8.

17 Functionalized Carbon Nanotubes and Their Enhanced Polymers

J Yan and Z Fan, Harbin Engineering University, Harbin, People’s Republic of China
L Zhi, National Center for Nanoscience and Technology, Beijing, People’s Republic of China
© 2012 Elsevier B.V. All rights reserved.

8.17.1 Introduction 439

8.17.2 CNT Synthesis Techniques 441

8.17.2.1 Arc Discharge 441

8.17.2.2 Laser Ablation 443

8.17.2.3 Chemical Vapor Deposition 446

8.17.3 Functionalization of CNTs 448

8.17.3.1 Noncovalent Functionalization 449

8.17.3.1.1 Surfactant functionalization of CNTs 450

8.17.3.1.2 Biomacromolecule functionalization of CNTs 451

8.17.3.1.3 Polymer functionalization of CNTs 452

8.17.3.1.4 Endohedral functionalization 453

8.17.3.2 Covalent Functionalization 453

8.17.3.2.1 Defect functionalization 454

8.17.3.2.2 Covalent sidewall functionalization 455

8.17.3.3 Applications 457

8.17.3.3.1 Field-effect transistors 457

8.17.3.3.2 Electrochemical sensors and biosensors 458

8.17.3.3.3 Catalysis 460

8.17.3.3.4 Energy storage 461

8.17.3.3.5 Mechanically reinforced composites 462

8.17.4 CNT–Polymer Nanocomposites 463

8.17.4.1 CNT–Polymer Interactions 463

8.17.4.2 Fabrication of CNT–Polymer Nanocomposites 463

8.17.4.2.1 Solution processing 464

8.17.4.2.2 Melt processing 465

8.17.4.2.3 In situ polymerization 466

8.17.4.2.4 Other methods 466

8.17.4.3 Properties of CNT/Polymer Nanocomposites 467

8.17.4.3.1 Mechanical properties 467

8.17.4.3.2 Electrical properties 469

8.17.4.3.3 Thermal properties 470

8.17.4.3.4 Optical properties 471

8.17.4.3.5 Electrochemical properties 471

8.17.4.4 Applications 473

References 473

8.17.1 Introduction carbon nanotubes (SWNTs), which consist of single layer of

graphene sheet seamlessly rolled into cylindrical tubes.4,5
Elemental carbon in sp2 hybridization can form a variety of MWNTs can be visualized as concentric ‘rings’ of SWNTs
fascinating structures, such as graphite (three dimensional, spaced with a spacing of
0.34 nm, and an SWNT can be
3D), graphene (2D), carbon nanotubes (CNTs, 1D), and full­ visualized as a hollow cylinder, formed by rolling over a gra­
erene (0D).1 CNTs are well-ordered, all-carbon and hollow phite sheet. It can be uniquely characterized by a vector ~ C in
graphitic nanomaterials with a high aspect ratio, lengths from terms of a set of two integers (n, m) corresponding to graphite
several micrometers to millimeters or even centimeters with vectors~ a 2 (Figure 2(a)), given by eqn [1].6,7 In addition,
a 1 and~
diameters ranging from about one to tens of nanometers.2 This the geometric structure described by ~ C determines their electro­
fascinating new class of materials was first observed by Endo in nic properties, that is, metallic or semiconducting, according to
1975 and later by Iijima (1991) in the soot produced during the the relations in eqns [2] and [3]:8
arc discharge synthesis of fullerenes.3 According to their (super)
~
C ¼ n~
a 1 þ m~
a2 ½1
structures, CNTs can be classified into two types (Figure 1): (1)
multiwalled carbon nanotubes (MWNTs), which are composed j n − m j ¼ 3q; q ≠ 0; metallic ½2
of multiple layers of concentric cylinders with a spacing of ca.
j n − m j ¼ 3q  1; q ≠ 0; semiconducting ½3
0.34 nm between the adjacent layers; and (2) single-walled

Polymer Science: A Comprehensive Reference, Volume 8 doi:10.1016/B978-0-444-53349-4.00217-X 439

440 Functionalized Carbon Nanotubes and Their Enhanced Polymers

12000
11000
10000
9000
8000

Number
7000
6000
5000
4000
3000
2000
1000
0

90

92

94

96

98

00

02

04

06

08

10
19

19

19

19

19

20

20

20

20

20

(a)
Figure 1 (Super) structure illustrations of (a) a MWNT and (b) a SWNT.
Adapted with permission from Zhao, Y. L.; Stoddart, J. F. Acc. Chem. Res.
2009, 42, 1161.4 Copyright 2009 American Chemical Society.
where n and m are positive integers and q is an integer. Figure 2(a)
illustrates an SWNT unit cell, showing different geometric struc­
tures bound by the chiral angle θ. Computer-generated images of
CNTs with zigzag (θ = 0°), armchair (θ = 30°), and chiral
(0° < θ < 30°) conformations are shown in Figure 2(b). It is
worth noting that ‘armchair’ CNTs are always metallic.
From the discovery of CNTs in 1991 until the end of 2009,
roughly 51 000 scientific reports have been published on this
topic. This extraordinary explosion of CNT reports is illustrated
in Figure 3 with a histogram detailing the number of CNT
publications per year. Due to their intrinsic properties
(see Table 1), which include high surface area, unique physical
properties and morphology, good chemical stability, high elec­
trical conductivity, and their inherent size and hollow
geometry, CNTs have attracted enormous attention for their
fundamental behavior and for their use in a wide variety of
applications in nanoelectronic devices, energy storage devices,
composite materials, catalysts and catalyst supports, probe tips
for scanning probe microscopes or in the automotive and
is
20
Publication year
(b)
Figure 3 Histogram detailing the number of CNT-related publications per
year between 1991 and 2010. Data obtained from ISI Web of Knowledge.
aerospace industries for the dissipation of electrostatic
charges.10 For example, the estimated high Young’s modulus
and tensile strength of CNTs have lead to speculations for their
possible use in composite materials with improved mechanical
properties.11 CNTs are suitable as electron field emitters
because of their nanosize, structural perfection, high electrical
conductivity, and excellent chemical stability with an applica­
tion in flat-panel displays.12 MWNTs have also been used to
electrocatalyze an oxygen reduction reaction, which is impor­
tant for fuel cells.13 Li-intercalated SWNT materials showed
large reversible capacity of 1000 mAh g−1, which is an advan­
tage for using them as battery electrodes.14 The extraordinary
high and reversible hydrogen adsorption in SWNT materials
has attracted much attention due to the possibility of using
them as high-capacity hydrogen storage media.15 It was pro­
posed to use CNTs as central elements of electronic devices
including field-effect transistors (FETs), single-electron transis­
tors and rectifying diodes,16 and logic circuits.17 Since CNTs
have relatively straight and narrow channels in their cores, they
have been used as templates to create nanowires of various
compositions and structures.18

Zigzag
Tube ax

(8,0)
(7,0) (8,1)
acc
(6,0) (7,1)
(5,0) (6,1) (7,2)
(4,0) (5,1) (6,2)
(3,0) (4,1) (5,2) (6,3)
(2,0) (3,1) (4,2) (5,3)
(1,0) (2,1) (3,2) (4,3) (5,4)
→
na1 (0,0) (1,1) (2,2) (3,3) (4,4)
Armchair
→
C
Θ
→
a1 →
ma2
→
a2 Metallic
Semiconductor
Armchair Zigzag Chiral

(a) (b)
Figure 2 (a) Definition of the chiral vector describing the unit cell of an SWNT. (b) Computer-generated images of armchair (n, n), zigzag (n, 0), and chiral
(n, m) nanotubes, where n > m > 0 by definition.7 Details about relations between structural parameters of SWNTs can be found in Reference 9. Adapted with
permission from See, C. H.; Harris, A. T. Ind. Eng. Chem. Res. 2007, 46, 997. Copyright 2009 American Chemical Society. Dresselhaus, M. S.;
Dresselhaus, G.; Saito, R. Carbon 1995, 33, 883.7,9
 Functionalized Carbon Nanotubes and Their Enhanced Polymers 441

Table 1 Outstanding properties of CNTs

Attribute Assessment References

Thermal conductivity:
5800 W m−1 K−1 > Diamond 20

Young’s modulus:
1 TPa Stiffer than any other material 21
Tensile strength: 150 GPa
100 times the strength of steel 22
Maximal electrical current
100 times greater than for copper wires 23
density: > 109 A cm−2

Carrier mobility:
105 cm2 V−1 s−1

> Hole mobility in Si 24
(room temperature)

Reprinted from See, C. H.; Harris, A. T. Ind. Eng. Chem. Res. 2007, 46, 997, 7 Copyright 2007 American Chemical Society; Burghard, M.
Surf. Sci. Rep. 2005, 58, 1,19 Copyright 2005 with permission from Elsevier.

8.17.2 CNT Synthesis Techniques
For most of the above applications, however, it is highly desirable
to prepare CNTs under the control of their growth, length, dia-
meter, and crystallinity at low costs.25,26 Currently, there are three
major techniques commonly used to grow CNTs, including arc
discharge,26 laser ablation,27 and various chemical vapor deposi­
tion (CVD).28 Other published methods include plastic
pyrolysis,29 flame synthesis,29 and liquid hydrocarbon synthesis.30
These methods will not be discussed in detail because they are not
currently developed to the extent required for large-scale CNT
Table 2 Comparison of the established techniques for CNT synthesis
synthesis. A brief comparison of established techniques is given
in Table 2. The industrial application of the CNTs requires rapid
development of techniques for large-scale production of
defect-free CNTs.31 In this section, the major progress in the meth­
ods for CNT production will be outlined and discussed briefly.
8.17.2.1 Arc Discharge
During arc discharge process, carbon atoms are evaporated by
plasma of helium gas ignited by high currents passed through
opposing carbon anode and cathode (Figure 4).33,34 In the

Method Arc discharge Laser ablation CVD

Description Arc evaporation of graphite in the Vaporization of graphite target by Decomposition of

presence of inert gas; CNT formed on laser; CNT formed on receiver hydrocarbons over transition
electrodes during quenching during quenching metal catalyst to form CNTs
Operating temperature >3000 °C >3000 °C <1200 °C
Operating pressure 50–7600 Torr generally under vacuum 200–750 Torr generally under 760–7600 Torr
vacuum
Average diameter of the 1.3–1.4 nm 1.4 nm 1 nm
SWNTs
Maximum production rate 120 g day−1 50 g day−1 50 kg day−1
Advantages Good-quality CNTs Good-quality CNTs; Easy scale-up; synthesis on
single-conformation SWNT templates possible
formed (10, 10)
Disadvantages Difficult to scale-up Difficult to scale-up; expensive Quality of CNTs not as good

Reprinted from See, C. H.; Harris, A. T. Ind. Eng. Chem. Res. 2007, 46, 997; Copyright 2007 American Chemical Society. Balasubramanian, K.; Burghard, M. Small 2005, 1, 180.25
7

Helium in Manometer

Teflon insulator Teflon insulator

Water in Water in

Graphite rods

Water out
Water out

O-rings Water-cooled O-rings

system

Vacuum gauge Vacuum pump

Figure 4 Schematic illustration of arc discharge apparatus employed for fullerene and nanotube production. Adapted with permission from Terrones, M.
Int. Mater. Rev. 2004, 49, 325.32
442 Functionalized Carbon Nanotubes and Their Enhanced Polymers
most common laboratory-scale production scheme, the direct
current (DC) arc operates in a 1–4-mm-wide gap between two
graphite electrodes with the diameter of 6–12 mm, which are
installed vertically or horizontally in a water-cooled chamber
filled with helium gas at subatmospheric pressure.6 The carbon
arc technique for generating CNTs appears very simple; how­
ever, obtaining high yields of CNTs is very difficult and requires
careful control of experimental conditions.6 Helium gas and
DC current are more important to maximum yield; the position
of the electrode axis does not noticeably affect the MWNT
quality or quantity. In addition, a constant feed rate and arc
current are required for the duration of synthesis in the most
stable and high-yield arc process.35 It has been indicated that
the optimal conditions for CNT growth involve passage of a DC
(80–100 A) through two highly pure graphite electrodes (out­
side diameter 6–10 mm, separation about 1–2 mm) in a
helium atmosphere (500 Torr).32 Parameters of the MWNTs,
as assessed by transmission electron microscopy (TEM) obser­
vations, strongly depend upon the arc parameters.
In 1991, Iijima26 reported the preparation of a new type of
finite carbon structures composed of needle-like tubes. The tubes
were produced using an arc discharge evaporation method simi­
lar to that used for the synthesis of fullerene (Figure 4). The
carbon needles, ranging from 4 to 30 nm in diameter and up to
1 mm in length, were grown on the negative end of the carbon
electrode. TEM images indicated that each of the needles con­
sisted of coaxial tubes of graphitic sheets, ranging in number
from 2 to about 50, later called MWNTs (Figure 5).
Later, TEM study of the morphology of the carbon micro­
tubules synthesized by arc discharge process revealed that there
were many variations in shape, especially near the tips of
(a) (b) (c)
3 nm
Figure 5 Homogeneous CNTs of hexagonal network: TEM images
(a), (b), and (c) for three MWNTs first reported by Iijima in 1991.
Reprinted by permission from Macmillan Publishers Ltd: Iijima, S. Nature
1991, 354, 56,26 Copyright 1991.
the tubes.36 A topological model was constructed in which
pentagons and heptagons played a key role in the tube tip
shapes. A model for an open-ended growth has been proposed
by Iijima et al.,37 in which the carbon atoms are captured by the
dangling bonds, and a layer-by-layer (LBL) growth, in which
the nanotubes thickens. The nucleation of positive (pentagons)
and negative (heptagons) disclinations on open-tube ends
results in changes of growth directions, accordingly producing
CNTs with different morphologies.
In 1992, a breakthrough in MWNT produced by arc dis­
charge was first made by Ebbesen and Ajayan,38 who achieved
growth and purification of high-quality MWNTs at the gram
level. The synthesized MWNTs have lengths on the order of
10 μm and diameters in the range of 5–30 nm. The CNTs are
typically bound together by strong van der Waals interactions
and form tight bundles. MWNTs produced by arc discharge are
usually very straight, indicating their high crystallinity. For
as-grown materials, there are few defects such as pentagons or
heptagons present on the sidewalls of the CNTs.
A further increase in MWNT production rate was expected
by employing thicker graphite rods in larger and more power­
ful arc reactors. This expectation was achieved with the
construction of a large-scale arc reactor with a 350-l chamber
(Figure 6(a)) capable of vaporizing up to 75-mm-diameter
graphite rods.39 The cylindrical cathode deposits, obtained in
this scaled-up process (Figure 6(b)), contain soft core within
the outer hard shell. Under optimal conditions, the core mate­
rial has a columnar structure. The diameter of the column and
separation are about the same as in small-diameter deposits. In
addition, the column length in large deposits is commonly
much lower (
3–5 mm) due to the lower plasma stability in
the arc gap. Optimal conditions for MWNT production include
the same range of helium pressure and arc gap widths but
at substantially lower current densities compared to
laboratory-scale anodes. It has been implied that the large-scale
reactor described above is very close to the optimum size and
power for MWNT synthesis in the arc and will probably remain
the largest reactor in the world for the next few years.39 During
the arc process, the next logical step for increasing output of
MWNTs will be automation of large-scale reactors, which will
render the production process nearly continuous.
Arc discharge has been developed into an excellent method
for producing both MWNTs and SWNTs with high quality. For
the growth of SWNTs, a metal catalyst is usually needed in the
arc discharge system. In 1993, Iijima and Ichihashi5 and
Bethune et al.40 almost simultaneously reported the arc dis­
charge and catalyst-assisted synthesis of SWNTs. Iijima used
arc discharge chamber, which was filled with a gas mixture of
10 Torr methane and 40 Torr argon. Two vertical thin electro­
des were installed in the center of the chamber. The cathode,
namely the lower electrode, had a shallow dip to hold a small
piece of iron during the evaporation. The arc discharge was
generated by operating a DC current of 200 A at 20 V between
the electrodes. All of the three used components, iron,
methane, and argon, were critical for the synthesis of SWNTs.
TEM images of the obtained samples indicated the presence of
SWNT threads, which were curved and tangled together to form
bundles. The SWNTs were in diameters of
1 nm with a broad
diameter distribution between 0.7 and 1.65 nm. Since then, the
growth of SWNTs has been studied using different elements
and compounds.41–46
 Functionalized Carbon Nanotubes and Their Enhanced Polymers 443

(a) (b)

Figure 6 (a) Industrial arc discharge reactor for producing CNTs. It features vaporization of up to 1 kg of anode per hour. (b) Cathode deposits produced
with industrial apparatus from 65- and 25-mm-diameter graphite anodes (two rear deposits) and with laboratory-scale arc discharge installation from
8-mm-diameter anode (front deposit) during
1 h runs. With kind permission from Springer Science+Business Media: Loutfy, R.O.; Lowe, T.P.;
Moravsky, A.P.; Katagiri, S. In Perspectives of Fullerene Nanotechnology, Ōsawa, E., Ed.; Springer: The Netherlands, 2002; pp. 35.39 Copyright 2002.

In the arc discharge synthesis of CNTs, Bethune and co-
workers40 used thin electrodes with bored holes filled with a
mixture of pure powdered metals (Fe, Ni, or Co) and graphite
as anodes. The electrodes were vaporized with a current of
95–105 A in 100–500 Torr of helium gas. TEM analysis of the
obtained samples revealed that only cocatalyzed CNTs had
single-atomic-layer walls with uniform diameters of
1.2  0.1 nm (Figure 7).
Large quantities of SWNTs were grown through the arc
discharge technique by Journet and his co-workers.47 The arc
was generated between two graphite electrodes in a reactor
under helium atmosphere with 660 mbar. The anode had a
hole drilled at its end, filled with a mixture of metallic catalyst
(Ni–Co, Co–Y, or Ni–Y) and graphite powder. The arc was
generated by a current of 100 A at a maintained constant vol­
tage drop of 30 V. Scanning electron microscopy (SEM)
observation exhibited that the deposited material seemed to
be composed of large amounts (
80%) of entangled carbon
ropes (Figure 8(a)). The high-resolution TEM images showed
that the ropes had diameters from 5 to 20 nm. The tube
diameters were around 1.4 nm and the average distance
between them was
1.7 nm (Figure 8(b)). The X-ray diffrac­
tion (XRD) patterns showed periodic arrangement of the tubes
in the ropes, which leads to the conclusion of a unique growth
mechanism that does not depend on the detailed experimental
conditions but depends much more on the kinetics of carbon
condensation in a nonequilibrium situation.47
CNTs produced from carbon vapor generated by arc dis-
charge of graphite usually have fewer structural defects than
those produced by catalytic CVD techniques, which are mainly
attributed to the higher growth temperature that ensures perfect
annealing of defects in tubular graphene sheets. Additionally,
MWNTs produced by the high-temperature method are per-
fectly straight, compared to entangled tubes produced at low
temperatures in metal-catalyzed CVD processes. Furthermore,
nowadays the arc discharge method remains the easiest and
cheapest method to obtain high quantities of SWNTs, but the
as-produced CNTs are less pure than those produced by laser
ablation. Therefore, many experimental and theoretical studies
are still undergoing to improve the SWNT yields in the arc
process and to provide a comprehensive understanding of the
growth mechanism. Scaling-up, optimizing, and controlling
the arc discharge process to make it commercially viable is
still an important challenge.6

8.17.2.2 Laser Ablation

100 Å
Figure 7 TEM image of a bare section of the prepared SWNT. Reprinted
by permission from Macmillan Publishers Ltd: Bethune, D. S.; Klang, C. H.;
de Vries, M. S.; et al. Nature 1993, 363, 605.40 Copyright 1993.
Historically, laser ablation was the first method used to pro­
duce fullerene nanostructures in the gas phase.49 The combined
use of high-power lasers and high-temperature furnaces offers
an alternative route to produce CNTs. In particular, laser vapor­
ization of a graphite target (Figure 9), sealed in argon
atmosphere in a silica tube and inside a furnace at 1200 °C,
could generate MWNTs.32,50
In 1995, during fullerene production experiments using a
laser vaporization apparatus with an ablated graphite sample
positioned in an oven, Guo’s group50 at Rice University found
that close-ended MWNTs were produced in the gas phase
through homogeneous carbon vapor condensation in a hot
argon atmosphere. The CNT growth using this technique
could be explained in terms of the attachment of incoming
carbon species at the edges of adjacent growing graphene
tubules, responsible for prolonged lifetime of the open struc­
ture, which finally results in a multilayered CNTs.50 The
444 Functionalized Carbon Nanotubes and Their Enhanced Polymers

