J. Phys. Chem.

B 2009, 113, 9741–9748 9741

Electrospinning Fabrication of High Strength and Toughness Polyimide Nanofiber

Membranes Containing Multiwalled Carbon Nanotubes

Dan Chen,† Tianxi Liu,*,† Xiaoping Zhou,§ Wuiwui Chauhari Tjiu,‡ and Haoqing Hou*,§
Key Laboratory of Molecular Engineering of Polymers of Ministry of Education, Department of
Macromolecular Science, Laboratory of AdVanced Materials, Fudan UniVersity, Shanghai 200433, People’s
Republic of China, Institute of Materials Research and Engineering, Agency for Science, Technology and
Research (A*STAR), 3 Research Link, Singapore 117602, and College of Chemistry and Chemical Engineering,
Jiangxi Normal UniVersity, Nanchang 330027, People’s Republic of China
ReceiVed: March 19, 2009; ReVised Manuscript ReceiVed: May 23, 2009

Polyimide (PI) and PI nanocomposite fibers containing different amounts of multiwalled carbon nanotubes
(MWNTs) were produced for the first time by electrospinning. The membranes prepared were composed of
highly aligned nanofibers and showed significant enhancement in mechanical properties, compared with the
membranes prepared by conventional solution-casting method. Surface-functionalized MWNTs were
homogeneously dispersed and highly aligned along the fiber axis, whereas most of the pristine MWNTs
formed aggregates or bundles and even protruded out of the electrospun nanofibers. The thermal and mechanical
properties of polyimide matrix were significantly improved with the incorporation of MWNTs. And the
elongation at break of the nanofiber membranes can reach 100% for the nanotube loading level of 3.5 wt %.
It was found that electrospinning the in situ prepared MWNT/poly(amic acid) solution can achieve better
polymer chain orientation and thus better mechanical properties of the as-prepared membranes. Our study
demonstrates a good example for the preparation of high-performance polymer/carbon nanotube nanocomposites
by using electrospinning.

1. Introduction route for the production of aligned carbon nanotube based

nanocomposites.
Polyimides (PIs) are a class of representative high-perfor-
Electrospinning utilizes an external electrostatic field to
mance polymers possessing the cyclic imide and being usually
generate high surface areas on small fibers with diameters on
combined with aromatic groups in the backbone chains. the nanometer scale and thus is widely used as an effective
Aromatic polyimides have been extensively investigated due method to continuously produce polymer nanofibers.12-19 The
to their excellent thermal stability, mechanical properties, along electrospun nanofibrous membranes can be used as optical
with their good chemical resistance and dielectric properties. sensors, tissue-engineering scaffolds, nanocomposites, and
In the past decade, carbon nanotubes (CNTs) based polymer protective clothing because of their high porosity, high gas
nanocomposites have attracted much attention as CNTs are permeability, and large surface area per unit mass.13,20-22 Among
considered as the ideal reinforcing nanofillers owing to the these applications, mechanical strength and toughness are
combination of low density, high aspect ratio, high stiffness, extremely important, and one potential avenue for improving
and extremely high strength. Transferring the superior properties the mechanical properties of these membranes is to fabricate
of CNTs to polyimide matrix in lightweight and ultrahigh CNT/polymer nanofiber membranes. A wide range of polymer/
strength nanocomposites can be realized by fabricating PI CNT nanocomposite fibers with diameters ranging from several
nanocomposites with uniform carbon nanotube dispersion.1-6 nanometers to several micrometers have been fabricated by
On the one hand, however, CNTs cannot be effectively dispersed electrospinning.19,13,23-26 However, the nanofibrous polymer
in polymer matrixes because of their high surface area, and the nanocomposites produced by electrospinning are usually not as
agglomeration usually leads to the deterioration of the properties strong or tough as desired due to weak nanofiber interactions,
of materials. On the other hand, it is not easy to achieve poor CNT dispersion, and the unoptimized orientations for
alignment of CNTs in the matrixes, which prevents the CNTs polymer chains and CNTs in the electrospun fibers.
from being efficiently used as the ideal reinforcing fillers. So far, only a few studies have described the preparation of
Although significant progress in the dispersion of CNTs in polymer/CNT nanocomposites by electrospinning.23-26 Delozier
polyimide matrix has been made,3,7,8 alignment of the nanotubes et al. fabricated single-walled carbon nanotube (SWNT)/PI
in the matrix still remains a challenge. Usually, the CNT/PI nanocomposite fibers by electrospinning.5 However, there was
nanocomposites can be fabricated by melt processing,1,9,10 no significant SWNT alignment in the electrospun nanofibers
solution casting,11 and electrospinning.5 Among these commonly and the physical properties of the nanofibers and the membranes
used approaches, electrospinning has emerged as an effective were not investigated. Until now, there were no reports about
the fabrication of multiwalled carbon nanotube (MWNT)/
* To whom correspondence should be addressed. E-mail: txliu@ polyimide nanofibers by electrospinning. In this study, neat PI
fudan.edu.cn (T.L.); [email protected] (H.H.). and MWNT/PI nanofibers and the nanofiber membranes with
†
Fudan University.
‡
Agency for Science, Technology and Research. CNT concentrations ranging from 1 to 10 wt % were fabricated
§
Jiangxi Normal University. by electrospinning. The dispersion and alignment morphologies
10.1021/jp9025128 CCC: $40.75  2009 American Chemical Society
Published on Web 07/01/2009
9742 J. Phys. Chem. B, Vol. 113, No. 29, 2009 Chen et al.

