH functionality also depends on the oxida-
tion procedures and oxidizing agents [97]. Nanotube ends
can be opened during the oxidation process.
The presence of carboxylic acid groups on the nan-
otube surface is more convenient than others because a
variety of chemical reactions can be conducted with this
group. The presence of –COOH or –OH groups on the nan-
otube surface helps the attachment of organic [58,59,98]
or inorganic materials, which is important for solubiliz-
ing nanotubes. CNTs have been covalently functionalized
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867 841

Table 3
Covalent functionalization of CNTs.

Nanotube type Preparation approach Polymer/organic molecules Catalyst/reagent References

MWNT Grafting from (ROP) Poly(␧-caprolactone) Sn(Oct)2 [138]

MWNT Grafting from (ROP) Poly(L-lactide) Sn(Oct)2 [139]

SWNT Grafting from (ROP) Nylon-6 Sodium [125,126]

MWNT

MWNT Grafting from (ATRP) Poly(methyl methacrylate) AIBN [127]

MWNT Grafting from (ATRP) Polystyrene CuBr [129]
MWNT Grafting from (ATRP) Polystyrene Cu(I)Br/PMDETA [130]
MWNT Grafting from (ATRP) Poly(acrylic acid) Cu(I)Br/PMDETA [131]
MWNT Grafting from (ATRP) Poly(tert-butyl acrylate) Cu(I)Br/PMDETA [132]
MWNT Grafting from (ATRP) Poly(N-isopropylacrylamide) Cu(I)Br/PMDETA [133]
MWNT Grafting from (ATRP) Glycerol Monomethacrylate Cu(I)Br/PMDETA [136]

SWNT Grafting to Polyethylene glycol – [111,121]

MWNT

MWNT Grafting to Polyimide – [117]

SWNT Grafting to Poly(amido amine) – [122]
MWNT Grafting to Poly(␧-caprolactone)-diol – [345]

SWNT Grafting to Poly(vinyl acetate-co-vinyl alcohol) – [114]

MWNT

MWNT Grafting to Poly(2-vinyl pyridine) – [119]

SWNT Cycloaddition of azomethine ylides 3,4-dihydroxybenzaldehyde N-methylglycine [346]
MWNT Cycloaddition of azomethine ylides 7-bromo-9,9-dioctyl fluorine-2-carbaldehyde L-lysine [347]

SWNT Cycloaddition of azomethine ylides Amino-acid Paraformaldehyde [348]

MWNT

SWNT Cycloaddition of azomethine ylides Peptides, Nucleic acids R-NHCH2 COOH [349]
MWNT

MWNT [4 + 2] Cycloadditions 3,6-diaminotetrazine Temp. [350]

SWNT [4 + 2] Cycloadditions Triazolinedione Temp. [351]
SWNT [4 + 2] Cycloadditions 2,3-dimethoxy-1,3-butadiene Cr(CO)6 [352]

SWNT [2 + 1] Cycloadditions Alkyl azidoformate Nitrene [106]

Dipyridyl imidazolidene Carbene

SWNT [2 + 1] Cycloadditions Dichlorocarbene Carbene [353]

MWNT

SWNT [2 + 1] Cycloadditions PEG di-azidocarbonate ester Nitrene [354]

SWNT Radical additions Polystyrene Nitroxide [355]
SWNT Radical additions Methoxyphenylhydrazine Microwave [356]

with thiocarboxilic and dithiocarboxylic esters that help
crosslinking between CNTs [99]. CNTs can be functionalized
at end caps or at the sidewall to enhance their disper-
sion as well as solubilization in solvents and in polymer
matrices [91,100]. SWNTs were fluorinated at their side
walls by passing elemental fluorine at different temper-
atures [101]. The fluorinated SWNTs exhibited improved
solubility in isopropanol or dimethyl formamide by ultra-
sonication [102,103]. Fluorinated SWNTs may be converted
to side wall alkylated SWNTs by reaction with Grignard
reagent or alkyllithium compounds that are soluble in chlo-
roform [104]. SWNTs have also been solubilized by direct
functionalization of their side walls by nitrenes [105,106],
carbenes [106], and arylation [107,108].
Functionalization of CNTs with polymer molecules
(polymer grafting) is particularly important for process-
ing of polymer/CNT nanocomposites [109,110]. Two main
categories “grafting to” and “grafting from” approaches
have been reported for the covalent grafting of polymers to
nanotubes. The “grafting to” approach is based on attach-
ment of as-prepared or commercially available polymer
molecules on the CNT surface by chemical reactions, such
as amidation, esterification, radical coupling, etc. The poly-
mer must have suitable reactive functional groups for
preparation of composites in this approach. Fu et al. [111]
reported functionalization of CNTs by using “grafting to”
method. They refluxed CNTs containing carboxylic acid
groups with thionyl chloride to convert acid groups to
acylchlorides. Then, the CNTs with surface-bound acylchlo-
ride moieties were used in the esterification reactions
with the hydroxyl groups of dendritic poly(polyethylene
glycol) polymer. Another example of the “grafting to”
approach has been reported by Qin et al. [112]. They
grafted SWNTs with polystyrene (PS) with functional-
ized end groups PS (–N3 ), via a cycloaddition reaction.
Polymer grafted CNTs have been formed by covalently
attaching nanotubes to highly soluble linear polymers, such
as poly(propionylethylenimine-co-ethylenimine) (PPEI-EI)
via amide linkages or poly(vinyl acetate-co-vinyl alcohol)
(PVA-VA) via ester linkages [113,114]. The resulting PVA-
grafted CNTs were soluble in PVA solution and PVA-CNT
nanocomposites films showed very high optical quality
842 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 3. TEM pictures of raw MWNTs (upper) and surface-modified MWNTs (lower). Reprinted with permission from Ref. [95]. Copyright 2005, Wiley-VCH,
Germany.
without any observable phase separation. Many other lin-
ear polymers such as poly(sodium 4-stryrenesulfonate)
[115], poly(methyl methacrylate) (PMMA) [116], poly-
imide [117,118], poly-(2-vinylpyridine) [119], PPEI-EI
[120], and poly(m-aminobenzenesulfonic acid) [35] as
well as dendrons [121], dendrimers [122], and hyper-
branched polymers [123] have been successfully bonded to
CNTs.
A novel route to polymer reinforcement via preparation
of polymer-functionalized nanotubes using organometallic
approach has been reported [124]. In the work, CNTs were
first functionalized by organometallic n-butyl lithium, and
then covalently attached to a chlorinated polypropylene
via a coupling reaction. The main limitation of the “grafting
to” method is that the grafted polymer content is quite low
due to the relatively small fraction of active sites on the
CNT, and the depressing effects of steric hinderence in the
reactivity of polymer [123].
In the “grafting from” approach, the polymer is
bound to the CNT surface by in-situ polymerization of
monomers in presence of reactive CNTs or CNT sup-
ported initiators. The main advantage of this approach
is that the polymer-CNTs composites can be prepared
with high grafting density. This approach has been
used successfully to graft many polymers such as
polyamide 6 [125,126], PMMA [127,128], PS [129,130],
poly(acrylic acid) (PAA) [131], poly-(tert-butyl acrylate)
[132], poly(N-isopropylacrylamide) (NIPAM) [133], poly(4-
vinylpyridine) [134], and poly(N-vinylcarbazole) [135] on
CNT via radical, cationic, anionic, ring-opening, and con-
densation polymerizations. Gao et al. [136] described
the functionalization of MWNTs with a hydrophilic poly-
mer, glycerol monomethacrylate (GMA) by the “grafting
from” approach. In this work, the oxidized MWNTs
were treated with thionyl chloride, glycol, and 2-
bromo-2-methylpropionyl bromide to produce MWNT-Br
macroinitiators for the atom transfer radical polymeriza-
tion of GMA as shown in Scheme 1. The grafted polymer
content can be controlled by the feed ratio of monomer
to macroinitiators. The hydroxyl groups of the polyGMA
chains grafted on the MWNTs are highly active and can be
further converted to carboxylic acid groups. MWNTs were
covalently functionalized with poly(L-lysine) by a surface
initiated ring-opening polymerization method [137]. Zeng
et al. [138] reported “grafting from” approach based on
in-situ ring-opening polymerization of ␧-caprolactone to
covalently graft biodegradable poly(␧-caprolactone) onto
CNT surfaces. CNT-graft-poly(L-lactide) by using surface-
initiated ring-opening polymerization has been studied by
Chen et al. [139].
A few additional techniques for functionalization of
CNTs into polymer matrixes have been utilized. Yan et al.
[140] used Ar plasma for the generation of defect sites
in the SWNT caps and sidewalls, with subsequent UV-
grafting of 1-vinylimidazole from the defect sites. Yang et
al. [141] obtained soluble MWNTs via amidation reaction
of octadecylamine with purified MWNTs when they were
mixed with copolymers of methyl and ethyl methacrylate
(poly(MMA-co-EMA)).
2.4. Functionalization using click chemistry
“Click” chemistry, coined for the Huisgen [3 + 2] dipo-
lar cycloaddition reaction [142], is an ideal reaction for
material synthesis and modification and for self assembly
of nanomaterials. A Cu (I)-catalyzed Huisgen [3 + 2] dipo-
lar cycloaddition reaction between terminal alkynes and
azides resulting in the formation of 1,2,3-triazoles has been
utilized elegantly in recent years [143,144]. This reaction is
very useful for synthesizing small molecules [145], den-
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867 843

Scheme 1. Functionalization of MWNTs with PolyGMA by atom transfer radical polymerization. Reprinted with permission from Ref. [136]. Copyright
2005, American Chemical Society, USA.

drimers [146,147], dendronized polymers [148–150], and
biologically derived macromolecular structures [151]. Click
chemistry benefits by the facile introduction of azide and
alkyne groups into organic and polymer molecules, the sta-
bility of these groups to many reaction conditions, and the
tolerance of the reaction in presence of other functional
groups. The main advantages of click chemistry are its tol-
eration of other functional groups, a short reaction time,
and high yield, high purity, and regiospecificity, as well
as its suitability for use under aqueous conditions [152].
Azides and acetylenes are stable across a broad range of
organic reaction conditions and in biological environments,
yet they are highly energetic functional groups and the
products are screened directly from the reaction mixture
because no protecting groups are used. The triazole is used
as a rigid linker that can mimic the atom placement and
electronic properties of a peptide bond without the same
susceptibility to hydrolytic cleavage [153,154], as shown in
Scheme 2.
Apart from the synthetic promise, triazole moieties
are relatively stable to metabolic degradation and can
participate in hydrogen bonding, which may be useful
in the context of bimolecular targets and solubility, and
is extremely stable to hydrolysis, oxidation or reduction
[144]. Click chemistry may be an ideal modular method-
ology for the introduction of a wide variety of molecules
onto the surface of CNTs [155–157] as shown in Fig. 4. By
applying this approach, one can easily functionalize CNTs
with desired molecules, which enhance their importance
from nanoelectronics to nanobiotechnology.
An application of the Huisgen cycloaddition to the func-
tionalization of SWNTs with PS was reported by Adronov
and co-workers [155]. To achieve a high degree of function-
alization by using alkyne groups on the nanotube surface
with the Pschorr-type arylation, subsequent introduction
of PS was achieved by first installing azide functionality
at the polymer chain end. The Cu(I)-catalyzed formation
of 1,2,3-triazoles by coupling azide-terminated polymer
and alkyne-functionalized SWNTs was found to occur in
an efficient manner under a variety of favorable conditions.
This resulted in relatively high nanotube graft densities, full
control over polymer molecular weight, and good solubil-
ity in organic solvents. The grafted PS was further modified
via sulfonation and the sulfonated PS grafted CNTs were
highly soluble in aqueous medium and insoluble in organic
medium [158].
Cho and co-workers [156] focused on the covalent
attachment of bioactive molecules with SWNTs (Scheme 3).
The functionalization of the SWNTs was achieved by cova-
lently bonded organic molecules derived from amino acids
through click chemistry. The alkyne-functionalized SWNTs
were prepared by the treatment of p-amino propargyl
ether with SWNTs using a solvent free diazotization pro-
cedure to produce alkyne functionalized CNTs. In order

Scheme 2. The coupling of azides and alkynes created triazole linkages in absence and presence of Cu(I) catalyst, the useful topological and electronic
feathers with nature’s ubiquitous amide connectors. Reprinted with permission from Ref. [153,154]. Copyright 2002, Wiley-VCH, Germany and Copyright
2004, American Chemical Society, USA.
844 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867

Fig. 4. Typical scheme of click chemistry for functionalization of carbon nanotube [156].

to attach different azides derived from amino acids, a
series of well-defined chiral azides from corresponding
␣-amino acids were prepared. The alkyne functionalized
SWNTs in dimethylformamide (DMF)-pyridine-butanol
solution were treated with azide-functionalized amino
acid compound, followed by CuI, ascorbic acid and N,N -
diisopropylethylamine. The 1,2,3-triazole ring has been
utilized as a linker between the chiral molecules and
SWNTs, which can provide a new strategy for the attach-
ment of bioactive molecules like peptides, polysaccharides
and others [156]. They also functionalized SWNTs by
the covalent attachment of azide moiety containing
polyurethane (PU) with alkyne functionalized SWNTs using
click chemistry approach. The CNTs were functionalized
with PCL-based PU using click chemistry, followed by the
reaction of alkyne-decorated CNTs and azide-moiety con-
taining PCL-diol [159].
Hybrid materials based on CNTs and metal nanopar-
ticles are under consideration for major roles for several
applications, including catalytic, optical, electronic and
magnetic applications [160–162]. Gao and co-workers
[162] reported magnetic nanohybrids from magnetic
nanoparticles and polymer coated nanomaterials via a
Cu(I)-catalyzed azide alkyne cycloaddition reaction. The
nanohybrids were prepared from Fe3 O4 nanoparticles
and polymer coated MWNTs. The authors prepared con-
trolled size Fe3 O4 nanoparticles then functionalized with
azide moieties (Fe3 O4 -N3 ) and finally with alkyne moieties
(Fe3 O4 -Alk). MWNTs were separately modified with poly-
mer containing abundant azide groups (MWNT-pAz) and
polymer containing abundant of alkyne groups (MWNT-
pAlk). (Fe3 O4 -N3 ) and (Fe3 O4 -Alk) were coupled with
polymer coating nanotubes to give magnetic nanohy-
brids of MWNT-pAz@Fe3 O4 and MWNT-pAlk@Fe3 O4 ,
respectively. Fig. 5 presents the TEM images of both
MWNT-pAz and MWNT-pAlk, evenly decorated with
magnetic nanoparticles. Cho and co-workers [163] pre-
pared gold nanoparticles functionalized SWNTs using a
click chemistry approach. Gold nanoparticles containing
octanethiol were prepared by the reduction of tetra-
chloroauric acid using sodium borohydride in presence of
alkanethiol. The alkyl thiol protected gold nanoparticles
were further treated with azidoundecane thiol to yield
azide moiety containing gold nanoparticles, which were
reacted with alkyne functionalized SWNTs. Campidelli et
al. [157] decorated SWNTs with phthalocyanine using a
click coupling approach. The authors functionalized SWNTs
with 4-(2-trimethylsilyl)ethynylaniline in the presence of
isoamyl nitrite, which were then treated with azide moi-
ety containing Zinc-phthalocyanine (ZnPc) in the presence
of CuSO4 and sodium ascorbate to give the nanotube-
phthalocyanine hybrid. They also studied the photovoltaic
properties of synthesized materials and observed that the
photocurrent of SWNT-ZnPc was higher and more stable
and reproducible than that of pristine SWNTs.
Layer-by-layer (LbL) covalent functionalization of
MWNTs was achieved by Gao and co-workers [164].
The clickable polymer poly(2-azidoethyl methacry-
late) was synthesized by atom transfer radical
polymerization (ATRP) and another clickable poly-
mer poly(propargyl methacrylate) was synthesized by
reverse addition–fragmentation chain transfer (RAFT)

Scheme 3. Scheme of application of click chemistry for synthesis of bioactive molecule bonded SWNT. (a) (i) CbzCl, 2 M NaOH solution, 0 ◦ C, 2 h, then 2 M
HCl, pH 3, (ii) SOCl2 , MeOH, RT, 8 h (iii) NaBH4 (excess), MeOH, RT over night. (b) (i) TsCl (1.2 equiv.), Et3 N (1.3 equiv.), 0 ◦ C to RT 4 h (ii) NaN3 , DMSO:1,4-
dioxane, 80 ◦ C, 16 h, 78–81% yields in two steps. (c) CuI (0.15 M), ascorbic acid (0.08 M) and DIPEA (0.17 M) in DMF-pyridene-butanol, RT, 14 h, followed by
80 ◦ C for 4 h [156].
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 5. TEM images of (a) Fe3 O4 -N3 , (b and c) MWNT-pAlk@Fe3 O4 , (d) MWNT-pAz@Fe3 O4 . Reprinted with permission from Ref. [162]. Copyright 2009, The
Royal Society of Chemistry, UK.
polymerization. Both polymers were alternately coated
on alkyne-modified MWNTs using the reliable Cu(I)-
catalyzed Huisgen 1,3-dipolar cycloaddition reaction.
Poly(2-azidoethyl methacrylate) was clicked on the
preprepared alkyne-modified MWNTs as the first poly-
mer layer. Alkyne side groups containing poly(propargyl
methacrylate) were coated as the second polymer layer
via click coupling. Poly(2-azidoethyl methacrylate) was
clicked on the second polymer layer coated MWNTs,
and the residual clickable azido groups of third layer
coated MWNTs were further clicked with alkyne-modified
rhodamine B and monoalkyne-terminated PS. The post
modification supports the usefulness of functionalized
MWNTs as a nanoplatform for further molecular design
and material synthesis. Due to formation of a crosslinked
polymer network, the covalent linkage offers several
advantages, such as high stability and good control
over the quantity and thickness of the polymeric layers.
The authors also reported a clickable macroinitiator
for building the amphiphillic polymer brushes on CNTs
[165]. The azido and bromo groups functionalized CNTs
were prepared by the reaction of poly(3-azido-2-(2-
845
bromo-2-methylpropanoyloxy)propyl methacrylate with
alkynated CNTs. Both the ATRP and click coupling could
be achieved by a one pot procedure using bromo and
azido moieties as initiators for PS and PEG grafting (Fig. 6).
The reaction could be easily accomplished with SWNTs
and MWNTs using “grafting to” and “grafting from”
approaches for functionalization with multiple kinds of
polymers.
Functionalization of CNTs with stimuli-responsive
materials is expected to be useful for manufactur-
ing advanced biosensors and bioprobes [166]. Li and
co-workers [167] introduced an alkyne functionalized nan-
otube surface using a carbamate linkage. The azide moiety
containing a thermoresponsive diblock copolymer com-
posed of N,N-dimethylacrylamide (DMA) and NIPAM was
covalently attached with alkynated MWNTs via the Cu(I)-
catalyzed [3 + 2] Huisgen cycloaddition. The copolymer
containing hydrophilic DMA, as well as a smart NIPAM
block, is capable of forming micelles with response to
changes in the aqueous solution temperature. The micelles
size and transition temperature can be controlled through
NIPAM block length. Due to the higher azide concentra-
846 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867