(a) (b)

1 μm

Figure 8 (a) SEM and (b) high-resolution TEM images of the prepared SWNT by Journet and co-workers. Adapted with permission from Journet, C.;
Maser, W. K.; Bernier, P.; et al. Nature 1997, 388, 756.47

Graphite Water-cooled
Nd: YAG laser
target Cu collector
500 Torr Ar

1200 °C furnace

Figure 9 Schematic representation of the oven laser vaporization apparatus. Adapted with permission from Guo, T.; Nikolaev, P.; Thess, A.; et al. Chem.
Phys. Lett. 1995, 243, 49.48 Copyright 1995, with permission from Elsevier.

as-produced MWNTs are relatively short (
300 nm), although
the number of layers, ranging between 4 and 24, and the inner
diameter, varying between 1.5 and 3.5 nm, are very similar to
those of the MWNTs produced by arc discharge. A prevalence of
MWNTs with an even number of layers was observed, but no
SWNTs were detected (Figure 10).
For producing SWNTs using laser ablation processes, it is
quite necessary to use catalytic metal particles to catalyze their
growth. In this aspect, Thess and co-workers27 were the first to
obtain SWNT bundles using graphite rods with small amounts
of Ni and Co as targets at 1200 °C. The XRD analysis and TEM
observation showed that the synthesized CNTs were

(a) (b)

Figure 10 TEM images of typical laser vaporization-grown nanotubes. (a) A 14-layer nanotube with 2.7 nm inner diameter. (b) A nine-layer nanotube
with 3.4 nm inner diameter adhering to an eight-layer ‘nanocapsule’. Adapted with permission from Guo, T.; Nikolaev, P.; Rinzler, A. G.; et al. J. Phys.
Chem. 1995, 99, 10694.50 Copyright 1995 American Chemical Society.
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
remarkably homogeneous in diameters and they formed bun­
dles with 5–20 nm in diameter and tens to hundreds of
micrometers in length. These authors also reported that the
bundles mainly composed of (10, 10) CNTs and formed a 2D
triangular lattice with lattice constant a = 1.7 nm through van
der Waals bonding.
In 1997, Qin and Iijima52 tried to repeat the previous experi­
ments performed by Thess et al.27 However, they have found that
the CNTs showed narrower diameters, and only less than 20% of
the CNTs exhibited armchair chirality. This demonstrates the
difficulties in repeating the laser process to produce CNTs.
Maser and his co-workers51,53 managed to produce SWNTs
using a CO2 laser focused on a graphite–metal target in 1998
(Figure 11). The authors stated that it is possible to produce a
high yield of SWNT bundles without an additional furnace. The
authors observed that the best atmospheres to generate CNTs
are argon and nitrogen, whereas helium produces only small
amounts of SWNTs.53–55 Similarly, Dillon and co-workers56
D
B micrometer size, the thermal conductivity losses were signifi­
A achieved. The generation rate of the soot product was 5 g h−1
C
Figure 11 Evaporation chamber used by Maser and his co-workers. The
laser beam (A) is guided into the evaporation chamber and focused onto
the graphite–metal composite target rod (B). Inert gas is introduced
through a nozzle (C). Products are collected on the Cu wire system inside
the quartz tube (D), leading to the filter and pumping unit. Adapted with
permission from Maser, W. K.; Munoz, E.; Benito, A. M.; et al. Chem.
Phys. Lett. 1998, 292, 587.51 Copyright 1998, with permission from
Elsevier.
(a)
1 µm
Figure 12 (a) TEM image of the material synthesized by the continuous-wave laser powder method. (b) High resolution TEM image (HRTEM) of the
‘cross section’ for an SWNT bundle. Adapted with permission from Bolshakov, A. P.; Uglov, S. A.; Saveliev, A. V.; et al. Diamond Relat. Mater. 11 2002,
927.54 Copyright 2002, with permission from Elsevier.
445
reported that the diameter of the CNTs depends upon the
laser power. The diameters of the CNTs became narrower as
the laser pulse power was increased. Other laser experiments
revealed that porous targets of graphite–CoNi(nitrate) yielded
twice as much SWNT material compared to the standard
metal–carbon target.57 The yield of SWNTs grows as the pres­
sure of argon gas increases from
10 kPa to the optimum value
of
66 to 80 kPa.58,59 This behavior corresponds to the adjust­
ment of the optimum cooling rate for the laser plume. It is
worth noting that the flow rate of argon gas in the laser reactor
can also influence yields of the SWNT.58 As soon as linear flow
rate reaches a sufficiently high critical value, which is equal to

2 to 3 cm s−1 for a given experimental geometry,58 SWNT
abundance in the soot is greatly decreased. This result can be
explained by the temperature decrease in a few centimeters
along the growth zone of SWNTs caused by high-velocity
argon. The yield of SWNT formation depends on the metal
content in the target.59–62 Much higher than the optimal con­
centration (
1–2 at.%) of metals in the target leads to the
formation of larger metal particles (more than 30 nm in dia­
meter), which are useless in the production of SWNTs under
common laser ablation conditions owing to too-low carbon
diffusion rate through such particles, resulting in the low yield
of SWNTs.
Two methods were developed to possibly scale up SWNT
production using laser ablation.54,63 In 2002, Bolshakov and
co-workers54 reported that SWNTs were synthesized by the
continuous-wave laser powder method, which is based on the
introduction of mixed graphite and Ni/Co powders into
1100 °C hot argon gas stream irradiated coaxially by a 2 kW
continuous-wave CO2 laser. Because the particles were of
cantly decreased and more energy by effective ablation was
and the SWNT abundance in the soot was 20–40%; besides, the
diameter of the as-prepared CNTs was 1.2–1.3 nm (Figure 12).
In the ultrafast pulses from a free-electron laser (FEL)
method,63 the
3-μm-wavelength light pulses of
400 fs
length at a pulse repetition rate of 75 MHz were generated to
vaporize the graphite–metal target by Eklund’s group at
Pennsylvania State University (Figure 13(a)). The light beam
was focused to give the pulse intensity of
500 GW cm−2,
which was about 1000 times greater than that in Nd:YAG
laser systems. In the 1000 °C hot zone of quartz reactor, a jet
of preheated argon was directed parallel to the surface of rotat­
ing graphite target containing the Ni/Co or the Ni/Y catalyst.
(b)
10 nm
446 Functionalized Carbon Nanotubes and Their Enhanced Polymers

(a) Quartz Metal-loaded

tube graphite rod
Spindle
1000 °C hot zone

Plasma plume

Nozzle
Argon
Nanotube
Input FEL spray

(b) (c)

d = 1.35 nm

d = 1.3 nm

d = 1.4 nm

10 nm 10 nm

Figure 13 (a) Schematic illustration of the interaction geometry between the infrared ultrafast pulsed radiation from the FEL and the carbon–metal target.
HRTEM images of as-prepared SWNT soot supported on a holy carbon grid, produced with (b) NiY catalysts and (c) NiCo catalysts. Adapted with
permission from Eklund, P. C.; Pradhan, B. K.; Kim, U. J.; et al. Nano Lett. 2002, 2, 561.63 Copyright 2002 American Chemical Society.

Then, the produced SWNT soot was collected on a cold finger at
a rate of 1.5 g h−1. SWNTs of 1–1.4 nm in diameter and
5–20 μm in length were produced in 8–200-nm-thick bundles
(Figures 13(b) and 13(c)). If the FEL was upgraded and work­
ing at 100% power, a yield of 45 g h−1 could be expected.63
It is very important to mention that the laser technique is
not economically advantageous because the process involves
high-purity graphite rods, the required laser powers are high (in
some cases, two lasers need to be used), and the amount of
CNTs that can be produced per day is not as high as that from
arc discharge and CVD methods.32 However, CNTs produced
by laser ablation are commonly purer (up to about 90% purity)
than the other two methods.
8.17.2.3 Chemical Vapor Deposition
While the arc discharge method is capable of producing large
quantities of unpurified CNTs, considerable efforts are being
directed toward production processes that offer more control­
lable strategies to CNT synthesis. Another class of processes that
seems to offer the best chance of controllable and selective
production of CNTs with defined properties is CVD.64–67
CVD, also known as the hydrocarbon pyrolysis process, is
essentially a thermal dehydrogenation reaction whereby a tran­
sition metal catalyst, for example, iron, nickel, or cobalt, is used
to lower the required temperature to ‘crack’ a gaseous hydro­
carbon feed into carbon and hydrogen (Figure 14).7
CVD methods have been successfully used in making car­
bon fibers, filaments, and CNT materials since two decades
ago.34,69–71 However, CNTs (formed along with carbon nano­
fibers) were first synthesized by Endo72 in 1988 through the
catalytic decomposition of benzene vapors using only iron
catalyst at 1100 °C. Two similar approaches were carried out
by Joseyacaman and co-workers73 in 1993 and Ivanov et al.74,75
in 1994 to grow MWNTs. The CVD technique has been subse­
quently improved and optimized. Generally, the CVD process
includes heating a catalyst material to high temperatures in a
tube reactor and flowing a hydrocarbon gas, usually ethylene or
acetylene, through the tube reactor for a period of time. CNTs
grown over the catalyst are then collected upon cooling the
system to room temperature.
The key parameters in CVD growth of CNTs include the
hydrocarbons, catalysts, and growth temperature. For MWNT
growth, most of the CVD methods use methane,76 ethylene, or
acetylene74,77 as the carbon feedstock and the growth tempera­
ture is typically in the range of 550–750 °C. The active catalytic
species are commonly prepared on a substrate using one of the
four techniques: (1) sol–gel, (2) impregnation, (3) metallo­
organic CVD, or (4) coprecipitation methods.74,78–80 They
can also be formed in situ, for example, via the decomposition
of volatile metallo-organic compounds within the reactor,
without the substrate, which is known as the floating catalyst
method.81 Nanosized metal catalytic powders have also been
employed directly in the synthesis of CNTs.7 The most
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
Hinged furnace
Flow meter
Pressure gauge
CH4
Two-way valve
Figure 14 Schematic experimental setup for methane CVD synthesis of SWNTs. Adapted with permission from Cassell, A. M.; Raymakers, J. A.;
Kong, J.; Dai, H. J. J. Phys. Chem. B 1999, 103, 6484.68 Copyright 1999 American Chemical Society.
common metals used as catalyst are Fe,67 Co,74,77 or Ni82
nanoparticles, which have also been found to be optimal in
the arc discharge and laser ablation techniques.
In 1995, Yudasaka and co-workers82 reported the growth of
MWNTs by CVD method under special conditions, including
2-methyl-1,2′-naphthyl ketone as a starting material, the tem­
perature of 700 °C, and the size of a Ni catalyst with a round
shape of 20–30 nm in diameter. TEM images showed that both
the outside and inside diameters of the CNTs are 17–27 and
10–17 nm, respectively.
Zhang’s group76 at Xiamen University synthesized MWNTs
by catalytic decomposition of CH4 or CO using Ni–MgO as a
catalyst. The as-prepared CNTs are more or less twisted, with
the outer diameter of 15–20 nm and the length of up to 10 μm.
The experimental results also indicated that the
rate-determining step was dependent upon the preparation
conditions (feed gas used, reaction temperature, flow rate of
the feed gas, etc.) during the growing process of CNTs.
A major drawback of MWNT growth by CVD is the high
defect densities in their structures due to the relatively low
growth temperature, which cannot provide sufficient thermal
energy to anneal CNTs into perfectly crystalline structures.
Therefore, growing perfect MWNTs by CVD method is still a
challenge until now.
While CVD processes are primarily used to produce
MWNTs, they have also been used to produce SWNTs. In
1998, Dai’s group68,83,84 at Stanford University reported that
high-quality SWNTs could be obtained by CVD process using
methane as carbon feedstock, reaction temperatures in the
range of 850–1000 °C, and alumina-supported catalyst materi­
als. The authors have also found that high growth temperatures
are advantageous to the formation of SWNTs, which have small
diameters and thus high strain energies, and allow for nearly
defect-free tube structures.
The chemical and textural properties of the catalyst materi­
als are crucial to the yield and quality of SWNTs. Highly porous
catalysts with strong metal–support interactions and high sur­
face areas could produce SWNTs of better quality at larger
quantities. The strong interactions can effectively prevent
metal species from aggregating and forming unwanted large
447
Three-way
connector
Two-way valve
Ar
particles. Metal–support interactions are highly dependent
upon the type of support materials and the type of metal
precursor being used in preparation of the catalysts; it has
been found that alumina materials are generally far superior
catalyst supports than is silica.34 In addition, large surface area
and a highly porous structure of the catalyst can significantly
increase the yields of SWNTs,85 since the former can provide
high densities of catalytic sites and the latter ensures the rapid
diffusion and efficient supply of carbon feedstock to the cata­
lytic sites.
More recently, Su and co-workers86 made a significant pro­
gress in obtaining an excellent catalyst for methane CVD
growth of SWNTs. In their investigation, the catalyst was pre­
pared using sol–gel technique followed by supercritical drying
at high pressure and temperature conditions. The catalyst
exhibited ultrahigh specific surface area (540 m2 g−1) and
large mesopore volume (
1.4 ml g−1), which was preserved
by the supercritical drying condition where the strong forces
from surface tensions at the liquid–gas interfaces within the
pores are nonexistent. The catalyst produced abundant SWNTs
in CVD. The total amount of high-quality SWNTs produced
was higher than twice the weight of the catalysts. Evidently, this
is indeed a substantial improvement over previous results.
Generally speaking, understanding the chemistry involved in
preparation of catalysts and CNT growth could lead to further
breakthroughs toward scaling up of the growth of perfect
SWNT materials.
CVD of methane for the growth of bulk amounts of SWNTs
has been investigated by Flahaut and co-workers87 using
catalysts based on mixed oxide spinels in 1999. Good-quality
and -quantity SWNTs were obtained using nanoparticles of a
Fe0.5Co0.5 alloy as a catalyst. TEM images showed that the dia­
meters of the SWNTs were 0.8–5 nm. Colomer and co-workers88
recently reported the growth of bulk quantities of SWNTs by
CVD of methane using cobalt catalyst supported on magnesium
oxide materials. The as-produced SWNTs could be separated
easily from the support by a simple acidic treatment to obtain
a product with high yields (70–80%) of SWNTs.
A wide range of transition metals and rare earth promoters
have been intensively investigated for the synthesis of both
448 Functionalized Carbon Nanotubes and Their Enhanced Polymers
SWNTs and MWNTs by CVD. In general, a transition metal
comprises the sole or most component in the catalyst particles
used, regardless of the support of catalysts. As mentioned
above, Fe, Co, and Ni are the most common metals that are
found to be successful in the growth of SWNTs and MWNTs.
Bimetallic catalysts composed of Fe, Ni, or Co and some rare
earth metals have also been studied.89 Lee and co-workers90
have reported that, as co-catalysts, Pd, Cr, and Pt are found to
decrease the temperature of CNTs growth to 500–550 °C in the
C2H2 CVD process. They also found that Pd is the most efficient
co-catalyst for the growth of CNTs on Co–Ni catalytic particles
deposited on a silicon oxide substrate. The CNTs produced at
500 °C with Pd-modified catalysts are primarily straight with a
bamboo structure, while Cr yields curled nanofibers and gra­
phite whiskers are produced with added Pt at 550 °C.
The choice of carbon feedstock is another key parameter to
the growth of high-quality and defect-free SWNTs with less
amorphous carbon overcoating. Various gaseous and liquid
hydrocarbon feedstocks are used to produce CNTs via thermal
catalytic decomposition. These range from light gases such as
CH4,68,83,84 C2H4,91 C2H2,90 and CO81 to heavier aromatic
liquids such as xylene67 and benzene,92 And among all hydro­
carbon molecules, methane is the most stable at high
temperatures against self-decomposition. Hafner’s group93 at
Rice University synthesized high-quality SWNTs by CVD pro­
cess using supported catalysts, ethylene as carbon feedstock,
and growth temperature at
800 °C. In this study, low
partial-pressure ethylene was employed in order to reduce the
formation of amorphous carbon due to the self-decomposition
of ethylene at the high growth temperature. They have also
observed that SWNTs could grow continuously to arbitrary
length under specific conditions.
Catalyst particles can be generated in situ from gas phase for
the growth of CNTs by CVD. Andrews and co-workers67 synthe­
sized aligned MWNTs with high purity through the catalytic
decomposition of a ferrocene–xylene mixture at
675 °C in a
quartz tube reactor and over quartz substrates in 1999. Xylene
was selected as the hydrocarbon source, since it boils (boiling
point,
140 °C) below the decomposition temperature of fer­
rocene (
190 °C). Accordingly, the process could be operated
at atmospheric pressure and moderate temperatures, and could
be scaled up for continuous or semicontinuous production of
MWNTs. Cheng et al.28 at the Chinese Academy of Science
reported a method that employs benzene as the carbon feed­
stock, hydrogen as the carrier gas, and ferrocene as the
precursor of catalyst for SWNT growth. In this method, ferro­
cene was vaporized and carried into a reaction tube by benzene
and hydrogen gases. The reaction tube was heated at
1100–1200 °C and then the vaporized ferrocene decomposed
in the reactor, which led to the formation of iron nanoparticles
for catalyzing the growth of SWNTs. However, the generation
of amorphous carbon could be a problem with this approach
as benzene pyrolysis is expected to be significant at 1200 °C.
More recently, Nikolaev and co-workers81 developed a
gas-phase catalytic process to grow bulk quantities of SWNTs
with CO as the carbon feedstock and the growth temperature in
the range of 800–1200 °C. Catalytic particles for SWNT growth
were generated in situ by thermal decomposition of iron penta­
carbonyl in a reactor heated to the growth temperature. CO
provided the carbon feedstock for the growth of CNTs over the
iron catalyst particles. It is well known that CO is a very stable
molecule and does not produce unwanted amorphous carbo­
naceous material at high temperatures. However, this also
indicates that CO is not an efficient carbon source for CNT
growth. To enhance the carbon feedstock of CO, Smalley’s
group has modified the method using high-pressure CO (up
to 10 atm) to significantly speed up the disproportionation of
CO molecules into carbon, and thus enhance the growth of
SWNTs. TEM images demonstrated that the produced SWNTs
are as small as 0.7 nm in diameter, which is the same as that of
a C60 molecule.81 The authors have also found that the yield of
SWNTs can be effectively increased by introducing a small
concentration of methane into the high-pressure CO reactor
at growth temperatures of 1000–1100 °C.
Likewise, pyridine has been used as a feedstock for CNT
production, primarily aimed at the production of N-containing
CNTs.94,95 It has been found that the CNTs produced by the
pyrolysis of pyridine over silica-supported Fe or Co catalysts
incorporate significant amounts of N into the structure of CNTs
(ranging from C10N to C33N).95
CVD and gas-phase catalytic growth of CNTs have been
widely pursued in recent years because of their significant
potential for scale-up production of CNTs. With continued
effort in this area, it is expected that large quantities (up to
tons) of CNTs of high quality can be produced in the near
future. However, more efforts are still needed to overcome
some problems in terms of the morphology control, the amor­
phous carbon coating, and the catalyst particles embedded
within the tube.46
8.17.3 Functionalization of CNTs
Since the discovery of CNTs in 1991 by Iijima,26 they have
attracted much attention of many researchers and scientists
around the world. This extraordinary interest stems from their
outstanding and unique structural, mechanical, and electronic
properties. In fact, apart from being the best and the most easily
available 1D model system, CNTs also show strong application
potential in electronics, scanning probe microscopy, chemical
and biological sensing, reinforced composite materials, nano­
composite materials, energy storage system, and in many other
areas.25,96 However, CNTs tend to aggregate together into bun­
dles and the solubility in aqueous solvents is very limited due
to the strong intertube van der Waals interactions.96,97 This has
made them very difficult to be manipulated and purified, and
has restricted their practical applications to a considerable
extent.4,98
Currently, a key challenge for chemists and materials scien­
tists is how to break the cohesion of aggregated CNTs in order
to obtain a good dispersion in the selected solutions or
matrices. To improve upon the properties of the CNTs, low
cost and industrially feasible approaches to their modification
have been carried out vigorously in recent times,25,99–109
including covalent or noncovalent functionaliza­
tions.4,19,25,96–98,100,110–114 Depending on the methods used,
functional groups can be introduced onto the surface of CNTs.
Meanwhile, it would improve the solubility and processability
of CNTs and endow CNTs with multifunctional applications by
integrating other functional groups or materials onto their sur­
face. A functionalized CNT might have mechanical, optical, or
electrical properties that are different from those of the pristine
 Functionalized Carbon Nanotubes and Their Enhanced Polymers 449

CNT. Therefore, it is an interesting and emerging topic to
functionalize CNTs for various applications.98
8.17.3.1 Noncovalent Functionalization
Noncovalent functionalization is mainly based on supramole­
cular complexation using various adsorption forces, such as
van der Waals force, hydrogen bonds, electrostatic force, and
π stacking interactions.134–139 All these functionalizations are
exohedral derivatizations. Noncovalent functionalization
mainly involves surfactants, biomacromolecules, or wrapping
with polymers (Table 3). A special case is the endohedral
functionalization of CNTs, that is, the filling of the CNTs with
atoms or small molecules (Figure 15). Compared to the che­
mical functionalization, noncovalent functionalization has the
advantages that it could be operated under relatively mild
reaction conditions and the perfect graphitic structure of
CNTs could be well maintained.98 In addition, noncovalent

Table 3 Noncovalent functionalization of CNTs

Polymer or surfactant Nanotube type Preparation method References

Surfactants
Cationic (cetyltrimethylammonium bromide, CTAB) SWNTs Microemulsion 115
Cationic (CTAB) SWNTs Ultrasonication 116
Cationic (cetyltrimethylammonium 4-vinylbenzoate, CTVB) SWNTs Sonication 117
Cationic ([2-(methacryloyloxy)ethyl]trimethylammonium chloride, MATMAC) MWNTs Emulsion polymerization 118, 119
Anionic (SDS) MWNTs Ultrasonication 120
Anionic (SDBS) SWNTs Ultrasonication 121, 122
Anionic (SDBS) SWNTs Bath sonication 123
Nonionic (Triton X-100) MWNTs, SWNTs Ultrasonication 124, 125
Nonionic (Triton X-305) MWNTs Ultrasonication 126
Biomacromolecules
Proteins/DNA MWNTs Immobilization 127
Glucose (dextran) SWNTs Dialysis 104
β-1,3-Glucans SWNTs Electroactive interaction 128
Chitosan SWNTs Ultrasonication 128
Polymers
Poly(4-vinyl pyridine) SWNTs Sol–gel chemistry 129
Poly(phenyl acetylene) MWNTs Solution mixing 130
PmPV MWNTs Solution mixing 131
SWNTs 132
Poly(styrene)–poly(methacrylic acid) SWNT Solution mixing 133
MWNT

Adapted with permission from Sahoo, N. G.; Rana, S.; Cho, J. W.; et al. Prog. Polym. Sci. 2010, 35, 837.97 Copyright 2010, with permission from Elsevier.

