Composites Science and Technology 103 (2014) 6371

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Composites Science and Technology

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

CNT buckypaper/thermoplastic polyurethane composites with enhanced

stiffness, strength and toughness
Jin-Hua Han a,b, Hui Zhang a,, Ming-Ji Chen a, Guo-Rui Wang a,c, Zhong Zhang a,
a
National Center for Nanoscience and Technology, China, Beijing 100190, China
b
University of the Chinese Academy of Sciences, Beijing 100049, China
c
University of Science and Technology of China, Hefei 230027, China

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

Article history: Carbon nanotube buckypaper/thermoplastic polyurethane elastomer composites were successfully fabri-
Received 17 April 2014 cated. At certain polyurethane contents, the composites exhibited simultaneous improvements in stiff-
Received in revised form 19 July 2014 ness (up to 6 GPa), strength (up to 120 MPa), ductility (up to 30%) and toughness (up to 36 MJ/m3).
Accepted 17 August 2014
The measured elastic modulus of the composites could be predicted by MoriTanaka model. The possible
Available online 23 August 2014
reinforcing mechanisms were discussed by Raman spectroscopy and SEM fractography. The results
revealed that ductile polymers are very promising matrix in balancing the key mechanical properties
Keywords:
of buckypaper, which are beyond the commonly used brittle thermosettings, e.g. epoxy resin.
A. Carbon nanotubes
A. Polymermatrix composites (PMCs)
2014 Elsevier Ltd. All rights reserved.
A. Nano composites
B. Mechanical properties

1. Introduction interactions between tubes. Moreover, the random alignment of

Buckypaper (BP) is a freestanding mat made of randomly-dis-
tributed carbon nanotubes (CNTs) [1]. In the past decade, BP has
drawn increasing attention due to its remarkable thermal and elec-
trical conductivities, superior mechanical properties and low den-
sity. It is believed to be a good candidate for many applications,
such as electrodes [24], actuators [1,58], sensors [911], heat
conductors [1214] and as reinforcement for polymer composites
[1520]. In particular, the BP/polymer composites are potential
candidates for lightweight multifunctional structural materials
with high mechanical performance [15].
BP is typically fabricated by ltering aqueous suspensions of
CNTs [1]. The mechanical properties of BPs prepared by ltration
are relatively weak, resulting in somewhat difculty in handling
them in practice. The modulus and tensile strength of the unmod-
ied BPs reported in literatures usually fall into the range of
0.25 GPa [2123] and 233 MPa [3,2426], respectively, whereas
the elongation at break is relatively low and varies from 0.5% to 4%,
specically no more than 15% [27], indicating their brittle nature.
This is due to CNTs in BP are loosely stuck together only by the
Van der Waals force, i.e. no strong physical and/or chemical
Corresponding authors.
E-mail addresses: zhangh@nanoctr.cn (H. Zhang), zhong.zhang@nanoctr.cn
(Z. Zhang).
CNTs in BP also hinders the load bearing capacity.
To improve the mechanical properties of BPs, researchers have
developed many approaches to modify CNTs, such as chemically
crosslinking [22,24,2831], physically aligning [15,32], or binding
by polymer binders [1519,21,25,3336]. For the latter one, the
commonly-used polymer binders are thermosetting resins, such
as epoxy and bismaleimide resins [15,19], which have been widely
applied for brous composites in industry. Although the resultant
composites show high modulus and strength compared to the neat
BP, they also inherit the intrinsic low fracture toughness and brit-
tleness of the thermosetting resins. In some case, the elongation at
break of the composites prepared is only 2.5% [15]. Such a remark-
able imbalance of the key mechanical properties may limit the
applications of BP composites greatly. So far, only few works have
been focused on the toughness of the BP composites and the
related toughening method [3739].
Based on such a background, in this work, we tried to use a
more ductile polymer, i.e. thermoplastic polyurethane elastomer
(TPU) for preparing the BP-based composites. The tensile proper-
ties and toughness were evaluated on the BP and its composite
samples having various TPU fractions. The elastic moduli of the
BP/TPU composites could be predicted by MoriTanaka model. It
was demonstrated that after being modied by TPU, the modulus,
strength, elongation at break and toughness of the composites
simultaneously gained signicant improvements compared to that
of the neat BP. In situ Raman spectrums and SEM of the fracture