Fig. 6. Synthesis of amphiphilic/Janus polymer brushes-grafted multiwalled and single-walled carbon nanotubes (MWNTs and SWNTs) by a combination of
click chemistry and atom transfer radical polymerization (ATRP) approach. Reprinted with permission from Ref. [165]. Copyright 2008, American Chemical
Society, USA.

tion on their periphery, micelles afford improved grafting
efficiency and solubility of nanotubes, compared to coils in
solution.
The oligosaccharide ˇ-cyclodextrin is well known
to encapsulate biological molecules in its hydrophobic
cavities in an aqueous solution, enhancing its utility as
a drug carrier and enzyme mimic. Zheng et al. reported
a ˇ-cyclodextrin-modified SWNT nanohybrid through
Huisgen cycloaddition [168]. Mono-6-(p-toluenesulfonyl)-
ˇ-cyclodextrin, prepared by reaction of ˇ-cyclodextrin
with p-toluenesulfonyl chloride, was treated with
sodium azide to convert it to an azide-functionalized
cyclodextrin. Purified SWNTs were reacted with p-(2-
propynyloxy)-benzenamine in o-dichlorobenzene (ODCB)
using a diazotization coupling procedure to produce
alkyne-functionalized SWNTs. The azide-functionalized
cyclodextrin was further reacted with alkynated SWNTs
via click coupling. The ˇ-cyclodextrin functionalized
SWNTs show good solubility in water, enhancing
their biological importance for drug delivery appli-
cations.
Though there are not so many examples of employ-
ing the click chemistry for CNT functionalization, related
papers are increasingly reported recently. Scheme 4 shows
the attachment of different functionalities on CNTs via click
coupling. The wide range of attached molecules enhances
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Scheme 4. The attachment of different functionalities on CNTs via click coupling.
the importance of click chemistry and opens the new vista
of CNTs based nanomaterials.
3. Preparation methods of polymer/CNT
nanocomposites
As emphasized in the preceding, the dispersion of CNTs
in polymer matrices is a critical issue in the preparation
of CNT/polymer composites. Better reinforcing effects of
CNTs in polymer composites will be achieved if they do
not form aggregates and as such, they must be well dis-
persed in polymer matrixes. Currently there are several
methods used to improve the dispersion of CNTs in poly-
mer matrices such as solution mixing, melt blending, and
in-situ polymerization method.
3.1. Solution mixing
In this approach, a dispersion of CNTs in a suitable sol-
vent and polymers are mixed in solution. The CNT/polymer
composite is formed by precipitation or by evaporation
of the solvent. It is well known that it is very difficult
to properly disperse pristine CNTs in a solvent by sim-
ple stirring. A high power ultrasonication process is more
effective in forming a dispersion of CNTs. Ultrasonic irradi-
ation has been extensively used in dispersion, emulsifying,
crushing, and activating the particles. By taking advan-
tage of the multi-effects of ultrasound, the aggregates and
entanglements of CNTs can be effectively broken down. For
example, Li et al. [169] used a simple solution–precipitation
technique to improve the dispersion of CNTs in a poly-
847
carbonate solution by sonication at a frequency of 20 kHz
for 10 min. They showed that the CNTs were uniformly
dispersed in polycarbonate matrix on its consolidation. In
this case, ultrasonic wave as well as mechanically stirring
played important roles in the formation of the composites
with a uniform particle size. The chemical effects of ultra-
sound are associated with the rapid (microsecond time
scale), violent collapse of cavitation bubbles created as
the ultrasonic waves pass through a liquid medium [170].
Sonochemical theory and the corresponding studies sug-
gested that ultrasonic cavitation can generate a high local
temperature of 5000 K and a local pressure of 500 atm
[171], which is a very rigorous environment. Safadi et al.
[172] dispersed MWNTs in PS using ultrasonication and
dismembrator at 300 W for 30 min. Uniform dispersions of
CNTs in PS were achieved by using sonication. Recently Cho
and co-workers successfully prepared PU/MWNTs com-
posites with better dispersion of CNTs up to 20 wt% in PU
[173]. In the research, the necessary weight fractions of
carboxylate MWNTs were first dispersed in DMF solution
under sonication at room temperature for 1 h using a high
power ultrasonic processor. Thereafter, PU was added into
this solution and stirred for 1 h. The mixtures were then
sonicated again for 1 h. The SEM photographs of the cross-
sectional fracture of composites of the achieved dispersion
for the investigated MWNTs are shown in Fig. 7. The homo-
geneous dispersion in the composites was achieved by the
addition of a higher amount of MWNT-COOH (20 wt%).
Using a proper surfactant is another efficient method to
disperse higher loading of nanotubes [70,174,175]. The
use of non-ionic surfactants such as polyoxyethylene-8-
848 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 7. SEM micrographs of PU/CNT composites: (a) 10 wt% pristine MWNT and (b) 20 wt% MWNT-COOH. Reprinted with permission from Ref. [173].
Copyright 2006, Wiley-VCH, Germany.
lauryl has been demonstrated to improve the dispersion
and strong interaction between MWNTs and epoxy resins
[42].
Barrau et al. [176] found that amphiphilic palmitic acid
facilitate an efficient dispersion of CNTs in an epoxy matrix.
The hydrophobic part of palmitic acid is absorbed onto
the nanotube surface, whereas the hydrophilic head group
induces electrostatic repulsions between nanotubes, pre-
venting their aggregation. The co-solvent also affects the
dispersion of nanotubes in polymer matrix. Recently, Cam-
poneschi et al. [177] reported on the use of trifluoroacetic
acid as a co-solvent for the dispersion of MWNTs in a
conjugated polymer poly(3-hexylthiophene), and PMMA
through a solution process. Scanning electron microscopy
(SEM), optical microscopy, and light transmittance studies
revealed that the better dispersion of CNTs in poly-
mer matrixes was obtained by using trifluoroacetic acid.
Many other polymer composites such as PU/CNT [178],
PS/CNT [179–181], epoxy/CNT [180,182,183], Poly(vinyl
alcohol)/CNT [184], P(MMA-co-EMA)/CNT [141], polyacry-
lonitrile/CNT [185], and polyethylene(PE)/CNT [186] have
been fabricated by this method.
3.2. Melt mixing
For solution mixing, the matrix polymer must be sol-
uble in at least one solvent. This is problematic for many
polymers. Melt mixing is a common and simple method,
particularly useful for thermoplastic polymers. In melt pro-
cessing, CNTs are mechanically dispersed into a polymer
matrix using a high temperature and high shear force
mixer or compounder [187]. This approach is simple and
compatible with current industrial practices. The shear
forces help to break nanotube aggregates or prevent their
formation. Zhang et al. [188] prepared nylon-6/MWNTs
composites containing 1 wt% MWNTs via a melt com-
pounding method using a Brabender twin-screw mixer.
SEM image showed a homogeneous dispersion of MWNTs
achieved through the matrix polymer, associated with
significant enhancements in mechanical properties. Boc-
chini et al. [189] fabricated MWNTs/linear low density
polyethylene (LLDPE) nanocomposites via melt-blending
using a Brabender Plasticorder internal mixer. MWNTs
dispersed in LLDPE delay thermal and oxidative degra-
dation with respect to that for virgin LLDPE. PE/MWNT
nanocomposites were prepared using twin screw melt
compounding [190]. Microscopic observations across the
length scales and X-ray diffraction measurements indicate
that the MWNTs are very well distributed and dispersed in
the PE matrix. Melt mixing has been successfully applied
for the preparation of different polymers-CNT compos-
ites such as polypropylene/CNT [191–193], high density
PE/CNT [194], polycarbonate/CNT [195–197], PMMA/CNT
[198–201], polyoxymethylene/CNT [202], polyimide/CNT
[203], PA6/CNT [204], etc. The disadvantage of this method
is that the dispersion of CNTs in a polymer matrix is quite
poor compared to the dispersion that may be achieved
through solution mixing. In addition, the CNTs must be
lower due to the high viscosities of the composites at higher
loading of CNTs.
3.3. In-situ polymerization
In this polymerization method, the CNTs are dispersed
in monomer followed by polymerization. A higher percent-
age of CNTs may be easily dispersed in this method, and
form a strong interaction with the polymer matrixes. This
method is useful for the preparation of composites with
polymers that can not be processed by solution or melt
mixing, e.g., insoluble and thermally unstable polymers.
Hu et al. [205] synthesized MWNT-reinforced polyimide
nanocomposites by in-situ polymerization of monomers in
the presence of acylated MWNTs, as shown in Scheme 5. In
this work, MWNTs were functionalized with acyl groups,
and then reacted with 3,3 ,4,4 -biphenyltetracarboxylic
dianhydride to form MWNT-poly(amic acid). The final
MWNT-polyimide nanocomposite films were obtained
by imidization of MWNT-poly-(amic acid) at 350 ◦ C for
1 h under vacuum. In this method, the CNTs were uni-
formly dispersed in polymer matrix. Recently, Cho et
al. fabricated MWNTs-reinforced polyimide nanocompos-
ites by in-situ polymerization using 4,4 -oxydianilline,
MWNT-COOH, and pyromellitic dianhydride followed by
casting, evaporation, and thermal imidization [206]. A
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Scheme 5. Outline of the preparation of MWNT-polyimide nanocom-
posite films. Reprinted with permission from Ref. [205]. Copyright 2006,
Wiley-VCH, Germany.
homogeneous dispersion of MWNT-COOH was achieved
in polyimide matrix as evidenced by scanning electron
microscopy (Fig. 8). This method has been widely used
for the preparation of PMMA-CNT composites [207–210].
Jia et al. [207] first synthesized PMMA by in-situ radical
polymerization method. They used free radical initiator of
2,21 -azobisisobutyronitrile, AIBN, to initiate open CNTs ␲-
bonds to participate in PMMA polymerization, forming a
strong interface between the CNTs and the PMMA matrix.
Other researchers used similar free radical initiator AIBN
to prepare SWNT-PMMA composites by in-situ polymer-
ization [127,211].
Conducting polymers are attached to CNTs surfaces
by in-situ polymerization to improve the processability,
and electrical, magnetic and optical properties of CNTs
[212–215]. Cho and co-workers [216] described a simple
approach to the synthesis of MWNT/polypyrrole (PPy) nan-
otubes by the in-situ chemical polymerization of pyrrole on
the CNTs using ferric chloride as an oxidant. They inves-
tigated the effect of the monomer concentration on the
coating and properties of the resulting complex nanotubes.
By changing the pyrrole/MWNT ratio, the layer thickness
of PPy could be easily controlled in MWNT-PPy complex
nanotubes, as shown in Fig. 9. Long et al. [213] synthe-
Fig. 9. TEM photographs of PPy-coated MWNTs: (a) MWNT:PPy = 1:2; (b) MWNT:PPy = 1:5. Reprinted with permission from Ref. [216]. Copyright 2007,
Elsevier Science Ltd., UK.
849
Fig. 8. SEM images of PI/MWNTs nanocomposites: PI/MWNT-COOH
5 wt%. Reprinted with permission from Ref. [206]. Copyright 2007, Elsevier
Science Ltd., UK.
sized the CNT/PPy nanocables through an in-situ chemical
oxidative polymerization method. They showed that the
conductivity of nanocables increased with increasing nan-
otube weight percentage.
In-situ polymerization method has also been used
for the preparation of polyurethane/CNT nanocomposites.
PU/MWNT composites were synthesized by two in-situ
polymerization methods [217]. In one method, a calculated
amount of carboxylate MWNT and 1,4-butanediol (BD) was
added to a prepolyurethane solution in the subsequent
chain-extension step. In the second method, the neces-
sary weight fractions of MWNTs were first dispersed in
poly(␧-caprolactone)diol (PCL). Thereafter, 4,4 -methylene
bis(phenylisocyanate) (MDI) was added into this mixture.
The chain extender BD was added to this prepolymer
and the final PU-MWNTs composite was synthesized. The
MWNTs were relatively well dispersed in the PU matrix
of the PU-MWNT sample in second method. Xia and Song
[218] found that MWNTs could be individually dispersed in
850 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 10. FT-IR spectra of samples obtained (a) during prepolymerization (first step) with reaction time and (b) during reaction of prepolymer with
functionalized MWNTs (second step). Reprinted with permission from Ref. [220]. Copyright 2006, Wiley-VCH, Germany.
the PU matrix by in-situ polymerization method with the
aid of a dispersing agent. But SWNTs were not dispersed
well in this method. Later they synthesized PU/SWNTs
nanocomposites using PU-grafted SWNT which improved
the dispersion of SWNT in the PU matrix and strengthened
the interfacial interaction between the PU and SWNT [219].
A novel concept has been proposed to prepare
PU-MWNTs composite via in-situ polymerization of a pre-
polymer in the presence of carboxylated MWNTs [220].
Synthesis of PU/MWNT nanocomposites was carried out
in a two-step process as follows. First, prepolymer was
prepared from a reaction of MDI and PCL at 80 ◦ C for
90 min in a four-neck cylindrical vessel equipped with a
mechanical stirrer. In the second stage, a calculated amount
of carboxilated MWNTs was added to the prepolymer at
110 ◦ C, and they were reacted for 150 min to obtain the
final crosslinked MWNT-PU nanocomposite. In this case,
any chain extender was not used at the second stage reac-
tion. PU chains were crosslinked to MWNTs by a reaction
between the carboxylic acid groups of the MWNTs and
the NCO groups of prepolyurethane (Fig. 10). These PU-
crosslinked MWNTs composites were never dissolved in PU
solvents such as N,N-dimethylformamide, dimethyl sulfox-
ide, dimethylacetamide, or tetrahydrofuran.
The in-situ polymerization of caprolactam in the pres-
ence of SWNTs allowed the continuous spinning of
SWNTs-PA6 fibers [221]. In addition, caprolactam is an
excellent solvent for carboxylic acid-functionalized SWNTs
(SWNTs-COOH). This allows the efficient dispersion of the
SWNTs and subsequent grafting of PA6.
4. Preparation of CNT nanocomposites using
dendritic polymers
Due to their three-dimensional globular and sphere-
like structural architectures, dendritic polymers (DP) such
as dendrimeric and hyperbranched polymers, have gen-
erated great excitement in polymer research, owing to
their wide range of applications from drug delivery to
chemical sensors [222–224]. Dendrimers have unique size,
controlled and symmetric structure with ideally branch-
ing units without any structural defects [225,226], but
require a multi-step synthesis reaction, whereas the Hyper-
branched polymers exhibit a randomly branched structure,
with a single step synthesis process [227,228]. Recently,
dendritic polymers have been used to enhance the dis-
persion of CNTs in polymer matrices, taking advantage
of their highly functionalized three-dimensional globular,
non-entangled structures. They exhibit higher solubility
and lower viscosity in the melt and solution states com-
pared to linear polymers of the same molar mass [229,230].
Dendritic polymer/CNT nanocomposites may be formed via
covalent and non-covalent functionalization of CNTs. Den-
dritic polymers are effective for enhancing mechanical and
electrical properties of polymer nanocomposites because
the pristine CNTs can be used to obtain well dispersed CNTs
in polymer matrix, without any CNT modification.
4.1. CNT nanocomposites via covalently functionalized
CNT-dendritic polymers
Grafting of dendritic polymers on CNTs is a novel
approach for fabricating the nanomaterials and nan-
odevices [231–234]. Newkome and co-workers [235]
fabricated unique CdS quantum dot composite assemblies
using dendronized SWNTs. Acyl chloride functionalized
MWNTs were treated with amino-polyester dendron to
prepare [(Den)n -SWNT]. The ester groups were further
changed into carboxylic groups using formic acid, and
reacted with Cd(NO3 )2 to generate encapsulated CdS quan-
tum dots tethered to the SWNT surface. An electrode
material based on hyperbranched polymer-functionalized
MWNTs for lithium batteries showed good reversible
capacities and excellent capacity retention [236]. Sun and
co-workers [237], prepared the dendron functionalized
CNTs via amidation and esterification and their photo-
physical properties were studied. Prato and co-workers
[238] reported the synthesis of SWNTs functionalized with
polyamidoamine dendrimers. The dendrimers present on
the nanotube sidewalls have been further functionalized
with porphyrin moieties, and the photophysical properties
of nanoconjugates have studied. Under visible light irra-
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Scheme 6. Synthetic process for the MWNT-hyperbranched polyether nanohybrids. Reprinted with permission from Ref. [233]. Copyright 2004, American
Chemical Society, USA.
diation, porphyrin-SWNT nanoconjugate give rise to fast
charge separation (1.5 ± 0.5) × 1010 s−1 evolving from the
photoexcited porphin chromophores. Haddleton and co-
workers [239] described a poly(amidoamine) dendrimer
(PAMAM) functionalized MWNTs via ester linkage. The
dendron functionalized MWNTs were used as a tem-
plate for the deposition of silver nanoparticles on the
MWNT surface. Park and co-workers [240] studied the
antimicrobial effects of silver nanoparticles functionalized
PAMAM-MWNTs nanohybrids. The dendritic-MWNTs/Ag
was found to have a stronger antimicrobial effect than
dendritic-MWNTs. The role of the architecture of dendritic
molecules on CNT photoelectrical behavior has also been
discussed [241]. These super-structured CNTs exhibit a
peculiar response to electron beams. Gao and co-workers
[233] prepared multihydroxyl hyperbranched polymer on
the surface of MWNTs. In situ ring-opening polymerization
was employed for growing multihydroxyl dendritic macro-
molecules on the surface of MWNTs, as shown in Scheme 6.
Tree like multihydroxy hyperbranched polyether were
covalently grafted on the MWNTs using MWNTs-OH as an
initiator. The amount of polymer grafted is controllable
using this approach. The molecular weight of the grafted
hyperbranched polymer increases with increasing a feed
ratio of the monomer.
Biocompatible polymers on CNTs are arousing
interest due to the great significance of the nanohy-
brids in bionanotechnology [242,243]. Mueller and
co-workers [244] prepared hyperbranched glycopoly-
mers functionalized MWNTs by atom transfer radical
polymerization of 3-O-methacryloyl-1,2:5,6-di-O-
isopropylidene-D-glucofuranose (MAIG) and self
condensing vinyl copolymerization of MAIG and AB*
inimer, 2-(2-bromoisobutyryloxy)ethyl methacrylate. The
hyperbranched glycopolymers are biocompatible and
water soluble, and the resulting polymer-functionalized
MWNTs would be very useful for bionanotechnology
applications. Hyperbranched poly(citric acid) (PCA)
851
grafted MWNTs based nanocomposites were synthesized
by Hekmatara and co-workers [245]. The CNT-g-PCA
nanocomposites were soluble in water freely. Hong et al.
[246] reported the coating of MWNTs with hyperbranched
polymer shell by self-condensing vinyl polymerization
(SCVP) of 2-((bromobutyryl)-oxy) ethyl acrylate via
ATRP. The synthesized hyperbranched polymers have
a large number of functional groups facilitating further
functionalization of MWNTs and providing a method to
homogeneously disperse MWNT conducting layers within
electroluminescent devices.
Core–shell nanostructures were prepared by Xie and
co-workers [234,247] with MWNTs and hyperbranched
poly(urea-urethane)s (HPU) as the hard core and the soft
shell, respectively The authors have synthesized HPU-
functionalized MWNTs by a polycondensation method;
the solution rheology of HPU functionalized MWNTs were
studied. A large number of proton-donor and proton-
acceptor groups were located in the HPU functionalized
MWNT; intra- and intermolecular H-bonds were easily
formed by their interactions. At low temperature, shearing
forces induce conversion from intra- to intermolecular H-
bonds. The rheological behavior of the HPU-functionalized
MWNT solutions showed a strong dependence on concen-
tration, temperature, and thermal and shearing prehistory.
Baek and co-workers [248,249] prepared hyperbranched
poly(ether ketone)s (PEK) grafted MWNTs using an in
situ polymerization method. Hyperbranched ether–ketone
polymer containing different monomer ratios were synthe-
sized in the presence of MWNTs to afford PEK-g-MWNTs
nanocomposites. Due to the molecular architecture of
hyperbranched polymers, the morphology of the nanocom-
posites resembles mushroom-like clusters on MWNTs
stalks [250]. The resultant nanocomposites were soluble in
most strong acids, such as trifluoroacetic acid, methanesul-
fonic acid and sulfuric acid. UV curable functional groups
containing hyperbranched polymers were synthesized for
modification of CNTs [251]. The hyperbranched polyester
852 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 11. Current AFM images of linear (a) and hyperbranched (b) polyurethane nanocomposites containing pristine multi-walled carbon nanotubes of
20 wt% [254].
functionalized MWNTs were reacted with difunctional
molecules synthesized from toluene 2,4-diisocyanate and
hydroxylethyl acrylate to get UV curable hyperbranched
polymer. The modified MWNTs containing large amount
of UV-curable acrylate group were dispersed with UV cur-
able aliphatic urethane acrylate resins. In the presence of
UV irradiation, crosslinking reaction developed between
MWNTs and acrylate resins, leading to the covalent bond-
ing of MWNTs to the matrix, a more stable coupling than
simply physical bonding. Due to the excellent mechanical
properties of MWNTs, both the tensile strength and tough-
ness of the nanocomposites were enhanced by nearly 41%
and 105%, respectively, with only 0.1 wt% MWNTs.
4.2. CNT nanocomposites via non-covalently
functionalized CNT-dendritic polymers
The disruption of electronic conjugation by covalent
modification motivates research on non-covalent func-
tionalization of CNTs. In fact, excellent modification of
CNTs through non-covalent interaction between the ␲-
system of CNT and the functional group of polymer can
be achieved. Star and Stoddart [252] studied the disper-
sion and solubilization of SWNTs with a hyperbranched
polymer (poly[(m-phenylenevinylene)-co-(2,5-dioctoxy-
p-phenylene) vinylene] (PmPV). The hyperbranched poly-
mer exhibits more efficiency at dispersing nanotube
bundles than its parent PmPV polymer. The branching
of PmPV makes it less efficient for wrapping bundles of
SWNTs. They studied the molecular modeling of hyper-
branched polymer and found that the pockets provided
by the hyperbranched polymer offer a better fit for the
SWNTs. Cho and co-workers [253] also prepared the hyper-
branched polyurethane (HBPU)-MWNTs nanocomposites
using an in situ polymerization method. They prepared
different hard segment containing PU nanocomposites via
a two step process. Novel dispersion of MWNTs in the
HBPU matrix was observed, as well as good solubility
of nanocomposites in organic solvents. Because of the
good dispersion of MWNTs in the polymer matrix, the PU
nanocomposites showed dominant shape recovery prop-
erties of 84–96%, and enhanced mechanical properties.
They also studied the dispersion of high concentration
MWNTs (5–40 wt%) using an HBPU matrix [254]. The
MWNTs dispersion was analyzed on the basis of surface
morphology using current AFM images (Fig. 11), including
dispersions of 20 wt% MWNT in linear, as well as hyper-
branched polymer matrix. The aggregated MWNTs were
observed in linear PU/MWNTs nanocomposites, whereas
well dispersed MWNTs were observed for HBPU/MWNTs
nanocomposites. Compared to linear PU nanocomposites,
the hyperbranched nanocomposites give remarkable high
electrical conductivity.
Nakamoto and co-workers [255] presented the con-
struction of insulating conducting wire composed of
SWNTs and phenolic polymers as a conducting wire
and as an insulating coating, respectively. A hyper-
branched phenolic polymer (HBP) was synthesized from
3,4,5-trimethoxytoluene (A2 ) and 1,3,5-tribromomethyl-
2,4,6-trimethoxybenzene (B3 ) using a Lewis acid-catalyzed
polycondensation method. Fig. 12 shows the TEM and AFM
images for the samples. The images show the covering
of the SWNT surface by HBPs, which indicates solubiliza-
tion of SWNTs with physical adsorption of HBPs. In the
presence of HBP polymer, SWNTs were homogeneously
dispersed in DMF solution, in contrast to the use of lin-
ear polymer, where SWNTs were insoluble in DMF, even
after sonication. The authors also studied the impact of sol-
vent on the solubility of SWNTs with HBP. The SWNTs were
sparsely soluble in THF solution with HBP, whereas typi-
cally SWNTs van Hove singularities were found with HBP in
DMF. A non-covalent method for preparing the crosslinked
amphiphillic hyperbranch polymer micelle-encapsulated
CNTs was proposed to improve the dispersion of CNTs in
water [256]. Fig. 13 shows the TEM images of uncrosslinked
and crosslinked encapsulated CNTs. Zheng and co-workers
[257] reported an MWNTs based solvent-free nanofluids at
room temperature using hyperbranched poly(amine-ester)
(HPAE). Acid functionality containing MWNTs were homo-
geneously dispersed in HPAE matrix. The ternary amine
of HPAE were protonated with the carboxylic groups of
MWNTs via an acid–base reaction, which leads to ionic
attachment on the surface of MWNTs as well as hydro-
gen bonding interaction between the –OH, C O groups
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Fig. 12. (a) TM-AFM height image of SWNTs solubilized by extended HBP. (b) Height profile along dash line in (a). (c) Proposed structure of hybrids
composed of HBP and SWNTs on mica surface. The extended TM-AFM (d) height and (e) phase images in box area in (a). Reprinted with permission from
Ref. [255]. Copyright 2008, Elsevier Science Ltd., UK.
and the ternary amine groups to form a homogeneous
hybrid system. The preparation of fluorinated oligomeric
aggregates/CNTs nanocomposites possessing a higher dis-
persibility and stability in water is of particular interest
for developing new fluorinated functional materials [258].
Sawada et al. [259] synthesized a dendrimer copolymer
containing fluoroalkyl segments [260] for the dispersion of
SWNTs in water. They demonstrated that the fluorinated
dendrimer block copolymers could form new fluorinated
molecular aggregates to have higher dispersion ability,
not only for SWNTs and fullerenes, but also for mag-
netic nanoparticles in water. Valentini et al. [261] reported
naphthalenediimide modified electrically conducting den-
drimer poly(amidoamine)/SWNTs nanocomposites. The
electric conductance of SWNTs drastically increased upon
adsorption of the conducting dendrimer, owing to the
interaction between SWNTs and the conducting den-
drimer.
The effective immobilization of glucose oxidase (GOx)
on the CNT surface is a key issue for developing a glucose-
based biosensor [262–264]. Zhu and co-workers [265]
prepared the glucose biosensor based on layer-by-layer
electrostatic adsorption of glucose oxidase and dendrimer-
encapsulated Pt nanoparticles on MWNTs. LBL technique
provide a favorable microenvironment to keep the bioac-
tivity of glucose oxidase, and prevent enzyme molecule
leakage. The enzyme electrode showed good character-
istics, such as short response time, high sensitivity, and
stability. The (GOx/Pt-DENs)4 /CNTs electrode showed bet-
853
ter chronoampermetric response than the unmodified
CNTs electrode.
5. Mechanical properties of polymer/CNT
nanocomposites
As remarked above, their extraordinary mechanical
properties and large aspect ratio make CNTs excellent can-
didates for the development of CNT-reinforced polymer
nanocomposites. Indeed, a wide range of polymer matrixes
have been used for the development of such nanocompos-
ites. This section focuses on the mechanical properties of
composites of CNT composites in two polymer matrixes
well represented in the literature.
5.1. Polyurethane/CNT composites
Polyurethane is one of the most versatile materials
today. It is widely used in coatings, adhesives, shape
memory polymers, medical fields and composites. PU is
consisting of alternating hard and soft segments. The
hard segment is composed of alternating diisocyanate and
chain-extender molecules (i.e., diol or diamine), whereas
the soft segment is formed from a linear, long-chain diol.
Phase separation occurs in PUs because of the thermo-
dynamic incompatibility of the hard and soft segments.
PU/CNT composites [266–275] are of significant current
interest. The mechanical properties for different PU com-
posites are summarized in Table 4.
854 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867