(a) (b)

SWNT

(c) (d)

(e)
Figure 15 Different possibilities of the functionalization of SWNTs: (a) covalent sidewall functionalization, (b) defect group functionalization,
(c) noncovalent exohedral functionalization with surfactants through π stacking, (d) noncovalent exohedral functionalization with polymers, and
(e) endohedral functionalization with, for example, C60. Adapted with permission from Hirsch, A. Angew. Chem. Int. Ed. 2002, 41, 1853.100
450 Functionalized Carbon Nanotubes and Their Enhanced Polymers
functionalization of CNTs can effectively preserve their desired
properties, while their solubility is improved quite remarkably.
8.17.3.1.1 Surfactant functionalization of CNTs
The prospect of functionalizing the outer surface of CNTs in a
noncovalent way in order to preserve the extended π network of
the CNTs is quite attractive. In the search for nondestructive
purification methods, it has been shown that CNTs can be
readily transferred to the aqueous phase through noncovalent
functionalization with surface-active molecules.140–142 It is
believed that the CNTs are in the hydrophobic interiors of the
corresponding micelles, resulting in stable dispersions. When
the hydrophobic part of the amphiphile contains an aromatic
group, especially strong π–π interactions occur between the
aromatic group and the graphitic sidewalls of the CNTs.110
The distinct structural feature of a surfactant originates from
its duality, namely the hydrophilic region of the molecule or
the polar head groups, and the hydrophobic region or the tail
groups that are usually composed of one or few hydrocarbon
chains. Those amphiphilic molecules can adsorb at the inter­
face between immiscible bulk phases, such as oil and water, air
and water, or particles and solution, acting to reduce the surface
tension.
Surfactants act as ‘solubilizers’ to disperse CNTs via physical
adsorption, and the procedures of solubilization are very sim­
ple. CNTs are placed in a solution containing solubilizer and
then subjected to sonication treatment for a while. During
sonication, the provided mechanical energy can overcome the
van der Waals interactions between the CNT bundles and leads
to the exfoliation of CNTs. At the same time, solubilizer mole­
cules adsorb onto the surfaces of the CNT walls. Solubility of
CNTs in a solvent depends on the type, the concentration of the
solubilizer, and the purity of the CNTs. The mechanism for
dispersion of CNTs by the solubilizer is believed to be an
‘unzipping’ mechanism proposed by Strano and co-workers143
at Rice University in 2003.
CNTs can be well dispersed in water using anionic, cationic,
and nonionic surfactants, such as sodium dodecyl sulfate
(SDS) and sodium dodecylbenzene sulfonate (SDBS), cetyltri­
methylammonium bromide (CTAB), Brij, Tween, Triton X, and
siloxane polyether copolymer (PSPEO).113,144–148 SDS149–151
and SDBS152,153 are commonly used to decrease the aggrega­
tion of CNTs in water. SDS has a weaker interaction with the
CNT surface compared to that of SDBS and Triton X-100
because it does not have a benzene ring. Indeed, π–π interac­
tions of the benzene rings on the surfaces of graphite can
SDBS
C12H25 −Na+ CH3(CH2)11OSO3
SO3
SO3−
SO3− SO3−
SO4−
SO3− SO3−
SO4−
SO3− SO3− SO4−
Figure 16 Schematic representation of how surfactants may adsorb onto the CNT surface. Adapted with permission from Islam, M. F.; Rojas, E.;
Bergey, D. M.; et al. Nano Lett. 2003, 3, 269.123 Copyright 2003 American Chemical Society.
significantly increase the binding and surface coverage of sur­
factant molecules to graphite.96,123 SDBS performs better than
Triton X-100 due to its head group and slightly longer alkyl
chain. Figure 16 represents the adsorption of different surfac­
tants onto the surfaces of CNTs.
In 2002, O’Connell and co-workers154 reported the prepara­
tion of individually dispersed SWNTs by sonication in a
cylindrical micelle of SDS. The authors found that aggregation
of CNTs into bundles otherwise quenches the fluorescence
through interactions with metallic tubes and substantially
broadens the absorption spectra. Gao and co-workers obtained
homogeneous dispersion of MWNTs under the optimized
composition of 0.5 wt.% MWNTs and 2.0 wt.% SDS relative
to water. The interactions between CNTs and SDS through the
hydrophobic part can cause a steric repulsion and higher nega­
tive surface charge, which improves the dispersion of CNTs.150
With the use of noncovalent functionalization by the sur­
factant Triton X-100,155 the surfaces of the CNTs were changed
from hydrophobic to hydrophilic. Consequently, the hydro­
philic surface of the CNT–Triton conjugate interacted with the
hydrophilic surface of biliverdin reductase, which created a
water-soluble complex of the immobilized enzyme.
Ultracentrifugation, gel electrophoresis, and Raman spectro­
scopy analyses revealed the presence of the enzyme and
interactions with the conjugates of CNT–Triton.110,155
However, it has been believed that simple alkyl chains of
surfactants such as SDS, sodium dodecyl sulfonate (SDSA), and
dodecyltrimethylammonium bromide (DTAB), could usually
form nonspecific hydrophobic interactions with CNTs,122,154
which consequently cause the surfactant molecules to pack
relatively loosely around CNTs.113
The structure of surfactants is quite diverse and their nature
determines the dispersion efficiency of CNTs in solution.
Surfactant molecules containing aromatic groups can form
the specific and directional π–π stacking interactions with the
CNT surface. Interactions of SDS and structurally related SDBS
with SWNTs have been compared to explore the role of the
aromatic groups.123 SDS and SDBS have the alkyl chain with
the same length, but the latter has a phenyl ring attached
between the alkyl chain and the hydrophilic group. The pre­
sence of the phenyl ring can make SDBS surfactant more
effective for solubilization of CNTs compared to SDS
(Figure 17), due to the formed π–π stacking between the
SWNTs and phenyl rings of SDBS within the micelle. The π–π
interactions of the benzene rings with the CNT surface are
believed to increase the adsorption ratio of surfactants.123
SDS Triton X-100
− Na+ O(CH2CH2O)N -H C8H17
N = approx. 9.5
SO4−
SO4−
SO4−
SO4−
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
Figure 17 Vials (6 ml) containing aqueous dispersions of (left to right)
SDS–high-pressure carbon monoxide process (HiPCO) SWNTs at
0.5 mg ml−1 and Triton X-100–HiPCO SWNTs at 0.8 mg ml−1 after sitting
for 5 days, and SDBS–HiPCO SWNTs at 20 mg ml−1 after sitting for 2
months. Adapted with permission from Islam, M. F.; Rojas, E.;
Bergey, D. M.; et al. Nano Lett. 2003, 3, 269.123 Copyright 2003 American
Chemical Society.
This technique has enabled the immobilization of a wide range
of biomolecules on the sidewalls of CNTs with high specifici­
ties and efficiencies, which is very interesting for the
development of biosensors.4,100
The length and the shape of the alkyl chain are also quite
important for the interaction of surfactants with CNTs: longer
and more branched alkyl groups are better than linear and
straight ones.123,156 In addition, the merit of a dispersant con­
taining double bonds, and with similar head group and tail
length, was proved by particle size analysis of Tween-60 and
Tween-80 nonionic surfactants.113,157
Compared to conventional surfactants with alkyl chains,
silicone polymer surfactants possess better properties such as
superwettability and notably low surface tension.113 PSPEO is
a new amphiphilic macromolecule surfactant with a comb
polymer molecular structure, consisting of hydrophobic –Si–
O–Si– main chain and hydrophilic pendant parts of
(a)
100 nm
Figure 18 TEM images of the MWNT/PSPEO at lower (a) and higher (b) magnifications. Adapted with permission from Hu, C. Y.; Liao, H. L.; Li, F. Y.;
et al. Mater. Lett. 2008, 62, 2585.144 Copyright 2008, with permission from Elsevier.
451
polyethylene oxide. In 2008, Hu and co-workers reported that
MWNTs could be easily solubilized with PSPEO in water by
noncovalent functionalization. HRTEM images revealed that
PSPEO was adsorbed on the surface of MWNTs, creating a
5–10-nm adsorption layer to hinder the aggregation of CNTs
(Figure 18). The strong attachment of PSPEO to MWNTs
results in the observed upshift of the G band of Raman
spectra.144
The charge of ionic surfactants may result in the electrostatic
repulsion between the surfactant molecules, which can also sta­
bilize the CNT colloids. The nonionic surfactants stabilize the
CNTs in solution not by electrostatic interactions but primarily
by steric interactions. As a result, it has been reported that bulky
hydrophilic groups have an advantage in the case of CNTs sus­
pended with nonionic surfactants probably due to the improved
steric stabilization provided by longer polymeric groups.122
Though the interactions of surfactant molecules and CNT
surfaces have already been intensively investigated, the exact
way in which surfactant molecules organize on the CNT surface
is still unclear. In addition, for preparing uniform and stable
suspensions of CNTs, the concentration of both CNTs and
surfactants should be controlled strictly. In most of articles
published in this field, it seems that the choice of the concen­
trations of CNTs and surfactants is based on trial and error.113
8.17.3.1.2 Biomacromolecule functionalization of CNTs
More recently, the solubilization of SWNTs associated noncova­
lently with biomacromolecules in both aqueous and organic
solutions has been investigated to some extent.103,104,158,159
The biomacromolecules, including simple saccharides and poly­
saccharides,104,158,159 proteins,158 enzymes, and DNA were
usually used in the noncovalent functionalization of SWNTs.4
In 2002, Star’s group159 at the University of California
found that SWNTs were not soluble in an aqueous starch solu­
tion; however, they could be soluble in an aqueous solution of
starch–iodine complex. These observations suggest that iodine
preorganizes the backbone of the amylose in starch into a
helical geometry and accordingly makes its hydrophobic cavity
accessible to a single SWNT or bundle. The formation of such
(b)
PSPEO
PSPEO
20 nm
452 Functionalized Carbon Nanotubes and Their Enhanced Polymers
starch-wrapped SWNT complexes is driven by simultaneous
enthalpic and entropic gains resulted from creating favorable
van der Waals interactions and expelling out considerable
small iodine molecules, which were located inside the helix,
into the solvent by a ‘pea-shooting’ type of mechanism. This
results in a simple protocol for the purification of SWNTs under
ambient conditions, using the easily available starch–iodine
complex. The reversible solubilization of starch-wrapped
SWNTs in water solution has been further investigated by the
assistance of enzymatic hydrolysis, using the commercially
available amyloglucosidase from Rhizopus mold. Adding this
enzyme to an aqueous solution of starch-wrapped SWNTs
could lead to the precipitation of all the SWNTs within
10 min, as indicated by light-scattering measurements and
also by changes that are clearly visible to the naked eye. This
reversible water solubilization of SWNTs in aqueous solution
using starch could provide a cheap and easy way to produce
integrated biological CNT devices for applications.4
Since then, a whole host of different saccharides and poly­
saccharides, such as ammonium-modified curdlan,128,160
lactose-appended schizophyllan,161 n-decyl-β-D-maltoside,162
n-octyl-β-D-glucoside,162 γ-cyclodextrin,163 η-cyclodextrin,164
O-carboxymethyl chitosan,165 carboxymethyl amylase,103 chit­
osan,165 curdlan,128,166,167 sulfonate-modified curdlan,128
pullulan,103 poly(ethylene glycol)-modified O-carboxymethyl
chitosan,165 phospholipid–dextran,168 schizophyllan,166,167
and a hydrophobic dextran derivative104 have also been used
to assist the noncovalent functionalization of SWNTs. The
research has been aided and abetted by the following facts:
(1) such saccharides and polysaccharides have almost no light
absorption in UV-Vis wavelength region, therefore, the SWNT
hybrids can be characterized by photochemical experiments
and (2) the saccharide- and polysaccharide-coated SWNT
hybrids are usually believed to be biocompatible and may be
useful for various medicinal applications.4
Direct, nonsurfactant-assisted immobilization of metal­
lothionein proteins127,169 and streptavidin170 has also been
pursued on MWNTs. The hydrophobic regions of the proteins
are probably important for the adsorption on the surfaces of
CNT. A monoclonal antibody, specific for C60 fullerenes, could
also be directly bound to SWNTs.171 It has been thus indicated
that the binding site of this IgG antibody is a domain of
hydrophobic amino acids. The mechanism of protein immo­
bilization on surfaces of CNTs may be the nucleophilic
(a)
20 nm
40 nm
350 nm
Figure 19 A bundled pair of copolymer-encapsulated SWNTs from unpurified material (a) and purified encapsulated SWNTs (b). Adapted with
permission from Kang, Y. J.; Taton, T. A. J. Am. Chem. Soc. 2003, 125, 5650.177 Copyright 2003 American Chemical Society.
substitution of N-hydroxysuccinimide by an amine group on
the protein. In this case, noncovalent functionalization is
usually achieved by the interaction of delocalized π bonds on
the wall of CNTs caused by sp2 hybridization with π bonds of
polymer molecules of the matrix.4,100
8.17.3.1.3 Polymer functionalization of CNTs
The dispersion of CNT in both water172,173 and organic sol­
vents174 may be enhanced by the physical association of
polymers with CNTs, which can be explained by the ‘wrapping’
mechanism172 that attributed to the specific and strong inter­
actions between the polymer and the CNTs. Polymers can wrap
around CNTs and easily form supramolecular complexes with
CNTs.175 In these cases, π stacking and van der Waals interac­
tions between the polymer and the surface of CNT are
responsible for the close association of the structures.96
Blau and co-workers175,176 prepared a CNT–polymer
hybrid by suspended SWNTs in organic solvents poly
(p-phenylenevinylene-co-2,5-dioctyloxy-m-phenylenevinylene)
to wrap the copolymer around the CNTs. The electrical prop­
erties of these hybrids were improved relative to those of the
individual components. A noncovalent method has been
used to functionalize SWNTs by encapsulating SWNTs within
cross-linked and amphiphilic poly(styrene)-block-poly(acrylic
acid) copolymer micelles (Figure 19).177 This encapsulation
significantly enhanced the dispersion of SWNTs in a wide
variety of polar and nonpolar solvents and polymer matrices
because the copolymer shell was permanently fixed. Thus,
encapsulated SWNTs may be stabilized with respect to typi­
cal polymer processing and recovery from the polymer
matrix.
Curran and co-workers4,131 have reported the preparation
of a poly(m-phenylenevinylene)-co-(2,5-dioctoxy-p-phenylene)
vinylene (PmPV)/MWNT composite and found that the intro­
duction of MWNTs could significantly increase the electrical
conductivity of the PmPV polymer by up to eight orders of
magnitude. Stoddart et al.178,179 have prepared PmPV/SWNT
hybrids and obtained some interesting results from two key
experiments, indicating that the PmPV polymer is in close elec­
trical contact with SWNTs and that the polymer wraps itself
around bundles of the SWNTs, rather than around individual
CNTs, which then aggregates to form ropes. It has been sug­
gested by control experiments that only PmPV-wrapped SWNTs
show on/off differences for negatively and positively biased
(b)
Inset
1 μm
350 nm
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
junctions and unwrapped SWNT devices exhibit no optically
modulated response.4
MWNTs were reported to successfully functionalize with
water-soluble poly(2-ethyl-2-oxazoline) (PEOX) through the
polymer wrapping process by Tan and co-workers180 in 2007.
The functionalized MWNTs exhibit excellent and stable disper­
sion in water as well as other organic solvents such as ethanol
and N,N-dimethylformamide (DMF).
In 2001, O’Connell and his co-workers181 reported that
SWNTs had been reversibly solubilized in water in the grams
per liter concentration range by noncovalently associating
them with various linear polymers such as polyvinylpyrroli­
done (PVP) and polystyrene sulfonate (PSS). PVP is a polymer
with a hydrophobic alkyl backbone and hydrophilic pendant
groups, which can be envisaged to coil around the CNTs so that
its backbone is in good contact with the surface of CNTs and
consequently pyrrolidone groups are exposed to water.154,181
Polynucleotides are rearranged in an opposite way to PVP,
since they have a hydrophilic sugar–phosphate backbone
with relatively hydrophobic aromatic nucleotide bases as pen­
dants. A recent study has shown that polynucleotides could
form various helical wrappings around the CNT so that aro­
matic nucleotide bases are in close contact with the SWNT.113
Nonwrapping approaches have also been used for disper­
sion and solubilization of CNT in different medias.182 In these
cases, copolymers of various structures and compositions act
efficiently as stabilizers, and may be tailored in order to dis­
perse the CNTs in a variety of solvents. Nativ-Roth and co­
workers133 suggested that the block copolymers could adsorb
on CNTs by a nonwrapping mechanism, and the solvophilic
blocks act as a steric barrier, which leads to the formation of
stable dispersions of individual SWNTs and MWNTs above a
threshold concentration of the polymer. The strong π–π inter­
action between polymer backbone and surface of CNTs led to
soluble SWNTs.96
Pyrene, a group with a large aromatic system, has demon­
strated a very high affinity for the surface of CNTs. It is widely
accepted that the pyrene is an efficient moiety for noncovalent
functionalization of CNTs.183 In fact, the interaction of the
aromatic system of pyrene with CNTs is very effective, there­
fore, functionalized pyrenes have been used to anchor proteins
and small biomolecules.158 Chen and co-workers158 have
developed a method to immobilize proteins and small biomo­
lecules onto succinimidyl pyrenebutyrate-modified SWNTs.
Pyrene-bearing molecules have also been proved effective for
binding sidewalls of SWNTs through noncovalent interactions.
As such, pyrenes bearing hydrophilic groups such as ammo­
nium ions, carboxylates, and block copolymer components can
result in CNTs with aqueous solubility.113
Anthracenes are another kind of polyaromatic molecules
forming specific π–π interactions with CNTs. The adsorption
of anthracenes on CNTs seems to be very strong, since the
molecules remain adsorbed after extensive washing with
organic solvents. However, anthracenes can be replaced by
pyrenes, which can form stronger interactions with CNTs.
Heterocyclic polyaromatic molecules such as porphyrins and
phthalocyanines can also form effective interactions with
CNTs. Murakami and his co-workers184 have found that por­
phyrin is capable of dispersing SWNTs for long periods in
organic solvents. It has been believed that the nature of the
interaction of heterocyclic aromatic molecules with SWNTs is
453
van der Waals forces, essentially the same as in the case of
polyaromatic compounds such as pyrene.113
The polymer-encapsulated MWNTs have been successfully
prepared through ultrasonically initiated in situ emulsion poly­
merizations of n-butyl acrylate (BA) and methyl methacrylate
(MMA) in the presence of MWNTs.185 Another noncovalent
method for functionalization of SWNTs was also developed
by encasing the SWNTs within cross-linked, amphiphilic copo­
lymer micelles.177 This encapsulation significantly improves
the dispersion of SWNTs in a wide variety of polar and non­
polar solvents and polymer matrices.113
8.17.3.1.4 Endohedral functionalization
The inner cavity of SWNTs offers space for the storage of guest
molecules (Figure 15(e)).186,187 Up to now, the uptake and the
endohedral chemistry of metals and metal salts have been
widely investigated.100,186–188 For instance, gold and platinum
nanothreads have been successfully created in the capillaries of
the CNTs, by treating the SWNTs with the corresponding per­
chlorometallic acids at elevated temperatures. In some cases,
the as-prepared nanothreads are single crystals. The incorpora­
tion of fullerenes such as C60189,190 or metallofullerenes such as
Sm@C82191 are especially impressive examples of the endohe­
dral chemistry of SWNTs, and may enable the creation of some
new materials for molecular-scale devices. The incorporation is
usually pursued at defect sites localized at the ends or in the
sidewalls. The encapsulated fullerenes tend to form chains that
are coupled by van der Waals forces. Sometimes, such arrays are
called ‘bucky peapods’.110,190 Upon annealing, the encapsu­
lated fullerenes can coalesce in the internal of the SWNTs,
resulting in new, concentric, endohedral CNTs with a diameter
of
0.7 nm. The process of such reactions inside the CNTs
could be monitored in real time by means of HRTEM
observation.191
The structures and energetics of several types of all-carbon
peapods made by C60 encapsulated inside SWNTs were calcu­
lated, and the interactions between the SWNTs and the C60
molecules revealed a minimal diameter of SWNTs for exother­
mic encapsulation of 11.74 Å and a radial deformation of the
C60 cage as a linear function of the diameter of SWNTs.110,192
The activation energy for the translation of individual C60
molecules inside the SWNTs is very low. An individual full­
erene C60 can diffuse freely inside the pod. And the major factor
controlling the dynamics of molecular transport in the peapods
is the interaction between C60 molecules.192
Small proteins have also been entrapped in the inner hol­
low channels of opened CNTs by simple adsorption, thus
forming natural nano test tubes.110,193,194
8.17.3.2 Covalent Functionalization
Covalent functionalization of CNTs is based on the formation
of a covalent bond between functional entities and the carbon
backbones of CNTs,98,110 conducted at the termini of the CNTs
or at their sidewalls. It could also be divided into direct cova­
lent sidewall functionalization and indirect covalent
functionalization (defect functionalization). Direct covalent
sidewall functionalization is associated with a change of hybri­
dization from sp2 to sp3 and a simultaneous loss of
conjugation. The latter takes advantage of chemical transforma­
tions of the already present defect sites, which can be the open
454 Functionalized Carbon Nanotubes and Their Enhanced Polymers
ends and holes in the sidewalls, terminated, for example, by
carboxylic groups, and pentagon and heptagon irregularities in
the hexagon graphene framework. Oxygen-containing sites,
formed through oxidative purification, usually have been con­
sidered as defects.110 The disadvantage of covalent
functionalization is that the perfect structure of CNTs has to
be destroyed, resulting in significant changes in their physical
properties.98
8.17.3.2.1 Defect functionalization
One of the most commonly used techniques for functionaliza­
tion of CNT is the ‘oxidative purification’ by liquid-phase or
gas-phase oxidation, which usually introduces carboxylic
groups and some other oxygen-containing functionalities
such as hydroxy, carbonyl, ester, and nitro groups into the
CNTs,110 coined as defect functionalization. The purpose of
the oxidative treatment is to oxidatively remove the metallic
catalyst particles (Fe, Co, or Ni) used during the synthesis
process and the amorphous carbon, which is a by-product of
most synthetic methods.195 The presence of carboxyl groups
can lead to a reduction of van der Waals interactions between
the CNTs, strongly facilitating the breakdown of CNT bundles
into individual CNTs. Additionally, the attachment of suitable
groups enables the CNTs soluble in aqueous or organic sol­
vents, which opens the possibility of further modifications
through subsequent solution-based chemistry.
The defect functionalization of CNTs was first discovered by
Liu et al.195 in 1998 as a result of efforts to purify SWNTs.
Purification has been achieved by refluxing as-produced
SWNTs and amorphous carbon in 2.6 M HNO3 and then sus­
pending the SWNTs in water of pH 10 with surfactants. When
the SWNTs are recovered through filtration, they are found to
be free of amorphous carbon. In addition to eating away the
amorphous carbon, HNO3 is found to have important effects
on the structure of the CNTs themselves. Over short periods,
HNO3 intercalates reversibly into bundles of CNTs, whereas
over long periods, HNO3 can disorder or exfoliate the
bundles.195,196
A major milestone in the emerging area of CNT chemistry
was the development of an oxidation process for SWNTs invol­
ving intensive ultrasonic treatment in a mixture of concentrated
nitric and sulfuric acid.197 Such drastic conditions lead to the
opening of the caps of CNTs and the formation of holes in the
sidewalls, followed by an oxidative etching along the walls with
the concomitant release of carbon dioxide. The resultant
products are CNT fragments with lengths in the range of
100–300 nm with the ends and sidewalls decorated with a lot
of various oxygen-containing groups (mainly carboxyl groups).
CNTs functionalized in this manner basically maintain their
pristine electronic and mechanical properties.25,198
Up to date, purification treatment has been realized using
boiling nitric acid,199,200 sulfuric acid201 or mixtures of both
acids,199 ‘piranha’ (sulfuric acid–hydrogen peroxide)195 or gaseous
O CH3(CH2)17NH2
C C
OH
Figure 21 Gas-phase amidation of oxidatively purified SWNT with ODA to obtain zwitterionic functionalization products. Adapted with permission from
Hirsch, A.; Vostrowsky, O. In Functional Molecular Nanostructures, Vol. 245, 2005, pp 193.110
R−O
O
OH O
R − OH
O O
R
HNO3 O
Δ OH R − NH
O
R − NH2 O
NH
R
Figure 20 Defect functionalization of CNTs, followed by subsequent
esterification or amidization of the carboxyl groups. Adapted with per­
mission from Balasubramanian, K.; Burghard, M. Small 2005, 1, 18025
oxygen,202 ozone,203 or air as oxidant204 at elevated temperatures,
or combinations of nitric acid and air oxidation.15,110
The oxidatively introduced carboxyl groups can provide
active sites for further modifications, as they enable covalent
coupling of molecules through the creation of amide and ester
bonds (Figure 20). The carboxylic groups can be further acti­
vated via chemical conversion into acyl chloride groups with
thionyl chloride,195,197 and the formed acyl chlorides can be
transformed to carboxamides by amidation.110 By this method,
the CNTs can be provided with a wide range of functional
moieties, for which purpose bifunctional molecules are often
utilized as linkers. Illustrative examples are CNTs equipped
with dendrimers, nucleic acids, enzymes, metal complexes, or
semiconductor and metal nanoparticles.25,205 Chen and co­
workers197,206 were the first to report the functionalization of
oxidatively treated SWNTs with alkyl amines and less nucleo­
philic aniline derivatives. The conversion of the acid
functionality to the amide of octadecylamine (ODA) could
lead to the first shortened, soluble SWNTs.110,197 A gas-phase
derivatization procedure was pursued for direct amidization of
oxidized SWNTs using simple aliphatic amines (Figure 21). In
some cases, a little amount of chemically formed amides and a
large portion of physisorbed amines were observed.25 Acyl
chloride-functionalized SWNTs are very vulnerable to reaction
with other nucleophiles, for example, alcohols. The Haddon
group at Riverside reported the preparation of soluble
O
+
NH3(CH2)7CH3
−
O
 Functionalized Carbon Nanotubes and Their Enhanced Polymers 455

