J. Phys. Chem.

C 2009, 113, 4779–4785 4779

Significant Improvement of Mechanical Properties Observed in Highly Aligned

Carbon-Nanotube-Reinforced Nanofibers

Jianying Ji,† Gang Sui,† Yunhua Yu,† Yanxin Liu,† Yuanhua Lin,‡ Zhongjie Du,†
Seungkon Ryu,§ and Xiaoping Yang*,†
Key Laboratory of Beijing City on Preparation and Processing of NoVel Polymer, Department of Materials
Science and Engineering, Beijing UniVersity of Chemical Technology, Beijing 100029, P. R. China, State Key
Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua UniVersity, Beijing 100084, P. R. China, and Chungnam National UniVersity, 220, Gung-dong,
Yuseong-gu, Daejeon 305-764, Korea
ReceiVed: March 9, 2008; ReVised Manuscript ReceiVed: January 22, 2009

Continuous macroscopic aligned polyacrylonitrile (PAN) composite nanofiber sheets embedded with highly
aligned PAN-grafted multiwalled carbon nanotubes (MWCNTs) have been prepared by electrospinning followed
by hot-stretching. Homogeneous and highly aligned MWCNTs in the polymer matrix were obtained by hot-
stretching of the electrospun fibers, which led to a significant enhancement in the mechanical performance of
the resulting composite nanofiber sheets. After hot-stretching, the tensile strength and modulus of an electrospun
PAN nanofiber sheet (containing 2 wt % grafted MWCNTs) increased by 320.7% and 204.5%, respectively,
compared with the values for the pristine PAN terpolymer. In addition we show, for the first time, that a
Raman mapping method can be successfully employed to investigate the distribution and alignment of
MWCNTs in nanofiber sheets.

Introduction respectively, for 5% CNTs in a polyacrylonitrile (PAN) matrix].

Polymer nanocomposites exhibit excellent physical and
electrical properties, making them suitable for a variety of
applications in biomaterials, microelectronics, and optics.1-3 In
such polymer nanocomposites, carbon nanotubes (CNTs) have
been widely used as fillers because of their desirable mechanical
performance, high electrical conductivity, and low mass density.4
It is generally believed that the key factors in optimizing the
reinforcing effects of CNTs in polymer nanocomposites are the
degree of dispersion of the CNTs, their alignment, and the
interface adhesion between the CNTs and the polymer matrix.5-7
Unfortunately, because of their high aspect ratio and strong van
der Waals attractions, multiwalled carbon nanotubes (MWCNTs)
tend to aggregate, resulting in an inhomogeneous dispersion in
polymer matrixes.8 Furthermore, the surface of MWCNTs
provides poor interfacial adhesion to the matrix, which limits
effective load transfer from the matrix to the nanotubes.9 A
covalent grafting method has been developed in an attempt to
overcome these limitations.10 Many types of polymer chains can
be covalently attached to the nanotube surface through “grafting
to”11-14 and “grafting from”15-17 methods. These grafted
polymer chains tightly cover the outer wall of the nanotubes,
which leads to improved dispersion and interface adhesion.18
Electrospinning technology has also been shown to be an
effective method for improving the dispersion and alignment
of CNTs in polymer matrixes.19-23 Recently, Hou et al.24,25 used
a rotating drum to collect electrospun composite nanofibers
containing MWCNTs in an attempt to improve the alignment
of MWCNTs along the fiber axis and observed significant
increases in tensile strength and modulus [∼75% and 72%,
* Corresponding author. Fax: +86-10-64412084. E-mail: yangxp@
mail.buct.edu.cn.
†
Beijing University of Chemical Technology.
‡
Tsinghua University.
§
Chungnam National University.
10.1021/jp8077198 CCC: $40.75  2009 American Chemical Society
Published on Web 02/27/2009
Ko and co-workers26 also prepared continuous CNT-filled
nanofibers by electrospinning and reported that the modulus
improved by 120% in nanofibers containing 4 wt % single-
walled CNTs. To orient the polymer chains in an electrospun
poly(ethylene oxide) (PEO) nanofiber, Kakade et al.27 applied
an external electric field during the electrospinning process and
obtained greatly improved orientation of the polymer chains and
macroscopically aligned PEO polymer nanofibers.