Fig. 13. TEM images of (A) empty micelles, (B) uncrosslinked e-MWNT, and (C and D) crosslinked e-MWNT. Reprinted with permission from Ref. [256].
Copyright 2008, Elsevier Science Ltd., UK.

Incorporation of CNTs into PU can dramatically increase
the tensile strength and modulus. For example, the addition
of carboxylated MWNTs into the PU matrix by solvent mix-
ing improved the tensile strength and modulus of the PU
matrix [173,276] as shown in Fig. 14. The tensile strength
of a composite containing 10 wt% of MWNT-COOH was
enhanced by 108% as compared to pure PU, while an
increase of 68% was achieved by incorporating the same
amount of raw MWNTs in the PU matrix. Finally, the ten-
sile strength and modulus of nanocomposites increased
from 7.6 MPa in pure PU to 21.3 MPa (an increase of 180%)
and 50 to 420 MPa (an increase of 740%), respectively,
when the functionalized MWNTs content reached 20 wt%
in composites. The hydrophilic functional groups on the

Table 4
Mechanical properties of PU-CNT composites.

Nanotube type Preparation method % of modulus improvement at % of tensile strength Reference

1% CNT improvement at 1% CNT

SWNT Solution 25 50 [357]

MWNT-functional Solution 140 20 [162]
MWNT-functional Solution – 63 [279]
SWNT-functional Electrospining 250 104 [281]
MWNT Addition polymerization 561 397 [280]
MWNT In-situ polymerization 35 114 [277]
MWNT-functional In-situ polymerization 54 25 [358]
MWN-functional Solution 12 6 [274]
MWNT In-situ polymerization 90 90 [359]
MWNT-functional In-situ polymerization 40 7 [266]
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867 855

SWNTs (SWNT-g-PU) and poly(propylene glycol)-grafted

Fig. 14. Stress–strain profiles of PU composites at different MWNT
loading. Reprinted with permission from Ref. [173]. Copyright 2006,
Wiley-VCH, Germany.
MWNTs were helpful in improving the interaction with
–CONH– groups in PU. Therefore, the strong interaction
between the functionalized MWNTs and the PU matrix
greatly enhanced the dispersion as well as the interfa-
cial adhesion, thus strengthening the overall mechanical
performance of the composite. The mechanical properties
of composites depends on the acid treatment tempera-
ture of the CNTs. Composites containing MWNTs reacted
at 90 ◦ C resulted in a greater increased modulus com-
pared with those at 140 ◦ C, indicating that severe surface
modification lowers mechanical properties [95]. Kuan et
al. [277] incorporated amino functionalized MWNTs into
waterborne PU. They found an increase in modulus from
77 MPa for the polymer to 131 MPa for a 4 phr compos-
ite (an increase of 70%) and a tensile strength increase
from 5.1 MPa to 18.9 MPa (an increase of 270%) at the same
loading level. Covalent bond formation between amino
functionalized MWNTs and PU promoted increased interfa-
cial strength and tensile strength. MWNT is more effective
to the improvement of modulus, whilst SWNT is better for
elongation and tensile strength. The different reinforcing
effects of MWNT and SWNT on PU were correlated to the
shear thinning exponent and the shape factor of CNTs in
polyol dispersion.
Polymer grafting is very effective in increasing disper-
sion and the mechanical properties of composites due to
its strong chemical bonding between polymer and CNTs.
Xia et al. [278] studied polycaprolactone-based PU-grafted
MWNTs into PU by in-situ polymerization. Mechanical
property improvements were observed in both cases. The
incorporation of 0.7 wt% SWNT-g-PU into PU improved
the Young’s modulus by ∼278% and ∼188% compared to
the pure PU and ungrafted pristine SWNT/PU composites,
respectively. This is due to the better dispersion of SWNT-
g-PU and MWNT-g-PU and stronger interfacial interactions
between the CNTs and PU. Wang and Tseng [279] also
found that adding 1–10 wt% PU functionalized MWNT to
PU increased the tensile strength by 63–210%. The storage
modulus and soft segment Tg (from tan ␦) increased with
increasing PU-functionalized MWNT in the PU. The Tg of
the soft segments of the nanocomposite films shifted from
−20 to −5 ◦ C, suggesting that PU functionalized MWNTs
are compatible with the amorphous regions of the soft
segments in the PU matrix. Recently McClory et al. [280]
reported thermosetting PU-MWNTs nanocomposites by an
addition polymerization reaction. The Young’s modulus
increased by 97 and 561% on the addition of 0.1 wt% and
1 wt% MWNTs in the PU, respectively, whereas ultimate
tensile strength increased by 397% when either 0.1 or 1 wt%
MWNTs added to PU. In this composite, the percentage
of elongation-at-break increased from 83 to 302% on the
addition of 0.1 wt% CNT compared to pure PU resin.
Improvement of mechanical properties has been
reported for melt-processed composite fibers. Young’s
modulus of composite fibers increased by 27 folds com-
pared to unfilled PU fiber. Sen et al. [281] studied the
fabrication of membranes of SWNT-filled PU by the
electrospinning technique. The tensile strength of ester-
functionalized SWNT/PU membranes was enhanced by
∼104%, and the tangent modulus improved by ∼250%
compared to PU membrane. So, these enhancements in
mechanical properties can be attributed to the high dis-
persion of CNTs through the polymer matrix and good
interfacial interaction between CNT and PU.
5.2. Polyimide/CNT nanocomposites
Polyimide (PI) is a candidate polymer for a variety of
applications such as packaging materials, circuit boards,
and interlayer dielectrics due to their good dielectric
properties, flexibility, high glass transition temperature,
excellent thermal stability, and radiation resistance. Poly-
imides serve as excellent polymer matrices for polymeric
CNT nanocomposites [282,283]. The mechanical properties
for different PI composites are summarized in Table 5.

Table 5
Mechanical properties of PI-CNT composites.

Nanotube type Sample type CNT content (wt%) % of modulus improvement % of tensile strength improvement Reference

SWNT-functional Film 1 89 9 [287]