(a) (b)

O O n-C18H37 O O
C n C
O OCOCH3
C
O n-C18H37

(c)
O

O O
C H2 O
O C
O
O

Figure 22 (a) SWNT–ester, SWNT–COO–(CH2)17–CH3. (b) Ester from SWNT–COOH and PVA-VA. (c) Dendritic-type benzyl alcohol ethers. Adapted with
permission from Hirsch, A.; Vostrowsky, O. In Functional Molecular Nanostructures, Vol. 245, 2005, pp 193.110

ester-functionalized SWNTs: SWNT–COO(CH2)17CH3,
obtained by reaction of SWNTs with octadecyl alcohol in
2002.207 The preparation of soluble polymer-bound and den­
dritic ester-functionalized SWNTs has been achieved by Sun
and co-workers through attaching poly(vinyl acetate-co-vinyl
alcohol) (PVA-VA)208 and hydrophilic and lipophilic
dendron-type benzyl alcohols,209 respectively, to
SWNT–COCl (Figure 22). Another intriguing application of
the carboxyl groups is the formation of an anhydride at the
ends of CNTs, through which rings of CNTs are accessible.25,210
8.17.3.2.2 Covalent sidewall functionalization
While the two-step functionalization of CNTs through the oxida­
tive introduction of carboxyl groups followed by the formation of
amide or ester linkages does allow for a stable chemical modifica­
tion, it has only a relatively weak effect on the electrical and
mechanical properties of the CNTs. In comparison, addition
reactions enable the direct coupling of functional groups onto
the π-conjugated carbon framework of the CNTs. The required
reactive species (atoms, radicals, carbenes, or nitrenes) are com­
monly produced through thermally activated reactions, and
small-diameter CNTs are preferred in this case as they exhibit
higher chemical reactivity due to their increased curvature.211 A
series of addition reactions have been briefly documented, the
most important of which are listed in Figure 23.25
More recently, the strategies for addition reactions to the
sidewalls of CNTs have been developed very fast and the func­
tionalization degrees have reached at least 10%, compared with
that of only 1–3% in the early experiments.100,212 However, at
the present stage, the addition mechanisms are not yet clear. In
principle, the addition reaction could be initiated exclusively
on the intact sidewall or in parallel at defective sites from which
the reaction could further proceed.25
The direct covalent attachment of functional moieties to the
sidewalls strongly enhances the solubility of the CNTs. The excel­
lent solubility of CNTs modified with organic groups has been
intensively investigated for their effective purification.213 During
this procedure, small particles are first separated from the solution

H F
Cl
N-R
Cl
H F
NaNH3 or
H2 Plasma
(C6H4)HgCCl2Br F2
>150 °C
R-N
O3 O NaBH4 OH
Br-CH(COOR)2 O
O OH