http://dx.doi.org/10.1016/j.compscitech.2014.08.015
0266-3538/ 2014 Elsevier Ltd. All rights reserved.
64 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371

surfaces of the samples were also investigated to unveil the
possible reinforcing mechanisms.
2. Experimental
2.1. Preparation of BP
90 mg MWCNTs (68 nm in diameter, up to 50 lm in length,
and purity >93 wt.%, FloTube 7000, CNano Technology Ltd., Bei-
jing, China) were ultrasonically dispersed in 300 mL deionized
water at 400 W for 20 min, with the aid of the surfactant (1.8 g Tri-
ton X-100); the dispersion was centrifuged at 4000 rpm for 30 min
to eliminate the catalyst and aggregations; thereafter the superna-
tant (100 mL) was ltrated through a polyvinylidene uoride
microporous lter membrane (47 mm in diameter, 0.22 lm in pore
size) under vacuum. After ltration, the BP was thoroughly washed
with lots of deionized water to remove the adsorbed surfactant,
dried in air, and peeled off from the lter membrane carefully,
resulting in 20 lm thick lm.
2.3.2. Weight fraction of TPU resin in BP composite samples
TGA experiments were carried out using a TA Instrument SDT
Q600 on the BP composite samples. The samples were held at
100 C for 5 min to eliminate the residual water, and then heated
to 800 C at a heating rate of 10 C/min under nitrogen atmosphere
with the nitrogen ow rate of 100 mL/min. Three tests were per-
formed on each sample to obtain an average value of the residue
percent of the samples.
From TGA thermograms in Fig. 1, the residue percent of the as-
prepared BP (RBP) and the neat TPU resin (RTPU) is estimated to be
76% and 6.6%, respectively. For a BP/TPU composite sample, the
weight fraction of TPU resin (wTPU) can be estimated from the fol-
lowing equations:
wTPU  RTPU wBP  RBP Rcompos 1
wBP 1  wTPU 2
where Rcompos is the residue percent of the composite sample
obtained from TGA; wBP is the weight fraction of the as-prepared
BP in the composite samples.

2.3.3. Volume fraction of TPU resin and pore in BP composite samples

2.2. Preparation of BP/TPU composites
TPU (Elastollan 1185A10, MFI value <20, BASF Co.) was dis-
solved in N,N-dimethylformamide to form solutions of 0.01 wt%.
A certain amount of solution was ltered through the BP under
vacuum to inltrate BP. After inltration, the composite samples
were obtained by drying the resin-wetted BP at 60 C under vac-
uum for 24 h to eliminate the solvent completely. The amount of
TPU solutions was varied to obtain the composite samples contain-
ing various TPU fractions. As shown in Table 1, the composite sam-
ples are designated as BP/TPU-x, where x indicates the amount of
TPU solution. Higher x value indicates larger amount of TPU
solution used for inltration.
2.3. Characterization
2.3.1. Morphology analysis
The thickness of the samples was determined by an optical
microscope (Leica DM 4000 M). A eld emission scanning electron
microscope (SEM, Hitachi S-4800) was used to observe morpholo-
gies of the samples. Nitrogen adsorptiondesorption experiments
were performed on the as-prepared BP and BP/TPU-x composites
at 77 K using a TriStar II 3020 surface area and porosity analyzer
(Micromeritics, USA). Before measurement, the samples were
degassed in vacuum at 150 C for more than 12 h. The specic sur-
face area of the samples was calculated from the 0.06 to 0.2 p/p0
region of the adsorption isotherm using BrunauerEmmettTeller
(BET) analysis, while pore size and pore size distribution were esti-
mated using BarretJoynerHalenda (BJH) method from the N2
desorption isotherm.
Even after impregnation with TPU resin, there are still some
micro pores inside the BP composites. The volume fraction of pore
(vpore) and the TPU resin (vTPU) in BP composite samples can be esti-
mated according to Eq. (3), as suggested by Ashra et al. [40]:
qcompos  wTPU
v TPU 3
qTPU
qcompos  wBP qcompos  wTPU
v pore 1  v BP  v TPU 1   4
qBP qTPU
where vBP is the volume fraction of the as-prepared BP in the com-
posite samples; qTPU is the density of the TPU resin and equals to
1.12 g/cm3; qcompos is the density of the BP composite sample, which
is obtained by dividing the mass of a composite sample by its vol-
ume; qBP used here is the real density of the as-prepared BP, which
is estimated to be 1.71 g/cm3. (It is calculated according to the den-
sities and weight fractions of MWCNTs and Triton X-100. The den-
sities of MWCNTs and Triton X-100 are 2.1 and 1.07 g/cm3,
respectively; their weight fractions are 76% and 24%, obtained from
the TGA thermogram of the as-prepared BP, see Fig. 1. It is worth
noting that the as-prepared BP is actually composed of the ran-
domly-distributed MWCNTs, adsorbed Triton X-100 and pores
inside. That is why the qBP value is obviously higher than the stack-
ing density of BP reported in the literature [27,40].)
2.3.4. Mechanical properties
A dynamic mechanical analyzer (TA, DMA Q800) was employed
to evaluate mechanical properties of the as-prepared BP and their
composites. Samples were cut manually by a razor blade into strips
(30 mm  2 mm) and then dried at 60 C for 12 h under vacuum
before tests. The static tensile tests were conducted in ramp

