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Mechanical and electrical properties of a MWNT/epoxy composite

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 Composites Science and Technology 62 (2002) 1993–1998
www.elsevier.com/locate/compscitech

Mechanical and electrical properties of a MWNT/epoxy composite

A. Allaouia, S. Baia,b, H.M. Chengb, J.B. Baia,*
a
Laboratory of Mechanics of Soils, Structures and Materials, CNRS UMR 8579, Ecole Centrale Paris, 92295 Châtenay-Malabry, France
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, CAS, 72 Wenhua Road, Shenyang 110016, PR China

Received 26 March 2002; received in revised form 7 July 2002; accepted 8 July 2002

Abstract
Multi-walled carbon nanotube/epoxy resin composites have been fabricated. By choosing an over-aged hardener, relatively soft
and ductile matrix, a rubbery epoxy resin, has been obtained. This made possible to evaluate the effect of nanotube addition on the
whole stress-strain curve up to high strain level. The mechanical and electrical properties of the composite with different weight
percentages of nanotubes have been investigated. The Young’s modulus and the yield strength have been doubled and quadrupled
for composites with respectively 1 and 4 wt.% nanotubes, compared to the pure resin matrix samples. Conductivity measurements
on the composite samples showed that the insulator-to-conductor transition took place for nanotube concentration between 0.5%
and 1 wt.%.
# 2002 Published by Elsevier Science Ltd.
Keywords: B. Mechanical properties; B. Electrical properties; Multi-walled carbon nanotubes