Although significant advances have been achieved, optimiza-
tion of the macromolecular chain orientation of a polymer and
alignment of CNTs in the electrospun nanofibers still remains
a considerable technological challenge. Using current methods,
the spray speed of polymer solutions is far higher than the speed
of the receiver, which could be a flat plate, rotating drum, or
copper filament drum.2,25,28 The consequent rapid formation of
electrospun composite nanofibers does not allow for the
sufficient stretching of MWCNTs within the available mil-
lisecond range, which leads to the entanglement of MWCNTs
in the final composite nanofibers.29
A postspinning straining treatment was proposed by Wagner
and co-workers29 as a way of improving the mechanical
performance of such nanofibers. Postspinning in the vicinity of
the glass transition temperature has also been shown to be an
effective method of improving the mechanical performance of
micrometer-scale fibers. Miaudet et al.30 reported that hot-
stretched micrometer fibers exhibited mechanical behavior
different from that of CNT fibers and developed a new hot-
stretching technology for the fabrication of nanocomposite fibers
of CNTs with poly(vinyl alocohol) (PVA).31
In this work, we describe how electrospinning followed by
hot-stretching can be used to prepare composite nanofiber sheets
of a grafted MWCNT/PAN terpolymer. Our results indicate that
hot-stretching can improve the alignment of the MWCNTs, the
orientation of the polymer chains, and the interface adhesion
4780 J. Phys. Chem. C, Vol. 113, No. 12, 2009
SCHEME 1: Schematic View of the Chamber Employed
for Hot-Stretching of the Polymer Sheets
between the MWCNTs and the matrix. Additionally, we show
that a Raman mapping method can be successfully employed
to characterize the distribution and alignment of CNTs in the
nanofiber sheets.
Experimental Section
Materials. MWCNTs (purity, g 95%; diameter, 15-20 nm)
were supplied by Shenzhen Nanotech Port Co. Ltd., Shenzhen,
China, and used as received. PAN terpolymer (93.0 wt %
acrylonitrile, 5.3 wt % methyl acrylate, and 1.7 wt % itaconic
acid, with an average molecular weight of 100000 g/mol) was
supplied by Courtaulds Co., Nottingham, Nottinghamshire, U.K.
Concentrated sulfuric acic (98%), nitric acid (70%), and N,N′-
dimethylformamide (DMF, bp 153 °C) were purchased from
Beijing Chemicals Co., Beijing, China. N,N′-Dicyclohexylcar-
bodiimide (DCC) and 4-dimethylaminopyridine (DMAP) were
purchased from Shanghai Medpep Co., Shanghai, China.
PAN-Terpolymer-Grafted MWCNTs. PAN-terpolymer-
grafted MWCNTs were prepared by following our previously
reported procedure.32,33 Hydroxyl groups were produced on the
surface of the MWCNTs by acid oxidation of the as-received
MWCNTs for 1 h with a mixture of concentrated H2SO4 and
HNO3 (1:1, v/v). Then, 100 mg of acid-oxidized MWCNTs was
suspended in DMF (200 mL) by sonication for 30 min, after
which DCC (50 mg) and DMAP (25 mg) were added to the
suspension. PAN (0.5 mg) terpolymer was dissolved in DMF
(5 mL), and this solution was mixed with the suspension. This
suspension was then stirred for 48 h at 60 °C under nitrogen.
After vacuum filtration, the resulting black product was repeat-
edly washed with DMF and resuspended in DMF by sonication
for 30 min. The final PAN-terpolymer-grafted MWCNTs were
vaccuum-dried for 8 h at 100 °C to evaporate any remaining
DMF.
Electrospinning and Hot-Stretching. Suspensions were
prepared by ultrasonic mixing of PAN-terpolymer-grafted
MWCNTs (0, 0.5, 1, 2, and 3 wt %) into a PAN terpolymer/
DMF solution for 4 h. The suspension was electrospun at room
temperature (23 °C), with an applied voltage of 14 kV and a
distance of 140 mm between the spinneret and the fiber collector.
The electrospun composite nanofibers were collected in the form
of a sheet on a 16-cm-diameter rotating drum at a rotation speed
of 10.0 m/s for 3 h. The sheets (100 mm in length, 40 mm in
width) were hot-stretched along the nanofiber direction by
Ji et al.