of MWNTs in the electrospun nanofibers, as well as the thermal

and mechanical properties of the nanofiber membranes, were
studied in detail.

2. Experimental Section
2.1. Materials. 4,4′-Oxidiphthalic anhydride (ODPA) and
4,4′-oxidianiline (ODA) (Quzhou Kaiyuan Fine Chem. Co.)
were purified by sublimation before use. Pristine MWNTs with
a diameter range of 5-10 nm were commercially obtained from
Chengdu Institute of Organic Chemistry, Chinese Academy of
Sciences. The pristine MWNTs were refluxed in concentrated
HNO3 for 12 h with a weight ratio of the acid to the MWNTs
of 50:1, thus to remove the impurity of MWNTs and introduce
more carboxylic and hydroxyl groups onto the carbon nanotubes.
2.2. Preparation of the Electrospinning Solutions. The
precursor of polyimide, poly(amic acid) (PAA) was synthesized
from ODPA and ODA with an equivalent molar ratio. The
polycondensation was performed in DMAc (N,N-dimethylacet-
amide) at -3 °C, and the solid content of the pristine PAA
solution was 20%. Using an Ubbelodhe viscometer, the inherent
viscosity of the prepared PAA solution measured at 25 °C was
2.43 dL g-1. For the preparation of neat PAA solution used for
electrospinning, the pristine PAA solution was diluted by
DMAc, and for MWNT/PAA solutions, the pristine PAA
solution was diluted by MWNT/DMAc solution. As an example,
3.6 g of DMAc or MWNT/DMAc solution was added to 6 g of
pristine PAA solution by mechanical stirring at -3 °C for 6 h.
Prior to the solution mixing, the MWNT/DMAc solutions were Figure 1. TEM micrographs of (a) p-MWNT and (b) f-MWNT.
sonicated for 2 h to uniformly disperse the carbon nanotubes.
And, the solid content of all the electrospinning solutions was
fixed at 12.5 wt %. was used to observe the surface morphology of the electrospun
nanofiber membranes, and SEM was performed at an accelera-
The in situ polymerized PAA solution containing 1 wt %
tion voltage of 20 kV. Thermogravimetric analysis (Pyris 1
functionalized MWNTs was prepared by dispersing MWNTs
TGA) was performed under nitrogen flow from 100 to 800 °C
in DMAc via sonication for 2 h and then in situ synthesizing
at a heating rate of 20 °C min-1. Dynamic mechanical analysis
the MWNT/PAA solution by adding monomers into CNT
(DMA, Netzsch) of the nanocomposite membranes were carried
solution. The solid content of the in situ synthesized MWNT/
out under tensile membrane mode from 50 to 300 °C at a
PAA solution was 15%. As the incorporation of CNTs could
frequency of 1 Hz and heating rate of 3 °C min-1. Tensile tests
hinder the increase of molecular weight of PAA, the solid
of the nanofiber membranes were carried out on a CMT-8500
content of 1 wt % f-MWNT/PAA solution for electrospinning
electromechanical universal testing machine (SANS), and the
was kept to be 15%, in order to obtain uniform nanofibers free
samples were directly mounted to the sample clamps and
of beads.
stretched at a speed of 10 mm min-1. Tensile property values
2.3. Electrospinning and Imidization. Electrospinning was
reported here represent an average of the results for tests run
carried out using a syringe with a spinneret having a diameter
on at least five samples. Wide-angle X-ray diffraction (WAXD)
of 0.5 mm at an applied voltage of 20-25 kV at ambient
patterns were recorded with a Bruker GADDS X-ray diffrac-
temperature. The feeding rate was about 0.25 mL/h, and the
tometer equipped with a two-dimensional (2D) area detector
spinneret-collector distance was set to be 20 cm. The PAA
using Cu KR radiation under a voltage of 40 kV and a current
nanofibers were collected using a rotating disk collector with a
of 40 mA.
diameter of 0.30 m and a width of 8 mm. During electrospin-
ning, the linear speed of the rotating collector was about 24 m
3. Results and Discussion
s-1 because lower rotation speed cannot efficiently align the
nanofibers and higher rotation speed usually leads to the In order to improve the interfacial interaction and compat-
breakage of the nanofibers. All the membranes were first dried ibility between the MWNTs and the matrix, pristine MWNTs
at 60 °C in vacuum for 5 h to remove the residual solvent and (p-MWNTs) were treated with concentrated HNO3 to obtain
then thermally imidized in N2 atmosphere using the following the acid-functionalized MWNTs (f-MWNTs). Figure 1a shows
program to complete the imidization process: (1) heating up to the TEM micrograph of pristine MWNTs with high aspect ratio,
150 °C at a rate of 5 °C min-1 and annealing for 40 min; (2) and it can be seen that the diameter of the pristine MWNTs
heating up to 280 °C at a rate of 2 °C min-1 and annealing for with relatively smooth surface were several nanometers to about
40 min. 10 nm. Figure 1b shows the TEM image of a typical f-MWNT
2.4. Characterization. Transmission electron microscopy with diameter of about 6-8 nm, and one can clearly see the
(TEM) observations of nanofibers were performed under an presence of curvatures or defects (indicated by arrows) on the
acceleration voltage of 200 kV with a Philips CM 300 FEG rough surface of MWNTs after the acid functionalization. To
TEM. TEM specimens were prepared by directly collecting the evaluate the functionalization degree of MWNTs, the thermal
electrospun nanofibers onto copper grids during the fabrication stability of both p-MWNTs and f-MWNTs was investigated by
of membranes. A scanning electron microscope (SEM, Tescan) TGA under nitrogen atmosphere (as shown in Figure 2). The
Electrospinning Fabrication of Polyimide Nanofiber J. Phys. Chem. B, Vol. 113, No. 29, 2009 9743