Table 1
Basic information of the as-prepared BP and its composite samples.

Sample ABET (m2/g) dBJH (nm) Density (g/cm3) Volume fraction (vol.%)
TPU BPa (MWCNTs + Triton X-100) Pore
As-prepared BP 178 29.4 0.66 38.5 (23.8 + 14.7) 61.5
BP/TPU-1 101 25.8 1.11 14.8 55.2 (34.1 + 21.1) 30.0
BP/TPU-2 62 23.7 1.19 24.0 53.8 (33.2 + 20.6) 22.2
BP/TPU-3 35 22.2 1.25 33.9 51.2 (31.6 + 19.6) 14.9
BP/TPU-4 7 21.8 1.33 47.9 46.2 (28.5 + 17.7) 5.9
BP/TPU-5 0.2 22.1 1.28 72.4 27.6 (16.9 + 10.7)
a
The BP volume fractions in Table 1 are actually a sum of the volume fractions of MWCNTs and surfactant Triton X-100, therefore the volume fractions of the two
components are also listed in brackets.
 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371
100
80
Weight (%)
60
BP
40 BP/TPU-1
BP/TPU-2
BP/TPU-3
20 BP/TPU-4
BP/TPU-5
TPU
0 which agrees with the results obtained by TGA. The cumulative
100 200 300 400 500 600 700 800
o
Temperature ( C)
Fig. 1. TGA thermograms of the as-prepared BP, neat TPU resin and BP/TPU
composite samples with different TPU fractions.
displacement mode with a pre-strain 0.01% and at a ramp rate of
20 lm/min. The integrated area under the tensile curve, represent-
ing the energy to break the samples, was used to evaluate their
toughness. At least ve specimens were tested.
The stress transfer effectiveness of carbon nanotubes in the BP-
based composite samples (10 mm  2 mm  20 lm) was in-situ
evaluated by Raman spectroscopy (Renishaw 2000) under tensile
mode [41]. The excitation wavelength was 514 nm and the laser
points were focused on the center of the samples. The dependence
of G0 band value on the strain level was recorded. At least ve
specimens for each sample were repeated and the average G0 band
values were given.
3. Result and discussion
3.1. Microstructure characterization
3.1.1. Volume fractions of the components in BP composite samples
tested by TGA
Fig. 1 shows the TGA thermograms of the as-prepared BP, neat
TPU and BP/TPU composite samples, which were tested in nitro-
gen. For the as-prepared BP (black line in Fig. 1), the main weight
loss occurs in the temperature range of 100450 C, which is due to
the evaporation and degradation of the surfactant (The boiling
point of Triton X-100 is 270 C.).
According to the TGA results and Eqs. (1)(4), the volume frac-
tions of the components in BP composite samples are calculated
(Table 1). The as-prepared BP lm has a large amount of pores
inside (61.5 vol.%). Assuming the pores are neither compressed
nor expanded during inltration of TPU solution and can be com-
pletely occupied by TPU resin, the maximum volume fraction of
TPU resin in the composite should equal to 61.5 vol.% also. How-
ever, the actual volume fractions of TPU are obviously much lower
than the maximum value. This can be explained by two possible
reasons: (i) Like the foam materials, the pores in BP will diminish
under vacuum inltration; (ii) In some cases, the amount of TPU
solution is too low to occupy all the pores in the BP lm.
It can be seen from Table 1, with increasing amount of TPU solu-
tion, the volume fraction of the TPU resin increases and the pores
in the BP lm are gradually replaced with the TPU resin. The best