Figure 1. FTIR spectra of (a) acid-oxidized MWCNTs, (b) PAN-
terpolymer-grafted MWCNTs, and (c) PAN terpolymer.
applying a tensile force of 1.25 N in air at 140 °C for 5.0 min.
Scheme 1 shows a view of the chamber used for hot-stretching
of the sheets. The temperature of the chamber was controlled
by the circulation of hot air, and the tensile force was controlled
by the use of loads of appropriate weights.
Characterization. Fourier transform infrared (FTIR) spec-
trometry, transmission electron microscopy (TEM), and ther-
mogravimetric analysis (TGA) were used to confirm the
functionalization of the MWCNTs. Scanning electron micros-
copy (SEM, Hitachi S4700) was employed to observe the
morphologies of composite nanofibers, and Image J software
was used to measure the diameter of the nanofibers before and
after hot-stretching. Polarized Raman spectroscopy was per-
formed to determine the alignment of the MWCNTs in the
nanofiber sheets using a TY-HR 800 Raman spectrometer with
laser excitation at 532 nm. Tensile tests of the nanofiber sheets
were conducted along the collected nanofiber direction using a
universal testing machine (Instron 1121). Ten specimens with
lengths of 20 mm and widths of 5 mm were prepared for each
tensile test. The speed of the crosshead was 20 mm/min. The
cross-sectional area of the sample was calculated using the
weight of the sample and the densities of PAN terpolymer and
MWCNTs.
Results and Discussion
PAN-Terpolymer-Grafted MWCNTs. After the as-received
MWCNTs had been refluxed for 1 h with a mixture of
concentrated H2SO4 and HNO3 (1:1, v/v), hydroxyl functional
groups were produced on the surface of the MWCNTs, as
confirmed by X-ray photoelectron spectroscopy and FTIR
spectroscopy; the details were reported in our previous work.32,33
In the presence of DCC and DMAP, the hydroxyl groups present
on the acid-oxidized MWCNTs react with the carboxylic acid
groups in the PAN terpolymer to afford covalently bound
polymer chains on the surface of the MWCNTs. The procedure
is shown in Scheme 2. The resulting PAN-terpolymer-grafted
MWCNTs were characterized by FTIR spectroscopy, TEM, and
TGA.
Figure 1 shows the FTIR spectra of (a) acid-oxidized
MWCNTs, (b) PAN-terpolymer-grafted MWCNTs, and (c) PAN
terpolymer. A broad absorption peak in Figure 1a at around
3414 cm-1 can be assigned to the OsH stretching vibration of
the surface hydroxyl groups of the acid-oxidized MWCNTs.
After reaction of the PAN terpolymer with the MWCNTs, the
FTIR spectrum of the resulting material (Figure 1b) was very
Highly Aligned Carbon-Nanotube-Reinforced Nanofibers
Figure 2. (a) TEM image of PAN-terpolymer-grafted MWCNTs and (b) TGA curves of various samples.
SCHEME 2: Procedure for the Synthesis of PAN-Terpolymer-Grafted MWCNTs
similar to that of the PAN terpolymer itself (Figure 1c). The
sharp absorption peak at 2242 cm-1 can be assigned to the CtN
stretching vibration of nitrile groups, the peak at 1732 cm-1 to
the CdO stretching vibration, and the peak at 1452 cm-1 to a
CsH bending vibration.34 The similarity of the spectra in Figure
1b,c strongly indicates the presence of PAN terpolymer in the
grafted MWCNT. The obvious reduction in intensity of the
OsH stretching vibration in Figure 1b compared to that in
Figure 1a also suggests that the surface hydroxyl groups of the
MWCNTs have undergone a grafting reaction with the PAN.
Figure 2a shows TEM images of PAN-terpolymer-grafted
MWCNTs. The surface of the grafted MWCNTs has a smeared
appearance, and some amorphous materials can be seen to cover
the surface of the MWCNTs, as indicated by the arrows. Figure
2b shows TGA traces for the various materials. The as-received
MWCNTs (trace a) showed no significant weight loss up to
750 °C, whereas the neat PAN terpolymer (trace c) lost about
59% of its original weight below 640 °C. The TGA trace of
the PAN-terpolymer-grafted MWCNTs (trace b) is intermediate
between those of the MWCNTs and neat polymer. The weight
loss from 180 to 640 °C is about 39 wt %, associated with the
decomposition of the grafted polymer on the surface of the
MWCNTs. The plateau in the TGA trace after 650 °C can be
attributed to the MWCNTs and residues of the carbonized
polymer that undergo no further decomposition. Based on these
TGA traces, the amount of PAN terpolymer grafted on the
MWCNTs can be estimated,35 and the weight fraction of the
polymer in the grafted MWCNTs was calculated to be about
66%.