MWNT-functional Film 5 33 7 [206]
MWNT-functional Film 5 – 40 [285]
MWNT-functional Film 0.5 110 100 [289]
MWNT-functional Film 0.5 60 61 [290]
MWNT-functional Film 6.98 61 31 [284]
SWNT Film 1 10 10 [203]
SWNT Rod 1 0 11 [203]
SWNT Fiber 1 45 0 [203]
MWNT-functional Film 7.5 52 21 [282]
856 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Most studies report nanocomposites with CNT result
inimprovements in the mechanical properties of PI. For
example, in situ polymerized PI containing 5 wt% MWNT-
COOH showed increase in modulus (33%) and tensile
strength (7%) as compared to neat PI [206]. However,
compared to that of the neat PI, the modulus and ten-
sile strength of raw CNT/PI nanocomposites showed only
a slight increase.The better improvement in the tensile
strength and modulus of PI/MWNT-COOH may be caused
by the strong interactions between PI matrix and MWNT-
COOH. As discussed above, the functionalized MWNTs
prepared by acid treatment contain –COOH groups, which
facilitate improved interaction with –O– groups in the PI
chain.
Another study revealed moderate increases in the mod-
ulus and tensile strength of PI when mixed with plasma
modified MWNT [289]. The addition of 0.5 wt% of the
plasma modified MWNT to the PI increased the modulus
from 2.17 to 4.56 GPa and the tensile strength from 124.5
to 249 MPa, or increases of 110% and 100%, respectively.
These impressive results were attributed to chemical bond
formation between the plasma modified MWNT and the
PI. When the modified MWNTs content was higher (above
0.5 wt), the modulus and tensile strength were decreased
at high modified MWNT content. This result is consistent
with other reports [285,286]. Zhu et al. [285] found that the
tensile strength of the PI/MWNT composites increased with
increased MWNT content up to 5 wt%, then decreased with
further increase in MWNTs. The incorporation of 5 wt%
MWNTs into PI resulted in an enhanced tensile strength by
40% compared to pure PI, attributed to good dispersion of
MWNTs in the nanocomposite. At higher level of MWNTs,
the MWNTs could not be well-dispersed, agglomerating
to large clusters and resulting in a decrease of the tensile
strength. Jiang et al. [286] also observed that the Young
modulus of PI/MWNT composites improved by adding up
to 1.89 vol% MWNT and decreased with MWNT content
further increase.
A study utilizing SWNTs reported that the mechani-
cal properties of SWNT/PI composites with a low level
of SWNTs (0.30 wt%) showed a slight increase (5% tensile
strength and 18% Young modulus) compared to PI, whereas
composites with higher SWNT level (1 wt%) showed signifi-
cant improvement of the mechanical properties (9% tensile
strength and 90% Young modulus) [287].
The mechanical properties of PI/CNT composites
depend on the nature of any functionalization of the CNT.
At lower level of MWNT (up to 0.99 wt%), the tensile
properties of amine-modified MWNT/PI composites was
higher than that of acid-modified MWNT/PI composites
[284]. However, acid-modified MWNTs improved the ten-
sile properties of the PI more than amine-modified MWNT
for MWNTs content above 2.44 wt%. The acid-modified
MWNTs may form hydrogen bonds with the C O bonds of
the PI molecules. However, the bonding of amine-modified
MWCNT to polyamic acid may reduce its imidization. The
mechanical strength of polyamic acid is less than that of
PI and polyamic acid is more brittle than PI. So, amine-
modified MWNT is added to the PI matrix may affect the
mechanical properties of the polymer. The same group
also reinforced PI by the addition of vinyltriethoxysi-
lane functionalized MWNT [290]. They observed that the
modulus and tensile strength of 0.5 wt% functionalized
MWNT-PI composites increased 60 and 61%, respectively,
as compared to neat PI. This improvement of mechanical
properties depends on the ratio of vinyltriethoxysilane to
MWNTs. When the ratio of vinyltriethoxysilane to MWCNT
is 2:1, the composite showed better tensile properties than
other composites with different ratios and neat PI, because
only this ratio of vinyltriethoxysilane to MWCNT can form
interpenetrating network in PI matrix.
A number of other studies have observed increases
in modulus, but either no increase or decrease in ten-
sile strength [203,288]. Compared with the neat polymer,
the addition of CNTs resulted in increase in the modu-
lus and decrease in the tensile strength (18%). However,
the increase in the elastic modulus was small, e.g. 37%
for 14.3 wt% of CNT addition [288]. The improvement of
mechanical property SWNT/PI nanocomposite depends on
sample type, such as film, rod and fiber [203]. The ten-
sile modulus, ultimate strength, and elongation-at-break
were increased for the composite films with 1 wt% SWNT.
In case of extruded composite rod (∼1 mm in diameter),
there was no significant change in mechanical properties.
But the mechanical properties were significantly changed
when the extruded rods were drawn down to much smaller
diameters. Tensile strength and modulus were increased
with decreasing fiber diameter because of increased align-
ment induced by the post extrusion fiber drawing process.
6. Electrical conductivity of polymer/CNT
nanocomposites
CNTs exhibit the high aspect ratio and high con-
ductivity, which makes CNTs excellent candidates for
conducting composites. Percolation theory predicts that
there is a critical concentration at which composites con-
taining conducting fillers in insulating polymers become
electrically conductive. According to percolation theory,
 c = A(V − Vc )ˇ , where  c is the conductivity of the com-
posites, V is the CNT volume fraction, Vc is the CNT
volume fraction at the percolation threshold, and A and
ˇ are fitted constant. The percolation threshold has been
reported to ranging from 0.0025 wt% [291] to several wt%
[302]. The percolation threshold for the electrical con-
ductivity in polymer-CNT nanocomposites depends on
dispersion [291,292,183], alignment [293,294], aspect ratio
[292,295,296], degree of surface modification [95] of CNTs,
polymer types [301] and composite processing methods
[292]. The electrical conductivity and percolation threshold
of CNT-polymer composites are shown in Table 6.
The aligned CNTs in epoxy decrease the percolation
threshold by an order of magnitude compared to entan-
gled nanotubes [291]. The entangled CNTs were dispersed
completely during the shear intensive stirring process,
whereas aligned CNTs led to a superior dispersion after
shear-intensive processing. The well dispersed CNTs easily
form conductive paths due to their relatively homogeneous
dispersion of the nanoparticles, compared with that for the
aggregated CNTs. The percolation threshold in CNT/epoxy
composites with palmitic acid reduced by 2 compared to
those composites without palmitic acid, attributed to the
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
Table 6
Electrical conductivity of CNT-polymer composites.
Polymer type Nanotube type Percolation threshold (wt%)
Polystyrene MWNT 0.15–0.2
Polycarbonate SWNT-functional 0.11
Polystyrene SWNT-functional 0.045
Poly(vinyl acetate) XD grade CNT – 20
Poly(methyl methacrylate) MWNT 0.3
Poly(methyl methacrylate) SWNT 0.17
Poly(methyl methacrylate) SOCl2 -doped SWNT 0.17
Poly(vinyl alcohol) MWNT 5–10
Poly(vinyl acetate) SWNT 0.04
Epoxy MWNT 0.0025
efficient dispersion of CNTs in the epoxy matrix promoted
by the palmitic acid [176]. The electrical conductivity of
SWNT/epoxy nanocomposites with SWNTs aligned under a
25 T magnetic field was increased by 35% compared to sim-
ilar composites without magnetic aligned SWNTs [293]. In
contrast, Fangming et al. [294] found that the electric con-
ductivity of the aligned CNT in PMMA was 10−10 S/cm and
unaligned CNT was 10−4 S/cm for 2% SWNT/PMMA com-
posites. This indicates that the alignment of the nanotubes
in the composite decreased the electrical conductivity and
also the percolation threshold. The reason is that there
are fewer contacts between the nanotubes when they are
highly aligned in the composites, and so aligned composites
require more nanotubes to reach the percolation threshold.
The aspect ratio of the CNT has a tremendous influence
on the percolation threshold of the polymer nanocompos-
ites without varying other important parameters, such as
the polymer matrix or the dispersion and aggregation state
of the CNTs. Recently Grossiord et al. [300] reported that the
percolation threshold of polystyrene/MWNT nanocompos-
ites made from 2 wt% high-aspect ratio nanotubes grown
in vertically aligned films was 0.15–0.5 wt%, which is 5
times smaller than that for low aspect ratio industrically-
produced nanotubes polymer composites. They found
an electrical conductivity of 103 S/m with 2 wt% CNTs.
The percolation threshold was observed at 0.045 wt%
non-covalently functionalized, soluble SWNT loading for
a SWNT-PS composite, with a maximum conductivity
of 6.89 S/m at 7 wt% of nanotube loading. The same
preparation method for a SWNT-PC composite resulted
in a material for which the conductivity increased to
4.81 × 102 S/m at 7 wt% of nanotubes, with a very low per-
colation threshold reached at 0.11 wt% of nanotubes [301].
It is well known that chemical functionalization dis-
rupts the extended ␲-conjugation of nanotubes and hence
reduces the electrical conductivity of functionalized CNTs.
Silane-functionalized CNT/epoxy nanocomposites showed
lower electrical conductivity than that of the untreated
CNTs composites at identical nanotube content [297]. Cho
et al. [94] reported that the electrical conductivity of the
surface-modified MWNT composites was lower than that
of the unreacted MWNT composites that had the same nan-
otube content. This is attributed to increased defects in
the lattice structure of carbon-carbon bonds on the nan-
otube surface as a result of the acid treatment. In particular,
the severe modification of the nanotubes significantly low-
ered the conductivity. Several researchers reported that the
functionalization of CNTs can improve the electrical con-
857
CNT content (wt%) Maximum conductivity (S/m) Reference
2 103 [300]
7 4.81 × 102 [301]
7 6.89 [301]
4.8 × 103 [361]
40 3 × 103 [362]
10 1.7 × 103 [363]
13.5 104 [363]
60 100 [302]
4 ≈15 [360]
1 2 [291]
ductivity of the composites [298,299]. Tamburri et al. [298]
found that the functionalization SWNTs with –COOH and
–OH groups enhanced the composites conductivity com-
pared to untreated SWNTs.
7. Optical properties of polymer/CNT
nanocomposites
CNTs exhibit unique one-dimensional p-electron con-
jugation, mechanical strength, and high thermal and
chemical stability, which make them very attractive for
use in many applications. Optical limiting, an important
non-linear optical behavior, can develop with increasing
input fluence of a light pulse, such that the transmitted
fluence tends to a constant, independent of the input flu-
ence. For dispersions of CNTs in a number of solvents, it
appears that optical limiting is principally due to the non-
linear scattering due to bubbles formed by light absorption
induced heating, although sublimation, a gradual reduction
in size for a CNT at high temperature, may contribute, in
contrast to a minimal role of reverse saturable absorption
(RSA), an effect dependent on absorption by excited elec-
tronic states [303–305]. O’Flaherty et al. [306] reported that
the optical limiting of the poly(9,9-di-n-octylfluorenyl-2,7-
diyl)/MWNTs samples is dependent on the mass fraction
of CNTs. The magnitude of the non-linear effect increased
systematically when the mass fraction of the nanotubes
increased from 0.011 to 0.038. The non-linear optical
extinction of nanosecond laser pulses by a set of con-
jugated copolymer poly(para-phenylenevinylene-co-2,5-
dioctyloxy-meta-phenylenevinylene)/MWNTs composites
dispersed in solution has been reported [307]. In this case,
either the MWNTs or the polymer dominates the non-
linear response of the composite, depending on the relative
mass of polymer to nanotube. The non-linear extinction
was 0% for 0, 1.3, and 2.5 wt% MWNT at 10 J/cm2 , whereas
the samples with 3.6 wt% and 5.9 wt% MWNTs were a nor-
malized non-linear extinction of 12% and 41%, respectively.
Thus the materials display a dramatic improvement in the
optical-limiting performance when the MWNT mass con-
tent is increased from 1.3% to 3.6%.
Several polymer-coated and polymer-grafted MWNTs
were synthesized and their non-linear optical properties
of composites were investigated using 532 nm nanosec-
ond laser pulses [110]. The authors reported that the
optical limiting thresholds of the all composite samples
to be approximately 1 J cm−2 , which is similar to that
of the MWNT-DMF suspension. The results showed that
858 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867

Fig. 15. Optical and electrical properties of CNT/S-PEEK composite films: (a) transparent film on a labeled paper and (b) optical transmittance measurement.
Reprinted with permission from Ref. [311]. Copyright 2008, American Chemical Society, USA.

the polymers and processing methods do not change the
non-linear optical properties of MWNTs. The optical limit-
ing performance of double-C60-end-capped poly(ethylene
oxide)/MWNTs were also studied and found better
than the aqueous MWNTs suspension [308]. In case of
SWNT/poly(3-octylthiophenes) composite films, the opti-
cal properties did not significantly change with low fraction
of CNT changes [309]. In a study of the optical properties
of poly(para phenylene vinylene) (PPV)/CNT composites
[310], different concentration SWCNT-PPV films were pre-
pared using a solution mixing process, heated at 120 ◦ C.
The authors observed that the optical spectra at 120 ◦ C PPV
conversion temperature was dramatically changed with
respect to those obtained at 300 ◦ C. It was also found that
the effect of the low conversion temperature on all the opti-
cal spectra was similar to that of increasing the nanotube
concentration in standard PPV.
A novel preparation of optically transparent CNT/
polymer composites with highly aligned nanotubes has
reported recently [311]. First, CNT arrays were grown on
silicon by a CVD process. Uniform CNT sheets were then
pulled out of the arrays and stabilized on glass. Compos-
ite films were finally produced by spin-coating or casting
polymer solutions onto the CNT sheets, followed by evap-
oration of the solvents. Film thickness was controlled by
varying the concentration of polymer solutions and coating
times. PS, PMMA, and sulfonated poly(ether ether ketones)
derived composite films with more than 80% optical trans-
parency were prepared using this technique (Fig. 15). These
results suggest that the optical properties of the composites
can be tailored in a predetermined manner by controlling
the nanotube content, orientation and precursor conver-
sion temperature, thus opening a pathway for developing
optically functional materials.
8. Applications
As developed in the preceding sections, because of
their excellent mechanical, electrical, and magnetic prop-
erties, as well as nanometer scale diameter and high
aspect ratio, CNTs can be very useful materials in com-
posites to improve a particular property for specific
applications (Table 7). The addition of CNTs to ␲-
conjugated polymers was found to improve the quantum
efficiency of ␲-conjugated polymers because the inter-
action between the highly delocalized ␲-electrons of
CNTs and the ␲-electrons correlated with the lattice of
the polymer skeleton [3]. Such composites are widely
used in photovoltaic devices [312] and light-emitting
diodes [313]. CNT-conducting polymer composites have
a potential application in supercapacitors [314,315]. The
PANI/MWNTs composites electrodes showed much higher
specific capacitance (328 F g−1 ) than pure PANI electrodes
[316]. The capacitances of a CNT-polypyrrole composite-
CNT-poly(3-methyl-thiophene) composite based super-
capacitor prototype and a CNTs-CNTs-polypyrrole based
hybrid supercapacitor prototype were 87 and 72 F g−1 ,
respectively, much larger the 21 F g−1 for the CNTs/CNTs
corresponding supercapacitor prototype due to the Fara-
day effect of the conducting polymers [317].
CNTs are also widely used in actuators [318,319].
The addition of CNTs to PANI fibers increased the elec-

Table 7
Application of CNT-polymer composites.

Nanotube type Polymer type Applications References

SWNT Poly(3-octylthiophene) Photovoltaic devices [312]