quality of impregnation is found for the sample BP/TPU-4; here,
the volume fractions of pore and TPU resin in this sample are 5.9
and 47.9 vol.%, respectively. Further increasing the TPU amount,
however, results in unusually high volume fraction of TPU
65
(72.4 vol.%), probably due to the redundant resin on the sample
surface.
3.1.2. Pore size and size distribution in BP composite samples tested by
BET method
The impregnation quality of the composite samples can also be
evaluated by analyzing the specic surface area (ABET), and the pore
size distribution (Table 1 and Fig. 2). ABET of the BP is 178 m2/g,
which is comparable with those reported in literature, e.g.
197 m2/g [42]; the diameter of the pores in the BP is within the
range of 580 nm. After inltration, the ABET values and the mean
pore diameter (dBJH) of the BP/TPU samples decrease gradually,
implying the pores were occupied by the TPU resin step by step,
pore volume (integral area of the curves in Fig. 2) decreases with
TPU resin, also suggesting that the porosity in the sample
decreases. In addition, the pore size distribution becomes narrower
for the BP composite samples than the as-prepared BP.
3.1.3. SEM morphology of BP composite samples
The impregnation quality of the composite samples can be fur-
ther evaluated by observing SEM images of composite samples
from both surface and cross section directions, as shown in
Fig. 3. It can be seen that the BP is composed of randomly-
distributed MWCNTs, which tangle via the van der Waals force
and form uniform porous structure; no obvious clusters can be
found (Fig. 3a and b). In the sample of BP/TPU-1 (Fig. 3c and d),
the carbon nanotubes are relatively thicker in comparison with
those of the as-prepared BP lm, even though plenty of pores exist.
This indicates that the TPU resin has relatively good compatibility
with the carbon nanotubes and can be absorbed on the nanotubes,
but resin amount is not sufcient to occupy all the pores in the BP
lm. In the case of sample BP/TPU-4 (Fig. 3e and f), the TPU resin
impregnates the BP lm very well and the pores are almost com-
pletely occupied by the resin. While for the sample BP/TPU-5
(Fig. 3g and h), the TPU resin seems to be excess, a clear boundary
is recognized between pure resin and BP/TPU composite, i.e. this
sample has a layered microstructure.
3.2. Tensile properties of the BP composites
Fig. 4a presents the typical tensile curves of the neat TPU resin,
as-prepared BP and BP/TPU composite samples. As shown in the
inset of Fig. 4a, at current test conditions the neat TPU resin is ther-
moplastic rubber, namely, having low elastic modulus (21 MPa),
low failure strength (33 MPa) and high ductility (elongation at
0.05
BP
BP/TPU-1
0.04 BP/TPU-2
Pore Volume (cm3/gnm)
BP/TPU-3
BP/TPU-4
0.03 BP/TPU-5
0.02
0.01
0.00
5 10 50 100
Pore Diameter (nm)
Fig. 2. Pore size distribution in the as-prepared BP and BP/TPU composite samples.
66 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371

Fig. 3. SEM images showing the morphologies of the surface (left column) and cross section (right column) of BP lm and BP/TPU composite samples: (a, b) the as-prepared
BP, (c, d) BP/TPU-1, (e, f) BP/TPU-4, (g, h) BP/TPU-5.