1. Introduction [18,20] were treated. In this paper, a nanocomposite was

Carbon nanotubes (CNTs), one graphene layer
(SWNT) or many graphene layers wrapped onto them-
selves (MWNT) are a novel crystalline carbon form.
The recent theoretical and experimental investigations
indicate that they have properties suitable for applica-
tions in many fields. Their interesting mechanical (axial
Young modulus 1–5 TPa [1–7], high flexibility [8],
bending fully reversible up to a 110
critical angle for
SWNT [9]), and physical (metallic or semi-conducting
character [10,11], field emission, high thermal and elec-
trical conductivity, hydrogen adsorption, . . .) properties
have been the subject of many research works. The
CNT-based composites, which may be one of the most
promising applications, have been intensively studied
using different matrix materials, polymers [12–20], cera-
mics [21–23] and metals [24,25]. A review paper has been
published on the subject [26]. In the case of polymer
matrix, most papers dealt with relatively brittle and rigid
matrix, such as cured epoxy resin. And often, only
mechanical properties [15, 17] or physical properties
* Corresponding author. Tel.: +33-1411-31316; fax: +33-1411-
31430.
E-mail address: baijinbo@mssmat.ecp.fr (J.B. Bai).
0266-3538/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.
PII: S0266-3538(02)00129-X
prepared using an over-aged hardener so that the epoxy
matrix remains relatively soft and ductile even after
polymerization. Both mechanical and electrical proper-
ties were investigated to evaluate the change introduced
by the CNTs at different weight percentages (up to 4%).
With the ductile matrix, it is possible to evaluate the
influence of CNTs addition on the whole stress-strain
behavior, not only limited to the Young’s modulus.
2. Experimental
2.1. Materials
2.1.1. Matrix
Epoxy polymer matrix was prepared by mixing 15
parts by volume of epoxy resin (Bisphenol A-epi-
chlorhydrine) with 2 parts of aromatic hardener (tri-
ethylenetetramine). Epoxy resin contains one or more
epoxide groups that serve as cross-linking points when
the resin reacts with the hardener to form long chains,
the polymerization. The over-aged hardener used in this
work produced a rubbery epoxy matrix. The hardener
has an impact on the matrix structure and the cross-
linking ratio and by this way the molecular motions.
1994 A. Allaoui et al. / Composites Science and Technology 62 (2002) 1993–1998
2.1.2. MWNT
2.1.2.1. Synthesis. CNTs used in this study were syn-
thesized by (CVD) thermal decomposition of hydro-
carbon gas. Benzene was used as carbon source,
thiophene as growth promoter, ferrocene as catalyst and
hydrogen as carrier gas. The relative ratio of different
components in the reaction system was controlled by
adjusting the carrier gas flow rate. Through controlling
the reaction time and relative components of benzene,
thiophene and ferrocene, carbon nanotubes and carbon
nanofibers of different diameter and structure can be
obtained. The details of our CVD system will be pub-
lished elsewhere [27].
2.1.2.2. CNTs morphology. TEM observations were car-
ried out with a JEOL JEM 1200 EX operating at 120 kV
to examine the morphology of the CVD products. The
CNTs are MWNTs, with diameters in the range of 15–400
nm, the mean diameter being 100 nm, and average length
a few hundreds microns (Fig. 1). They are highly entan-
gled and randomly organized. There are some catalyst
particles, amorphous carbon and onions as impurities.
2.1.2.3. Raman spectroscopy. Raman spectra were
recorded with a DILOR LABRAM multi-channel con-
focal microspectrometer in backscattering mode using
an Ar+ laser excitation (514.5nm, 5mW; resolution
1cm1). The integration time was 100s and the spectra
were averaged over 2 accumulations. The incident laser
beam was focused onto the specimen surface through a
100 objective lens forming a laser spot of approximately
Fig. 1. Transmission electronic micrographs of CNTs.
2mm in diameter. The Raman spectra, obtained in the
range 1000–2000 cm1, shows a band at 1588 cm1 (G
band) due to the A(g1), E1(g) and E2(g) vibrational
modes, and a band at 1357 cm1 (D band) arising from
the disorder-induced A(g1) mode (Fig. 2). The G band is
wide and its intensity is lower than twice that of the D
band, which is typical of MWNT Raman spectra. The
width of the G band is related to the CNTs size distribu-
tion whereas the intensity of the D band decreases with
the degree of graphitization of the tubes. In this work,
Raman spectroscopy was mainly used to verify the multi-
walled nature of the CNTs and the overall homogeneity
of the sample. No meaningful differences were observed
at different Raman measurements points.
2.1.3. Composite preparation
The as-prepared CNTs material consists of aggregates
of different sizes. The bigger ones are millimetric or even
centimetric. This would be an obstacle to the uniform
dispersion of MWNT into the epoxy matrix. A proce-
dure of two steps was followed. The MWNT were first
dispersed in methanol solution under magnetic agitation
to reduce the maximum size of the aggregates to about
100 mm. After complete evaporation of methanol, the
obtained MWNT powder was then directly added to the
epoxy resin Bisphenol A/aromatic hardener mixture.
Finally, it was injected into sample moulds after manual
homogenization. The 4 wt.% samples were very viscous
and the homogenization process was difficult. The sam-
ples were placed between two metal plates under pressure
to reduce porosity forming during hardening. Before
 A. Allaoui et al. / Composites Science and Technology 62 (2002) 1993–1998
Fig. 2. Raman spectrum of the CVD MWNT.
mechanical and electrical measurements, the surfaces of
the specimens were mechanically polished to minimize
the influence of surface flaws, mainly the porosity.
2.1.4. Tensile tests and AC measurements procedure
Tensile tests of dog-bone shaped specimens (Fig. 3) were
performed at 25
C and at a constant cross-head rate of 1
mm/min on an Instron electro-mechanical testing
machine. The choice of this quite low loading rate is to