MWNT; SWNT Polyaniline, polypyrrole, poly-(3,4-ethylenedioxythiophene), Supercapacitors [314,316,317,364,365]
poly(3-methyl-thiophene
SWNT Nafion Actuators [318]
MWNT Poly(vinyl alcohol), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) [366]
MWNT Nafion Fuel cell [367]
MWNT-functional Sulfonated poly(arylene sulfone), [368]
SWNT; MWNT Polypyrrole Biosensors [369,324]
SWNT Poly(methyl methacrylate) Biocatalytic films [370]
SWNT-functional; DNA (polynucleotide) Gene delivery [371]
MWNT-functional
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
tromechanical actuation because the CNTs improved the
mechanical, electronic, and electrochemical properties of
the PANI fibers [320].
Composites based on CNTs are studied for a variety
of sensor applications [321,322]. For example, polypyr-
role or PANI deposited on single-walled CNT networks
that can be used as solid state pH sensors [323]. A DNA
sensor was created from a composite of polypyrrole and
CNTs functionalized with carboxylic groups to covalently
immobilize DNA onto CNTs [324]. In another example,
polypyrrole films doped with CNTs functionalized with
oligonucleotides were successfully implemented for DNA
biosensors using direct impedance measurements [325]. In
general, the presence of CNTs tends to increase the overall
sensitivity and selectivity of biosensors. The thermal trans-
port properties of polymer composites can be improved
with the addition of CNTs due to the excellent thermal
conductivity of CNTs. Such composite are quite attractive
for usages as printed circuit boards, connectors, thermal
interface materials, heat sinks, lids, housings, etc. [8].
The superior properties of CNTs are not limited to
electrical and thermal conductivities, but also include
mechanical properties, such as stiffness, toughness, and
strength. CNTs with their high aspect ratio and excellent
mechanical properties have the potential to strengthen and
toughen hydroxyapatite without offsetting its bioactivity,
thus opening up a wider range of clinical applications [326].
Bianco et al. studied the application of CNTs as new vec-
tors for the delivery of therapeutic molecules [327,328].
CNTs have been shown to cross cell membranes easily and
to deliver peptides, proteins, and nucleic acids into cells
[329,330].
CNTs were employed to reinforce the interfaces
between ultra high molecular weight PE polymer particles,
enhancing composite strength, stiffness, impact toughness
as well as structural damping [331]. These composites
are attractive for applications in aerospace and naval
engineering. The high strength and toughness-to-weight
characteristics of CNTs may also prove valuable as part
of composite components in fuel cells that are deployed
in transport applications, where durability is extremely
important.
9. Concluding remarks
There are several approaches for developing high
performance CNT-polymer nanocomposites utilizing the
unique properties of CNTs. The critical challenge is the
development of methods to improve the dispersion of CNTs
in a polymer matrix because their enhanced dispersion in
polymer matrices greatly improves the mechanical, elec-
trical and optical properties of composites. Despite various
methods, such as melt processing, solution processing, in-
situ polymerization, and chemical functionalization, there
are still opportunities and challenges to be found in order to
improve dispersion and modify interfacial properties. One
of challenges is to achieve the optimal functionalization of
CNTs, which can maximize interfacial adhesion between
CNTs and the polymer matrix. A specific functionalization
of CNTs is required for strong interfacial adhesion between
CNTs and a given polymer matrix, which may also simul-
859
taneously improve the dispersion of CNTs in the polymer
matrix.
The mechanical properties of CNT-polymer nanocom-
posites may be compromised between carbon–carbon
bond damage and increased CNT-polymer interaction due
to CNT functionalization. Similarly, electrical conductivity
of a CNT-polymer nanocomposite is determined by the neg-
ative effect of carbon–carbon bond damage and the positive
effect of improved CNT dispersion due to CNT functional-
ization. In either case, the choice and control of tailored
functionalization sites for chemical modification of CNTs
are necessary. As an example, selective CNT functional-
ization can be achieved via click chemistry by preparing
azide-functionalized polymers. However, this may be lim-
ited in the practical use owing to the need for multi-step
reactions for azide and alkyl groups to apply click chem-
istry. The employment of hyperbranched polymers for
improving CNT dispersion may be also useful because it
can result in enhanced electrical conductivity, as well as
mechanical properties of nanocomposites, without modi-
fication of CNT.
In practice, the problems regarding melt processing
need to be solved, as melt mixing is the most common com-
mercial method used to prepare CNT-polymer composites.
To achieve the best performance of CNT-polymer compos-
ites, it is important to choose the CNT functionalization
method, a suitable polymer matrix for CNT dispersion and
molecular interaction control with CNTs as well as poly-
mer composite processing conditions such as temperature,
shear rate, shear force, and mixing time. In conclusion, the
CNT functionalization and matrix polymer design for dis-
persion of CNTs and interfacial adhesion between CNTs and
a polymer matrix are the key challenges for development
of high performance CNT composites.
Acknowledgments
This work was supported by the SRC/ERC Program
of MOST/KOSEF (R11-2005-065) and A*STAR SERC Grant
(0721010018).
References
[1] Iijima S. Helical microtubules of graphitic carbon. Nature
1991;354:56–8.
[2] Bachtold A, Hadley P, Nakanishi T, Dekker C. Logic circuits with
carbon nanotube transistors. Science 2001;294:1317–20.
[3] Ago H, Petritsch K, Shaffer MSP, Windle AH, Friend RH. Compos-
ites of carbon nanotubes and conjugated polymers for photovoltaic
devices. Adv Mater 1999;11:1281–5.
[4] Kasumov AY, Deblock R, Kociak M, Reulet B, Bouchiat H, Khodos I, et
al. Supercurrents through single-walled carbon nanotubes. Science
1999;284:1508–11.
[5] Baughman RH, Cui C, Zakhidov AA, Iqbal Z, Barisci JN, Spinks GM,
et al. Carbon nanotube actuators. Science 1999;284:1340–4.
[6] Niu C, Sichel EK, Hoch R, Moy D, Tennet H. High power electrochem-
ical capacitors based on carbon nanotube electrodes. Appl Phys Lett
1997;70:1480–2.
[7] Ajayan PM, Iijima S. Capillarity-induced filling of carbon nanotubes.
Nature 1993;361:333–4.
[8] Xie XL, Mai YW, Ping X. Dispersion and alignment of carbon
nanotubes in polymer matrix: a review. Mater Sci Eng Rep
2005;49:89–112.
[9] Andrews R, Weisenberger MC. Carbon nanotube polymer compos-
ites. Curr Opin Solid State Mater Sci 2004;8:31–7.
860 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[10] Iijima S, Ichihashi T. Single-shell carbon nanotubes of 1-nm diam-
eter. Nature 1993;363:603–5.
[11] Bethune DS, Kiang CH, Devries MS, Gorman G, Savoy R, Vazquez
J, et al. Cobalt-catalyzed growth of carbon nanotubes with single-
atomic-layer walls. Nature 1993;363:605–7.
[12] Sugai T, Yoshida H, Shimada T, Okazaki T, Shinohara H. New
synthesis of high-quality double-walled carbon nanotubes by high-
temperature pulsed arc discharge. Nano Lett 2003;3:769–73.
[13] Bandow S, Takizawa M, Hirahara K, Yudasaka M, Iijima S. Raman
scattering study of double-wall carbon nanotubes derived from the
chains of fullerenes in single-wall carbon nanotubes. Chem Phys
Lett 2001;337:48–54.
[14] Guo T, Nikolaev P, Thess A, Colbert DT, Smalley RE. Catalytic growth
of single-walled nanotubes by laser vaporization. Chem Phys Lett
1995;243:49–54.
[15] Nikolaev P, Bronikowski MJ, Bradley RK, Rohmund F, Colbert DT,
Smith KA, et al. Gas-phase catalytic growth of single-walled carbon
nanotubes from carbon monoxide. Chem Phys Lett 1999;313:91–7.
[16] Joseyacaman M, Mikiyoshida M, Rendon L, Santiesteban JG. Cat-
alytic growth of carbon microtubules with fullerene structure. Appl
Phys Lett 1993;62:657–9.
[17] Huang SM, Woodson M, Smalley RE, Liu J. Growth mechanism of
oriented long single walled carbon nanotubes using fast-heating
chemical vapor deposition process. Nano Lett 2004;4:1025–8.
[18] Treacy MM, Ebessen TW, Gibson JM. Exceptionally high Young’s
modulus observed for individual carbon nanotubes. Nature
1996;381:678–80.
[19] Saito R, Dresselhaus G, Dresselhaus MS. Physical properties of car-
bon nanotubes. London: Imperial College Press; 1998.
[20] Chae HG, Liu J, Kumar S. Carbon nanotubes properties and applica-
tions. In: O’Connell MJ, editor. Carbon nanotube-enabled materials.
Boca Raton: Taylor & Francis Group, LLC; 2006.
[21] Ma C, Zhang W, Zhu Y, Ji L, Zhang R, Koratkar N, et al. Alignment and
dispersion of functionalized carbon nanotubes in polymer compos-
ites induced by an electric field. Carbon 2008;46:706–10.
[22] Ajayan PM, Schadler LS, Braun PV. Nanocomposite science and tech-
nology. Weinheim, Germany: Wiley-VCH, GmbH & Co. KgaA; 2003.
[23] Lu JP. Elastic properties of carbon nanotubes and nanoropes. Phys
Rev Lett 1997;79:1297–300.
[24] Li Y, Wang K, Wei J, Gu Z, Wang Z, Luo J, et al. Tensile properties
of long aligned double-walled carbon nanotube strands. Carbon
2005;43:31–5.
[25] Yu MF, Lourie O, Dyer MJ, Moloni K, Kelly TF, Ruoff RS. Strength
and breaking mechanism of multiwalled carbon nanotubes under
tensile load. Science 2000;287:637–40.
[26] Ajayan PM, Stephan O, Colliex C, Trauth D. Aligned carbon nanotube
arrays formed by cutting a polymer resin-nanotube composite. Sci-
ence 1994;265:1212–4.
[27] Moniruzzaman M, Winey KI. Polymer nanocomposites containing
carbon nanotubes. Macromolecules 2006;39:5194–205.
[28] Jamal A, Ali R, Somayeh M. Preparation and characterization of lin-
ear low density polyethylene/carbon nanotube nanocomposites. J
Macromol Sci Part B: Phys 2007;46:877–89.
[29] Li L, Li CY, Ni C, Rong LX, Hsiao B. Structure and crystallization
behavior of Nylon 66/multi-walled carbon nanotube nanocompos-
ites at low carbon nanotube contents. Polymer 2007;48:3452–60.
[30] Morales-Teyssier O, Sanchez-Valdes S, Ramos-de Valle LF. Effect of
carbon nanofiber functionalization on the dispersion and physical
and mechanical properties of polystyrene nanocomposites. Macro-
mol Mater Eng 2006;291:1547–55.
[31] Gryshchuk O, Karger-Kocsis J, Thomann R, Konya Z, Kiricsi I. Mul-
tiwall carbon nanotube modified vinylester and vinylester-based
hybrid resins. Compos Part A 2006;37:1252–9.
[32] Ghose S, Watson KA, Delozier DM, Working DC, Siochi EJ, Con-
nell JW. Incorporation of multi-walled carbon nanotubes into high
temperature resin using dry mixing techniques. Compos Part A
2006;37:465–75.
[33] Mrozek RA, Kim BS, Holmberg VC, Taton TA. Homogeneous, coaxial
liquid crystal domain growth from carbon nanotube seeds. Nano
Lett 2003;3:1665–9.
[34] Bliznyuk VN, Singamaneni S, Sanford RL, Chiappetta D, Crooker B,
Shibaev PV. Matrix mediated alignment of single wall carbon nan-
otubes in polymer composite films. Polymer 2006;47:3915–21.
[35] Zhao B, Hu H, Haddon RC. Synthesis and properties of a water-
soluble single-walled carbon nanotube-poly(m-aminobenzene
sulfonic acid) graft copolymer. Adv Funct Mater 2004;14:
71–6.
[36] Kanagaraj S, Varanda FR, Zhil’tsova TV, Oliveira MSA,
Simoes JAO. Mechanical properties of high density polyethy-
lene/carbon nanotube composites. Compos Sci Technol 2007;67:
3071–7.
[37] Kim JY, Han SI, Kim SH. Crystallization behaviors and mechani-
cal properties of poly(ethylene 2,6-naphthalate)/multiwall carbon
nanotube nanocomposites. Polym Eng Sci 2007;47:1715–23.
[38] Jin SH, Park YB, Yoon KH. Rheological and mechanical properties
of surface modified multi-walled carbon nanotube-filled PET com-
posite. Compos Sci Technol 2007;67:3434–41.
[39] Wang Z, Ciselli P, Peijs T. The extraordinary reinforcing efficiency
of single-walled carbon nanotubes in oriented poly(vinyl alcohol)
tapes. Nanotechnology 2007;18, 455709/1–9.
[40] Yang BX, Shi JH, Pramoda KP, Goh SH. Enhancement of stiffness,
strength, ductility and toughness of poly(ethylene oxide) using
phenoxy-grafted multiwalled carbon nanotubes. Nanotechnology
2007;18, 125606/1–7.
[41] Pham JQ, Mitchell CA, Bahr JL, Tour JM, Krishanamoorti R, Green PF.
Glass transition of polymer/single-walled carbon nanotube com-
posite films. J Polym Sci Part B Polym Phys 2003;41:3339–45.
[42] Gong XY, Liu J, Baskaran S, Voise RD, Young JS. Surfactant-assisted
processing of carbon nanotube/polymer composites. Chem Mater
2000;12:1049–52.
[43] Singh IV, Tanaka M, Zhang J, Endo M. Evaluation of effective
thermal conductivity of CNT-based nano-composites by ele-
ment free Galerkin method. Int J Numer Meth Heat Fluid Flow
2007;17:757–69.
[44] Sergei S, Xue L, Rahmi O, Pawel K, David GC. Role of thermal bound-
ary resistance on the heat flow in carbon-nanotube composites. J
Appl Phys 2004;95:8136–44.
[45] Sankapal BR, Setyowati K, Chen J, Liu H. Electrical properties of air-
stable, iodine-doped carbon-nanotube-polymer composites. Appl
Phys Lett 2007;91, 173103/1–3.
[46] Grossiord N, Miltner HE, Loos J, Meuldijk J, Van Mele B, Koning
CE. On the crucial role of wetting in the preparation of con-
ductive polystyrene-carbon nanotube composites. Chem Mater
2007;19:3787–92.
[47] Guo H, Sreekumar TV, Liu T, Minus M, Kumar S. Structure and prop-
erties of polyacrylonitrile/single wall carbon nanotube composite
films. Polymer 2005;46:3001–5.
[48] Ichida M, Mizuno S, Kataura H, Achiba Y, Nakamura A. Anisotropic
optical properties of mechanically aligned single-walled carbon
nanotubes in polymer. Appl Phys A 2004;78:1117–20.
[49] Weglikowska UD, Kaempgen M, Hornbostel B, Skakalova1 V, Wang
J, Liang J, et al. Conducting and transparent SWNT/polymer com-
posites. Phys Stat Sol B 2006;243:3440–4.
[50] Hirsch A. Functionalization of single-walled carbon nanotubes.
Angew Chem Int Ed 2002;41:1853–9.
[51] Nalwa HS, editor. Handbook of nanostructured materials and nan-
otechnology, vol. 5. New York: Academic Press; 2000.
[52] Ebbesen TW, Ajayan PM, Hiura H, Tanigaki K. Purification of nan-
otubes. Nature 1994;367:519–1519.
[53] Hiura H, Ebbesen TW, Tanigaki K. Opening and purification of car-
bon nanotubes in high yields. Adv Mater 1995;7:275–6.
[54] Kuznetsova A, Mawhinney DB, Naumenko V, Yates JT, Liu J, Smalley
RE. Enhancement of adsorption inside of single-walled nanotubes:
opening the entry ports. Chem Phys Lett 2000;321:292–6.
[55] Liu J, Rinzler AG, Dai H, Hafner JH, Bradley RK, Boul PJ, et al. Fullerene
pipes. Science 1998;280:1253–6.
[56] Mawhinney DB, Naumenko V, Kuznetsova A, Yates Jr JT, Liu J,
Smalley RE. Surface defect site density on singale walled carbon
nanotubes by titration. Chem Phys Lett 2000;324:213–6.
[57] Hu H, Bhowmik P, Zhao B, Hamon MA, Itkis ME, Haddon RC.
Determination of the acidic sites of purified single-walled carbon
nanotubes by acid-base titration. Chem Phys Lett 2001;345:25–8.
[58] Hemon MA, Chen J, Hu H, Chen Y, Itkis ME, Rao AM, et al. Dissolution
of single-walled carbon nanotubes. Adv Mater 1999;11:834–40.
[59] Chen J, Hamon MA, Hu H, Chen Y, Rao AM, Eklund PC, et al.
Solution properties of single-walled carbon nanotubes. Science
1998;282:95–8.
[60] Bandow S, Rao AM, Williams KA, Thess A, Smalley RE, Eklund PC.
Purification of single-wall carbon nanotubes by microfiltration. J
Phys Chem B 1997;101:8839–42.
[61] Duesberg GS, Burghard M, Muster J, Philipp G. Separation of car-
bon nanotubes by size exclusion chromatography. Chem Commun
1998:435–6.
[62] Chen RJ, Zhang Y, Wang D, Dai H. Noncovalent sidewall func-
tionalization of single-walled carbon nanotubes for protein
immobilization. J Am Chem Soc 2001;123:3838–9.
[63] Lordi V, Yao N. Molecular mechanics of binding in carbon-
nanotube-polymer composites. J Mater Res 2000;15:2770–9.
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[64] Guo Z, Sadler PJ, Tsang SC. Immobilization and visualization of DNA
and proteins on carbon nanotubes. Adv Mater 1998;10:701–3.
[65] O’Connell MJ, Boul P, Ericson LM, Huffman C, Wang Y, Haroz E, et al.
Reversible water-solubilization of single-walled carbon nanotubes
by polymer wrapping. Chem Phys Lett 2001;342:265–71.
[66] Steuerman DW, Star A, Narizzano R, Choi H, Ries RS, Nicolini C,
et al. Interactions between conjugated polymers and single-walled
carbon nanotubes. J Phys Chem B 2002;106:3124–30.
[67] Star A, Stoddart JF, Steuerman D, Diehl M, Boukai A, Wong EW, et
al. Preparation and properties of polymer-wrapped single-walled
carbon nanotubes. Angew Chem Int Ed 2001;40:1721–5.
[68] Paredes JI, Burghard M. Dispersions of individual single-walled car-
bon nanotubes of high length. Langmuir 2004;20:5149–52.
[69] Duesberg GS, Muster J, Krstic V, Burghard M, Roth S. Chromato-
graphic size separation of single-wall carbon nanotubes. Appl Phys
A 1998;67:117–9.
[70] Moore VC, Strano MS, Haroz EH, Hauge RH, Smalley RE, Schmidt
J, et al. Individually suspended single-walled carbon nanotubes in
various surfactants. Nano Lett 2003;3:1379–82.
[71] Islam MF, Rojas E, Bergey DM, Johnson AT, Yodh AG. High weight
fraction surfactant solubilization of single-wall carbon nanotubes
in water. Nano Lett 2003;3:269–73.
[72] Yurekli K, Mitchell CA, Krishnamootri R. Small angle neutron
scattering from surfactant assisted aqueous dispersion of carbon
nanotubes. J Am Chem Soc 2004;126:9902–3.
[73] Jiang L, Gao L, Sun J. Production of aqueous colloidal dispersions of
carbon nanotubes. J Coll Interf Sci 2003;260:89–94.
[74] Poulin P, Vigolo B, Launois P. Films and fibers of oriented single wall
nanotubes. Carbon 2002;40:1741–9.
[75] Sáfar GAM, Ribeiro HB, Malard LM, Plentz FO, Fantini C, Santos AP,
et al. Optical study of porphyrin-doped carbon nanotubes. Chem
Phys Lett 2008;462:109–11.
[76] Tan Y, Resasco DE. Dispersion of single-walled carbon nanotubes of
narrow diameter distribution. J Phys Chem B 2005;109:14454–60.