break up to 580%); at higher tensile strain (>400%), an obvious
strain hardening takes place due to the orientation of polymer mol-
ecules; the stretched sample can return to its original dimensions
almost immediately after unloading the applied stress. While, the
as-prepared BP shows poor mechanical properties (Fig. 4a black
line) with the elastic modulus of 1.37 GPa, failure strength of
11.58 MPa and elongation at break of 8%.
After introduction of TPU resin to as-prepared BP, the mechan-
ical properties of composite samples are found to be improved dra-
matically (Table 2 and Fig. 4b). The strain hardening of the neat
TPU resin disappears, even though in some cases the TPU fractions
in the composite samples are much high (e.g. BP/TPU-5). At very
high resin fraction (e.g. BP/TPU-5), the mechanical properties
decrease obviously, due to the excess TPU on sample surface
(Fig. 3h). The best mechanical properties are found in the case of
sample BP/TPU-4 with elastic modulus of 6 GPa, failure strength
of 123 MPa and toughness of 36 MJ/m3, corresponding to
3.4-fold improvement in elastic modulus, 9.6-fold improve-
ment in failure strength, and 50-fold improvement in toughness,
compared to those of the as-prepared BP lm.
3.3. Modeling of elastic modulus
The elastic modulus of a polymer reinforced with CNTs is gen-
erally determined by the elastic properties of its components
(CNTs and matrix), the interface interaction, aspect ratio,
 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371 67

(a) 140 40

Stress (MPa)
Strain rate: 20m/min @ R. T. 30
TPU

120 20
10
0
100 0 200 400 600
Strain (%)

Stress (MPa)
80

60

40

BP BP/TPU-1
20
BP/TPU-2 BP/TPU-3
BP/TPU-4 BP/TPU-5
0
0 10 20 30 40 50 60
Strain (%)

(b) 7 Modulus 40 160

Strength
6 Toughness 35 140

30 120

Toughness (MJ/m )
3
5

Strength (MPa)
Modulus (GPa)

25 100
4
20 80
3
15 60
2
10 40
1 5 20

0 0 0
Buckypaper BP/TPU-1 BP/TPU-2 BP/TPU-3 BP/TPU-4 BP/TPU-5
Samples

Fig. 4. Tensile curves (a) and key mechanical properties (b) of the neat TPU, as-prepared BP and BP/TPU composite samples.

Table 2
Mechanical performance of the as-prepared BP and its composite samples.

Sample Modulus (GPa) Failure strength (MPa) Elongation at break (%) Toughnessb (MJ/m3)
Experimental Predicted
As-prepared BP 1.37 0.05 11.58 0.28 8.89 0.94 0.69 0.12
TPUa 0.021 33 580 80
BP/TPU-1 3.52 0.22 3.86 70.22 2.43 25.93 5.03 15.48 1.34
BP/TPU-2 4.85 0.49 5.33 107.78 3.76 35.81 1.71 34.91 3.73
BP/TPU-3 5.53 0.65 6.75 116.17 4.08 28.09 4.2 29.04 1.67
BP/TPU-4 6.02 0.19 8.28 123.2 7.06 31.32 3.07 35.82 1.52
BP/TPU-5 1.78 0.15 40.45 3.53 51.31 5.52 19.63 2.59
a
From the data sheet of BASF corporation.
b
Toughness is calculated by integrating the area under the stressstrain curve.