Figure 2. TGA curves of p-MWNT and f-MWNT.

Figure 4. Schematic of the electrospinning process equipped with a

rotating collector.

nanofibers were very weak, the nanofibers could be easily

slipped or pulled out from each other, and therefore, nanofiber
membranes collected by this method usually possess poor
mechanical properties. In this study, a high-speed rotating
collector (as shown in Figure 4) was used to fabricate neat PI
and MWNT/PI membranes.
In order to demonstrate the high-speed rotation collecting
method can produce membranes with highly aligned electrospun
Figure 3. Photographs of p-MWNT and f-MWNT dispersed in DMAc. nanofibers, neat PAA nanofibers were also collected on a
stationary aluminum foil for comparison. As shown in Figure
3, the membrane collected without using the rotating collector
TGA results clearly indicated that the MWNTs were highly consisted of randomly oriented nanofibers (Figure 5a), whereas
functionalized (by about 10% at 600 °C) via acid treatment, the nanofibers collected by high-speed rotating method were
which was consistent with the TEM observations. Figure 3 highly aligned (Figure 5b). The SEM photograph of aligned
shows the typical photographs of the DMAc solutions of neat PI nanofiber membrane at a higher magnification is shown
p-MWNTs and f-MWNTs after being sonicated for 1 h and then in Figure 5c. It can be seen that the surfaces of the electrospun
stored for 2 months. It indicates that the f-MWNTs can be stably nanofibers were smooth and almost free of defects such as beads.
dispersed in DMAc due to the introduction of carboxyl or During the electrospinning process, the rotating collector was
hydroxyl groups to the MWNT surfaces. However, the DMAc connected to a negative electrode (about -5 kV) in order to
solution of p-MWNTs is not stable and the CNTs are deposited control the placement and alignment of the fibers, and the
at the bottle bottom only after a few days. nanofibers would track the electrical field lines and attach to
It is known that the diameter uniformity and absence of beads the negatively charged rotating collector.13 Some nanofibers were
in the electrospun nanofibers are of vital importance for entangled and could not be differentiated or separated individu-
fabricating membranes with good mechanical properties. As the ally (as shown in Figure 5c), probably because the fast jet of
polymer solution properties (viscosity, surface tension, etc.) and the nanofibers and the traction of the rotating collector make
electrospinning conditions (voltage, spinneret-collector dis- some of the nanofibers contacted and entangled with each other
tance, etc.) greatly influence the morphology of the electrospun during the electrospinning. In addition, the nanofibers may be
nanofibers, we made first efforts to optimize the electrospinning partially fused during the (subsequent) high-temperature imi-
conditions by changing these experimental parameters. In the dization process, and this may also lead to the entanglement of
present work, the average diameter of the nanofibers was the nanofibers.
controlled in the range of 200-300 nm to ensure the uniformity Besides neat PAA, PAA nanofiber membranes containing
of the electrospun nanofibers. In order to eliminate the influence pristine and acid-modified MWNTs were also fabricated by
of molecular weight on the mechanical properties of the electrospinning. During the electrospinning process, some
nanofiber membranes and investigate how the CNT incorpora- nanofibers were collected on copper grids for TEM observations.
tion influences the properties of electrospun membranes, the As shown in TEM image of Figure 6a, p-MWNTs were mostly
electrospinning solutions with different CNT loadings (0-10 agglomerated and could not be well dispersed in PAA matrix.
wt %) were prepared by mixing pristine PAA solution with The entangled nanotubes were prone to aggregate close to the
DMAc or CNT/DMAc solutions. nanofiber surface rather than being aligned well in the nanofi-