[77] Bandyopadhyaya R, Nativ-Roth E, Regev O, Yerushalmi-Rozen R.
Stabilization of individual carbon nanotubes in aqueous solutions.
Nano Lett 2002;2:25–8.
[78] Pei X, Hu L, Liu W, Hao J. Synthesis of water-soluble carbon
nanotubes via surface initiated redox polymerization and their tri-
bological properties as water-based lubricant additive. Eur Polym
J 2008;44:2458–64.
[79] Wu HX, Qiu XQ, Cao WM, Lin YH, Cai RF, Qian SX. Polymer-wrapped
multiwalled carbon nanotubes synthesized via microwave-
assisted in situ emulsion polymerization and their optical limiting
properties. Carbon 2007;45:2866–72.
[80] Cheng F, Imin P, Maunders C, Botton G, Adronov A. Soluble,
discrete supramolecular complexes of single-walled carbon nan-
otubes with fluorene-based conjugated polymers. Macromolecules
2008;41:2304–8.
[81] Yang L, Zhang B, Liang Y, Yang B, Kong T, Zhang LM. In situ syn-
thesis of amylose/single-walled carbon nanotubes supramolecular
assembly. Carbohydrate Res 2008;343:2463–7.
[82] Ogoshi T, Yamagishi TA, Nakamoto Y. Supramolecular single-
walled carbon nanotubes (SWCNTs) network polymer made by
hybrids of SWCNTs and water-soluble calix[8]arenas. Chem Com-
mun 2007:4776–8.
[83] Curran SA, Ajayan PM, Blau WJ, Carroll DL, Coleman JN, Dalton AB, et
al. A composite from poly(m-phenylenevinylene-co-2,5-dioctoxy-
p-phenylenevinylene) and carbon nanotubes: a novel material for
molecular optoelectronics. Adv Mater 1998;10:1091–3.
[84] Coleman JN, Dalton AB, Curran S, Rubio A, Davey AP, Drury A, et
al. Phase separation of carbon nanotubes and turbostratic graphite
using a functional organic polymer. Adv Mater 2000;12:213–6.
[85] McCarthy B, Coleman JN, Czerw R, Dalton AB, Carroll DL, Blau WJ.
Microscopy studies of nanotube-conjugated polymer interactions.
Synth Met 2001;121:1225–6.
[86] Dalton AB, Stephan C, Coleman CSJN, McCarthy B, Ajayan
PM, Lefrant S, et al. Selective interaction of a semiconjugated
organic polymer with single-wall nanotubes. J Phys Chem B
2000;104:10012–6.
[87] Kang Y, Taton TA. Micelle-encapsulated carbon nanotubes: a route
to nanotube composites. J Am Chem Soc 2003;125:5650–1.
[88] Shvartzman-Cohen R, Nativ-Roth E, Baskaran E, Levi-Kalisman
Y, Szleifer I, Yerushalmi-Rozen R. Selective dispersion of single-
walled carbon nanotubes in the presence of polymers: the
role of molecular and colloidal length scales. J Am Chem Soc
2004;126:14850–7.
[89] Shvartzman-Cohen R, Kalisman YL, Navi-Roth E, Yerushalmi-
Rozen R. Generic approach for dispersing single-walled carbon
861
nanotubes: the strength of a weak interaction. Langmuir
2004;20:6085–8.
[90] Nativ-Roth E, Shvartzman-Cohen R, Bounioux C, Florent M, Zhang
D, Szleifer I, et al. Physical adsorption of block copolymers to
SWNT and MWNT: a nonwraping mechanism. Macromolecules
2007;40:3676–85.
[91] Niyogi S, Hamon MA, Hu H, Zhao B, Bhowmik P, Sen R, et
al. Chemistry of single-walled carbon nanotubes. Acc Chem Res
2002;35:1105–13.
[92] Park H, Zhao J, Lu JP. Effects of sidewall functionalization on con-
ducting properties of single wall carbon nanotubes. Nano Lett
2006;6:916–9.
[93] Zhang X, Sreekumar TV, Liu T, Kumar S. Properties and structure of
nitric acid oxidized single wall carbon nanotube films. J Phys Chem
B 2004;108:16435–40.
[94] Cho JW, Kim JW, Jung YC, Goo NS. Electroactive shape-memory
polyurethane composites incorporating carbon nanotubes. Macro-
mol Rapid Commun 2005;26:412–6.
[95] Georgakilas V, Kordatos K, Prato M, Guldi DM, Holzingger M, Hirsch
A. Organic functionalization of carbon nanotubes. J Am Chem Soc
2002;124:760–1.
[96] Zhang Y, Shi Z, Gu Z, Iijima S. Structure modification of single-wall
carbon nanotubes. Carbon 2000;38:2055–9.
[97] Datsyuk V, Kalyva M, Papagelis K, Parthenios J, Tasis D, Siokou A,
et al. Chemical oxidation of multiwalled carbon nanotubes. Carbon
2008;46:833–40.
[98] Chen J, Rao AM, Lyuksyutov S, Itkis ME, Hamon MA, Hu H, et al.
Dissolution of full-length single-walled carbon nanotubes. J Phys
Chem B 2001;105:2525–8.
[99] Vasiliev I, Curran SA. Cross linking of thiolated carbon nanotubes:
an ab initio study. J Appl Phys 2007;102, 024317/1–5.
[100] Zhou O, Fleming RM, Murphy DW, Chen CH, Haddon RC,
Ramirez AP, et al. Defects in carbon nanostructures. Science
1994;263:1744–7.
[101] Mickelson ET, Huffman CB, Rinzler AG, Smalley RE, Hauge RH, Mar-
grave JL. Fluorination of single-wall carbon nanotubes. Chem Phys
Lett 1998;296:188–94.
[102] Mickelson ET, Chiang IW, Zimmerman JL, Boul PJ, Lozano J, Liu J, et
al. Solvation of fluorinated single-wall carbon nanotubes in alcohol
solvents. J Phys Chem B 1999;103:4318–22.
[103] Kelly KF, Chiang IW, Mickelson ET, Hauge RH, Margrave JL, Wang
X, et al. Insight into the mechanism of sidewall functionaliza-
tion of single-walled nanotubes: an STM study. Chem Phys Lett
1999;313:445–50.
[104] Boul PJ, Liu J, Mickelson ET, Huffman CB, Ericson LM, Chiang IW, et
al. Reversible sidewall functionalization of buckytubes. Chem Phys
Lett 1999;310:367–72.
[105] Bahr JL, Mickelson ET, Bronikowski MJ, Smalley RE, Tour JM. Disso-
lution of small diameter single-wall carbon nanotubes in organic
solvents? Chem Commun 2001:193–4.
[106] Holzinger M, Vostrowsky O, Hirsch A, Hennrich F, Kappes M, Weiss
R, et al. Sidewall functionalization of carbon nanotubes. Angew
Chem Int Ed 2001;40:4002–5.
[107] Bahr JL, Yang J, Kosynkin DV, Bronikowski MJ, Smalley RE, Tour JM.
Functionalization of carbon nanotubes by electrochemical reduc-
tion of aryl diazonium salts: a bucky paper electrode. J Am Chem
Soc 2001;123:6536–42.
[108] Bahr JL, Tour JM. Highly functionalized carbon nanotubes
using in-situ generated diazonium compounds. Chem Mater
2001;13:3823–4.
[109] Baek JB, Lyons CB, Tan LS. Grafting of vapor-grown carbon
nanofibers via in situ polycondensation of 3-phenoxybenzoic acid
in poly(phosphoric acid). Macromolecules 2004;37:8278–85.
[110] Jin Z, Sun X, Xu G, Goh SH, Ji W. Nonlinear optical properties of
some polymer/multi-walled carbon nanotube composites. Chem
Phys Lett 2000;318:505–10.
[111] Fu K, Huang W, Lin Y, Riddle LA, Carroll DL, Sun YP. Defunctionaliza-
tion of functionalized carbon nanotubes. Nano Lett 2001;1:439–41.
[112] Qin S, Qin D, Ford WT, Resasco DE, Herrera JE. Functional-
ization of single-walled nanotubes with polystyrene via graft-
ing to and grafting from methods. Macromolecules 2004;37:
752–7.
[113] Riggs JE, Guo Z, Carroll DL, Sun YP. Strong luminescence of solubi-
lized carbon nanotubes. J Am Chem Soc 2000;122:5879–80.
[114] Lin Y, Zhou B, Fernando KAS, Liu P, Allard LF, Sun YP. Polymeric car-
bon nanocomposites from carbon nanotubes functionalized with
matrix polymer. Macromolecules 2003;36:7199–204.
[115] Qin S, Qin D, Ford WT, Herrera JE, Resasco DE, Bachilo SM, et al. Solu-
bilization and purification of single-wall carbon nanotubes in water
862 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
by in situ radical polymerization of sodium 4-styrenesulfonate.
Macromolecules 2004;37:3965–7.
[116] Koshio A, Yudasaka M, Zhang M, Iijima S. A simple way to chem-
ically react single-wall carbon nanotubes with organic materials
using ultrasonication. Nano Lett 2001;1:361–3.
[117] Qu LW, Lin Y, Hill DE, Zhou B, Wang W, Sun X, et al. Polyimide-
functionalized carbon nanotubes: synthesis and dispersion in
nanocomposite films. Macromolecules 2004;37:6055–60.
[118] Park C, Ounaies Z, Watson KA, Crooks RE, Smith J, Lowther SE, et al.
Dispersion of single wall carbon nanotubes by in situ polymeriza-
tion under sonication. Chem Phys Lett 2002;364:303–8.
[119] Lou XD, Detrembleur C, Pagnoulle C, Jerome R, Bocharova V, Kiriy
A, et al. Surface modification of multiwalled carbon nanotubes by
poly(2-vinylpyridine): dispersion, selective deposition, and deco-
ration of the nanotubes. Adv Mater 2004;16:2123–7.
[120] Riggs JE, Walker DB, Carroll DL, Sun Y-P. Optical limiting proper-
ties of suspended and solubilized carbon nanotubes. J Phys Chem B
2000;104:7071–6.
[121] Sun Y-P, Huang W, Lin Y, Fu K, Kitaygorodskiy A, Riddle LA, et
al. Soluble dendron-functionalized carbon nanotubes: preparation,
characterization, and properties. Chem Mater 2001;13:2864–9.
[122] Sano M, Kamino A, Shinkai S. Construction of carbon nanotube stars
with dendrimers. Angew Chem Int Ed 2001;40:4661–3.
[123] Cao L, Yang W, Yang J, Wang C, Fu S. Hyperbranched
poly(amidoamine)-modified multi-walled carbon nanotubes via
grafting-from method. Chem Lett 2004;33:490–1.
[124] Blake R, Gunko YK, Coleman J, Cadek M, Fonseca A, Nagy JB, et
al. A generic organometallic approach toward ultra-strong carbon
nanotube polymer composites. J Am Chem Soc 2004;126:10226–7.
[125] Qu L, Veca LM, Lin Y, Kitaygorodskiy A, Chen B, McCall AM, et al.
Soluble nylon-functionalized carbon nanotubes from anionic ring-
opening polymerization from nanotube surface. Macromolecules
2005;38:10328–31.
[126] Yang M, Gao Y, Li H, Adronov A. Functionalization of multiwalled
carbon nanotubes with polyamide 6 by anionic ring-opening poly-
merization. Carbon 2007;45:2327–33.
[127] Park SJ, Cho MS, Lim ST, Cho HJ, Jhon MS. Synthesis and dispersion
characteristics of multi-walled carbon nanotube composites with
poly(methyl methacrylate) prepared by in-situ bulk polymeriza-
tion. Macromol Rapid Commun 2003;24:1070–3.
[128] Yao Z, Braidy N, Botton GA, Adronov A. Polymerization from the sur-
face of single-walled carbon nanotubes—preparation and charac-
terization of nanocomposites. J Am Chem Soc 2003;125:16015–24.
[129] Baskaran D, Mays JW, Bratcher MS. Polymer-grafted multi-
walled carbon nanotubes through surface-initiated polymeriza-
tion. Angew Chem Int Ed 2004;43:2138–42.
[130] Kong H, Gao C, Yan D. Functionalization of multiwalled carbon
nanotubes by atom transfer radical polymerization and defunction-
alization of the products. Macromolecules 2004;37:4022–30.
[131] Kong H, Luo P, Gao C, Yan D. Polyelectrolyte-functionalized
multiwalled carbon nanotubes: preparation, characterization and
layer-by-layer self-assembly. Polymer 2005;46:2472–85.
[132] Kong H, Gao C, Yan D. Constructing amphiphilic polymer brushes
on the convex surfaces of multi-walled carbon nanotubes by
in situ atom transfer radical polymerization. J Mater Chem
2004;14:1401–5.
[133] Kong H, Li W, Gao C, Yan D, Jin Y, Walton DRM, et al. Poly(N-
isopropylacrylamide)-coated carbon nanotubes: temperature-
sensitive molecular nanohybrids in water. Macromolecules
2004;37:6683–6.
[134] Qin S, Qin D, Ford WT, Herrera JE, Resasco DE. Grafting of poly(4-
vinylpyridine) to single-walled carbon nanotubes and assembly of
multilayer films. Macromolecules 2004;37:9963–7.
[135] Wu W, Zhang S, Li Y, Li J, Liu L, Qin Y, et al. PVK-modified single-
walled carbon nanotubes with effective photoinduced electron
transfer. Macromolecules 2003;36:6286–8.
[136] Gao C, Vo CD, Jin YZ, Li W, Armes SP. Multihydroxy polymer-
functionalized carbon nanotubes: synthesis, derivation, and metal
loading. Macromolecules 2005;38:8634–48.
[137] Li J, He WD, Yang LP, Sun XL, Hua Q. Preparation of multi-
walled carbon nanotubes grafted with synthetic poly(L-lysine)
through surface-initiated ring opening polymerization. Polymer
2007;48:4352–60.
[138] Zeng HL, Gao C, Yan DY. Poly(␧-caprolactone)-functionalized car-
bon nanotubes and their biodegradation properties. Adv Funct
Mater 2006;16:812–8.
[139] Chen GX, Kim HS, Park BH, Yoon JS. Synthesis of poly(L-lactide)-
functionalized multiwalled carbon nanotubes by ring-opening
polymerization. Macromol Chem Phys 2007;208:389–98.
[140] Yan YH, Cui J, Chan-Park MB, Wang X, Wu QY. Systematic studies of
covalent functionalization of carbon nanotubes via argon plasma-
assisted UV grafting. Nanotechnology 2007;18, 115712/1–7.
[141] Yang J, Hu J, Wang C, Qin Y, Guo Z. Fabrication and characterization
of soluble multi-walled carbon nanotubes reinforced P(MMA-co-
EMA) composites. Macromol Mat Eng 2004;289:828–32.
[142] Huisgen R. 1,3-Dipolar cycloadditions-introduction, survey, mech-
anism in 1,3-dipolar cycloaddition chemistry. In: Padwa A, editor.
1,3-Dipolar cycloaddition chemistry, vol. 1. New York: Wiley; 1984.
p. 1–176.
[143] Kolb HC, Finn MG, Sharpless KB. Click chemistry: diverse chem-
ical function from a few good reactions. Angew Chem Int Ed
2001;40:2004–21.
[144] Kolb HC, Sharpless KB. The growing impact of click chemistry on
drug discovery. Drug Disc Today 2003;8:1128–37.
[145] Tornøe CW, Christensen C, Meldal M. Peptidotriazoles on solid
phase: [1,2,3]-triazoles by regiospecific copper(I)-catalyzed 1,3-
dipolar cycloadditions of terminal alkynes to azides. J Org Chem
2002;67:3057–64.
[146] Joralemon MJ, OReilly RK, Matson JB, Nugent AK, Hawker CJ, Woo-
ley KL. Dendrimers clicked together divergently. Macromolecules
2005;38:5436–43.
[147] Wu P, Feldman AK, Nugent AK, Hawker CJ, Scheel A, Voit B, et al.
Efficiency and fidelity in a click-chemistry route to triazole den-
drimers by the copper(I)-catalyzed ligation of azides and alkynes.
Angew Chem Int Ed 2004;43:3928–32.
[148] Helms B, Mynar JL, Hawker CJ, Frechet JMJ. Dendronized lin-
ear polymers via click chemistry. J Am Chem Soc 2004;126:
15020–1.
[149] Malkoch M, Schleicher K, Drockenmuller E, Hawker CJ, Russell TP,
Wu P, et al. Structurally diverse dendritic libraries: a highly efficient
functionalization approach using click chemistry. Macromolecules
2005;38:3663–78.
[150] Lee JW, Kim JH, Kim BK, Shin WS, Jin SH. Synthesis of Frechet type
dendritic benzyl propargyl ether and Frechet type triazole den-
drimer. Tetrahedron 2006;62:894–900.
[151] Link AJ, Vink MKS, Tirrell DA. Presentation and detection of azide
functionality in bacterial cell surface proteins. J Am Chem Soc
2004;126:10598–602.
[152] Kumar I, Rode CV. Efficient synthesis of fused 1,2,3-triazolo-delta-
lactams using huisgen [3+2] dipolar cycloaddition click-chemistry
in water. Chem Lett 2007;36:592–3.
[153] Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. A stepwise
huisgen cycloaddition process: copper(I)-catalyzed regioselective
ligation of azides and terminal alkynes. Angew Chem Int Ed
2002;41:2596–9.
[154] Horne WS, Yadav MK, Stout CD, Ghadiri MR. Heterocyclic peptide
backbone modifications in an alpha-helical coiled coil. J Am Chem
Soc 2004;126:15366–7.
[155] Li H, Cheng F, Duft AM, Adronov A. Functionalization of single-
walled carbon nanotubes with well-defined polystyrene by click
coupling. J Am Chem Soc 2005;127:14518–24.
[156] Kumar I, Rana S, Rode CV, Cho JW. Functionalization of single-
walled carbon nanotubes with azides derives from amino acids
using click chemistry. J Nanosci Nanotech 2008;8:3351–6.
[157] Campidelli S, Ballesteros B, Filoramo A, Dıaz DD, Torre G, Torres T,
et al. Facile decoration of functionalized single-wall carbon nan-
otubes with phthalocyanines via click chemistry. J Am Chem Soc
2008;130:11503–9.
[158] Li H, Adronov A. Water soluble SWCNTs from sulfonation of
nanotube-bound polystyrene. Carbon 2007;45:984–90.
[159] Rana S, Cho JW. Synthesis and characterization of polyurethane-
functionalized carbon nanotubes with shape memory effect using
click chemistry. Proceed intern confer intelligent textiles 2007, Seoul,
Korea; 2007. p. 142–3.
[160] Wildgoose GG, Banks CE, Compton RG. Metal nanoparticles and
related materials supported on carbon nanotubes: methods and
applications. Small 2006;2:182–93.
[161] Voggu R, Suguna P, Chandrasekaran S, Rao CNR. Assembling cova-
lently linked nanocrystals and nanotubes through click chemistry.
Chem Phys Lett 2007;443:118–21.
[162] He H, Zhang Y, Gao C, Wu J. Clicked magnetic nanohybrids with a
soft polymer interlayer. Chem Commun 2009:1655–7.
[163] Rana S, Kumar I, Yoo HJ, Cho JW. Assembly of gold nanoparticles on
single-walled carbon nanotubes by using click chemistry. J Nanosci
Nanotech 2009;9:3261–3.
[164] Zhang Y, He H, Gao C, Wu J. Covalent layer-by-layer functionaliza-
tion of multiwalled carbon nanotubes by click chemistry. Langmuir
2009;25:5814–24.
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[165] Zhang Y, He H, Gao C. Clickable macroinitiator strategy to
build amphiphilic polymer brushes on carbon nanotubes. Macro-
molecules 2008;41:9581–94.
[166] Hong CY, Pan CY. Functionalized carbon nanotubes responsive to
environmental stimuli. J Mater Chem 2008;18:1831–6.
[167] Liu J, Nie Z, Gao Y, Adronov A, Li H. Click coupling between
alkyne-decorated multiwalled carbon nanotubes and reactive
PDMA-PNIPAM micelles. J Polym Sci Part A Polym Chem
2008;46:7187–99.
[168] Guo Z, Liang L, Liang JJ, Ma YF, Yang XY, Ren DM, et al. Covalently
␤-cyclodextrin modified single-walled carbon nanotubes: a novel
artificial receptor synthesized by click chemistry. J Nanopart Res
2008;10:1077–83.
[169] Li C, Pang XJ, Qu MZ, Zhang QT, Wang B, Zhang BL, et al. Fab-
rication and characterization of polycarbonate/carbon nanotubes
composites. Compos Part A 2005;37:1485–9.
[170] Xia H, Wang Q, Qiu G. Polymer-encapsulated carbon nanotubes
prepared through ultrasonically initiated in situ emulsion polymer-
ization. Chem Mater 2003;15:3879–86.
[171] Suslick KS. Sonochemistry. Science 1990;247:1439–45.
[172] Safadi B, Andrews R, Grulke EA. Multiwalled carbon nanotubes
polymer composites: synthesis and characterization of thin films.
J Appl Polym Sci 2002;84:2660–9.
[173] Sahoo NG, Jung YC, Yoo HJ, Cho JW. Effect of functional-
ized carbon nanotubes on molecular interaction and properties
of polyurethane composites. Macromol Chem Phys 2006;207:
1773–80.
[174] Vigolo B, Penicaud A, Coulon C, Sauder C, Pailler R, Journet C, et
al. Macroscopic fibers and ribbons of oriented carbon nanotubes.
Science 2000;290:1331–4.
[175] Saran N, Parikh K, Suh DS, Munoz E, Kolla H, Manhor SK. Fabri-
cation and characterization of thin films of single-walled carbon
nanotubes bundles on flexible plastic substrates. J Am Chem Soc
2004;126:4462–3.
[176] Barrau S, Demont P, Perez E, Peigney A, Laurent C, Laca-
banne C. Effect of palmitic acid on the electrical conductivity
of carbon nanotubes-epoxy resin composites. Macromolecules