Li/R-I or
NH2-CH2-COOH RCOO-OOCR
R-CHO
R(C6H4)N2+
R
R
COOR
N-R
COOR R
R

Figure 23 Overview of possible addition reactions for the functionalization of the nanotube sidewall. Adapted with permission from Balasubramanian, K.;
Burghard, M. Small 2005, 1, 180.25
456 Functionalized Carbon Nanotubes and Their Enhanced Polymers
F F F F F F
RMgBr or RLi
Figure 24 Treatment of fluorinated CNTs with strong nucleophiles and replacement of the fluorine substituents. Adapted with permission from
Hirsch, A.; Vostrowsky, O. In Functional Molecular Nanostructures, Vol. 245, 2005, pp 193.110
through chromatography or filtration, and then the covalently
attached groups are removed through thermal annealing.25
CNTs, once fluorinated, can serve as a staging point for
different kinds of sidewall chemical functionalizations. By
treating fluorinated CNTs with strong nucleophiles, such as
Grignard reagents, the fluorine substituents could be replaced
with relative ease and derivatized products, for example,
methyl-, butyl-, hexyl- and methoxyl CNTs, were formed
(Figure 24),110,214 which thus open a flexible strategy for pro­
viding the sidewalls with various types of functional groups.
Alcohols, amines, Grignard reagents, metal alkoxides, and alkyl
lithium compounds have been successfully employed as
nucleophilic reagents, resulting in up to 15% of the carbon
atoms of the sidewall for CNTs bearing a functional
group.25,215 Moreover, the CNTs can be covalently cross-linked
with each other by using a bifunctional reagent, such as an
α,ω-diamine with a sufficiently long carbon chain.25
Functionalization of CNTs with polymer molecules (polymer
grafting) is particularly crucial for processing of polymer/CNT
nanocomposites.96,216 Two main categories ‘grafting to’ and
‘grafting from’ approaches have been reported for the covalent
grafting of polymers to CNTs. The former is based on attachment
of as-prepared or commercially available polymer molecules on
the surface of CNTs by chemical reactions, such as amidation,
esterification, and radical coupling. The polymer must have
suitable reactive functional groups for the preparation of com­
posites in this approach. In 2001, Fu and co-workers217 reported
the CNTs functionalized by using ‘grafting to’ method. They
refluxed CNTs containing carboxylic acid groups with thionyl
chloride to convert acid groups to acyl chlorides. Then, these
CNTs were used in the esterification reactions with the hydroxyl
groups of dendritic poly(polyethylene glycol) polymer.
Polymer-grafted CNTs have been formed by covalently bonding
CNTs to highly soluble linear polymers, such as
poly(propionylethylenimine-co-ethylenimine) (PPEI-EI) through
amide linkages or PVA-VA through ester linkages.208,218 The
resultant PVA-grafted CNTs were soluble in PVA solution and
PVA–CNT nanocomposite films showed very high optical qual­
ity. Numerous other linear polymers such as poly(sodium
4-stryrenesulfonate),219 poly(methyl methacrylate)
(PMMA),220 polyimide,221 poly(2-vinylpyridine),222 PPEI­
EI,223 and poly(m-aminobenzenesulfonic acid)224 as well as
dendrons,209 dendrimers,225 and hyperbranched polymers226
have also been successfully bonded to CNTs. In the latter
approach, the polymer is bound to the surface of CNTs by
in situ polymerization of monomers in the presence of reactive
CNTs or CNT-supported initiators. The main virtue of this
approach is that the polymer–CNT composites can be prepared
with high grafting density. This approach has been successfully
used to graft lots of polymers such as polyamide-6,227
PMMA,228 polystyrene (PS),229 poly(acrylic acid) (PAA),230
poly-(tert-butyl acrylate),231 poly(N-isopropylacrylamide)
R R R R R R
R = CH3, C4H9, C6H13, OCH3
N
BF4−
N+ R
+ e− + N2
R R
Figure 25 Electrochemical reduction of an aryl diazonium salt, giving a
reactive radical that covalently attaches to a carbon surface. Adapted with
permission from Bahr, J. L.; Yang, J.; Kosynkin, D. V.; et al. J. Am. Chem.
Soc. 2001, 123, 6536.235 Copyright 2001 American Chemical Society.
(PNIPAM),232 poly(4-vinylpyridine),233 and poly
(N-vinylcarbazole)234 on surface of CNTs via radical, cationic,
anionic, ring-opening, and condensation polymerizations.96
The surface of the CNTs can also be functionalized by
covalent bond formation via electrochemical coupling of aro­
matic diazonium salts and phenyl residues (Figure 25).235 Guo
and co-workers236 reported a method for deposition of Pt
nanoparticles through covalent modification of CNTs with
4-aminobenzene in 2003. First, an ordered 4-aminobenzene
monolayer was grafted onto the as-prepared CNT paste elec­
trode by electroreduction of 4-nitrobenzenediazonium
tetrafluoroborate. Then, PtCl2− 6 was adsorbed onto the
4-aminobenzene monolayer-modified electrode surface by
electrostatic interaction. Finally, Pt nanoparticles could be
obtained by pulsed potentiostatic reduction.97
In 2001, Bahr’s group235 at Rice University reported the elec­
trochemical reduction of aryl diazonium salts using a bucky paper
electrode as a viable means of derivatization of SWNTs of small
diameters. Raman spectra of the SWNT paper exhibited distinct
changes after modification. Most important of all, an increase in
the relative intensity of the D line at
1290 cm−1 could also be
found, which is known to be sensitive to disorder within the
sp2-bonded carbon framework.236 The extent of modification
has been found to vary depending on the type of the used aryl
diazonium salt. After functionalization, up to 5% of carbon
atoms have been found to bear an aromatic residue correspond­
ing to a functionalization degree of 5%. The coupling mechanism
has been interpreted as involving the transfer of an electron from
the CNT, which reduces the diazonium salt to a highly reactive
phenyl radical that then attaches covalently to the sidewall of
CNTs. Moreover, the reactivity of CNTs could be enhanced by
their small diameters of down to 0.6 nm;81 large-diameter CNTs
are also found to be amenable to covalent electrochemical mod­
ification under particular conditions.25,236
Compared to the chemical functionalization approaches
based on electrochemistry, photochemical approaches have
also been employed to a much less extent up to now.
Photoirradiation has been successfully used to generate reactive
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
O O
Os
O O
O O
Os
O O
(a)
Figure 26 (a) Reaction scheme for sidewall osmylation of an SWNT using UV light and (b) resistance change of an individual metallic SWNT upon
exposure to OsO4 and O2 under UV-light irradiation. Adapted with permission from Cui, J. B.; Burghard, M.; Kern, K. Nano Lett. 2003, 3, 613.238 Copyright
2003 American Chemical Society.
species such as nitrenes in the course of sidewall addition reac­
tions.237 Cui and co-workers238 reported sidewall osmylation of
individual metallic SWNTs by exposing the SWNTs to osmium
tetroxide vapor under UV photoirradiation conditions. The
authors found that the covalent attachment of the OsO4 could
lead to an increase in the electrical resistance by up to several
orders of magnitude. The cycloaddition product could be exfo­
liated by UV light in vacuum or under oxygen atmosphere,
whereby the original resistance is restored (Figure 26). Later,
UV light-induced osmylation of SWNTs was also investigated
in organic solvents by Banerjee and Wong239 in 2004. Under
these conditions, OsO4 appears to react preferentially with the
metallic CNTs contained within the sample. This selectivity may
originate from the availability of electronic states at the Fermi
level in the metallic CNTs. The formation of an intermediate
charge-transfer complex is likely the basis for the observed selec­
tivity and reactivity of metallic tubes.25
To the best of our knowledge, relatively less research has
been carried out on the covalent functionalization of CNTs
with metal nanoparticles owing to the complicated process.98
In 2007, Nakamura et al.240 photolyzed cyclic disulfides with
SWNTs to achieve a sidewall modification of the SWNTs to
introduce sulfur-containing functional groups. A subsequent
treatment of sulfur-containing, substituent-modified SWNTs
with gold nanoparticles gave an attachment of gold on the sur­
face of SWNTs through thioalkylthiol linkage. In addition,
Coleman et al.241 introduced thiol groups onto the surface of
SWNTs under Bingel reaction conditions; afterward,
5-nm gold
colloids were grafted onto SWNTs by utilization of the gold–
sulfur binding interaction.98 In addition to the covalent and
irreversible van der Waals functionalization reactions mentioned
above, some metals with surface tensions of 100–200 mN m−1 or
less can make the surfaces of carbon wet.187,242 The strong inter­
actions between one of these metals, Ti, and CNTs have been
explored to form metal nanowires by depositing various metals
on Ti-covered SWNTs, which are suspended between two contact
points.243,244 This method might be used to produce pure metal
nanowires by removing the CNTs by burning away or to produce
metal–CNT contacts for applications of electronic devices. CNTs
can also be filled and decorated with metals by reacting them
with molten metals and/or metal complexes,245 including metals
457
106
OsO4 + O2 O2
Resistance (Ω)
105
I II III IV
104
103 104 105 106
Time (s)
(b)
formed during the synthesis process of CNTs,246 or by using
solution-phase chemistry.111,247
8.17.3.3 Applications
As described in the previous sections, due to their excellent
mechanical, electrical, and magnetic properties, as well as
nanometer-scale diameter and high aspect ratio, CNTs are very
helpful materials in composites to improve their properties for
specific applications. However, increasing evidence has sug­
gested that further functionalization of CNTs could enable the
CNTs with multiple functions, and such a strategy might offer an
effective platform for the practical applications of CNTs.
8.17.3.3.1 Field-effect transistors
Up to now, FETs are the most common electronic devices.
Currently, about 1019 FETs are produced per year, most of
them (
99%) on single-crystal silicon wafers as the building
blocks of integrated circuits for microprocessors, solid-state
memories, or mobile phones.248 As a result of the continuous
lateral and vertical scaling, state-of-the-art silicon FETs are
nanoelectronic devices; however, the miniaturization comes
at an expense of high cost. Therefore, alternative semiconduc­
tors compatible with silicon technology platforms but
providing higher carrier mobilities compared to silicon are of
great interest, especially when they fit naturally into a nanos­
cale FET architecture. An important milestone in this direction
was the fabrication of the first CNT-based FET in 1998 by Che
and co-workers.13 Since CNTs are characterized by very large
mobilities and near-ballistic transport, they hold great promise
for the next generation of nanoelectronics.248
The lack of appropriate synthetic methods that yield exclu­
sively semiconducting CNTs, which has stimulated lots of
attempts to either separate semiconducting CNTs from the
as-prepared material or selectively eliminate the metallic CNTs,
is a long-standing problem in the fabrication of
CNT–FETs.248,249 The separation approach has mainly relied
upon noncovalent chemical functionalization by various kinds
of polymers capable of selectively wrapping semiconducting
SWNTs, most prominently DNA and polyfluorenes.250,251
Moreover, self-sorting, semiconducting SWNT networks have
458 Functionalized Carbon Nanotubes and Their Enhanced Polymers
Metallic R N2
Negative potential
“Off” state
Semiconducting
Figure 27 Schematic of the fabrication concept of a FET starting from a sample containing both metallic and semiconducting CNTs. Adapted with
permission from Balasubramanian, K.; Burghard, M. Small 2005, 1, 180.25
been successfully prepared by spin coating CNTs from solution
onto appropriately surface-functionalized Si/SiO2 substrates.252
The principle of this method is based on the selective binding of
semiconducting CNTs by the terminal amino groups of the
silane layer on the silica.253 Efficient chemical methods to
remove the metallic CNTs in ensembles of CNTs include the
coupling of benzene diazonium salts (Figure 27)254 and
methane plasma etching.255 In the latter process, the metallic
CNTs within a film are preferentially functionalized, while the
semiconducting CNTs with diameters larger than 1.4 nm remain
largely unaffected. Accordingly, the functionalized metallic CNTs
can be permanently removed through thermal annealing.248
Preferential destruction of metallic CNTs has also been
carried out through selective photo-oxidation using laser irra­
diation of suitable wavelength.256 More recently, Zhang and
co-workers257 have demonstrated that long-arc Xe-lamp irra­
diation under ambient condition can also enable faster
destruction of metallic over semiconducting CNTs.
Substitution doping of CNTs is another promising approach.
As a first step in this direction, the synthesis of SWNTs
codoped with boron and nitrogen has recently been reported
by Xu’s group258 at Stanford University. In agreement with
theory, predicting a band gap in the order of 0.5 eV for a 10%
content of each boron and nitrogen, B/N co-doped SWNTs
(BCN-SWNTs) have been found to be completely semicon­
ducting and very suitable as FET channels. FETs made of
enriched semiconducting SWNT ensembles can easily reach
large on/off ratios exceeding 105, which is sufficient for
numerous practical applications.248,250,252
Significant improvement has also been achieved in the devel­
opment of FETs incorporating highly ordered SWNT arrays
produced via oriented CVD growth on quartz substrates.248
After the transfer of the arrays onto a polymer substrate and
selective electrical breakdown of the metallic CNTs, the devices
exhibit very good performance, including carrier mobilities of
1000 cm2 V−1 s−1, scaled transconductances as high as
3000 S m−1, and current outputs of up to 1 A.259 Very recently,
Forzani and co-workers260 reported a method to functionalize
SWNTs in a FET device for the selective detection of heavy- metal
ions in 2006. In their method, peptide-functionalized polymers
were electrochemically deposited onto SWNTs and the selective
detection of metal ions was performed by using appropriate
peptide sequences. The signal transduction mechanism of the
peptide-functionalized SWNT FETs has also been studied. It has
been observed that there was an obvious shift toward the nega­
tive direction of gate potential upon exposure to Ni2+ ions,
which is probably due to the weakening of the interactions
between the oligopeptides and the SWNTs.2
+
8.17.3.3.2 Electrochemical sensors and biosensors
The fact that all the carbon atoms in a CNT are surface atoms
makes them optimally suitable for components in chemical
sensors. Hence, it is not surprising that gas sensors made from
individual CNTs can display good sensitivities at room tem­
perature,261 compared to commercially available classical
semiconductor sensors, which in general operate above
200 °C.25 SWNTs can act as very sensitive chemiresistive sen­
sors; however, they are not as selective as that necessary for
practical sensing applications. Therefore, functionalizing
SWNTs with suitable metal has been investigated in order to
achieve greater chemical selectivity (Figure 28).25,262,263
There are numerous interests in using hydrogen as an energy
source, which puts forward a new demand for enhanced
hydrogen-sensing capabilities since leak detection is very impor­
tant to this potentially explosive reactant. SWNTs functionalized
with metal nanoparticles exhibit promising behavior as hydro­
gen sensors and they have been proven to be more sensitive and
selective to hydrogen by deposition of Pd/Pt nanoparticles on
the wall surface (Figure 29).263 In 2001, Kong and co-workers262
showed the fabrication of hydrogen sensors from individual
semiconducting SWNT functionalized with Pd nanoparticles.
Mubeen’s group264 has reported hydrogen nanosensors fabri­
cated by electrodeposition of Pd nanoparticles on SWNT
networks. Optimal sensors were assembled with a baseline resis­
tance of 10 kΩ and a Pd deposition charge of 0.05 °C, showing
excellent properties with a lower detection limit of 100 ppm and
a linear response of up to 1000 ppm. Low-density networks of
SWNTs with electrochemically functionalization using Pd
showed effective hydrogen sensing for even lower hydrogen
concentrations (
10 ppm).263,265
S D
VG
VSD
Figure 28 Illustration of a CNT network connecting source and drain
electrodes of an FET. Adapted with permission from Vairavapandian, D.;
Vichchulada, P.; Lay, M. D. Anal. Chim. Acta 2008, 626, 119.263 Copyright
2008, with permission from Elsevier.
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
100
Ω
Rel. resistance change (%)
80
60
40
20
++ + 0
(a)
Figure 29 (a) Fabrication of a hydrogen sensor from a CNT decorated with Pd nanoparticles; (b) change in electrical resistance of the sensor upon
contact with hydrogen at room temperature. Adapted with permission from Balasubramanian, K.; Burghard, M. Small 2005, 1, 180.25
Electrochemical detections of metal ions have been inten­
sively studied using CNT-functionalized electrode. In 2006,
Yuan and co-workers266 developed a mercury-free electrode
system by casting a dispersed solution of MWNTs in Nafion
on glassy carbon electrode, which was used to detect Eu(III) by
differential pulse adsorptive stripping voltammetry. In this
case, a wide linear range from 40 nM to 10 mM with lower
detection limit of 10 nM has been obtained. In addition, Sun
et al.267 used SWNT–Nafion film for the determination of Cd2+
in water in 2007, and Profumo’s group268 has prepared chemi­
cally functionalized MWNT electrode to detect trace amount of
As(III) and Bi(III) in a natural and high-salinity waters.
Composite films of CNTs with other materials, such as
conducting polymers or ceramics, are very fascinating materials
for the development of electrochemical sensors. Yang and co­
workers268,269 fabricated an electrode via electropolymeriza­
tion of acid chrome blue K at an MWNT-functionalized glassy
carbon electrode for simultaneous determination of dihydrox­
ybenzene isomers in real water samples through applying the
first-order linear sweep derivative voltammetry. Polypyrrole
(PPy) or polyaniline (PANI) was electrochemically deposited
on SWNT networks by Ferrer-Anglada and co-workers270 in
2006, which has been used as solid-state pH sensors.
Metal nanoparticles have received considerable attention in
recent years. Incorporation of these metal particles into CNTs
produces modified electrodes that have been observed to
enhance the electrocatalytic activity of numerous electrochemi­
cal reactions and therefore be used for sensing applications. For
instance, Luong and co-workers268,271 have reported the use of
metal nanoparticle/CNT nanocomposites for electrochemical
detection of trinitrotoluene (TNT) and other nitroaromatics.
An electrochemical biosensor is an analytical tool for sensitive
and selective detection of biomolecules. Considerable attention
has been paid to biosensors owing to their potential applications
in clinical chemistry, food industry, and environmental fields.
Glucose biosensor based on glucose oxidase (GOx) is still
regarded as a primary model system in the development of new
sensing materials and methods (Figure 30). Different kinds of
glucose biosensors have been fabricated in recent years. For
example, in 2006, Tsai and co-workers272 developed a nanobio­
composite film by incorporation of functionalized MWNTs and
459
N2 H2/N2 N2 Air
0 1 2 3 4 5 6 7 8 9
Time (min)
(b)
GOx into PPy film for a highly sensitive glucose biosensor, which
exhibited a sensitivity of 95 nA mM−1 with a linear range up to
4 mM and a response time of about 8 s. Huang et al.268,273 depos­
ited MWNTs and GOx on a graphite substrate using an LBL
assembly method to fabricate a glucose biosensor and the max­
imum current response to glucose was obtained at six layers of
MWNT/GOx with the detection limit of 90 μM. Wang and
Musameh274,275 designed a needle microsensor for ampero­
metric monitoring of glucose based on the package of a
binderless CNT–GOx composite within a 21-gauge needle.
The as-fabricated microsensor exhibited a low-potential,
highly selective, and sensitive determination of glucose with
a wide linear range (up to 35 mM), prolonged lifetime, and
independence of oxygen.
Very recently, considerable effort has been made in the devel­
opment of a highly sensitive and selective approach for the
detection of dopamine (DA), one of the important catecholamine
neurotransmitters in the mammalian central nervous system.
Wang and co-workers277 reported the fabrication of a poly(3­
methylthiophene)-modified glassy carbon electrode coated with
Nafion/SWNTs for highly selective and sensitive detection of DA.
The functionalized electrode greatly enhanced the voltammetric
signal and significantly suppressed the interferences as well. In
2008, Alarcon-Angeles and co-workers278 also developed a sensor
for DA detection by using β-cyclodextrin and MWNTs without
polymer. The increase in oxidation current for DA was probably
because of its diffusion through the β-cyclodextrin cavities and
the facile contact with the well-dispersed MWNTs. Moreover, Li
and co-workers268,279 have found that PPy–SWNT composite film
could be suitable for simultaneous detection of DA, ascorbic acid,
and uric acid, and it also showed a high electrocatalytic activity
toward the oxidation of nitrite.
Functionalized CNTs are promising materials for the
development of electrochemical DNA hybridization biosen­
sors as well. In 2005, a DNA sensor was developed from a
composite of PPy and CNTs, which were functionalized
with carboxylic groups to covalently immobilize DNA.280
In another example, PPy films doped with CNTs functiona­
lized with oligonucleotides were successfully implemented
into DNA biosensors, which offers great promise for
reagentless DNA hybridization analysis using direct
460 Functionalized Carbon Nanotubes and Their Enhanced Polymers

OH
C=O

(1)
OH NH2 OH NH2
FAD NH2
S S S S SWCNTs O=C
EDC NH EDC
S

FAD Glucose

NH FAD
C=O
NH
Gluconic CO
acid

e−
e−
apo-GOx

O=C
O CH
NH
NH
S S

O
N N

O N N
H H
HO H
FAD H2N HO H
NH2 NH HO H
N N H H
N N O O
H H O P OP O
O
O − O−
H H
OH OH

Figure 30 Assembly of the SWNT electrically contacted GOx electrode. Adapted with permission from Patolsky, F.; Weizmann, Y.; Willner, I. Angew.
Chem. Int. Ed. 2004, 43, 2113.276

impedance measurements.96,281 Li’s group282 reported a
nanoelectrode array based on vertically aligned MWNTs
embedded in SiO2 for ultrasensitive DNA detection. In
2003, Cai and co-workers2,283 also demonstrated the detec-
tion of DNA hybridization at a DNA-functionalized CNT
array using daunomycin as a redox label, which was inter-
calated into the double-stranded DNA–CNT assembly and
detected by differential pulse voltammetry. Yang and co-
workers284 reported a sensitive DNA hybridization biosen-
sor based on ZrO2 nanoparticles and MWNTs. The MWNT/
nano ZrO2/CS-functionalized glassy carbon electrode was
fabricated by uniform dispersion of ZrO2 nanoparticles
and MWNTs in chitosan. The hybridization reaction on
the electrode was measured by differential pulse voltamme­
try analysis in which electroactive daunomycin was used as
an indicator.268
8.17.3.3.3 Catalysis
Nanometer -scale dimensions of metal particles are favorable
for the enhanced diffusion rates and fast electron transfer
kinetics;, which are critical in the fields of catalysis research.
Therefore, CNTs are highly attractive material as both catalyst
supports and catalytic active materials.
Girishkumar and co-workers285 have prepared Pt nano­
particles through electrodeposition on optically transparent
electrodes of SWNTs for both methanol oxidation and oxy­
gen reduction reaction. These electrodes displayed greatly
improved catalytic performances, and the methanol oxida­
tion currents were about 10 times higher when the same
amount of Pt nanoparticles was supported on SWNTs.
Moreover, the current values detected for oxygen reduction
reactions were higher by a factor of 1.5 for Pt nanoparticles
supported on SWNT compared to unsupported Pt
particles.263
Gong’s group286 at Chinese Academy of Sciences has suc­
cessfully functionalized CNTs with MnO2 and synthesized an
electrochemically functional and structurally uniform nano­
composite. The resultant nanocomposite has been found to
possess an excellent electrocatalytic activity toward 4e reduc­
tion of O2 in alkaline solution and could be highly applicable
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
as an air electrode material for the electrocatalytic reduction of
O2 in alkaline fuel cells and metal/air batteries.287
In 2005, Cui and co-workers288 studied the electrocatalytic
oxygen reduction reaction by electrodepositing Pt nanoparti­
cles on MWNTs. A significant positive shift in oxygen reduction
potential and a concurrent increase in oxygen reduction current
have been observed. Pt nanoparticles deposited on MWNTs
also exhibited enhanced transfer rates of electrons as well as
stability for methanol oxidation.263,289
Use of bimetallic catalysts such as Pt–Ru has been com­
monly accepted in order to improve catalytic efficiency and
protect Pt from CO poisoning. Homogeneously dispersed
catalyst nanoparticles with a size range from 60 to 80 nm
were prepared by potentiostatic methods in 0.5 M H2SO4
aqueous solutions of ruthenium chloride and chloroplatinic
acid at a potential of –0.25 V.290 The Pt–Ru particles were
found to exhibit higher catalytic activity and stability com­
pared to pure Pt nanoparticles. Consequently, it is reasonable
to enhance the catalytic activity by incorporating bimetallic
nanoparticles into CNTs.263
Functionalized CNTs are also widely investigated in the pet­
rochemical and fine chemical industries for the synthesis of an
extensive kind of chemicals. In 2005, Zhang’s group292 found
that CNTs modified with Co nanoparticles were highly catalyti­
cally active and regioselective for the formylation of 1-octene.
Tessonnier and co-workers114,291 reported the intriguing catalytic
performances of Pd nanoparticles deposited completely on the
inner walls of MWNTs for the selective hydrogenation of cinna­
maldehyde to hydrocinnamaldehyde (Figure 31). These authors
also found that the Pd–MWNTs showed a notable increase in
selectivity, with hydrocinnamaldehyde being the major (> 80%)
product. In 2004, Ye et al.293 observed that the Pd–MWNTs were
excellent catalysts for the hydrogenation of olefins, including the
conversion of stilbene into 1,2-diphenylethane, with a conver­
sion efficiency of
96% after 10 min exposure.
Cinnamaldehyde
O O
>80% yield with Pd-MWNTs
≈50% yield with Pd-carbon
≈5
0%
Never observed
yie
ld
wi
th
Pd
-c
ar
bo
OH
Cinnamyl alcohol
Figure 31 Various reaction pathways in the hydrogenation of cinnamaldehyde, possible products, and the ratio of these products formed when using Pd
nanoparticles supported on MWNTs. Adapted with permission from Tessonnier, J. P.; Pesant, L.; Ehret, G.; et al. Appl. Catal. A Gen. 2005, 288, 203.291
Copyright 2005, with permission from Elsevier.
461
8.17.3.3.4 Energy storage
In 2004, Qu’s group294 at Chinese Academy of Sciences
reported a hybrid thin film containing Pt nanoparticles and
tetrakis(N-methylpyridyl)porphyrinatocobalt-modified MWNTs
on a glassy carbon electrode surface. This hybrid film electrode
exhibited remarkable electrocatalytic activity for oxygen
reduction and high stability with fascinating applications in
fuel cells. Zhao and co-workers295 have investigated Pt–Sn
nanoparticles on MWNTs as an anode catalyst for a direct
ethanol fuel cell, which may be useable as a potential mobile
power source. The results indicated that the performance of
the functionalized CNTs was much better than that of the
functionalized carbon black. Matsumoto and co-workers296
have studied the effect of loadings of platinum on CNTs.
They observed that 12 wt.% Pt deposited onto CNTs could
result in 10% higher voltages compared to 29 wt.% Pt depos­
ited on carbon black; this ultimately reduced the Pt wastage by
60% in polymer–electrolyte fuel cells.114
In 2006, Reddy and his co-workers297 fabricated array-like
electrodes formed by Fe3O4 shell/Cu core nanowires through a
two-step electrode design. These electrodes achieved excellent
rate performance (80% retention at 8 °C) and long cycle life
(100 cycles). Reddy and his co-workers298 reported array-like
electrodes formed by MnO2 shell/CNT core nanowires by a
combination of template, vacuum infiltration, and CVD meth­
ods and these electrodes showed higher capacity and better
cycle performance than did bulk MnO2 particles. They reported
coaxial MnO2/CNT arrays deposited inside porous alumina
templates as cathodes in a lithium battery (see Figure 32).298
The reversible capacity of the fabricated battery was increased
by an order compared to template-grown MnO2 nanotubes,
which makes them applicable electrodes for advanced Li ion
batteries. Zhang and co-workers299 reported the preparation of
nanostructured PANI/CNT array composite electrode by an
electrodeposition technique. The composite electrode exhibits
Hydrocinnamaldehyde
n OH
Phenyl propanol
462 Functionalized Carbon Nanotubes and Their Enhanced Polymers

(a) (b)

CNT
Alumina Infiltration
template and CVD
annealing
CNT
MnO2
Nanotubes
Au - backcoating
MnO2

CNT
Template
removal
MnO2
Nanotubes Au film 7/3/2008 HV spot mag WD HFW 1 μm
11:56:23 AM 10.00 kV 3.0 29 153 x 11.0 mm 5.12 μm Rice University

Figure 32 (a) Schematic diagram showing the fabrication of MnO2/CNT hybrid coaxial nanotube arrays inside an anodized aluminum oxide (AAO)
template using a combination of simple vacuum infiltration and CVD techniques. (b) SEM image and a schematic representation of a single coaxial
nanotube. Adapted with permission from Reddy, A. L. M.; Shaijumon, M. M.; Gowda, S. R.; Ajayan, P. M. Nano Lett. 2009, 9, 1002.298 Copyright 2009
American Chemical Society.