J. Phys. Chem. C, Vol. 113, No. 12, 2009 4781
Morphology of PAN/MWCNT Composite Nanofibers. As
shown in Figure 3a,b, the as-spun nanofibers were partially
aligned along the collecting direction, and the alignment of the
fibers became closer to parallel after hot-stretching. Also, the
diameters of the original as-spun fibers (100-220 nm) were
significantly reduced, to 60-190 nm, by hot-stretching.
As seen from the inset in Figure 3b, part of a carbon nanotube
was exposed at one end of some nanofibers. This nanotube had
a larger diameter (about 50 nm) than the original MWCNTs
(15-20 nm), and its surface was rougher than that of the original
CNTs; this indicates that some polymer becomes strongly
attached to the MWCNTs and that there is a strong interfacial
adhesion between the nanotubes and the PAN terpolymer matrix
in the composite nanofiber. This strong adhesion originates from
the PAN terpolymer molecule chains grafted on the surface of
the MWCNTs, which act as a link between the nanotubes and
the bulk PAN matrix.
Alignment of MWCNTs in the Composite Nanofiber
Sheets. Raman spectroscopy was used to analyze the changes
in alignment of the composite nanofiber after hot-stretching.
Figure 4 shows polarized Raman spectra of the 2 wt % grafted
MWCNT/PAN composite nanofiber sheet recorded (a) before
and (b) after hot-stretching, in which the VV curve represents
the spectrum when the polarization of the incident laser is
parallel to the nanofiber axis and the VH curve represents the
spectrum when the polarization of the incident laser is normal
to the nanofiber axis.
Before hot-stretching (Figure 4a), strong absorption peaks
appeared at 1349.76 and 1580.75 cm-1, which can be assigned
4782 J. Phys. Chem. C, Vol. 113, No. 12, 2009 Ji et al.

Figure 3. SEM images of 2 wt % grafted MWCNT/PAN terpolymer composite nanofiber sheets: (a) low-magnification and (b) high-magnification
SEM images of the original electrospun nanofiber; (c) low-magnification and (d) high-magnification SEM images after hot-stretching. The inset in
b is a high-magnification SEM image from a fractured surface of an electrospun nanofiber.

Figure 4. Polarized Raman spectra of 2 wt % grafted MWCNT/PAN composite nanofiber sheets (a) before and (b) after hot-stretching.

to the D and G bands, respectively, of the MWCNTs. The G
band is attributed to an in-plane E2g zone-center mode, and the
D band is ascribed to disorder-induced modes in the MWCNTs.
The shoulder peak at 1620.79 cm-1 is usually denoted as the
D′ band and has also been attributed to disorder-induced features
in the MWCNTs; a similar band was also observed in polyurea-
functionalized MWCNTs.36 Figure 4b shows the polarized
Raman spectra of the hot-stretched composite nanofiber sheets.
Both the G and D bands shift to higher wavenumbers after hot-
stretching, especially the G band (shift of ∼3.08 cm-1). This
blue shift indicates that there is an interfacial interaction between
the MWCNTs and the surrounding polymer (probably via the
COOH groups in the PAN polymer). Similar behavior was
observed for stretched single-walled carbon nanotube/poly-
isobutylene composites when compared to the unstretched
composites.37 There is an obvious difference in the intensity of
the G band for different polarization directions after hot-
stretching, which can be correlated to the alignment of CNTs
in the composites. Normally, the degree of CNT alignment can
be evaluated by the depolarization factor R, the ratio of the peak
intensities of the G band in the two polarization directions, i.e.,
parallel (VV configuration) and perpendicular (VH configura-
Highly Aligned Carbon-Nanotube-Reinforced Nanofibers
Figure 5. Polarized Raman mapping for a nanofiber sheet of a 2 wt % grafted MWCNT/PAN terpolymer composite: (a) sketch of polarized
Raman mapping scanning points; (b) polarized Raman mapping spectra of areas. 11-15 shown in a; (c) polarized Raman mapping spectra of areas
3, 8, 13, 18, and 23 shown in a; (d) R values for the data in b and c.
tion), to the fiber axis.38,39 Based on the data shown in Figure
4, the R values were 1.03 and 2.95 for samples before and after
hot-stretching, respectively. The marked increase in R can be
ascribed to the better alignment of CNTs after hot-stretching.