Usually, the electrospun nanofibers were spun onto a station- bers, thus leading to the coarseness of surface and the ununi-
ary plate collector, thus resulting in membranes or mats that formity of the diameters of the electrospun nanofibers.
consist of randomly arranged fibers. As the nanofibers were Figure 6b shows the TEM micrograph (at low magnification)
collected in nonwoven sheets and the interactions between the of PAA nanofibers with 2 wt % f-MWNTs. It can be seen that
9744 J. Phys. Chem. B, Vol. 113, No. 29, 2009 Chen et al.

Figure 5. SEM micrographs of neat polyimide membranes consisting of (a) nonaligned nanofibers; (b) aligned nanofibers under low magnification;
(c) aligned nanofibers under high magnification; (d) aligned nanofibers after tensile tests.

the surfaces of nanofibers were smooth, and no beads or other inclined to be entangled or agglomerated and protruded out of
defects were observed in the nanofibers. Figure 6c shows a TEM the nanofiber surface thus to reduce their surface energy. After
micrograph at high magnification for PAA nanofibers with 2 surface modification, however, the surface energy of the
wt % f-MWNTs. It was clearly seen that most of the carbon functionalized MWNTs decreased significantly, and thus almost
nanotubes were well dispersed and highly aligned along the no agglomerations or protrusions were observed in the PAA
nanofiber axis. Therefore, chemical functionalization of MWNTs nanofibers (Figure 6, parts b and c). And, with further increasing
can greatly improve their dispersion and orientation within the the f-MWNT content, even the functionalized CNTs have a
PAA nanofibers, especially at low carbon nanotube concentra- tendency to be aggregated and thus are preferably located in
tion. Figure 6d shows the TEM micrograph of PAA nanofibers the region close to the nanofiber surfaces. Such a phenomenon
containing 7.5 wt % f-MWNTs. Although some CNTs are was occasionally observed in the cases with high CNT loading
slightly folded or aggregated in the nanofiber, generally speak- levels, such as 7.5 and 10 wt % f-MWNTs (Figure 6, parts d
ing, homogeneous dispersion and high orientation of MWNTs and e).
can be still achieved even at this high nanotube loading level. In this study, the high degree of CNT alignment along the
When further increasing the MWNT concentration (e.g., 10 wt PAA nanofibers can be attributed to the successful functional-
%), the carbon nanotubes tended to form bundles or agglomera- ization of the MWNTs and appropriate adjusting of the
tions within the electrospun nanofibers significantly (Figure 6e). electrospinning conditions. Several factors may contribute to
It should be noted that one interesting phenomenon was the high alignment of MWNTs along the electrospun PAA
always observed for the electrospun PAA/CNT nanofibers: most nanofibers: (1) large electrostatic fields and the shear forces
of the pristine MWNT bundles were preferably located close present in the liquid jet during electrospinning; (2) the so-called
to the nanofiber surfaces or even protruded out of the nanofiber nanoscale confinement effect. There are not many permissible
surface (Figure 6a), whereas the functionalized MWNTs could orientations for carbon nanotubes in the electrospun nanofibers
be easily dispersed and thus uniformly distributed over the whole because of the large aspect ratio of the nanotubes and the nanoscale
nanofibers. It was also reported that the entangled or knotted diameter of the electrospun nanofibers;27 (3) the movement and
nanotubes were protruded out of the polycaprolactone nanofi- orientation of PAA chains during electrospinning will also be
bers.25 We suspected that this phenomenon could be attributed beneficial to the alignment of carbon nanotubes due to the
to the high surface energy of the pristine MWNTs which were interactions between the acid-modified CNTs and PAA chains.
Electrospinning Fabrication of Polyimide Nanofiber J. Phys. Chem. B, Vol. 113, No. 29, 2009 9745