2003;36:9678–80.
[177] Camponeschi E, Florkowski B, Vance R, Garrett G, Garmestani
H, Tannenbaum R. Uniform directional alignment of single-
walled carbon nanotubes in viscous polymer flow. Langmuir
2006;22:1858–62.
[178] Chen W, Tao X. Self-organizing alignment of carbon nan-
otubes in thermoplastic polyurethane. Macromol Rapid Commun
2005;26:1763–7.
[179] Qian D, Dickey EC, Andrews R, Rantell T. Load transfer and defor-
mation mechanisms in carbon nanotube-polystyrene composites.
Appl Phys Lett 2000;76:2868–70.
[180] Wong M, Paramsothy M, Xu XJ, Ren Y, Li S, Liao K. Physi-
cal interaction at carbon nanotube-polymer interface. Polymer
2003;44:7757–64.
[181] Kota AK, Cipriano BH, Duesterberg MK, Gershon AL, Powell
D, Raghavan SR, et al. Electrical and reheological perco-
lation in polystyre/MWCNT nanocomposites. Macromolecules
2007;40:7400–6.
[182] Sandler J, Shaffer MSP, Prasse T, Bauhofer W, Schulte K, Windle
AH. Development of a dispersion process for carbon nanotubes in
an epoxy matrix and the resulting electrical properties. Polymer
1999;40:5967–71.
[183] Song YS, Youn JR. Influence of dispersion states of carbon nan-
otubes on physical properties of epoxy nanocomposites. Carbon
2005;43:1378–85.
[184] Shaffer MSP, Windle AH. Fabrication and characterization of
carbon nanotube/poly(vinyl alcohol) composites. Adv Mater
1999;11:937–41.
[185] Chae HG, Sreekumar TV, Uchida T, Kumar S. A compar-
ison of reinforcement efficiency of various types of car-
bon nanotubes in polyacrylonitrile fiber. Polymer 2005;46:
10925–35.
[186] Bin Y, Kitanaka M, Zhu D, Matsuo M. Development of highly
oriented polyethylene filled with aligned carbon nanotubes
by gelation/crystallization from solutions. Macromolecules
2003;36:6213–9.
[187] Andrews R, Jacques D, Minot M, Rantell T. Fabrication of carbon
multiwall nanotube/polymer composites by shear mixing. Micro-
mol Mater Eng 2002;287:395–403.
[188] Zhang WD, Shen L, Phang IY, Liu T. Carbon nanotubes reinforced
nylon-6 composite prepared by simple melt-compounding. Macro-
molecules 2004;37:256–9.
863
[189] Bocchini S, Frache A, Camino G, Claes M. Polyethylene thermal
oxidative stabilisation in carbon nanotubes based nanocomposites.
Eur Polym J 2007;43:3222–35.
[190] McNally T, Potschkeb P, Halley P, Murphy M, Martin D, Bell SEJ, et al.
Polyethylene multiwalled carbon nanotube composites. Polymer
2005;46:8222–32.
[191] Lopez Manchado MA, Valentini L, Biagiotti J, Kenny JM. Thermal
and mechanical properties of single-walled carbon nanotubes-
polypropylene composites prepared by melt processing. Carbon
2005;43:1499–505.
[192] Valentini L, Biagiotti J, Kenny JM, Santucci S. Morphological
characterization of single-wall carbon nanotube/polypropylene
composites. Compos Sci Technol 2003;63:1149–53.
[193] Zhang H, Zhang Z. Impact behaviour of polypropylene filled with
multi-walled carbon nanotubes. Eur Polym J 2007;43:3197–207.
[194] Tang W, Santare MH, Advani SG. Melt processing and mechanical
property characterization of multi-walled carbon nanotube/high
density polyethylene (MWNT/HDPE) composite films. Carbon
2003;41:2779–85.
[195] Potschke P, Fornes TD, Paul DR. Rheological behavior of mul-
tiwalled carbon nanotube/polycarbonate composites. Polymer
2002;43:3247–55.
[196] Potschke P, Bhattacharyya AR, Janke A. Morphology and electri-
cal resistivity of melt mixed blends of polyethylene and carbon
nanotube filled polycarbonate. Polymer 2003;44:8061–9.
[197] Pötschke P, Bhattacharyya AR, Janke A. Melt mixing of polycarbon-
ate with multiwalled carbon nanotubes: microscopic studies on the
state of dispersion. Eur Polym J 2004;40:137–48.
[198] Jin Z, Pramoda KP, Xu G, Goh SH. Dynamic mechanical behav-
ior of melt-processed multi-walled carbon nanotube/poly(methyl
methacrylate) composites. Chem Phys Lett 2001;337:43–7.
[199] Zeng J, Saltysiak B, Johnson WS, Schiraldi DA, Kumar S. Process-
ing and properties of poly(methyl methacrylate)/carbon nano fiber
composites. Compos Part B 2004;35:173–8.
[200] Haggenmueller R, Gommans HH, Rinzler AG, Fischer JE, Winey KI.
Aligned single-wall carbon nanotubes in composites by melt pro-
cessing methods. Chem Phys Lett 2000;330:219–25.
[201] Gorga RE, Cohen RE. Toughness enhancements in poly(methyl
methacrylate) by addition of oriented multiwall carbon nanotubes.
J Polym Sci Part B Polym Phys 2004;42:2690–702.
[202] Zeng Y, Ying Z, Du J, Cheng HM. Effects of carbon nanotubes on
processing stability of polyoxymethylene in melt-mixing process.
J Phys Chem C 2007;111:13945–50.
[203] Siochi EJ, Working DC, Park C, Lillehei PT, Rouse JH, Topping CC,
et al. Melt processing of SWNT-polyimide nanocomposite fibres.
Compos Part B 2004;35:439–46.
[204] Meincke O, Kaempfer D, Weickmann H, Friedrich C, Vathauer
M, Warth H. Mechanical properties and electrical conductivity of
carbon-nanotube filled polyamide-6 and its blends with acryloni-
trile/butadiene/styrene. Polymer 2004;45:739–48.
[205] Hu N, Zhou H, Dang G, Rao X, Chen C, Zhang W. Efficient dispersion
of multi-walled carbon nanotubes by in situ polymerization. Polym
Int 2007;56:655–9.
[206] So HH, Cho JW, Sahoo NG. Effect of carbon nanotubes on mechanical
and electrical properties of polyimide/carbon nanotubes nanocom-
posites. Eur Polym J 2007;43:3750–6.
[207] Jia Z, Wang Z, Xu C, Liang J, Wei B, Wu D, et al. Study on poly(methyl
methacrylate): carbon nanotube composites. Mater Sci Eng A
1999;271:395–400.
[208] Putz KW, Mitchell CA, Krishnamoorti R, Green PF. Elastic modu-
lus of single-walled carbon nanotube/poly(methyl methacrylate)
nanocomposites. J Polym Sci Part B Polym Phys 2004;42:
2286–93.
[209] Sung JH, Kim HS, Jin HJ, Choi HJ, Chin IJ. Nanofibrous membranes
prepared by multiwalled carbon nanotube/poly(methyl methacry-
late) composites. Macromolecules 2004;37:9899–902.
[210] Hwang GL, Shieh YT, Hwang KC. Efficient load transfer to polymer-
grafted multiwalled carbon nanotubes in polymer composites. Adv
Funct Mater 2004;14:487–91.
[211] Velasco-Santos C, Martinez-Hernandez AL, Fisher FT, Ruoff R, Cas-
tano VM. Improvement of thermal and mechanical properties of
carbon nanotube composites through chemical functionalization.
Chem Mater 2003;15:4470–5.
[212] Karim MR, Lee CJ, Park YT, Lee MS. SWNTs coated by con-
ducting polyaniline: synthesis and modified properties. Synt Met
2005;151:131–5.
[213] Long Y, Chen Z, Zhang X, Zhang J, Liu Z. Electrical properties of multi-
walled carbon nanotube/polypyrrole nanocables: percolation-
dominated conductivity. J Phys D Appl Phys 2004;37:1965–9.
864 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[214] An KH, Jeong SY, Hwang HR, Lee YH. Enhanced sensivity of a gar
sensor incorporating single-walled carbon nanotube-polypyrrole
nanocomposites. Adv Mater 2004;16:1005–9.
[215] Fan J, Wan M, Zhu D, Chang B, Pan Z, Xie S. Synthesis, character-
izations, and physical properties of carbon nanotubes coated by
conducting polypyrrole. J Appl Polym Sci 1999;74:2605–10.
[216] Sahoo NG, Jung YC, So HH, Cho JW. Polypyrrole coated carbon
nanotubes: synthesis, characterization, and enhanced electrical
properties. Synth Met 2007;157. p. 179–374.
[217] Yoo HJ, Jung YC, Sahoo NG, Cho JW. Electroactive shape memory
polyurethane nanocomposites from in-situ polymerization with
carbon nanotubes. J Macromol Sci Part B Phys 2006;45:441–51.
[218] Xia H, Song M. Preparation and characterization of polyurethane-
carbon nanotube composites. Soft Matter 2005;1:386–94.
[219] Xia H, Song M. Preparation and characterization of polyurethane
grafted single-walled carbon nanotubes and derived polyurethane
nanocomposites. J Mater Chem 2006;16:1843–51.
[220] Jung YC, Sahoo NG, Cho JW. Polymeric nanocomposites of
polyurethane block copolymers and functionalized multi-walled
carbon nanotubes as crosslinkers. Macromol Rapid Commun
2006;27:126–31.
[221] Gao J, Itkis ME, Yu A, Bekyarova E, Zhao B, Haddon RC. Continu-
ous spinning of a single-walled carbon nanotube-nylon composite
fiber. J Am Chem Soc 2005;127:3847–54.
[222] Tomalia DA, Baker H, Dewald J, Hall M, Kallos G, Martin S, et
al. Dendritic macromolecules: synthesis of starburst dendrimers.
Macromolecules 1986;19:2466–8.
[223] Cloninger MJ. Biological applications of dendrimers. Curr Opin
Chem Biol 2002;6:742–8.
[224] Ishizu K, Tsubaki K, Mori A, Uchida S. Architecture of nanostruc-
tured polymers. Prog Polym Sci 2003;28:27–54.
[225] Zeng F, Zimmerman SC. Dendrimers in superamolecular chemistry:
from recognition to self-assembly. Chem Rev 1997;97:1681–712.
[226] Matthews OA, Shipway AN, Stoddart JF. Dendrimers-branching
out from curiosities into new technologies. Prog Polym Sci
1998;23:1–56.
[227] Gao C, Yan D. Hyperbranched polymers: from synthesis to applica-
tions. Prog Polym Sci 2004;29:183–275.
[228] Hawker CJ, Frechet JMJ. Preparation of polymers with controlled
molecular architecture. A new convergent approach to dendritic
macromolecules. J Am Chem Soc 1990;112:7638–47.
[229] Huang F, Gibson HW. Formation of supramolecular hyperbranched
polymer from self-organization of an AB2 monomer contain-
ing a crown ether and two paraquat moieties. J Am Chem Soc
2004;126:14738–9.
[230] Yates CR, Hayes W. Synthesis and applications of hyperbranched
polymers. Eur Polym J 2004;40:1257–81.
[231] Feng QP, Xie XM, Liu YT, Zhao W, Gao YF. Synthesis of
hyperbranched aromatic polyamide-imide and its grafting onto
multiwalled carbon nanotubes. J Appl Polym Sci 2007;106:
2413–21.
[232] Davis JJ, Coleman KS, Azamian BR, Bagshaw CB, Green MLH. Chem-
ical and biochemical sensing with modified single walled carbon
nanotubes. Chem Eur J 2003;9:3732–9.
[233] Xu Y, Gao C, Kong H, Yan D, Jin YZ, Watts PCP. Growing mul-
tihydroxyl hyperbranched polymers on the surfaces of carbon
nanotubes by in situ ring-opening polymerization. Macromolecules
2004;37:8846–53.
[234] Yang Y, Xie X, Yang Z, Wang X, Cui W, Yang J, et al.
Controlled synthesis and novel solution rheology of hyper-
branched poly(urea-urethane)-functionalized multiwalled carbon
nanotubes. Macromolecules 2007;40:5858–67.
[235] Hwang SH, Moorefield CN, Wang P, Jeong KU, Cheng SZD, Kotta
KK, et al. Dendron-tethered and templated CdS quantum dots on
single-walled carbon nanotubes. J Am Chem Soc 2006;128:7505–9.
[236] Wang X, Liu H, Jin Y, Chen C. Polymer-functionalized multi-walled
carbon nanotubes as lithium intercalation hosts. J Phys Chem B
2006;110:10236–40.
[237] Martin RB, Qu L, Lin Y, Harruff BA, Bunker CE, Gord JR, et al. Func-
tionalized carbon nanotubes with tethered pyrenes: synthesis and
photophysical properties. J Phys Chem B 2004;108:11447–53.
[238] Campidelli S, Sooambar C, Lozano DE, Ehli C, Guldi DM, Prato
M. Dendrimer-functionalized single-wall carbon nanotubes: syn-
thesis, characterization, and photoinduced electron transfer. J Am
Chem Soc 2006;128:12544–52.
[239] Tao L, Chen G, Mantovani G, York S, Haddleton DM. Modification
of multi-wall carbon nanotube surfaces with poly(amidoamine)
dendrons: synthesis and metal templating. Chem Commun
2006:4949–51.
[240] Yuan W, Jiang G, Che J, Qi X, Xu R, Chang MW, et al. Deposition of
silver nanoparticles on multiwalled carbon nanotubes grafted with
hyperbranched poly(amidoamine) and their antimicrobial effects.
J Phys Chem C 2008;112:18754–9.
[241] Valentini L, Trentini M, Mengoni F, Alongi J, Armentano I,
Ricco L, et al. Synthesis and photoelectrical properties of carbon
nanotube–dendritic porphyrin light harvesting molecule systems.
Diamond Rel Mater 2007;16:658–63.
[242] Gu L, Lin Y, Qu L, Sun YP. Carbon nanotubes as a scaffold to display
paired sugars in solution. Biomacromolecules 2006;7:400–2.
[243] Yang H, Wang SC, Mercier P, Akins DL. Diameter selective dispersion
of single-walled carbon nanotubes using a water soluble biocom-
patible polymer. Chem Commun 2006:1425–7.
[244] Gao C, Muthukrishnan S, Li W, Yuan J, Xu Y, Mueller AHE. Linear
and hyperbranched glycopolymer-functionalized carbon nan-
otubes: synthesis, kinetics, and characterization. Macromolecules
2007;40:1803–15.
[245] Adeli M, Bahari A, Hekmatara H. Carbon nanotube-graft-poly(citric
acid) nanocomposites. Nano 2008;3:37–44.
[246] Hong CY, You YZ, Wu D, Liu Y, Pan CY. Multiwalled carbon
nanotubes grafted with hyperbranched polymer shell via SCVP.
Macromolecules 2005;38:2606–11.
[247] Yang Y, Xie X, Wu J, Yang Z, Wang X, Mai YW. Multiwalled
carbon nanotubes functionalized by hyperbranched poly(urea-
urethane)s by a one-pot polycondensation. Macromol Rapid
Commun 2006;27:1695–701.
[248] Choi JY, Oh SJ, Lee HJ, Wang DH, Tan LS, Baek JB. In-situ
grafting of hyperbranched poly(ether ketone)s onto multiwalled
carbon nanotubes via the A3 + B2 approach. Macromolecules
2007;40:4474–80.
[249] Choi JY, Han SW, Huh WS, Tan LS, Baek JB. In situ graft-
ing of carboxylic acid-terminated hyperbranched poly(ether-
ketone) to the surface of carbon nanotubes. Polymer 2007;48:
4034–40.
[250] Jeon IY, Tan LS, Baek JB. Nanocomposites derived from in situ
grafting of linear and hyperbranched poly(ether-ketone)s contain-
ing flexible oxyethylene spacers onto the surface of multiwalled
carbon nanotubes. J Polym Sci Part A Polym Chem 2008;46:
3471–81.
[251] Zhou W, Xu J, Shi W. Surface modification of multi-wall carbon
nanotube with ultraviolet-curable hyperbranched polymer. Thin
Solid Films 2008;516:4076–82.
[252] Star A, Stoddart JF. Dispersion and solubilization of single-walled
carbon nanotubes with a hyperbranched polymer. Macromolecules
2002;35:7516–20.
[253] Rana S, Karak N, Cho JW, Kim YH. Enhanced dispersion of car-
bon nanotubes in hyperbranched polyurethane and properties of
nanocomposites. Nanotechnology 2008;19, 495707/1–8.
[254] Kim HH, Rana S, Cho JW, Lee JY. High concentration carbon nan-
otubes in hyperbranched polyurethane and their characteristics,
submitted.
[255] Ogoshi T, Saito T, Yamagishi T, Nakamoto Y. Solubilization of single-
walled carbon nanotubes by entanglements between them and
hyperbranched phenolic polymer. Carbon 2009;47:117–23.
[256] Zhou W, Lv S, Shi W. Preparation of micelle-encapsulated
single-wall and multi-wall carbon nanotubes with amphiphilic
hyperbranched polymer. Eur Polym J 2008;44:587–601.
[257] Zhang J, Zheng Y, Yu P, Mo S, Wang R. The synthesis of
functionalized carbon nanotubes by hyperbranched poly(amine-
ester) with liquid-like behavior at room temperature. Polymer
2009;50:2953–7.
[258] Sawada H, Shindo K, Iidzuka J, Ueno K, Hamazaki K. Solu-
bilization and applications of single-walled carbon nanotubes
into aqueous and organic media by the use of nanometer size-
controlled fluoroalkyl end-capped oligomeric aggregates. Eur
Polym J 2005;41:2232–9.
[259] Sawada H, Naitoh N, Kasai R, Suzuki M. Dispersion of single-
walled carbon nanotubes in water by the use of novel fluorinated
dendrimer-type copolymers. J Mater Sci 2008;43:1080–6.
[260] Yoshioka H, Suzuki M, Mugisawa M, Naitoh N, Sawada H. Synthesis
and applications of novel fluorinated dendrimer-type copolymer
by the use of fluoroalkyanoyl peroxide as a key intermediate. J Coll
Interf Sci 2007;308:4–10.
[261] Valentini L, Armentano I, Ricco L, Alongi J, Pennelli G, Mariani A,
et al. Selective interaction of single-walled carbon nanotubes with
conducting dendrimer. Diamond Rel Mater 2006;15:95–9.
[262] Zheng H, Xue H, Zhang Y, Shen Z. A glucose biosensor based on
microporous polyacrylonitrile synthesized by single rare-earth cat-
alyst. Biosens Bioelectron 2002;17:541–5.
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[263] Yi X, Xian JH, Yuan CH. Direct electrochemistry of horseradish
peroxidase immobilized on a colloid/cysteamine-modified gold
electrode. Anal Biochem 2000;278:22–8.
[264] Xu JJ, Chen HY. Amperometric glucose sensor based on
glucose oxidase immobilized in electrochemically generated
poly(ethacridine). Anal Chim Acta 2000;423:101–6.
[265] Xu L, Zhu Y, Tang L, Yang X, Li C. Biosensor based on
self-assembling glucose oxidase and dendrimer-encapsulated Pt
nanoparticles on carbon nanotubes for glucose detection. Electro-
analysis 2007;19:717–22.
[266] Sahoo NG, Jung YC, So HH, Cho JW. Synthesis of polyurethane
nanocomposites of functionalized carbon nanotubes by in-
situ polymerization methods. J Korean Phys Soc 2007;51:
S1–6.
[267] Potschke P, Haussler L, Pegel S, Steinberger R, Scholz G. Thermo-
plastic polyurethane filled with carbon nanotubes for electrical
dissipative and conductive applications. Kauts Gummi Kunst
2007;60:432–7.
[268] Lee CH, Liu JY, Chen SL, Wang YZ. Miscibility and proper-
ties of acid-treated multi-walled carbon nanotubes/polyurethane
nanocomposites. Polymer J 2007;39:138–46.
[269] Koerner H, Liu W, Alexander M, Mirau P, Dowty H, Vaia RA.
Deformation-morphology correlations in electrically conductive
carbon nanotube-thermoplastic polyurethane nanocomposites.
Polymer 2005;46:4405–20.
[270] Ryszkowska J, Jurczyk-Kowalska M, Szymborski T, Kurzydlowski KJ.
Dispersion of carbon nanotubes in polyurethane matrix. Physica E
2007;39:124–7.
[271] Meng Q, Hu J, Zhu Y. Shape-memory polyurethane/multiwalled
carbon nanotube fibers. J Appl Polym Sci 2007;106:837–48.
[272] Chen XH, Chen XJ, Lin M, Zhong WB, Chen XH, Chen ZH.
Functionalized multi-walled carbon nanotubes prepared by in
situ polycondensation of polyurethane. Macromol Chem Phys
2007;208:964–72.
[273] Xiong JW, Zheng Z, Qin X, Li M, Li HQ, Wang X. The thermal and
mechanical properties of a polyurethane/multi-walled carbon nan-
otube composite. Carbon 2006;44:2701–7.
[274] Kwon JY, Kim HD. Preparation and properties of acid-treated
multiwalled carbon nanotube/waterborne polyurethane nanocom-
posites. J Appl Polym Sci 2005;96:595–604.
[275] Sahoo NG, Jung YC, Cho JW. Electroactive shape memory
effect of polyurethane composites filled with carbon nan-
otubes and conducting polymer. Mater Manufac Proc 2007;22:
419–23.
[276] Sahoo NG, Jung YC, Yoo HJ, Cho JW. Influence of carbon nanotubes
and polypyrrole on the thermal, mechanical and electroactive
shape-memory properties of polyurethane nanocomposites. Com-