Raman mapping is known to be an effective technique for
providing detailed information regarding the distribution of a
specific compound in a composite material.40 For example,
Nepal et al.41 used this method to evaluate the spatial distribution
of SWCNTs in biopolymer layers. To obtain more detailed
information regarding the distribution and alignment of the
MWCNTs in the composite nanofiber sheets, we employed a
polarized Raman mapping technique; this is the first such
application of this technique. The whole mapping area was as
large as 10 µm × 10 µm, with increments of at least 2 µm
considering the beam light-spot diameter (∼2 µm). The beam
scanning time was chosen as 100 s for the VV configuration
and 200 s for the VH configuration. As shown in Figure 5a,
the polarized spectra of areas 11-15 correspond to scanning
points along the nanofiber direction, whereas the spectra of areas
3, 8, 13, 18, and 23 were taken along the perpendicular to the
nanofiber direction. Figure 5b,c shows typical polarized Raman
J. Phys. Chem. C, Vol. 113, No. 12, 2009 4783
spectra along the nanofiber direction and the perpendicular
direction, respectively. It can be seen that the intensities of the
G band in the VV configuration change very slightly and, in
both configurations, the R values are also almost constant (Figure
5d). We also measured other scanning points along these two
directions as marked in Figure 5a. The results indicated that
the distribution of MWCNTs in the sheet is homogeneous and
the degree of alignment of the MWCNTs in the sheet is high.
Mechanical Properties of Composite Nanofiber Sheets.
Tensile testing of the nanofiber sheets was conducted along the
collected nanofiber direction. Figure 6 shows stress-strain
curves of composite nanofiber sheets with various loadings of
MWCNTs. The average tensile strength and modulus of the pure
PAN terpolymer nanofiber sheet were found to be about 71.9
MPa and 2.2 GPa, respectively. When 2.0 wt % grafted
MWCNTs was incorporated into the nanofiber sheet, the tensile
strength and modulus increased to about 114.8 MPa and 3.2
GPa (see Figures 7 and 8), respectively, which indicates that
the presence of the grafted MWCNTs led to an obvious
reinforcement of the PAN nanofiber sheets. This behavior can
be ascribed to the homogeneous dispersion of the grafted
4784 J. Phys. Chem. C, Vol. 113, No. 12, 2009
Figure 6. Typical stress-strain curves for (a) electrospun pure PAN
terpolymer nanofiber sheets; (b) electrospun PAN terpolymer nanofiber
sheets with 2 wt % loading of grafted MWCNTs; (c) hot-stretched pure
PAN terpolymer nanofiber sheets; (d-f) hot-stretched PAN terpolymer
nanofiber sheets with 1, 2, and 3 wt % loadings of grafted MWCNTs,
respectively.
Figure 7. Experimental and calculated values of the modulus for
various grafted MWCNT/PAN terpolymer nanofiber sheet samples:
calculated results for (a) hot-stretched and (b) original electrospun
samples; experimental data for (c) hot-stretched and (d) original
electrospun samples.
MWCNTs and the strong interfacial interaction between the
MWCNTs and the PAN terpolymer in the composite nanofibers.
After hot-stretching, the tensile strength and modulus of the
pure PAN terpolymer fiber sheet were about 215.9 MPa and
3.6 GPa, respectively. These values represent significant in-
creases (of ∼200.3% and 63.6%, respectively) as compared to
the pristine nonstretched sample, which can mainly be attributed
to the unidirectional alignment and tight stacking of composite
nanofibers in the sheets and the high degree of orientation of
macromolecular chains in the nanofibers after hot-stretching.