Figure 7. (a) TGA curves of neat PI and its nanofiber membranes as

a function of f-MWNT content; (b) 5% weight loss temperature vs
f-MWNT content of the electrospun nanofiber membranes.

From the above results, it can be concluded that the fine

dispersion of carbon nanotubes is of vital importance for their
alignment within the electrospun nanofibers. When being
effectively debundled and well dispersed in the matrix, MWNTs
can be easily aligned in the polymer nanofibers by electrospin-
ning. Clearly, chemical functionalization and physical dispersion
method such as sonication treatment can significantly improve
the dispersion of MWNTs. However, some MWNTs are
definitely damaged or broken upon such treatments, and defects
and fragments of CNTs can be occasionally seen from the TEM
micrographs of the f-MWNT and the f-MWNT/PAA nanofibers,
which will somewhat deteriorate the performance of the
electrospun nanofibers. Therefore, how to efficiently modify the
carbon nanotubes without destroying their surface morphology
and achieve their homogeneous dispersion and high alignment
is still a great challenge.
Carbon nanotubes are usually used to enhance the thermal
stability of polymer materials because of their inertness to
thermal treatment. Figure 7a shows the TGA curves under
nitrogen atmosphere for neat PI and MWNT/PI nanofiber
membranes. It can be seen that all the electrospun nanofibers
possess excellent thermal stability and the residual weights of
Figure 6. TEM micrographs of PAA nanofibers containing (a) 1 wt %
p-MWNTs, (b) 2 wt % f-MWNTs (at low magnification), (c) 2 wt % the membranes increase with the increase of CNT content. As
f-MWNTs (at high magnification), (d) 7.5 wt % f-MWNTs, and (e) 10 wt % shown in Figure 7b, with increasing the MWNT concentration,
f-MWNTs. the 5% weight loss temperature (Td) increased gradually. Upon
incorporation of only 3.5 wt % CNT, the 5% weight loss
Therefore, a coupling effect of the above factors leads to a preferred temperature (i.e., thermal stability) of PI membranes is signifi-
alignment of MWNTs along the electrospun PAA nanofibers. cantly improved by about 20 °C, due to the fine dispersion of
9746 J. Phys. Chem. B, Vol. 113, No. 29, 2009 Chen et al.

Figure 8. DMA curves of (a) storage modulus (G′) and (b) tan(δ) vs
temperature for neat PI and PI/CNT nanofiber membranes.