superior rate performance (54 and 48 mAh g−1 at 60 and
260 °C rates, respectively) and high electrochemical stability
owing to its uniformly distributed PANI nanolayer (only
7–9 nm) and developed conductive networks.
Very recently, CNTs functionalized by pseudocapacitive mate­
rials have attracted more and more attention as supercapacitor
electrode materials. Jiang and his co-workers from Chinese
Academy of Sciences have synthesized RuO2/CNT nanocompo­
sites with well-dispersed RuO2 nanoparticles (diameter <2 nm)
on the surface of CNTs through an easy and efficient
solution-based method for potential applications in supercapaci­
tors as electrode materials. At a power density of 5 kW kg−1, the
CNT/RuO2 composite can still deliver an energy density of
16.8 Wh kg−1, which is about 5.8 times larger than that of pure
RuO2 (2.9 Wh kg−1).300 Our group has reported CNT/MnO2 com­
posites synthesized by reduction of potassium permanganate
under microwave irradiation.301 The maximum specific capaci­
tance of 944 F g−1 with a measured power density of 45.4 kW kg−1
in aqueous solution has been obtained. Zhang and co-workers302
described PANI/CNT array composite prepared by
electrodeposition of PANI onto CNT array as electrodes for super-
capacitors (Figure 33). The composite electrode displays high
specific capacitance (1030 F g−1), excellent rate capability (95%
capacity retention at 118 A g−1), and high stability (5.5% capacity
loss after 5000 cycles) due to the hierarchical porous structure,
large surface area, and superior electrical conductivity.
8.17.3.3.5 Mechanically reinforced composites
The superior potential of CNTs as reinforcements in polymer
composites is evident from the supertough composite fibers fabri­
cated by Dalton and co-workers303 in 2003. By optimizing the
‘coagulation spinning’ method, they spun several hundred meters
of composite fibers of 60 wt.% SWNT/poly(vinyl alcohol), which
exhibited a tensile strength of 1.8 GPa, comparable to that of a
spider silk. Using these fibers, they were able to fabricate
100-μm-diameter supercapacitors and electronic textiles. To further
exploit the inherent properties of polymers, it is highly desirable to
use a low concentration of fillers in the composites, usually much
lower than the 60 wt.% employed by Dalton et al.303,304

− − + − Macro/Mesopores
between CNTs
PANI + Ions within electrolyte
+ − + Graphite
(7 nm)- sheets
covered +
CNTs − +
− − PANI
− − layer
− −
+ Each
nanotube is
+
connected
−
− − directly with
+ − the current
+ collector
−
10 nm
Current collector (Ta foil)
(a) (b)
Figure 33 (a) Schematic representation of the microstructure and energy storage characteristics of the PANI/CNT array composite and (b) TEM image of
a PANI-covered CNT in the composite. Adapted with permission from Zhang, H.; Cao, G. P.; Wang, Z. Y.; et al. Electrochem. Commun. 2008, 10, 1056.302
Copyright 2008, with permission from Elsevier.
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
The first significant improvement in stiffness was observed
by Cadek et al.305 in 2002 using MWNTs as promising mechan­
ical reinforcement agents in PVA and poly(9-vinyl carbazole)
(PVK) matrix materials. It has been found that the modulus
increased from 7 to 12.5 GPa with 0.6 vol.% MWNTs in PVA
and from 2 to 6 GPa with 4.8 vol.% in PVK.306
In 2008, Kireitseu et al.307 described ultrahigh­
molecular-weight polyethylene/CNT composites prepared via
thermal spraying fabrication. CNTs were used to reinforce the
interfaces between polyethylene polymer particles and enhance
the strength, stiffness, impact toughness as well as structural
damping of the composite. These composites are quite promis­
ing for applications in aerospace and naval engineering.96
Gorga and co-workers increased the stiffness of PMMA
from 2.7 to 3.7 GPa by addition of 10 wt.% of MWNTs
(dY/dVf ≈ 17 GPa). In addition, increases in strength from 64 to
80 MPa and a 170% increase in toughness were also observed.308
In 2004, Meincke et al.309 reported the composites of MWNTs in
polyamide-6 on a corotating twin-screw extruder, which almost
doubled the modulus from 2.6 to 4.2 GPa at 12.5 wt.% of MWNTs,
corresponding to a reinforcement value of dY/dVf ≈ 34 GPa.
However, there was a significant accompanied reduction in ducti­
lity from 40% to just 4%. Liu and co-workers310 and Zhang and co­
workers311 also reported the composites of MWNTs in
polyamide-6. They observed a threefold increase in modulus
from 0.4 to 1.24 GPa with addition of only 2 wt.% of MWNTs,
corresponding to a considerable improved value of 64 GPa. In
addition, yield strength was significantly increased from 18 to
47 MPa with similar increases in ultimate tensile strength.306
In 2005, Manchado and co-workers312 prepared SWNT/
polypropylene (PP) composite by introduction of small
amounts of SWNTs into isotactic PP via shear mixing. These
results indicated that low amounts of SWNTs added (less than
1 wt.%) led to an increase in the rate of polymer crystallization
with no substantial changes in the crystalline structure. A mod­
ulus increase from 0.85 to 1.19 GPa with addition of 0.75 wt.%
SWNTs and a strength increase from 31 to 36 MPa with addi­
tion of 0.5 wt.% SWNTs were also observed.306
8.17.4 CNT–Polymer Nanocomposites
Polymers and polymer-based composite materials are being uti­
lized more and more widely in an increasing number of industrial
applications including transportation, automotive, aerospace,
sporting goods, energy, and infrastructure sectors owing to their
high durability, high strength, light weight, design and process
flexibility, and so on.313 Because of their superior properties,
CNTs can be used as ideal reinforcing agents for
high-performance polymer composites. Ajayan and co-workers314
reported the first polymer nanocomposites using CNTs as a filler
in 1994. The number of articles and patents with regard to poly­
mer composites containing CNTs is increasing every year.304 All
kinds of polymer matrices are used for composites, for instance,
thermoplastics,315 thermosetting resins,316 liquid-crystalline poly­
mers,317 water-soluble polymers,224 conjugated polymers,318 and
so on. The properties of polymer composites, including tensile
strength,319 tensile modulus,320 toughness,321 glass transition
temperature,322 thermal conductivity,323 electrical conductiv­
ity,324 solvent resistance,325 and optical properties,326 can be
effectively improved through the addition of CNTs.96
463
8.17.4.1 CNT–Polymer Interactions
Debonding will occur when either the interface of CNT–matrix
fails or the matrix fails under large shear stresses near the inter­
face.327 In either case, it is necessary to consider the interaction
between CNTs and polymer in the adjacent interface. However,
much attention should be paid here, since it is still unclear
what the relationship should be between binding energy of the
matrix–CNT and the interfacial shear strength. In 2000, Lordi
and Yao328 found that both the binding energy and frictional
forces played only a minor role in determining the strength of
the interface but that helical polymer conformations are neces­
sary. However, it is clear that the binding of CNT to matrix is
dependent on the type of matrix.327,329
Extensive studies indicate that interfacial interactions with
CNTs cause an interfacial region of polymer with morphology
and properties different from the bulk. In 2002, McCarthy and
co-workers330 found that conjugated polymers could wrap
around MWNTs and thicker coatings appeared surprisingly
regular. In addition, dendritic polymer growth has been
observed to nucleate from defects on the CNTs.330 Coleman
and Ferreira331 found that polymer wrapping could minimize
energy for purely geometric reasons. Computational molecular
dynamics studies by Wei and co-workers327,332 at Stanford
University showed that polyethylene could be adsorbed onto
SWNT in ordered monolayers.
It has been found by Barber and co-workers in 2003 that
these interfacial regions have different properties. In their pull­
out experiments, the matrix should have fractured before the
fracturing of interface, but in fact it did not. This suggests that
interfacial polymer had surprisingly high shear strength.333
Both Ding et al.334 and Potschke et al.335 observed that thick
layers (tens of nanometers) of polymer-coated CNTs usually
protrude from fracture surfaces of composite, indicating the
existence of both high interfacial shear strength and a layer of
high-shear-strength polymer. Coleman’s group336 also
observed the similar behavior but was able to link it to the
formation of a high-strength crystalline coating. Assouline and
co-workers found the nucleation of crystallinity in the presence
of CNTs owing to CNTs that acted as nucleating agents. The
crystallites were found to be fibrillar in morphology as com­
pared to spherical in pure polymers.337 Observations of
crystallinity nucleation have also been made by other
groups.338–340 It had been previously observed that the nuclea­
tion of transcrystallinity by nanofibers could improve the
interfacial shear strength as well.327,341
While there is much debate as to the nature of the polymer
morphology at the interface, it is obvious that this phenom­
enon is in relation to the mechanical reinforcement process and
is therefore intriguing for further studies.327
8.17.4.2 Fabrication of CNT–Polymer Nanocomposites
Fabrication approaches have overwhelmingly focused on
improving the dispersion of CNTs, since better dispersion of
CNTs in the polymer matrices has been found to significantly
improve the properties of polymers. Nowadays, there are sev­
eral methods commonly used to improve the dispersion of
CNTs in polymer matrices, such as solution mixing, melt
blending, and in situ polymerization method.
464 Functionalized Carbon Nanotubes and Their Enhanced Polymers
8.17.4.2.1 Solution processing
This is the most commonly used method for fabricating
CNT–polymer nanocomposites because it is amenable to
small sample sizes and in the mean time very effective. In this
method, a dispersion of CNTs in a suitable solvent and poly­
mers are mixed in solution, and then CNT–polymer
nanocomposite is formed via precipitation or evaporation of
the solvent.96,304,327,342 One of the advantages of this method
is that agitation of the CNT powders in a solvent favors the
dispersion of CNTs. Almost all the solution processing meth­
ods are variations on a general theme, which can be
summarized as follows: (1) dispersion of CNTs in a solvent
or polymer solution by violent agitation; (2) mixing of CNTs
and polymer in solution by energetic agitation; and (3) con­
trolled evaporation of solvent, leaving a composite film.306,327
It is well known that dispersing pristine CNTs is very difficult,
especially SWNTs, in a solvent by simple stirring, so an intensive
agitation process is highly required in forming a good dispersion
of CNTs. In general, energetic agitation is provided by magnetic
stirring, shear mixing, reflux, or, most commonly, ultrasonica­
tion. Ultrasonication can be employed in two forms: mild
sonication in a bath or high-power sonication using a tip or a
horn. Ultrasonication has been intensively used in dispersing,
emulsifying, crushing, and activating various particles. By taking
advantage of the multieffects of ultrasound, the agglomerated
and entangled CNTs can be effectively broken down. For exam­
ple, Chen and co-workers343 employed a simple solution
precipitation technique to improve the dispersion of CNTs in a
polycarbonate solution by ultrasonication assistance at a fre­
quency of 20 kHz for 10 min. They observed that the CNTs
could be uniformly dispersed in polycarbonate matrix. In this
case, ultrasonic wave as well as mechanical stirring played
important roles in the formation of the composite with uniform
dispersion of CNTs. The chemical effects of ultrasonication are
associated with the rapid (microsecond time scale), violent col­
lapse of cavitation bubbles created as the ultrasonic waves pass
through a liquid medium.185 Sonochemical theory and the cor­
responding studies suggest that ultrasonic cavitation can
generate a local temperature as high as 5000 K and a local
pressure reaching 500 atm,344 which is a quite rigorous environ­
ment for composition.96
An early example of solution mixing process is reported by
Jin and co-workers.345 In this work, MWNTs produced by arc
discharge were dispersed in chloroform by ultrasonication for
1 h. Then, polyhydroxyaminoether was dissolved in the disper­
sion of MWNT–chloroform, followed by another hour of
sonication. The resultant suspension was finally poured into a
Teflon mold and dried in ambient conditions overnight in a
fume hood. High loading levels of up to 50 wt.% and quite
good dispersions were achieved by this method.327
In most subsequent investigations, a slight change was
made. Shaffer and Windle346 first dispersed chemically functio­
nalized catalytic MWNTs in water, which was then carefully
blended with solutions of PVA in water to obtain a composite
dispersion. Finally, the dispersion was drop cast to form films
with up to 60 wt.% of CNTs. In 2000, Qian and co-workers347
employed a high-energy ultrasonic probe to disperse MWNTs
in toluene, then mixed the dispersed suspension with a dilute
PS solution in toluene, followed by ultrasonic agitation before
drop casting to form films. The polymer solution with low
viscosity allowed the CNTs to move freely in the matrix. The
1.4
Nanotube (wt.%)
1.2
1
0.8
0.6
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Length scale (μm)
300 nm
Figure 34 TEM image of MWNT/PS thin film (arrows indicate regions of
polymer shrinkage): inset shows distribution of CNT lengths. Adapted
with permission from Harris, P. J. F. Int. Mater. Rev. 2004, 49, 31.342
mixture was cast on glass and the solvent was removed to yield
MWNT-doped films (Figure 34). This technique has been used
subsequently by several other research groups.348,349 In 2003,
Ruan and co-workers327,350 employed a similar method but
used magnetic stirring and ultrasonication to disperse CNTs,
which were then combined with polymer by reflux.
It should be pointed out that high-power ultrasonication
for a long time usually shortens the length of CNTs and reduces
the aspect ratio, which is adverse to the properties of compo­
sites.304,351 Additionally, this method depends on the efficient
dispersion of CNTs in the relevant solvent, and the choice of
solvent is usually made based on the solubility of the polymer.
However, in most cases, CNTs without functionalization can­
not be well dispersed in most solvents. In order to overcome
this problem, numerous research groups have used additives
such as surfactants to disperse CNTs before mixing with the
polymer solution.349,352,353 The most commonly used surfac­
tants are derivatives of SDS.327
Islam et al.123,304 dispersed SWNTs (20 mg ml−1) in water
with the assistance of surfactant SDBS using low-power,
high-frequency (12 W, 55 kHz) ultrasonication for 16–24 h.
Atomic force microscopy observations exhibited that

63  5% of SWNT bundles were exfoliated into single tubes
and most of SWNT objects were isolated SWNTs, which was
less than a quarter of the SWNTs by mass. The nonionic surfac­
tants such as polyoxyethylene-8-lauryl (CH3-(CH2)11
(OCH2CH2)7OCH2CH3) have also been reported to improve
the dispersion and strong interaction between MWNTs and
epoxy resins.96,322
Using a surfactant to improve the dispersion of CNTs may
be problematic, since the surfactant exists in the resultant
nanocomposite and might deteriorate the properties of the
product. For example, Bryning and co-workers354 reported
that the thermal conductivities of the surfactant–SWNT/epoxy
composites were much lower, while the interfacial thermal
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
resistances were higher than those of the composites prepared
without surfactant at the same loading degree of CNTs. The
surfactant molecules can also affect the polymer matrix as
shown by Sundararajan and co-workers355 in 2004, where
Triton X-100 induced crystallization in polycarbonate, result­
ing in the influence of the composites on the transparency and
mechanical properties. One alternative approach to
surfactant-assisted dispersion is the functionalization of CNTs
to further improve their dispersion and interfacial adhesion to
the polymer matrix.304
Barrau and co-workers356 have found that amphiphilic pal­
mitic acid could be favorable for an efficient dispersion of
CNTs in an epoxy matrix. The hydrophobic part of palmitic
acid was absorbed onto the surface of CNTs, whereas the
hydrophilic head group induced electrostatic repulsions
between CNTs, effectively preventing their aggregation. The
cosolvent has also been found to affect the dispersion of
CNTs in polymer matrix. Very recently, Camponeschi et al.357
reported the use of trifluoroacetic acid as a cosolvent for the
dispersion of MWNTs in a conjugated polymer poly
(3-hexylthiophene) and PMMA via a solution process. SEM,
optical microscopy, and light transmittance studies indicated
that a better dispersion of CNTs in polymer matrices was
obtained by using trifluoroacetic acid. Many other polymer
composites such as polyurethane/CNT,358 PS/CNT,359 epoxy/
CNT,360 poly(vinyl alcohol)/CNT,346 P(MMA-co-EMA)/
CNT,361 polyacrylonitrile/CNT,362 and polyethylene/CNT363
have also been fabricated by this method.96
8.17.4.2.2 Melt processing
Although solution processing is a valuable technique for both
dispersion of CNTs and formation of composites, it is usually
unsuitable for many other polymers that are difficult to be
dissolved. Melt processing is a common and simple alternative
approach, which is particularly useful for dealing with those
thermoplastic polymers.306,364,365 In melt processing, CNTs are
commonly dispersed mechanically into a polymer matrix using
a high-temperature and high-shear-force mixer or compoun­
der.96,366 The shear forces are helpful to break aggregates of
CNTs or prevent their formation. This type of techniques is
based on the fact that thermoplastic polymers soften when
being heated. Amorphous polymers can be processed above
their glass transition temperature, while semicrystalline poly­
mers need to be heated above their melting temperature to
induce sufficient softening. Merits of this technique are its
speed and simplicity, as well as its compatibility with standard
industrial techniques.40,306
Generally speaking, melt mixing involves the melting of
polymer pellets to form a viscous liquid. Any additives, such
as CNTs, can be introduced into the melt by high-speed shear
mixing. Bulk samples can then be obtained by compression
molding, injection molding, or extrusion. However, it is crucial
that process conditions should be optimized, not just for dif­
ferent types of CNTs but for the whole range of polymer–CNT
combinations. This is because CNTs can affect melt properties
such as viscosity, resulting in unexpected degradation of poly­
mers under high shear rates.327,367
An early study on the melt mixing of MWNTs and polymer
was pursued by Jin and co-workers368 in 2001. PMMA was
mixed with 26 wt.% MWNTs in a laboratory mixing molder at
200 °C. Then, the melt was compression -molded under 8–9 MPa
465
at 210 °C in a hydraulic press to form composite slabs. TEM
observations indicated that dispersion of MWNTs was good
even at high content of MWNTs. Andrews and co-workers364
found that commercial polymers such as high-impact PS, PP,
and acrylonitrile–butadiene–styrene could be melt processed
with MWNTs to form composites. These polymers were mixed
with MWNTs at high loading level in a high-shear mixer to form
masterbatches, which were followed by mixing with pure polymer
to form samples with lower mass fraction. Films were finally
formed by compression molding. Numerous studies of the dis­
persion of CNTs during mixing process suggested that the
dispersion of CNTs can be significantly improved with the total
mixing energy, while the average length of CNTs decreases with
mixing energy.327
In 2003, Potschke’s group367 blended masterbatches con­
taining MWNTs in pure polycarbonate in a microcompounder
at 260 °C. Then, test samples were prepared by extruding
through a circular die. The authors found that a small-scale
extruder could be just as efficient as a larger scale model.
Gorga and Cohen308 also employed extrusion method, who
mixed PMMA with both SWNTs and MWNTs in dry state before
using a twin-screw extruder at 130 °C to extrude the sample
through a cylindrical die. The CNTs were found to be aligned
by melt drawing the extruded rods. However, some polymer
degradation was observed in the composites, probably resulted
from the higher shear rates needed to overcome the increased
viscosity in the presence of the CNTs.327
Injection molding is another method used to fabricate com­
posites. In 2004, Meincke et al.309 mixed polyamide-6,
acrylonitrile–butadiene–styrene, and MWNTs in a twin-screw
extruder at 260 °C. Then, the extrudate was broken up into
pellets and injection molded to fabricate test samples.
Subsequent TEM studies revealed that there were very good
dispersions of CNTs in the composite.
For extensive applications, fibers are more applicable than
bulk materials. Melt mixing can be used for producing not only
bulk polymer composites but also composite fibers. Fiber proces­
sing is generally similar to melt processing and commonly
involves a process such as extrusion to produce an elongated
sample, which can then be drawn into a fiber.306 One of the
early studies on melt mixing of polymer–CNT composite fibers
was pursued by Haggenmueller and co-workers369 in 2000.
During their reported process, SWNTs and PMMA were first dis­
persed in dimethy fumarate, mixed, and dried. The resultant films
were broken up and hot pressed to form a new film followed by
repeating as many as 25 times. Then, the resultant composite film
was extruded through a 0.6-mm cylindrical die and drawn under
tension to form a fiber. Interestingly, the authors observed that
the dispersion of CNTs was improved after each melting step.
After many repeating steps, the composite was composed of
well-dispersed, highly aligned CNTs. However, their production
process was rather complicated and time consuming.
In 2002, Andrews and his co-workers364 also produced
polymer–CNT composite fibers by melt mixing. The composite
was extruded through a 0.3-mm-diameter die and then rapidly
drawn to a final diameter of 20–75 μm. Two studies from
Shambaugh’s group370,371 described fibers spun from PP and
SWNTs using a ram extruder through a 1.27-mm die. Fibers were
drawn at high speed onto take-up roll to obtain final fibers with
diameters of 50–60 μm. The alignment was improved even
further by postdrawing at elevated temperatures.
466 Functionalized Carbon Nanotubes and Their Enhanced Polymers
Sandler and co-workers365 have compared different fibers
made from polyamide-12 with different fillers: arc-MWNTs,
and both aligned and entangled CVD–MWNTs. Polymer pel­
lets and CNTs were mixed in a twin-screw microextruder and
then the extrudate was chopped and fed into a capillary rhe­
ometer with 1-mm die. Fibers were spun at 0.5 m s−1 to produce
a resulting fiber with diameter of 125 μm. It could be observed
that the dispersion and alignment was much better for the
CVD–MWNTs than for the arc-MWNTs. In addition, voids
were also found in the fibers fabricated from arc-MWNTs.327
Compared to solution processing method, melt processing
is generally less effective to disperse CNTs in polymer matrices.
Moreover, this method is limited to lower concentrations due
to the high viscosities of the composites at higher loadings of
CNTs.96,304
8.17.4.2.3 In situ polymerization
In in situ polymerization process, the CNTs are dispersed in
monomers rather than polymers, followed by polymerization
of monomers. This method can provide a better dispersion of
CNTs at a higher concentration of CNTs with a stronger interac­
tion between CNTs and the polymer matrices. Besides, in situ
polymerization is a very convenient processing method that
allows the preparation of composites with high loading of
CNTs and provides excellent miscibility with almost any other
polymers. This technique is particularly useful for the fabrication
of the polymers that are usually insoluble and thermally unstable
and cannot be processed by solution or melt processing.306
An early study on in situ polymerization was employed for
the synthesis of PMMA–MWNT composites by Jia and
co-workers372 in 1999. In their reported work, in situ radical
polymerization was performed using a radical initiator
2,2′-azobisisobutyronitrile (AIBN) to initiate the π bonds in
CNTs to participate in the polymerization of PMMA, conse­
quently forming a strong interface between the MWNTs and
the PMMA matrix. Since then, some other groups have also
used AIBN as an initiator of in situ radical polymerization to
introduce functionalized MWNTs and SWNTs into PMMA
matrices.306,373,374
In situ polymerization was very useful as well for the fabri­
cation of polyamide/CNT composites. For example,
polyamide-6/MWNT composites have been successfully pre­
pared by in situ hydrolytic polymerization of ε-caprolactam in
the presence of pristine and carboxylated MWNTs.375
ε-Caprolactam monomer was found to form an electron trans­
fer complex with MWNTs, yielding a uniform, polymerizable
master solution, which was very beneficial for the formation of
composites with well-dispersed MWNTs. In 2005, Gao and co­
workers376 reported a new and improved chemical-processing
technology that enables the continuous spinning of SWNT/
polyamide-6 fibers via the in situ ring-opening polymerization
of caprolactam in the presence of SWNTs. In addition, this
process resulted in an interesting hybrid material with charac­
teristics of both the fiber and the matrix, and with excellent
compatibility between the SWNTs and nylon 6.306
In situ epoxidation has also been applied to prepare and
process epoxy–polymer composites. For instance, carboxyl-
and fluorine-functionalized SWNTs have been introduced
into epoxy polymers through the formation of covalent
bonds by in situ epoxy ring-opening esterification and
amine-curing chemical reactions.377 Later, the authors further
reported a CNT/epoxy composite by direct covalent bonding
between the matrix and SWNTs using functionalized SWNTs,
which were prepared via diamine reactions with alkylcarboxyl
groups directly attached to the sidewalls of SWNTs.306,378
In situ polymerization method can be employed to prepare
polyurethane/CNT nanocomposites as well. Polyurethane/
MWNT composites were synthesized by two different in situ
polymerization methods.379 In one method, a calculated
amount of carboxylate-functionalized MWNTs and
1,4-butanediol was added into a prepolyurethane solution in
the subsequent chain extension step. In the other method,
MWNTs with necessary weight fractions were first dispersed in
poly(ε-caprolactone)diol. Then, 4,4′-methylene bis(phenyl iso­
cyanate) was added into this mixture. Subsequently, the chain
extender 1,4-butanediol was added into this prepolymer and
finally the polyurethane/MWNT composite was synthesized.
SEM observations indicated that MWNTs were dispersed rela­
tively homogeneously in the polyurethane matrix of the MWNT/
polyurethane sample in the second method. Xia and Song380
observed that MWNTs could be individually dispersed in the
polyurethane matrix by in situ polymerization method with the
assistance of a surfactant. But SWNTs could not be dispersed very
well by this method. Later on, they synthesized polyurethane/
SWNT nanocomposites using polyurethane-grafted SWNTs,
which significantly improved the dispersion of SWNTs in the
polyurethane matrix and strengthened the interfacial interaction
between the polyurethane and SWNTs.96,381
In situ polymerization process has also been applied for the
preparation of other CNT/polymer composites. For example, in
2002, Kumar and co-workers382 have described new ultra-
strong poly(p-phenylene benzobisoxazole) (PBO) composites
synthesized by in situ PBO polymerization in the presence of
SWNTs in poly(phosphoric acid). After the polymerization,
SWNT/PBO composite fibers were spun from the
liquid-crystalline solution by dry-jet spinning.306
8.17.4.2.4 Other methods
Rather than avoiding the high viscosities of CNT/polymer mix­
ture, some research groups decreased the temperature to further
increase the viscosity to the point of processing in the solid
state. Solid-state mechanochemical pulverization methods
(using pan milling377 or twin-screw pulverization382) have
been employed to mix MWNTs with various polymer matrices.
Pulverization method can be applied alone or followed by melt
mixing. Nanocomposites prepared in this way have the merit of
possibly grafting the polymer on CNTs, which is probably
responsible for the good dispersion, improved interfacial adhe­
sion,377 and improved tensile modulus.377,382
An innovative latex fabrication method for making CNT/poly­
mer composites involves dispersing CNTs in water and then
adding into a suspension of latex nanoparticles.383
Freeze-drying and subsequent processing of this colloidal mixture
produce composites with uniform dispersion of CNTs even in a
highly viscous matrix such as PS with high molecular weight.383
This intriguing approach can be applicable for polymers that can
be synthesized by emulsion polymerization or formed into arti­
ficial latexes, for example, in high-shear conditions.304
Another interesting method, first reported by Mamedov384–386
and later refined by others, is the LBL assembly method. This
involves building up a layered composite film by alternate dip­
ping of a substrate into dispersions of SWNTs and polyelectrolyte
 Functionalized Carbon Nanotubes and Their Enhanced Polymers 467