waviness, entanglement, orientation, and volume fraction of the with partial exfoliated nanoclay, graphite, carbon nanotube or
reinforcement. Several empirical or semi-empirical equations short, misaligned carbon ber, as well as some system with
have been proposed to predict the modulus of CNTs-polymer porous structure [40,4549], thus this model is applied here to
composites. The commonly-used equations are the mixing law, t the modulus of the BP/TPU composites.
HalpinTsai model and MoriTanaka model. The mixing law is For the MoriTanaka model, the effective stiffness tensor CC of
more suitable for continuous and parallel orientated reinforce- the composite can be computed using the expression [50],
ment in the composite. Even though it has been modied by D  Eh D Ei1
Cox [43] and Krenchel [44] to model the modulus of short-ber CC CM V f C f  C M AN 1  V f I V f AN 5
reinforced composites, it is still difcult to apply it to intricate
multi-phase composites. HalpinTsai equation also faces the where CM and Cf is the stiffness tensors of the matrix phase and the
same problem. While in our work, based on Table 1, due to the ller, respectively, Vf is the volume fraction of the ller, I is the
partially impregnation of the resin, the BP/TPU composites are fourth order unit tensor, and the terms in the angular brackets rep-
actually very complicated system, which consist of four phases, resent the average over all orientations. The dilute mechanical
including TPU resin, medium content of CNTs (2030% by vol- strain concentration tensor, AN, can be expressed as,
ume), Triton X-100, and pores. Previous studies have established   1  1
the validity of the MoriTanaka approach for predicting the AN I S C M Cf  CM 6
properties of complicated multi-phase composites reinforced
68 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371
where S the fourth order Eshelby tensor. The elements of the
Eshelby tensor are functions of the aspect ratio of the ller,
s = L/D, and the Poissons ratio of the matrix. The expression of
Eshelby tensor can be found in elsewhere [48].
For simplication, the BP/TPU composites can be considered as
a two-phase system composed of un-impregnated region (I) and
ideally-impregnated region (II). As depicted in Fig. 5a, un-impreg-
nated region (I) consists of the un-wetted MWCNTs, surfactant as
well as pores, while ideally-impregnated region (II) consists of
the wetted MWCNTs and TPU resin. For convenient calculation,
un-impregnated region (I) could be simplied to numerous spher-
ical inclusions, which are uniformly distributed in ideally-impreg-
nated region (II) [40].
The calculation is divided into two stages. At rst, the stiffness
tensor of region (II) is computed, by assuming MWCNTs as ellipsoi-
dal inclusions of aspect ratio, s = L/D = 500, randomly oriented and
perfectly bonded with the TPU matrix. The volume fraction of the
MWCNTs is equal to that in the resultant composites, as it is dif-
cult to get the precise value of the MWCNTs volume fraction in this
region; Afterwards, region (II) with the computed stiffness tensor
Fig. 5. Prediction of moduli of the BP/TPU composite samples using MoriTanaka model: (a) a schematic diagram showing two distinct regions in the composite samples,
(b) a owchart demonstrating how to estimate the moduli by the model.
is then considered as the effective matrix phase in the second stage
of the calculation, in which the region (I) is the inclusion phase. The
modulus and the Poissons ratio of region (I) were assumed to
equal those of neat BP (1.37 GPa and 0.2; the BP is reported to
have negative Poissons ratio at lower strains [51]). The volume
fractions of the two regions can be roughly estimated from Table 1,
and shown in Fig. 7b. Combining the parameters of two regions
(Fig. 7b), the moduli of resultant composite samples can be calcu-
lated using MoriTanaka modeling and the predicted values are
listed in Table 2. The predicted values generally show a similar ten-
dency in comparison with the experimental values, even though
the former ones are somewhat higher than the latter ones. The
overestimation could be due to the overestimated MWCNTs vol-
ume fraction in region (II) as well as the overestimated interfacial
bonding between the MWCNTs and the TPU resin. Moreover, in the
MoriTanaka model, the nanotubes are considered straight ellip-
soidal inclusions, their curvature is not taken into account. While
in the BP/TPU system studied here the nanotubes are curved and
entangled, their high Youngs modulus will not be fully exploited
in the composite [49].
 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371 69

(a) 2690 The downshifting rate of the G0 band is a measure of load trans-
BP fer efciency between nanotubes (or between nanotubes and
2688
BP/TPU-4 matrix). At low strains (<8%), the downshifting rate for the BP/
Wavenumber (cm-1)