The hot-stretched composite nanofiber sheets with 2 wt %
grafted MWCNTs also exhibited marked increases in tensile
strength of ∼163.5% (from 114.8 to 302.5 MPa) and in modulus
of ∼109.3% (from 3.2 to 6.7 GPa), which can be ascribed to
the improved alignment of MWCNTs within the sheet and the
enhanced interfacial interaction between the nanotubes and the
polymer matrix. Similar behavior was also observed for the
tensile strength and modulus of composite nanofiber sheets with
varying loadings of grafted MWCNTs (Figures 7 and 8).
Ji et al.
Figure 8. Experimental and calculated values of tensile strength for
various grafted MWCNT/PAN terpolymer nanofiber sheet samples:
calculated results for (a) hot-stretched and (b) original electrospun
samples; experimental data for (c) hot-stretched and (d) original
electrospun samples.
Normally, for a unidirectional discontinuous nanofiber-
reinforced composite system, the modified Halpin-Tsai
equation7,29,42 can be used to estimate the composite longitudinal
modulus, EL
1 + 2(lf /df)ηLVf
EL ) Em (1)
1 - ηLVf
In eq 1, ηL ) [(Ef/Em) - 1]/[(Ef/Em) + 2(lf/df)], where Em and
Ef are the tensile modulus values of the matrix and nanotube,
respectively, and lf/df is the aspect ratio of the nanotube. The
volume fraction, Vf, can be estimated from the weight fractions
and densities of MWCNTs and PAN, respectively. Here, we
take the density of MWCNTs as 1.8 g · cm-3, the density of
PAN as 1.12 g · cm-3, the aspect ratio of the nanotubes as 55,
and the modulus (Ef) of the MWCNTs as 450 GPa.29 Thus, we
can calculate the composite modulus by eq 1, and the values
are shown in Figure 7a,b.
As previously reported, a model based on a composite with
short aligned fibers can be used to predict the tensile strength
of a PAN fiber reinforced with nanotubes29,42
σcomposite ) (1 - σfr/2lfτ)σfVf + σm(1 - Vf) (2)
where r is the radius of the nanotube, τ is the tube-matrix
interfacial shear strength, and rm is the strength of the matrix.
Here, we use the values σf ) 30 GPa, σm ) 30 MPa, r ) 8.5
nm, lf ) 1000 nm, and τ ) 150 MPa, as previously reported.43
The values of the tensile strength calculated for various nanofiber
sheets are illustrated in Figure 8a,b.
As shown in Figures 7 and 8, the experimental results are in
good agreement with the calculated data for the grafted
MWCNT/PAN composites when the loading of grafted
MWCNTs is below 2 wt %. However, when the loading of
MWCNTs increased to 3 wt %, the experimental values of the
tensile strength and modulus deviated from the calculated results;
this can mainly be ascribed to the poor dispersion of highly
concentrated MWCNTs in the nanofibers, caused by the high
viscosity of the electrospinning solution.
As shown in Figures 7 and 8, all of the hot-stretched samples
exhibited superior mechanical properties, which indicates that
the alignment of the carbon nanotubes is improved greatly
during hot-stretching and demonstrates that a combination of
Highly Aligned Carbon-Nanotube-Reinforced Nanofibers
electrospinning and hot-stretching is a successful way to obtain
high-performance composite nanofiber sheets.
Conclusions
Hot-stretching is a facile and effective method for enhancing
the mechanical properties of grafted MWCNT/PAN terpolymer
composite nanofiber sheets. Macrostructure analysis shows that,
after hot-stretching, electrospun nanofibers exhibit excellent
macroscopic alignment. Polarized Raman mapping spectroscopy
is a very useful technique for characterizing the improved
alignment and distribution of MWCNTs in the PAN terpolymer
matrix. Compared with the properties of the pristine PAN
terpolymer, the tensile strength and modulus of hot-stretched
grafted MWCNT/PAN terpolymer composite nanofiber sheets
increased by as much as 320.7% and 204.5%, respectively, with
a 2 wt % loading of MWCNTs in the PAN matrix.
Acknowledgment. The authors acknowledge financial sup-
port from National Natural Science Foundation of China (Nos.
50503004 and 30471907), the European Aeronautic Defence
and Space Company EADS (France2007-DCR/SP-001189-1),
the National High Technology Research and Development
Program of China (2007AA03Z351), and the Program of New
Century Excellent Talents (NCET) of Universities in China.
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