solutions. In this case, as many as 40 layers have been built up. In
order to further improve the structural integrity of the film,
cross-linking could be employed. After every fifth deposition
cycle, a layer of CNTs was replaced with a layer of polyacrylamide
to introduce carboxyl functionalities for amide cross-linking
between polyelectrolytes. Then, the film was heated to 120 °C
for 30 min to form amide bonds between polyacrylamide and
polyethylisophthalate. This method has remarkable advantages:
various properties of resulting film, such as thickness and ratio of
CNTs to polymer, can be controlled easily, and very high loading
levels of CNTs can also be obtained.327
In order to obtain CNT/polymer composites with very high
loadings of CNTs, Vigolo and co-workers387 developed a coa­
gulation spinning method to produce composite fibers
predominately composed of CNTs in 2000. This method dis­
persed SWNTs with the aid of a surfactant and coagulated the
SWNTs into a mesh by wet spinning it into an aqueous poly
(vinyl alcohol) solution, followed by converting the mesh into
a solid fiber by a slow draw process. In addition, Mamedov’s
group has reported a fabrication method based on sequential
layering of chemically functionalized SWNTs and polyelectro­
lytes to reduce phase separation. The resulting composites held
a loading of SWNTs as high as 50 wt.%.304,384
Finally, electrospinning is another method used recently to
form composite-based fibers from solution. In 2003, Ko and
co-workers388 developed electrospinning as a method to fabri­
cate CNT/polymer composite fibers and yarns. Composite
dispersions of SWNTs and either poly(lactic acid) or polyacry­
lonitrile in DMF were initially produced. Then, the dispersion
was placed in a pipette with a 0.9-mm nozzle. A wire was
placed in the pipette and connected to a steel plate, which
was placed
15 cm below the nozzle, via a high-voltage
power supply of 25 kV. When the power supply was turned
on, the composite solution was charged, forcing it out of the
nozzle and toward the auxiliary electrode. This could make
the solvent evaporate rapidly, resulting in the coalescence of
the composite into a fiber, which could be collected from the
steel plate. Fibers with diameters of 10 nm to 1 μm could be
fabricated in this manner. Yarns were also produced by collect­
ing the fibers on a rotating drum and twisting them.327
8.17.4.3 Properties of CNT/Polymer Nanocomposites
8.17.4.3.1 Mechanical properties
As described above, the remarkable mechanical properties and
large aspect ratio make CNTs excellent candidates for the devel­
opment of CNT-reinforced polymer nanocomposites. Very
recently, considerable polymer matrixes have been used for
the development of such nanocomposites (Table 4).
Shaffer and Windle346 were the first to pursue a systematic
investigation of the mechanical properties of CNT/polymer
composites in 1999. Their process for preparing MWNT/PVA
composites has been described in the previous section. There
was very limited reinforcement with the storage modulus
increasing from
6 GPa for the polymer to 12 GPa for the
60 wt.% composite film. After the theory for short-fiber com­
posites was developed, an elastic modulus of 150 MPa for
CNTs was achieved from the experimental data derived at
room temperature. This value is extremely below the values
reported for isolated CNTs (
30 GPa).391 The low value pri­
marily stems from the poor stress transfer other than the
weakness of the CNTs themselves. Above the glass transition
temperature of the polymer (
85 °C), CNTs had a more sig­
nificant effect on the properties of the composite.342
In 2000, the mechanical properties of MWNT/PS compo­
sites were investigated by Qian and co-workers347 using tensile
testing. It could be found that the modulus increased from
1.2 GPa for PS to 1.62 and 1.69 GPa for composites with 1 wt.

Table 4 Mechanical properties of CNT/polymer composite

Max. CNT
YPoly YMax content d Y/d Vf
CNT type Polymer (GPa) (GPa) (wt.%) (GPa) References

CVD–MWNT PVA
6.3
12.6 60
4.7 346

CVD–MWNT PS 1.2 1.69 1
74 347
Arc-MWNT PVA 7 12.6 0.6 990 305
Arc-MWNT PVK 2 5.6 4.8 75 305
CVD–MWNT poly(styrene-co-butyl acrylate) (PSBA) 0.52  10−3 3.54  10−3 8.3 35  10−3 349
CVD–MWNT PS 1.53 3.4 2.5 122 389
CVD–MWNT high density polyethylene (HDPE) 0.98 1.35 1 57 350
Arc-MWNT methyl-ethyl methacrylate copolymer (MEMA) 0.71 2.34 1 272 348
CVD–MWNT PC 0.8 1.04 15
2.4 367
CVD–MWNT PMMA 2.7 3.7 10
17 308
CVD–MWNT polyamide-6 (PA6) 2.6 4.2 12.5 34 309
CVD–MWNT PA6/acrylonitrile/butadiene/styrene (ABS) 1.97 2.51 7.5 11
CVD–MWNT Nylon 0.4 1.24 2 64 310
Arc-MWNT PP 0.85 1.19 0.75 68 312
SWNT PMMA 3.1 6.0 6
57 369
SWNT PP 6.3 9.8 1
530 370
SWNT low-melt-flow-rate (LMFR) PP 0.91 2.09 1
179 371
high-melt-flow-rate (HMFR) PP 1.47 3.35 1
285
SWNT PP 0.4 1.4 5
38 390
CVD–MWNT PS 1.2 3.0 5
36 364

Adapted with permission from Coleman, J. N.; Khan, U.; Blau, W. J.; Gun’ko, Y. K. Carbon 2006, 44, 1624.328 Copyright 2006, with permission from Elsevier.
468 Functionalized Carbon Nanotubes and Their Enhanced Polymers
(b)
(a)
1 μm
Figure 35 In situ observation of crack nucleation and propagation in MWNT–PS thin films as induced by thermal stresses. The cracks propagate along
weak MWNT-PS interfaces or the regions with relatively low MWNT density. The MWNTs are inclined to align and bridge the crack wake then break and/or
pull out of the matrix (see MWNTs A-D). Adapted with permission from Qian, D.; Dickey, E. C.; Andrews, R.; Rantell, T. Appl. Phys. Lett. 2000, 76, 2868.347
% short (
15 μm) and long (
50 μm) MWNTs, respectively. In
addition, the tensile strength increased from 12.8 MPa for pris­
tine PS to 16 MPa for both types of CNTs at 1 wt.% loading. In
order to further understand the reinforcement mechanism,
Qian and co-workers studied the formation of cracks inside a
TEM and observed the appearance of crazes where cracks were
bridged by CNTs. When the width of crazes reached
800 nm,
the CNTs were found to either fracture or pull out of the matrix,
suggesting that the bonding of interfacial is not completely
uniform with some weak spots facilitating the pullout. In addi­
tion, it is also demonstrated that CNTs are limited
mechanically by their weakest points, which are related to
their structural defects (Figure 35).327
PVA was revisited as a matrix material by Cadek and co­
workers305 in 2002. They pursued nanohardness tests on
spun-cast films of MWNTs produced by arc discharge in both
PVA and PVK. The authors found that the modulus increased
from 7 to 12.6 GPa with 0.6 vol.% MWNTs in PVA and from 2 to
5.6 GPa with 4.8 vol.% in PVK. These increases are equivalent to
reinforcement values of dY/dVf = 990 and 75 GPa for PVA and
PVK, respectively. However, the value for PVA is probably artifi­
cially improved because modulus value for PVA is known to be
close to 2 GPa,327 indicating that the reinforcement value for
PVA should be scaled down to dY/dVf
280 GPa.
An early work on the mechanical properties of bulk CNT/
polymer composites was studied by Jin and co-workers.368
They observed an increase in Young’s modulus from 0.7 to
1.63 GPa for PMMA doped with 17 wt.% MWNTs samples by
dynamic mechanical analysis (DMA) tests, which corresponds
to a level of reinforcement of
7 GPa, similar to that achieved
by Shaffer and Windle’s327 first study in 1999.
Liu and co-workers310 fabricated composites from MWNTs
in polyamide-6. The authors found a threefold increase in
modulus from 0.4 to 1.24 GPa with the addition of only 2 wt.
% MWNTs, which corresponds to an impressive reinforcement
value of dY/dVf
64 GPa. In addition, a significant increase in
yield strength from 18 to 47 MPa was observed with similar
increases in ultimate tensile strength. Moreover, no obvious
decrease in toughness was observed, since the ductility fell
only slightly from 150 to 110%. These intriguing results were
believed to be attributed to very good dispersion and adhesion
as observed by microscopy observations.327
A
C
500 mm
In 2005, Manchado’s group312 blended small amounts of
SWNTs into isotactic PP. An increase in modulus from 0.85 to
1.19 GPa at 0.75 wt.% SWNTs was observed. Besides, the
strength slightly increased from 31 to 36 MPa with the addition
of 0.5 wt.% SWNTs. Both properties were observed to fall off at
higher loading levels. The ductility only dropped more or less
from 493 to 402%, demonstrating that the introduction of
SWNTs did not cause any obvious decrease in toughness. This
work corresponds to a reinforcement value of
dY/dVf
68 GPa.327
An early work on CNT/epoxy composites by Ajayan and his
co-workers314 was described in 1994. They reported a study of
the mechanical behavior of MWNT/epoxy composites in both
tension and compression.392 They found that the compression
modulus was higher than the tensile modulus, indicating that
load transfer to the MWNTs in the composites was much higher
in compression. The authors also suggested that during load
transfer to MWNTs, only the outer layers are stressed in tension;
however, all the layers respond in compression. CNT/epoxy thin
films prepared by Xu and co-workers393 exhibited superior
mechanical properties. Compared to pristine resin thin films,
for which the elastic modulus was
4.2 GPa, a 20% increase in
modulus was found with the addition of 0.1 wt.% MWNTs. The
increase was primarily due to partial alignment of the MWNTs
induced by spin coating. SEM observations showed that
pulled-out CNTs were often covered with polymer, which indi­
cated strong interfacial adhesion. Similar results were obtained
by Gojny’s group394 in 2003. Their research showed that func­
tionalized MWNTs with amine groups significantly enhanced
bonding with the epoxy matrix.342 Accordingly, the outer shells
of the MWNTs often remained embedded in the matrix after
pullout, as shown in Figure 36.
In 2004, Yang and co-workers361 fabricated composites
from MWNT in p(MMA-co-EMA). An increase in stiffness from
1.64 to 2.62 GPa with introduction of 10 wt.% MWNTs
(dY/dVf
15 GPa) was observed. While the strength also
increased from 55 to 73 MPa, the material became very brittle
at higher contents of MWNTs. In addition, there was no sig­
nificant difference between functionalized and pristine
MWNTs. Blake et al.395 functionalized MWNTs via covalently
attaching chlorinated PP to their surfaces and mixed with
chlorinated PP (Figure 37). It has been found that stiffness
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
50 nm
Figure 36 Image of epoxy-coated MWNTs subject to tensile stress as a
result of electron irradiation: telescopic pullout of outer layer of MWNTs
has occurred. Adapted with permission from Gojny, F. H.; Nastalczyk, J.;
Roslaniec, Z.; Schulte, K. Chem. Phys. Lett. 2003, 370, 820.394 Copyright
2003, with permission from Elsevier.
increased from 0.22 to 0.68 GPa, corresponding to a reinforce­
ment of 72 GPa. Moreover, both strength and toughness
increased from 12.5 to 49 MPa and from 24 to 108 J g−1, respec­
tively,327 indicating superior mechanical performances.
Hwang and co-workers396 reinforced PMMA by addition of
PMMA-grafted MWNTs. An increase in modulus as measured
by DMA from 2.9 to 29 GPa with addition of 20 wt.% MWNTs
(dY/dVf
115 GPa) has been observed. The significant
enhancement is primarily attributed to the successful functio­
nalization of MWNTs. In addition, good dispersion and a
continued increase in modulus enhancement was observed
up to 20 wt.% of MWNTs, which is unprecedented.327
Olek and co-workers have described LBL composites using
MWNTs and PEI. They used two types of MWNTs: ‘hollow’ and
‘bamboo.’385 The bamboo composites showed moduli and
strengths of
4.5 GPa and
150 MPa, respectively, while the
hollow MWNT composites showed slightly lower values of

2 GPa and
110 MPa, respectively. After the hollow CNTs
were boiled in HNO3 before fabrication of composite in
order to further emphasize the importance of CNT type and
50
CPP
0.075 vol.%
40
0.15 vol.%
0.3 vol.%
0.6 vol.%
Stress (MPa)
30
20
10
0
0 100 200
Figure 37 Stress–strain curves for a range of composites fabricated from functionalized MWNTs and chlorinated PP. Adapted with permission from
Blake, R.; Gun’ko, Y. K.; Coleman, J.; et al. J. Am. Chem. Soc. 2004, 126, 10226.395 Copyright 2004 American Chemical Society.
469
quality, much lower modulus and strength values of
0.2 GPa
and 35 MPa, respectively, were obtained.327
8.17.4.3.2 Electrical properties
The most accessible near-term application for CNT-reinforced
polymer composites involves their electrical properties. The
intrinsic high conductivity of CNTs makes them a reasonable
choice for fabricating conductive polymers. Owing to their high
aspect ratios, CNTs have the added advantage of achieving
percolation at lower concentrations compared to spherical fil­
lers. Percolation describes the range of compositions in which a
3D network of the filler is formed. When the percolation is
reached, the conductivity will increase significantly as the net­
work creates a continuous conductive path.6,96 According to
the percolation theory, σc = A(V–Vc)β, where σc is the conduc­
tivity of the composites, V and Vc are the volume fraction of
CNTs and the corresponding volume fraction of CNTs at the
percolation threshold, respectively, and A and β are fitted con­
stants.6 Percolation composition ranges from as low as 0.0225
to 0.04 wt.% have been reported by many groups without
having achieved ideal dispersion.397 Considerable research
groups have reported percolation thresholds of less than 1 wt.
% CNTs,48,73,81,398 where in some cases, excellent dispersion of
CNTs is realized. The percolation threshold for the electrical
conductivity in CNT/polymer nanocomposites depends on
aspect ratio,399 dispersion,399 alignment,400 degree of surface
modification94 of CNTs, polymer types,401 and fabrication
process of composites.399 The electrical conductivity and the
percolation threshold of CNT/polymer composites are briefly
listed in Table 5.96
Bryning and co-workers410 described SWNT/epoxy compo­
sites using SWNTs with two different aspect ratios of
150 and