high aspect ratio MWNTs in the matrix. For the cases of CNT
loading level above 3.5 wt %, the increasing trend of the Td
slightly decreases, probably indicating the occurrence of some
CNT agglomerations. When the CNT content is up to 10 wt %,
the decomposition temperature is enhanced by about 30 °C.
There are two competing factors during the decomposition of
PI composites. On the one hand, the chemical functionalization
can remove the impurity of MWNTs and assist the fine
dispersion of nanotubes in the matrix thus improving the thermal
stability of materials. On the other hand, however, the carboxyl
or hydroxyl groups introduced into the MWNTs are easily
decomposed at high temperature and may deteriorate the thermal
stability of PI matrix. Hence, excessive destruction of the surface
nanostructure of carbon nanotubes by chemical modifications
(in order to achieve fine nanotube dispersion) would not play a
positive role in the improvement of certain physical properties Figure 9. Stress-strain curves for (a) neat PI membranes prepared
by casting and electrospinning; (b) neat PI and f-MWNT/PI nanofiber
such as thermal stability of the nanocomposites. membranes with different CNT contents; (c) neat PI, 1 wt % f-MWNT/
Parts a and b of Figure 8 depict the DMA results showing PI nanofiber membranes fabricated by electrospinning of solution-mixed
storage modulus (G′) and tan(δ) versus temperature curves for and in situ polymerized MWNT/PAA solutions.
neat PI and its CNT nanofiber membranes. The moduli of
nanofiber membranes steadily increased with the concentration To compare the mechanical properties of aligned nanofiber
of MWNTs (Figure 8a). However, the change of Tg (glass membranes with those of the conventional solution-cast film,
transition temperature) did not show any trend. We suspect the neat PI films were also prepared by directly casting on glass
complex and variable changes of Tg may be attributed to the plates. The representative stress-strain curves of neat PI
following reasons: (1) the difference or variation in polyimide membranes prepared by casting and electrospinning are shown
chain orientation in the electrospun nanofibers (as the Tg reflects in Figure 9a. Although the tensile modulus and yield strength
the chain mobility or constraints), (2) the presence of micro- of neat PI membranes prepared by casting and electrospinning
defects in the nanofibers and the membranes, and (3) the were nearly the same, the tensile strength and elongation at break
experimental errors brought about during the DMA measurements. (or toughness) of electrospun membrane were much higher than
Electrospinning Fabrication of Polyimide Nanofiber J. Phys. Chem. B, Vol. 113, No. 29, 2009 9747

TABLE 1: Summary of Mechanical Properties of the Electrospun Neat PI and Its Nanofiber Membranes As a Function of
f-MWNT Concentration
yield strength tensile strength tensile modulus elongation at
sample (MPa) (MPa) (GPa) break (%)
neat PI nanofiber membrane 128.2 ( 15 186.8 ( 20 2.47 ( 0.34 64.1 ( 10
f-MWNT (1%)/PI 170.7 ( 20 206.1 ( 30 2.67 ( 0.23 73.1 ( 16
f-MWNT (2%)/PI 175.3 ( 20 214.7 ( 15 2.78 ( 0.13 73.8 ( 8.0
f-MWNT (3.5%)/PI 200.9 ( 16 239.7 ( 21 2.56 ( 0.15 90.5 ( 11
f-MWNT (5%)/PI 176.5 ( 31 223.4 ( 17 2.99 ( 0.31 89.9 ( 24
f-MWNT (7.5%)/PI 164.6 ( 25 199.5 ( 16 2.71 ( 0.30 86.9 ( 14
f-MWNT (10%)/PI 144.3 ( 30 168.4 ( 30 3.12 ( 0.21 71.2 ( 30