2686 -1
~-1.05cm /1% for BP/TPU-4 TPU-4 (1.05 cm1/1%) is much larger than that for the BP
2684 (0.48 cm1/1%). This may be ascribed to the improved intertube
fracture
adhesions with the help of TPU resin.
2682
-1
~-0.48cm /1% for BP
For the BP/TPU-4, when the tensile strain reaches a certain
2680 fracture point (10%), the G0 band value does not change any more. This
2678 implies that the applied load has exceeded the interaction of the
adjacent tubes, and further added stress will lead to the relative
2676
slippages of the tubes or the extension of the ductile TPU resin
2674 rather than the extension of carboncarbon bonds as elucidated
0 5 10 15 20 25 30 35 in the Fig. 6b. These events (especially for the TPU extension) can
Strain (%) dissipate fracture energy and contribute to the enhanced tough-
ness of the BP composites.
(b) Fig. 7 shows SEM images of the fracture surfaces after tensile
tests. As shown in Fig. 7(a and b), the fracture of the BP may be
caused by the relative slippage of the MWCNTs owing to their
weak interactions. Comparatively, almost no pores are found on
the BP/TPU-4 (Fig. 7(c and d)); the carbon nanotubes are seen to
be wetted by TPU resin; the permanent dentate-like deformation
Fig. 6. Raman spectrums analysis: (a) variation of G0 band with applied strain, (b) of the composite sample is observed (see arrows in Fig. 7d). All
possible failure mechanisms for BP/TPU-4 composite sample. these features support the fact that the interface between nano-
tubes and resin is fairly good, which may promote the stress trans-
3.4. Possible reinforcing mechanisms of the BP composite samples fer. The good interfacial bonding can be ascribed to Triton X-100,
which has been demonstrated by previous works [54,55]. The
Due to its sensitivity to the interatomic distance, Raman spec- hydrophobic octyl group of Triton X-100 may interact with CNTs
troscopy has been widely used to evaluate the load-bearing capac- through adsorption, while the hydrophilic segment may interact
ities of carbon nanollers in composites by analyzing the Raman with the TPU resin through hydrogen bonding, thus favoring the
shifts of the characteristic peaks [41,52,53]. To estimate the load- interfacial adhesion.
bearing capacities of the MWCNTs in the BP and the BP/TPU com-
posites, in situ Raman measurement was conducted on tensioned
4. Conclusions
samples, and the variation of the G0 band (2684 cm1, for
MWCNTs powder) was investigated. Fig. 6a shows that before ten-
The thermoplastic polyurethane elastomer was successfully
sion, the G0 band values of the as-prepared BP and BP/TPU-4 are
used to enhance the key mechanical properties of BP. At a proper
2684 cm1and 2687.4 cm1, respectively, indicating the
TPU volume fraction (48 vol.%), the composite obtained remarkable
MWCNTs are slightly compressed in the composite. During
improvements in modulus, failure strength, elongation at break
tension, both the G0 bands downshift to lower frequency.
and toughness, compared to those of the neat BP lm. The

Fig. 7. SEM images of fracture surfaces taken from tensile samples: (a, b) the as-prepared BP and (c, d) for BP/TPU-4 composite sample.
70 J.-H. Han et al. / Composites Science and Technology 103 (2014) 6371

improvement can be attributed to the good MWCNTs-TPU interfa- [21] Xu G, Zhang Q, Zhou W, Huang J, Wei F. The feasibility of producing MWCNT
paper and strong MWCNT lm from VACNT array. Appl Phys A
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This project was jointly supported by the National Key Basic
morphology and achievable moduli in manufacturable materials. J Appl Phys
Research Program of China (Grant Nos. 2012CB937503 and 2004;95(8):4335.
2013CB934203), a key international collaboration project (Grant [27] Mechrez G, Suckeveriene RY, Tchoudakov R, Kigly A, Segal E, Narkis M.
No. 2011DFR50200) of the Ministry of Science and Technology of Structure and properties of multi-walled carbon nanotube porous sheets with
enhanced elongation. J Mater Sci 2012;47(16):613140.
China, and the National Natural Science Foundation of China (Grant [28] Zhang X, Sreekumar TV, Liu T, Kumar S. Properties and structure of nitric acid
No. 11225210). oxidized single wall carbon nanotube lms. J Phys Chem B
2004;108(42):1643540.
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