380. A smaller percolation threshold was observed for the
composites with the higher aspect ratio of SWNTs. Bai and
Allaoui411 have observed more than an eightfold decrease for
the threshold concentration in MWNT/epoxy composites when
the length of MWNTs was increased from 1 to 50 μm. Generally
speaking, the percolation threshold decreases with better
300 400 500 600 700
Strain (%)
470 Functionalized Carbon Nanotubes and Their Enhanced Polymers
Table 5 Electrical conductivity of CNT/polymer composites
Percolation threshold
Polymer CNT type (wt.%)
PS MWNTs 0.15–0.2
Polycarbonate SWNTs 0.11
PS SWNTs 0.045
PVA XD grade − 20
CNTs
PMMA MWNTs 0.3
PMMA SWNTs 0.17
PMMA SOCl2-doped SWNTs 0.17
Poly(vinyl alcohol) MWNTs 5–10
PVA SWNTs 0.04
Epoxy MWNTs 0.0025
Adapted with permission from Sahoo, N. G.; Rana, S.; Cho, J. W.; et al. Prog. Polym. Sci. 2010, 35, 837.96 Copyright 2010, with permission from Elsevier.
dispersion, because well-dispersed CNTs have higher aspect
ratios compared to aggregated CNTs.304
Alignment of the CNTs in the polymer matrix has a profound
effect on the electrical conductivity and its percolation threshold.
When the CNTs are highly aligned in the composites, there are
fewer contacts between the CNTs, resulting in an increase in
contact resistance and consequently a decrease in electrical con­
ductivity and a higher percolation threshold compared to those in
a composite with randomly oriented CNTs. This field has been
intensively investigated by Du and co-workers412 using a series of
SWNT/PMMA composites, where the alignment degree of CNTs
was controlled by the melt fiber-spinning conditions. At a fixed
concentration of SWNTs (2 wt.%), the electrical conductivity par­
allel to the alignment direction increased sharply with a decrease
in alignment, which the authors took as orientation percola­
tion.304 Du and co-workers413 reported that the electric
conductivity of SWNT/PMMA composite with aligned CNTs
was 10−10 S cm−1, while it was 10−4 S cm−1 for the composite
with unaligned CNTs at the same content of SWNTs (2%). This
suggests that the alignment of the CNTs in the composite
decreases both the electrical conductivity and the percolation
threshold, which is because there are fewer contacts between the
CNTs when they are highly aligned in the composites.96
As is well known to all, chemical functionalization disrupts
the extended π conjugation of CNTs and consequently reduces
the electrical conductivity of functionalized CNTs.
Silane-functionalized CNT/epoxy nanocomposites exhibited
lower electrical conductivity than did untreated CNT compo­
sites at the same content of CNTs.414 In 2005, Cho and
co-workers415 observed that the electrical conductivity of the
surface-functionalized MWNT composites was lower than that
of the untreated MWNT composites with the identical content
of CNTs. This is attributed to the increased defects in the lattice
structure of carbon–carbon bonds on the surface of CNTs due
to the acid treatment.96 Generally, the severe functionalization
of CNTs can significantly lower the conductivity of the compo­
sites. However, several researchers have found that the
functionalization of CNTs could improve the electrical conduc­
tivity of the composites.416 In 2005, Tamburri and
co-workers416 reported that the functionalization of SWNTs
with –COOH and –OH groups enhanced the conductivity of
composites compared to untreated SWNTs.
CNT content Maximum conductivity
(wt.%) (S m−1) References
2 103 402
7 4.81  102 403
7 6.89 403
4.8 404
40 3  103 405
10 1.7  103 406
13.5 104 406
60 100 407
4 ≈ 15 408
1 2 409
8.17.4.3.3 Thermal properties
The thermal conductivity k of carbon materials is controlled
by atomic vibrations or phonons. Nanocomposites with
superior thermal conductivity have promising applications,
such as printed circuit boards, connectors, thermal interface
materials, heat sinks, and other high-performance thermal
management systems. The excellent thermal conductivity of
individual CNTs led to early expectations that it will effec­
tively enhance the thermal conductivity of polymer
nanocomposites, as CNTs do with the electrical conductivity.
Compared to the orders of magnitude enhancement in elec­
trical conductivity with very low loading of CNTs (less than
0.1 wt.%), the thermal conductivity of the composites has
shown only modest improvement. However, the highest
reported thermal conductivity of CNT is on the order of
103 W (m K)−1, while it is
0.1 W (m K)−1 for typical thermo­
plastics. Therefore, phonons entering a CNT/polymer
composite are much more likely to travel through the matrix
than are electrons, since the contrast in thermal conductivity
(kCNTs/kpolymer) is
104, while the contrast in electrical con­
ductivity (σCNTs/σpolymer) is
1015–1019. Additionally, the
lack of contrast in thermal conductivity and the design of
CNT/polymer composites with high thermal conductivity
must also address the high interfacial thermal resistance
between CNTs. The thermal conductivity of composites will
also depend upon the previously mentioned factors, such as
aspect ratio, dispersion, and alignment of CNTs, and might be
more sensitive to metal impurities.304
Biercuk and co-workers417 described an epoxy composite
containing 1 wt.% raw SWNTs, which exhibited a 125%
increase in thermal conductivity at room temperature com­
pared to pristine epoxy. Choi’s group400 reported a 300%
increase in thermal conductivity at room temperature with
3 wt.% SWNTs in epoxy, with an additional increase (10%)
when magnetically aligned CNTs were used. Du and
co-workers418 reported an infiltration method to produce a
bicontinuous morphology of epoxy and a CNT-rich phase
and observed an
220% increase in thermal conductivity
with
2.3 wt.% loading of SWNTs. This two-phase material
with very poor dispersion at the nanoscale indicates a new
method circumventing the need for excellent dispersion to
produce desirable properties.304
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
The enhancement in thermal conductivity discussed above
is remarkably below the prediction of the engineering rule of
mixing. This discrepancy is primarily attributed to the extraor­
dinary small thermal conductance (G
12 MW (m2 K)−1) of the
CNT/polymer interface, in other words, high interfacial ther­
mal resistance.419 This interfacial thermal resistance was caused
by the constraints that the energy contained in high-frequency
phonon modes within the CNTs must first be transferred to
low-frequency modes through phonon–phonon coupling in
order to be exchanged with the surrounding medium.304
One alternative to decrease the high thermal interfacial
resistance is the introduction of covalent bonds between
CNTs and the matrix polymer.304 Huxtable and co-workers419
observed a significant decrease in the thermal boundary resis­
tance for CNT matrix in the presence of chemical bonding
using classical molecular dynamics. However, such bonds
could decrease the intrinsic conductivity of CNTs via acting as
scattering centers for phonons propagating along the CNTs. Liu
and Fan420 described 2 wt.% carboxylic acid-functionalized
MWNTs in poly(dimethylsiloxane) and observed that chemical
functionalization degraded the thermal conductivity more
severely than predicted by Huxtable and his co-workers.419
In recent years, Huang and co-workers421 reported an inter­
esting result on thermal conductivity, which was enhancement
by introducing CNTs in polymer composites. Starting with an
aligned MWNT arrays (0.05–0.5 mm high), they embedded the
arrays with silicone elastomers through an injection molding
process. The thermal conductivity of the resulting composite
with an addition of 0.4 vol.% (0.3 wt.%) aligned MWNTs is

115–280% higher than either the pristine polymer or a com­
posite with 0.4 vol.% of randomly oriented MWNTs.304
8.17.4.3.4 Optical properties
CNTs exhibit unique 1D π electron conjugation, superior mechan­
ical strength, and high thermal and chemical stability, which make
them highly promising for use in numerous applications. Optical
limiting, an important nonlinear optical behavior, can develop
with increasing input fluence of a light pulse such that the trans­
mitted fluence tends to keep constant, independent of the input
fluence.96 For dispersions of CNTs in various solvents, it seems
that optical limiting is principally nonlinear scattering, which is
attributed to bubbles formed by light absorption-induced heating,
although sublimation, a gradual decrease in size for CNTs at high
temperature, may contribute an effect dependent on absorption
by excited electronic states.96,422,423
In one of the early studies on this topic, Chen and co­
workers342,424 observed third-order optical nonlinearity in an
SWNT/polyimide composite. O’Flaherty and co-workers425
reported that the optical limiting of the poly(9,9-di-n­
octylfluorenyl-2,7-diyl)/MWNT samples was dependent upon
the mass fraction of CNTs in the composites and found that the
magnitude of the nonlinear effect increased with the mass
fraction of the CNTs increasing from 0.011 to 0.038.
In a study of the optical properties of poly(para-phenylene
vinylene) (PPV)/CNT composites by Mulazzi and his co-work­
ers426 in 2005, SWNT–PPV films with different concentrations
were fabricated through a solution mixing process and heated
at 120 °C. It has been found that the optical spectra at 120 °C
PPV conversion temperature were significantly changed com­
pared to those obtained at 300 °C. The effect of low conversion
temperature on all the optical spectra was observed to be quite
471
similar to that of increasing the concentration of CNTs in
standard PPV.96
More recently, a novel optically transparent CNT/polymer
composites with highly aligned CNTs has been developed by
Peng.427 Uniform CNT sheets that were grown on silicon by a
CVD process were pulled out of the arrays and stabilized on
glass. Then, composite films were fabricated by spin coating or
casting polymer solutions onto the CNT sheets, followed by
evaporation of the solvents. Film thickness was controlled
through varying the concentration of polymer solutions and
coating times. Using this process, composite films derived from
PS, PMMA, and sulfonated poly(ether ether ketones) with
more than 80% optical transparency were successfully fabri­
cated. These results indicate that the optical properties of the
composites can be tailored in a predetermined manner through
controlling the content of CNTs, orientation, and conversion
temperature of precursor, consequently paving a new way for
developing optically functional materials.96
8.17.4.3.5 Electrochemical properties
As one of the conducting and porous carbons, CNTs also possess
ultrahigh mechanical strength, good electrical properties, high
specific area, and high aspect ratio. Their application in electro­
chemical double-layer capacitors has been studied
extensively.428,429 Conducting polymers are the third group of
candidate materials for supercapacitors owing to their good
electrical conductivity, large pseudocapacitance, and relatively
low cost.430 The most commonly used conducting polymers
include PANI, PPy, and poly(3,4-ethylenedioxythiophene)
(PEDOT). Conducting polymers have a ultrahigh specific capa­
citance, which is close to that of ruthenium oxides, for example,
775 F g−1 for PANI,431 480 F g−1 for PPy,432 and 210 F g−1 for
PEDOT.433 However, conducting polymers commonly have
poor mechanical stability due to the swelling and shrinkage,
attributed to repeated intercalation and depletion of ions during
charging and discharging processes.434,435 Therefore, construct­
ing CNT/conducting polymer composites is even more
interesting and promising, since it can combine two relatively
cheap materials to gain the large pseudocapacitance of the con­
ducting polymers coupled with the conductivity and mechanical
strength of the CNTs.436 Up to now, extensive research on CNT/
polymer composites as electrode materials for supercapacitors
has been pursued by considerable research groups (see Table 6).
In 2004, Zhou and co-workers437 prepared PANI-coated
SWNTs by polymerization of aniline containing well-dissolved
SWNTs for supercapacitors. Electrochemical studies indicated
that the composite electrode exhibited much higher specific
capacitance and better power characteristics. Accordingly, it is
more promising for application in supercapacitor than pure
PANI electrode. Later, Sivakkumar and co-workers438 synthe­
sized MWNT/PANI composite via in situ chemical
polymerization to further improve the cycleability of the pure
PANI supercapacitor. The composite exhibited a high initial
specific capacitance of 606 F g−1 and good capacitance reten­
tion, which is believed to depend on the charging potential.
Fan’s group at Tsinghua University described a novel
method to prepare interesting paper-like CNT/PANI compo­
sites by using the CNT network as the template. Compared to
the conventional brittle CNT/PANI composites, these
paper-like composites were much thin and flexible
(Figure 38). This work demonstrates a new approach, which
472 Functionalized Carbon Nanotubes and Their Enhanced Polymers

Table 6 Some results of CNT/polymer composite materials for supercapacitors

Capacitance Potential window

Sample (F g−1) (V) Scan rate Electrolyte System References

MWNT/PANI 240 −0.2 to 0.8 0.25 A g−1 1 M NaNO3 2-Electrode 439

MWNT/PPy 506 −0.6 to 0.2 0.002 A g−1 1 M H2SO4 3-Electrode 440
MWNT/PANI 670 −0.4 to 0.2 0.002 A g−1 1 M H2SO4 3-Electrode 440
SWNT/PPy 265 −0.9 to 0 0.01 A g−1 7.5 M KOH 3-Electrode 441
MWNT/PANI 560 0 to 1 1 mV s−1 0.1 M H2SO4 3-Electrode 442
CNT array/PANI 1030 −0.2 to 0.7 5.9 A g−1 1 M H2SO4 3-Electrode 443
MWNT/PANI 424 0 to 0.8 0.1 A g−1 1 M H2SO4 2-Electrode 444
MWNT/PPy 250 −0.4 to 0.6 10 mV s−1 1 M KCl 3-Electrode 445
MWNT/PANI 224 −0.2 to 0.8 0.5 A g−1 1 M NaNO3 3-Electrode 439
MWNT/PANI 606 0 to 0.4 1 A g−1 1 M H2SO4 2-Electrode 438
MWNT/PANI 322 −0.2 to 0.8 10 mV s−1 1 M H2SO4 2-Electrode 446
SWNT/PANI 463 0 to 0.7 0.01 A cm−2 1 M H2SO4 3-Electrode 447
SWNT/PANI
230 −0.2 to 0.8 0.05 A g−1 1 M NaNO3 3-Electrode 437

(a) (b)
450
BP/PANI
400
350
300
Cs (F g−1)

250
CNTP/PANI
Power density (W kg−1)

200
1000
150 100

100 10 PANI
1
50 1 10
Energy density (Wh kg−1)
0
0.0 0.5 1.0 1.5
Current density (A g−1)

(c) (d)

PE film Separator
Metal current
collector

Paper-like CNT/PANI
nanocomposite
Metal current
collector

Figure 38 (a) Digital macrograph of the flexible CNT/PANI composite. (b) Specific capacitances vs. different discharge current densities and Ragone
plots. (c) Schematic of the flexible supercapacitor unit made of CNT/PANI and (d) a digital picture that shows that a red LED glowed well even when the
device was rolled up around a cuvette. Adapted with permission from Meng, C. Z.; Liu, C. H.; Fan, S. S. Electrochem. Commun. 2009, 11, 186.444
Copyright 2009, with permission from Elsevier.
 Functionalized Carbon Nanotubes and Their Enhanced Polymers
may transform a brittle polymer into flexible films. Meanwhile,
these film electrodes showed much superior electrochemical
performance such as higher specific capacitance, lower internal
resistivity, and more stability under different current loads.
These paper-like composite electrodes have promising applica­
tions in new kinds of energy storage devices.
8.17.4.4 Applications
With continuous developments in the synthesis and produc­
tion of CNTs, CNT/polymer composite materials are a
near-term application and will see innovations that take full
advantage of their special properties.
Depending upon the achieved conductivity level, CNT/con­
ducting polymer composites have extensive applications as
electrostatic dissipative (ESD) materials, electromagnetic inter­
ference (EMI) materials, and high-conducting materials.6 ESD
materials are characterized as possessing a surface resistance
between 1012 and 105 Ω square−1, which could be applicable
for carpeting, floor mats, wrist straps, and electronic packaging.
For EMI applications, the surface resistance should be less than
105 Ω square−1. EMI applications commonly include portable
phone parts and frequency shielding coatings for military air­
craft and electronics. High-conducting materials can serve as
weight-saving replacements for metallic materials when pro­
duced as multifunctional composites (mechanical/electrical).
Besides, conducting plastics have potential applications in
automotive industry as body panels and bumpers, since they
can be painted without a conducting primer. High conductors
will serve as interconnects and may replace wiring harnesses in
transportation systems where weight saving is still an issue.6
Structural applications for CNT-reinforced polymers gener­
ally include aviation, automotive, military, and space-related
parts.6,307 The combination of high strength and light weight
can make these materials candidates for aircraft parts and car
bodies. Bulletproof vests could adapt to bulletproof garments
made of woven CNT composite fibers, which would cover the
entire torso instead of only the front and the back. Lightweight
radiation/impact shields and space suits could also be fabri­
cated from these composites. With consideration to
small-concentration composite systems, the z-axis properties
of composites could be improved, consequently enabling the
composite systems for a wide application base.
Once CNT/polymer composites are spun into fibers, they
will be used in the fabrics with multifunctional capabilities. In
addition to high strength, these fibers could be woven into
textiles to generate garments with superior sensing and EMI
shielding capabilities.
Another large application range for CNT/polymer compo­
sites is the incorporation of CNTs into polymers for use as
protective coatings and paints. Thermally conducting coatings
have been used in the aviation and space industries to act as aids
in deicing aircraft wings in cold weather through the application
of current to the coating. Another application is heat dissipation
on space vehicles, where the coating could serve as a space
radiator to replace the liquid heat rejection systems. Protective
coatings containing CNTs could also be applied to mitigate
damage to aircraft, which is usually caused by lightning strikes.
Biocatalytic composites prepared using SWNTs have potential
applications as antifouling paints and biosensor coatings.448
CNT/polymer coatings may find their way into shielding
473
systems for both radiation and impact protection. The introduc­
tion of MWNTs into epoxy cured by ultraviolet radiation could
act as a coating to resist radiation.6,449
The thermal transport properties of polymer composites can
be significantly improved with the addition of CNTs due to the
excellent thermal conductivity of CNTs. Such composites are
quite promising for usages as printed circuit boards, connec­
tors, thermal interface materials, heat sinks, lids, housings, and
so on.96,450
The unique electronic structure of CNTs makes them ideal
candidate materials for composite devices. SWNT/poly
(3-octylthiophene) composite possesses properties suitable
for use in photovoltaic cells.451 Composites with PMPV have
been reported to be effective in organic light-emitting diodes as
electron transport layers.452 Actuators based on SWNT/Nafion
composites have potential applications as microswitches and
artificial muscles.453 CNT/polyimide composites have been
investigated for use as ultrafast optical switches.424 Such mate­
rials exhibited optical delay times less than 1 ps at a wavelength
of 1.55 μm and showed great potential as all-optical switches.
MWNTs dispersed in a photoresist epoxy can be applicable in
the production of microelectromechanical systems such as
electroplating molds, sensors, and actuators.6,449
CNT/conducting polymer composites have a potential
application in supercapacitors.454,455 The MWNT/PANI com­
posite electrodes exhibited much higher specific capacitance
(328 F g−1) than did pure PANI electrodes.456 Zhang and co­
workers443 prepared CNT array/PANI composite electrodes by
electrodeposition of PANI onto CNT array (CNTA) electrodes.
A maximum specific capacitance of 1030 F g−1 has been
obtained in 1 M H2SO4 electrolyte. Meanwhile, the electrode
exhibits excellent long cycle life along with
94.5% specific
capacitance retained after 5000 cycle tests. The reason for the
superior performance is believed that this composite presents
high ionic and electronic conductivity, high utilization of elec­
trode materials, and best accommodation of the volume
changes during charge/discharge.96
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478 Functionalized Carbon Nanotubes and Their Enhanced Polymers

Biographical Sketches
Jun Yan received his BS degree (2005) and PhD degree (2010) from College of Material Science and Chemical Engineering
at Harbin Engineering University. Currently he is pursuing his postdoctoral research at Harbin Engineering University,
China. His research interests mainly focus on design and synthesis of functional carbonaceous nanocomposites, as well as
their applications for energy conversion and storage devices.

Zhuangjun Fan received his PhD in 2003 at the Institute of Coal Chemistry, CAS. After carrying out postdoctoral research at
Professor Fei Wei’s group in Tsinghua University, he joined Harbin Engineering University in 2006 as a professor. His
research interests are in the fields of nanocarbon hybrid materials for energy storage and water treatment.

Linjie Zhi received his PhD in 2000 at the Institute of Coal Chemistry, CAS. He then moved to the Institute of Chemistry,
CAS, as a postdoc. From 2003 he worked with Prof. Müllen at the Max-Planck Institute for Polymer Research for 2 years
before assuming the position of project leader there until the end of 2007. He is currently a professor in the National Center
for Nanoscience and Technology of China. His research interests focus on carbon-rich materials and their application in
energy-related areas.