pos Sci Technol 2007;67:1920–9.
[277] Kuan HC, Ma CCM, Chang WP, Yuen SM, Wu HH, Lee TM. Synthesis,
thermal, mechanical and rheological properties of multiwall car-
bon nanotube/waterborne polyurethane nanocomposite. Compos
Sci Technol 2005;65:1703–10.
[278] Xia H, Song M, Jin J, Chen L. Poly(propylene glycol)-grafted multi-
walled carbon nanotube polyurethane. Macromol Chem Phys
2006;27:1945–52.
[279] Wang TL, Tseng CG. Polymeric carbon nanocomposites from
multiwalled carbon nanotubes functionalized with segmented
polyurethane. J Appl Polym Sci 2007;105:1642–50.
[280] McClory C, McNally T, Brennan GP, Erskine J. Thermosetting
polyurethane multiwalled carbon nanotube composites. J Appl
Polym Sci 2007;105:1003–11.
[281] Sen R, Zhao B, Perea D, Itkis ME, Hu H, Love J, et al. Prepara-
tion of single walled carbon nanotube reinforced polystyrene and
polyurethane nanofibers and membranes by electrospinning. Nano
Lett 2004;4:459–64.
[282] Yuen SM, Ma CCM, Chiang CL, Lin YY, Teng CC. Preparation and
morphological, electrical, and mechanical properties of polyimide-
grafted MWCNT/polyimide composite. J Polym Sci Part A Polym
Chem 2007;45:3349–58.
[283] Ounaies Z, Park C, Wise KE, Siochi EJ, Harrison JS. Electrical
properties of single wall carbon nanotube reinforced polyimide
composites. Compos Sci Technol 2003;63:1637–46.
[284] Yuen SM, Ma CCM, Lin YY, Kuan HC. Preparation, morphol-
ogy and properties of acid and amine modified multiwalled
carbon nanotube/polyimide composite. Compos Sci Technol
2007;67:2564–73.
[285] Zhu BK, Xie SH, Xu ZK, Xu YY. Preparation and properties of the
polyimide/multi-walled carbon nanotubes nanocomposites. Com-
pos Sci Technol 2006;66:548–54.
865
[286] Jiang X, Bin Y, Matsuo M. Electrical and mechanical properties of
polyimide-carbon nanotubes composites fabricated by in situ poly-
merization. Polymer 2005;46:7418–24.
[287] Yu A, Hu H, Bekyarova E, Itkis ME, Gao J, Zhao B, et al. Incorporation
of highly dispersed single-walled carbon nanotubes in a polyimide
matrix. Compos Sci Technol 2006;66:1190–7.
[288] Ogasawara T, Ishida Y, Ishikawa T, Yokota R. Characterization
of multi-walled carbon nanotube/phenylethynyl terminated poly-
imide composites. Compos Part A 2004;35:67–74.
[289] Chou WJ, Wang CC, Chen CY. Characteristics of polyimide-based
nanocomposites containing plasma-modified multi-walled carbon
nanotubes. Compos Sci Technol 2008;68:2208–13.
[290] Yuen SM, Ma CHM, Chiang CL, Teng CC, Yu YH. Poly(vinyl-
triethoxysilane) modified MWCNT/polyimide nanocomposites—
preparation, morphological, mechanical, and electrical properties.
J Polym Sci Part A Polym Chem 2008;46:803–16.
[291] Sandler JKW, Kirk JE, Kinloch IA, Shaffer MSP, Windle AH. Ultra-low
electrical percolation threshold in carbon-nanotube-epoxy com-
posites. Polymer 2003;44:5893–9.
[292] Li J, Ma PC, Chow WS, To CK, Tang BZ, Kim JK. Correlations between
percolation threshold, dispersion state, and aspect ratio of carbon
nanotubes. Adv Funct Mater 2007;17:3207–15.
[293] Choi ES, Brooks JS, Eaton DL, Al Haik MS, Hussaini MY, Garmestani
H, et al. Enhancement of thermal and electrical properties of carbon
nanotube polymer composites by magnetic field processing. J Appl
Phys 2003;94:6034–9.
[294] Fangming D, Fisher JE, Winey KI. Coagulation method for preparing
single-walled carbon nanotube/poly(methyl methacrylate) com-
posites and their modulus, electrical conductivity, and thermal
stability. J Polym Sci Part B Polym Phys 2003;41:3333–8.
[295] Bai JB, Allaoui A. Effect of the length and the aggregate size of
MWNTs on the improvement efficiency of the mechanical and elec-
trical properties of nanocomposites-experimental investigation.
Compos Part A 2003;34:689–94.
[296] Bryning MB, Islam MF, Kikkawa JM, Yodh AG. Very low conductivity
threshold in bulk isotropic single-walled carbon nanotube-epoxy
composites. Adv Mater 2005;17:1186–91.
[297] Ma PC, Kim JK, Tang BZ. Effects of silane functionalization on the
properties of carbon nanotube/epoxy nanocomposites. Compos Sci
Technol 2007;67:2965–72.
[298] Tamburri E, Orlanducci S, Terranova ML, Valentine F, Palleschi
G, Curulli A, et al. Modulation of electrical properties in single-
walled carbon nanotube/conducting polymer composites. Carbon
2005;43:1213–21.
[299] Li S, Qin Y, Shi J, Guo ZX, Li Y, Zhu D. Electrical properties of
soluble carbon nanotube/polymer composite films. Chem Mater
2005;17:130–5.
[300] Grossiord N, Loos J, Laake LV, Maugey M, Zakri C, Koning CE, et
al. High-conductivity polymer nanocomposites obtained by tailor-
ing the characteristics of carbon nanotube fillers. Adv Funct Mater
2008;18:3226–34.
[301] Ramasubramaniam R, Chen J, Liu H. Homogeneous carbon nan-
otube/polymer composites for electrical applications. Appl Phys
Lett 2003;83:2928–30.
[302] Li HC, Lu SY, Syue SH, Hsu WK, Chang SC. Conductivity enhancement
of carbon nanotube composites by electrolyte addition. Appl Phys
Lett 2008;93, 033104/1–3.
[303] Mishra SR, Rawat HS, Mehendale SC, Rustagi KC, Sood AK, Bandy-
opadhyay R, et al. Optical limiting in single-walled carbon nanotube
suspensions. Chem Phys Lett 2000;317:510–4.
[304] Vivien L, Riehl D, Hache F, Anglaret E. Nonlinear scattering ori-
gin in carbon nanotube suspensions. J Nonlinear Opt Phys Mater
2000;9:297–307.
[305] Sun X, Xiong Y, Chen P, Lin J, Ji W, Lim JH, et al. Investigation of an
optical limiting mechanism in multiwalled carbon nanotubes. Appl
Opt 2000;39:1998–2001.
[306] O’Flaherty SM, Murphy R, Hold SV, Cadek M, Coleman JN, Blau
WJ. Material investigation and optical limiting properties of
carbon nanotube and nanoparticle dispersions. J Phys Chem B
2003;107:958–64.
[307] O’Flaherty SM, Hold SV, Brennan ME, Cadek M, Drury A, Coleman JN,
et al. Nonlinear optical response of multiwalled carbon-nanotube
dispersions. J Opt Soc Am B 2003;20:49–58.
[308] Goh HW, Goh SH, Xu GQ, Lee KY, Yang GY, Lee YW, et al. Optical lim-
iting properties of double-C60-end-capped poly(ethylene oxide),
double-C60-end-capped poly(ethylene oxide)/poly(ethylene
oxide) blend, and double-C60-end-capped poly(ethylene
oxide)/multiwalled carbon nanotube composite. J Phys Chem B
2003;107:6056–62.
866 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
[309] Kymakis E, Amaratunga GAJ. Optical properties of polymer-
nanotube composites. Synt Metal 2004;142:161–7.
[310] Mulazzi E, Perego R, Aarab H, Mihut L, Faulques E, Lefrant S, et al.
Optical properties of carbon nanotube-PPV composites: influence
of the PPV conversion temperature and nanotube concentration.
Synth Met 2005;154:221–4.
[311] Peng H. Aligned carbon nanotube/polymer composite films with
robust flexibility, high transparency, and excellent conductivity. J
Am Chem Soc 2008;130:42–3.
[312] Kymakis E, Amaratunga GAJ. Single-wall carbon nanotube/
conjugated polymer photovoltaic devices. Appl Phys Lett
2002;80:112–4.
[313] Fournet P, Coleman JN, Lahr B, Drury A, Blau WJ, O’Brien DF, et
al. Enhanced brightness in organic light-emitting diodes using a
carbon nanotube composite as an electron-transport layer. J Appl
Phys 2001;90:969–75.
[314] Frackowiak E, Khomenko V, Jurewicz K, Lota K, Béguin F. Super-
capacitors based on conducting polymers/nanotubes composites. J
Power Source 2006;153:413–8.
[315] Zhou CF, Kumar S, Doyle CD, Tour JM. Functionalized sin-
gle wall carbon nanotubes treated with pyrrole for electro-
chemical supercapacitor membranes. Chem Mater 2005;17:
1997–2002.
[316] Dong B, He BL, Xu CL, Li HL. Preparation and electrochemi-
cal characterization of polyaniline/multi-walled carbon nanotubes
composites for supercapacitor. Mater Sci Eng B 2007;143:7–13.
[317] Xiao Q, Zhou X. The study of multiwalled carbon nanotube
deposited with conducting polymer for supercapacitor. Elec-
trochim Acta 2003;48:575–80.
[318] Landi BJ, Raffaelle RP, Heben MJ, Alleman JL, VanDerveer W, Gennett
T. Single wall carbon nanotube-Nafion composite actuators. Nano
Lett 2002;2:1329–32.
[319] Koerner H, Price G, Pearce NA, Alexander M, Vaia RA. Remotely
actuated polymer nanocomposites—stress-recovery of carbon-
nanotube-filled thermoplastic elastomers. Nature Mater
2004;3:115–20.
[320] Mottaghitalab V, Xi B, Spinks GM, Wallace GG. Polyaniline fibres
containing single walled carbon nanotubes: enhanced performance
artificial muscles. Synth Met 2006;156:796–803.
[321] Chen HW, Wu RJ, Chan KH, Sun YL, Su PG. The application of
CNT/Nafion composite material to low humidity sensing measure-
ment. Sensor Actuat B-Chem 2005;104:80–4.
[322] Cai H, Cao X, Jiang Y, He P, Fang Y. Carbon nanotube-enhanced elec-
trochemical DNA biosensor for DNA hybridization detection. Anal
Bioanal Chem 2003;375:287–93.
[323] Ferrer-Anglada N, Kaempgen M, Roth S. Transparent and flexible
carbon nanotube/polypyrrole and carbon nanotube/polyaniline pH
sensors. Phys Stat Sol B 2006;243:3519–23.
[324] Cheng G, Zhao J, Tu Y, He P, Fang Y. A sensitive DNA electrochemical
biosensor based on magnetite with a glassy carbon electrode mod-
ified by muti-walled carbon nanotubes in polypyrrole. Anal Chim
Acta 2005;533:11–6.
[325] Cai H, Xu Y, He PG, Fang YZ. Indicator free DNA hybridization
detection by impedance measurement based on the DNA-doped
conducting polymer film formed on the carbon nanotube modified
electrode. Electroanalysis 2003;15:1864–70.
[326] White AA, Best SM, Kinloch LA. Hydroxyapatite–carbon nanotube
composites for biomedical applications: a review. Int J Appl Ceram
Technol 2007;4:1–13.
[327] Bianco A, Kostarelos K, Partidos CD, Prato M. Biomedical appli-
cations of functionalised carbon nanotubes. Chem Commun
2005:571–7.
[328] Pastorin G, Kostarelos K, Prato M, Bianco A. Functionalized carbon
nanotubes: towards the delivery of therapeutic molecules. J Biomed
Nanotech 2005;1:133–42.
[329] Shi Kam NW, Jessop TC, Wender PA, Dai H. Nanotube molec-
ular transporters: internalization of carbon nanotube-protein
conjugates into mammalian cells. J Am Chem Soc 2004;126:
6850–1.
[330] Pantarotto D, Partidos CD, Graff R, Hoebeke J, Briand JP, Prato M, et
al. Synthesis, structural characterization, and immunological prop-
erties of carbon nanotubes functionalized with peptides. J Am Chem
Soc 2003;125:6160–4.
[331] Kireitseu M, Hui D, Tomlinson G. Advanced shock-resistant and
vibration damping of nanoparticle-reinforced composite material.
Compos Part B 2008;39:128–38.
[332] Das D, Das PK. Superior activity of structurally deprived enzyme-
carbon nanotube hybrids in cationic reverse micelles. Langmuir
2009;25:4421–3.
[333] Shin JY, Premkumar T, Geckeler KE. Dispersion of single-walled car-
bon nanotubes by using surfactants: are the type and concentration
important? Chem Eur J 2008;14:6044–8.
[334] Doe C, Choi SM, Kline SR, Jang HS, Kim TH. Charged rod-like
nanoparticles assisting single-walled carbon nanotube dispersion
in water. Adv Funct Mater 2008;18:2685–91.
[335] Park I, Park M, Kim J, Lee H, Lee MS. Multiwalled carbon nanotubes
functionalized with PS via emulsion polymerization. Macromol Res
2007;15:498–505.
[336] Park I, Lee W, Kim J, Park M, Lee H. Selective sequestering of
multi-walled carbon nanotubes in self-assembled block copolymer.
Sensor Actuat B-Chem 2007;126:301–5.
[337] Kim HS, Park WI, Kang M, Jin HJ. Multiple light scattering mea-
surement and stability analysis of aqueous carbon nanotube
dispersions. J Phys Chem Solid 2008;69:1209–12.
[338] Wang H, Zhou W, Ho DL, Winey KI, Fischer JE, Glinka CJ, et al. Dis-
persing single-walled carbon nanotubes with surfactants: a small
angle neutron scattering study. Nano Lett 2004;4:1789–93.
[339] Lisunova MO, Lebovka NI, Melezhyk OV, Boiko YP. Stability of the
aqueous suspensions of nanotubes in the presence of nonionic sur-
factant. J Coll Interf Sci 2006;299:740–6.
[340] Barone PW, Strano MS. Reversible control of carbon nanotube
aggregation for a glucose affinity sensor. Angew Chem Int Ed
2006;45:8138–41.
[341] Numata M, Sugikawa K, Kaneko K, Shinkai S. Creation of hierar-
chical carbon nanotube assemblies through alternative packing
of complementary semi-artificial ˇ-1,3-glucan/carbon nanotube
composites. Chem Eur J 2008;14:2398–404.
[342] Yan LY, Poon YF, Chan-Park MB, Chen Y, Zhang Q. Individ-
ually dispersing single-walled carbon nanotubes with novel
neutral pH water-soluble chitosan derivatives. J Phys Chem C
2008;112:7579–87.
[343] Rouse JH. Polymer-assisted dispersion of single-walled carbon nan-
otubes in alcohols and applicability toward carbon nanotube/sol-
gel composite formation. Langmuir 2005;21:1055–61.
[344] Yuan WZ, Sun JZ, Dong Y, Haussler M, Yang F, Xu HP, et al. Wrapping
carbon nanotubes in pyrene-containing poly(phenylacetylene)
chains: solubility, stability, light emission, and surface photovoltaic
properties. Macromolecules 2006;39:8011–20.
[345] Jana RN, Cho JW. Thermal stability, crystallization behav-
ior and phase morphology of poly(␧-caprolactone)-diol-grafted
multi walled carbon nanotubes. J Appl Polym Sci 2008;110:
1550–8.
[346] Georgakilas V, Bourlinos A, Gournis D, Tsoufis T, Trapalis C,
Mateo-Alonso A, et al. Multipurpose organically modified carbon
nanotubes from functionalization to nanotube composites. J Am
Chem Soc 2008;130:8733–40.
[347] Xu G, Zhu B, Han Y, Bo Z. Covalent functionalization of multi-walled
carbon nanotube surfaces by conjugated polyfluorenes. Polymer
2007;48:7510–5.
[348] Georgakilas V, Tagmatarchis N, Pantarotto D, Bianco A, Briand JP,
Prato M. Amino acid functionalisation of water soluble carbon nan-
otubes. Chem Commun 2002:3050–1.
[349] Bianco A, Kostarelos K, Prato M. Applications of carbon nanotubes
in drug delivery. Curr Opin Chem Biol 2005;9:674–9.
[350] Hayden H, Gun’ko YK, Perova TS. Chemical modification of multi-
walled carbon nanotubes using a tetrazine derivative. Chem Phys
Lett 2007;435:84–9.
[351] Menard-Moyon C, Gross M, Bernard M, Turek P, Doris E, Mioskowski
C. Unexpected outcome in the reaction of triazolinedione with car-
bon nanotubes. Eur J Org Chem 2007:4817–9.
[352] Menard-Moyon C, Dumas FO, Doris E, Mioskowski C. Func-
tionalization of single-wall carbon nanotubes by tandem high-
pressure/Cr(CO)6 activation of diels-alder cycloaddition. J Am Chem
Soc 2006;128:14764–5.
[353] Cho E, Kim H, Kim C, Han S. Ab initio study on the carbon nan-
otube with various degrees of functionalization. Chem Phys Lett
2006;419:134–8.
[354] Holzinger M, Steinmetz J, Samaille D, Glerup M, Paillet M, Bernier
P, et al. [2+1] Cycloaddition for cross-linking SWCNTs. Carbon
2004;42:941–7.
[355] Liu Y, Yao Z, Adronov A. Functionalization of single-walled carbon
nanotubes with well-defined polymers by radical coupling. Macro-
molecules 2005;38:1172–9.
[356] Liu J, Zubiri MR, Vigolo B, Dossot M, Fort Y, Ehrhardt JJ, et al. Efficient
microwave-assisted radical functionalization of single-wall carbon
nanotubes. Carbon 2007;45:885–91.
[357] Buffa F, Abraham GA, Grady BP, Resasco D. Effect of nanotube
functionalization on the properties of single-walled carbon nan-
 N.G. Sahoo et al. / Progress in Polymer Science 35 (2010) 837–867
otube/polyurethane composites. J Polym Sci Part B Polym Phys
2007;45:490–501.
[358] Kwon J, Kim H. Comparison of the properties of waterbone
polyurethane/multiwalled carbon nanotube and acid-treated
multiwalled carbon nanotube composites prepared by in situ poly-
merization. J Polym Sci Part A Polym Chem 2005;43:3973–85.
[359] Guo SZ, Zhang C, Wang WZ, Liu TX, Tjiu WC, He CB, et al. Prepa-
ration and characterization of polyurethane/multiwalled carbon
nanotube composites. Polym Polym Compos 2008;16:501–7.
[360] Grunlan JC, Mehrabi AR, Bannon MV, Bahr JL. Water-based single-
walled-nanotube-filled polymer composite with an exceptionally
low percolation threshold. Adv Mater 2004;16:150–3.
[361] Yu C, Kim YS, Kim D, Grunlan JC. Thermoelectric behav-
ior of segregated-network polymer nanocomposites. Nano Lett
2008;8:4428–32.
[362] Kim HM, Kim K, Lee CY, Joo J, Cho SJ, Yoon HS, et al. Electrical
conductivity and electromagnetic interference shielding of mul-
tiwalled carbon nanotube composites containing Fe catalyst. Appl
Phys Lett 2004;84:589.
[363] Skakalova V, Dettlaff-Weglikowska U, Roth S. Electrical and
mechanical properties of nanocomposites of single wall carbon
nanotubes with PMMA. Synth Met 2005;152:349–52.
[364] Frackowiak E, Jurewicz K, Delpeux S, Beguin F. Nanotublar materials
for supercapacitors. J Power Source 2001;97–98:822–5.
[365] An KH, Jeon KK, Heo JK, Lim SC, Bae DJ, Lee YH. High-
capacitance supercapacitor using a nanocomposite electrode of
867
single-walled carbon nanotube and polypyrrole. J Electrochem Soc
2002;149:A1058–62.
[366] Dai CA, Hsiao CC, Weng SC, Kao AC, Liu CP, Tsai WB, et al. A mem-
brane actuator based on an ionic polymer network and carbon
nanotubes: the synergy of ionic transport and mechanical prop-
erties. Smart Mater Struct 2009;18, 85016/1–13.
[367] Thomassin JM, Kollar J, Caldarella G, Germain A, Jerome R, Detrem-
bleur C. Beneficial effect of carbon nanotubes on the performances
of Nafion membranes in fuel cell applications. J Membr Sci
2007;303:252–7.
[368] Joo SH, Park CP, Kim EA, Lee YH, Chang H, Seung D, et al.
Functionalized carbon nanotube-poly(arylene sulfone) composite
membranes for direct methanol fuel cells with enhanced perfor-
mance. J Power Sources 2008;180:63–70.
[369] Cosnier S, Ionescu RE, Holzinger M. Aqueous dispersions of SWCNTs
using pyrrolic surfactants for the electro-generation of homo-
geneous nanotube composites. Application to the design of an
amperometric biosensor. J Mater Chem 2008;18:5129–33.
[370] Rege K, Raravikar NR, Kim DY, Schadler LS, Ajayan PM,
Dordick JS. Enzyme-polymer-single walled carbon nan-
otube composites as biocatalytic films. Nano Lett 2003;3:
829–32.
[371] Sing R, Pantarotto D, McCarthy D, Chaloin O, Hoebeke J, Partidos
CD, et al. Binding and condensation of plasmid DNA onto functional-
ized carbon nanotubes: toward the construction of nanotube-based
gene delivery vectors. J Am Chem Soc 2005;127:4388–96.