those of the cast film, due to the high orientation of the As carbon nanotubes cannot be easily dispersed in polymer
electrospun nanofibers in the membranes. A steady increase or matrix, in situ polymerization was usually employed to fabricate
hardening of the stress after the yield point for the electrospun polymer nanocomposites with homogeneous nanotube disper-
membrane was observed. However, this was not seen for the sion. In order to investigate whether PI nanocomposites with
cast film. As shown in Figure 5c, not all the nanofibers in the better CNT dispersion can be obtained via in situ polymerization,
electrospun membranes were highly aligned along the rotation 1 wt % f-MWNT/PI nanofiber membrane was also fabricated
direction. At the early stage of the tensile tests, only some by electrospinning of in situ polymerized MWNT/PAA solution,
nanofibers may work and bear the load. And during the tensile compared with the case of the above electrospinning MWNT/
testing, most nanofibers in the membrane are extended and PAA solutions prepared by solution mixing. The stress-strain
suffered the load thus leading to a steady increase of tensile curves of neat PI nanofiber membrane and the ones containing
strength and an enhanced toughness. Figure 5d shows the surface with 1 wt % f-MWNTs are shown in Figure 9c. It can be seen
morphology of neat PI membrane after tensile testing. It can that the tensile strength and toughness of 1 wt % f-MWNT/PI
be seen that the nanofibers after the tensile test were aligned nanofiber membrane prepared by in situ polymerization were
better along the rotation direction and became much dense than slightly higher than that by solution mixing. However, the
the as-prepared electrospun membranes (Figure 5c). dispersion morphology of MWNTs did not show much differ-
Figure 9b shows the typical stress-strain curves of neat PI ence between the above two methods. Hence, the nanofiber
and PI nanofiber membranes with different contents of f- membranes were investigated by using WAXD. The 2D WAXD
MWNTs. The average tensile properties such as yield and tensile patterns obtained from the above electrospun membranes are
strengths, tensile modulus, and elongation at break are sum- shown in Figure 10a-c, respectively. It can be seen that the in
marized in Table 1. It can be seen that all the electrospun situ polymerized CNT/PI membranes possess much brighter
membranes display a linear elastic deformation at low strain reflection arcs and much sharper or clearer edges. This indicates
(<8%) followed by a plastic deformation up to failure. Generally, that the in situ polymerization method (Figure 10c) can fabricate
adding a small amount of carbon nanotubes (e.g., 1 wt %) can nanofiber membranes with higher chain orientation than the
dramatically improve the overall tensile properties of polyimide solution mixing method. Higher orientation of polyimide chains
membranes. With the increase of CNT content, the modulus of may be probably associated with the interactions between the
the membranes increased, and the 10 wt % CNT/PI membrane polymer chains and carbon nanotubes. During the in situ
possessed the highest tensile modulus among the systems studied polymerization, the CNTs may be first dispersed in DMAc
here. However, the optimized tensile or yield strength was solution and interact with monomers. The polymer chains are
observed for the membrane containing 3.5 wt % f-MWNTs, formed thereafter, thus resulting in better CNT/PAA interactions
and elongation at break can reach nearly 100%. When further and higher orientation of polymer chains. Therefore, higher
increasing the CNT concentration (from 3.5 to 10 wt %), all orientation of polymer chains may lead to better mechanical
the values of the tensile or yield strength and elongation at break property of in situ polymerized MWNT/PI membranes. The
began to gradually decrease. And for the membrane containing exact reasons for this phenomenon need to be further investigated.
10 wt % MWNTs, its tensile strength was even lower than neat
PI membrane. Therefore, the tensile results may indicate again 4. Conclusion
that CNT agglomerations are probably formed to certain extent In this contribution, high-performance polyimide nanofiber
when the CNT concentration is above 3.5 wt %. As is known, membranes containing carbon nanotubes have been developed
polyimide is one kind of ultrastrong polymer and usually by an electrospinning technique. All the electrospun nanofibers
possesses low toughness or elongation at break. Here, high- were highly aligned along the collector rotation direction. TEM
performance polyimide nanocomposites were successfully fab- micrographs indicated that the functionalized MWNTs were
ricated with high toughness and enhanced overall mechanical homogeneously dispersed in polyimide matrix, whereas the
properties by incorporation of carbon nanotubes. unmodified MWNTs were agglomerated and protruded out of
the nanofiber surfaces. The thermal and mechanical properties
of polyimide membranes were improved by the incorporation
of carbon nanotubes. The elongation at break of nanofiber
membranes can reach 100% for the nanotube loading level of
3.5 wt %. Two-dimensional WAXD results showed that
electrospinning of the in situ polymerized CNT/PAA solution
is an efficient way to improve polyimide chain orientation and
Figure 10. Two-dimensional WAXD patterns of electrospun (a) neat
thus achieve the membranes with better tensile strength and
PI membrane and 1 wt % MWNT/PI nanofiber membranes fabricated toughness. Such fabrication of high-performance PI/CNT nanofi-
by electrospinning of (b) solution-mixed and (c) in situ polymerized ber membranes is an important step toward utilizing carbon
MWNT/PAA solutions. nanotubes in polymer matrixes to achieve ultrastrong, tough,
9748 J. Phys. Chem. B, Vol. 113, No. 29, 2009 Chen et al.

and lightweight nanocomposites that can be used in defense or (10) Ghose, S.; Watson, K. A.; Sun, K. J.; Criss, J. M.; Siochi, E. J.;
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Natural Science Foundation of China (20774019, 50873027), (12) Xuyen, N. T.; Ra, E. J.; Geng, H. Z.; Kim, K. K.; An, K. H.; Lee,
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