compare later with the results of more brittle and more
rigid materials. The strain was measured with an extens-
ometer. The gauge length is 12.5 mm +/2.5 mm. The
thickness of samples after polishing is between 2 and 3 mm.
The AC spectroscopy measurements have been per-
formed with a Solartron 1260 Impedance/Gain Phase
Analyzer. A 1 VAC voltage, of known amplitude and
phase, was applied to a circuit equivalent to a resistor in
parallel with a capacitor and the output current was
measured. The complex impedance, Z, was conse-
quently calculated by the analyzer.
3. Results and discussion
3.1. Mechanical properties
The most tensile tests were performed to the limit
strain of extensometer, 25% while those of 4 wt.%
Fig. 3. Tensile test sample geometry.
1995
composite were conducted to break of the samples. The
stress–strain curves are shown in Fig. 4.
The resin obtained is very ductile. The maximum
stress levels reached are not those of a standard resin
(generally 30–50 MPa). The general tendency is that the
stress level is increased by the addition of CNTs which
play the role of reinforcement. The Young’s modulus
and the yield strength of the composite are doubled by
adding 1 wt.% of CNT and quadrupled with 4 wt.%
CNT. Moreover, two curves for the 1 wt.% composite
are presented and show reproducible results. The
mechanical properties of the composites are given in
Table 1. To have a better view of the effect of CNTs on
the mechanical behavior of the composites, the normal-
ized stress-strain curves are drawn in Fig. 5. In this fig-
ure the stress of composites of different CNTs wt.% is
divided by the stress of the pure matrix at the same
strain level. An almost constant reinforcement coeffi-
cient has been observed for the strain level higher than
2%. The ratio is about 2 for 1 wt.% CNTs composite
and 2.5 for 4 wt.% composite. It can be concluded that
the reinforcement role is much reduced in the case of 4
wt.% composite. The same phenomenon was observed
for Young’s modulus. The Young’s modulus of the
composites normalized by that of the pure matrix is
presented in Fig. 6. A slope decrease can be observed
for 4 wt.% composite The optical microscope observa-
tions revealed the presence of porosities and CNTs
aggregates (small size for the 1 wt.% composites and
large for the 4 wt.% samples). On the polished surface
of samples, there are some zones with very high local
Fig. 4. Tensile test stress–strain curves of the resin and its composites.
Table 1
Young’s modulus and stresses at different strain levels
CNTs Young’s Yield strength  10%Mpa
wt.% modulus MPa  0.2%MPa
0 E0=118 1 4
1 236(2*E0) 3 8
4 465(3.9*E0) 6 10
1996 A. Allaoui et al. / Composites Science and Technology 62 (2002) 1993–1998
Fig. 5. Normalized stress–strain curves of the composites.
Fig. 6. Normalized Young’s modulus of the composites.
CNT concentrations, as shown in Fig. 7 a. The dis-
tribution of CNTs is more homogeneous in the 1 wt.%
samples (Fig. 7b). This could explain partially the pre-
mature fracture occurred in 4 wt.% composites. On the
Fig. 7. (a) Optical micrographs of the surface of the 4 wt.% CNT composite. The porosities are marked by white arrows and the zones of very high
local CNT concentration by black arrows. (b) Optical transmission light micrograph of the surface of 1 wt.% CNT composite.
other hand, the porosity may be also another origin of
lower reinforcement effect of CNTs in the case of 4
wt.% samples compared to the 1 wt.% samples.
3.2. Electrical properties
The conductivity was investigated first using a simple
circuit. A direct voltage U=I V was applied directly on
the sample. The intensity I through the sample thickness
e and contact area S was measured, using a picoam-
peremeter. The DC conductivity was then calculated
using the following formula:  ¼ UI Se DC.
The AC impedance spectroscopy gives much reliable
results and allows studying the behavior at different
frequencies. The sample was disposed between two par-
allel electrodes, constituting, hence, a capacitor during
AC measurement. It was submitted to a sinusoidal per-
turbation of intensity 1 V with variable frequency. The
analyzer detected the current (intensity and phase)
through the sample at each frequency. Complex impe-
dance is calculated as a function of frequency. The AC
conductivity is given by the following relation:  ¼
Y0 Se AC, Y0 is the real part of the admittance
(Y=1/Z). To improve the electrical properties, MWNT
were used, because those Russian doll like nanotubes
are always conductive. This is not the case for SWNTs,
which can be semi-conductive or metallic as a function
of their chirality. The MWNT conductivity results from
the mean behaviour of the different rolled graphene
layers. The DC and AC electrical conductivity of
MWNT/epoxy composites are plotted as a function of
the weight percentage of nanotubes added to the matrix
(Fig. 8). We can observe that the AC and DC results are
in good agreement. Over the range of CNTs addition
studied, up to 4 wt.%, nine orders of magnitude change in
the conductivity was observed, corresponding to a per-
colation phenomenon. The AC and DC measurements
 A. Allaoui et al. / Composites Science and Technology 62 (2002) 1993–1998
Fig. 8. AC and DC conductivity as a function of CNT weight per-
centage at 100 Hz.
revealed the presence of a conduction threshold between
0.5 and 1 wt.%, a percolation threshold due to the con-
ductive path of interconnected nanotubes. The high
aspect ratio of CNTs allows reaching this threshold with
a small CNT fraction. The conductivity was calculated
at different frequencies (from 101 to 106 Hz). A plot of
the AC conductivity as a function of the frequency is
shown in Fig. 9. Two behaviors appeared: the insulators
with conductivity inversely proportional to the fre-
quency and the conductors with conductivity indepen-
dent of the frequency. The 0.5 wt.% composite behavior
is very similar to that of the matrix, except that its con-
ductivity is an order of magnitude higher. With that
weight percentage, the composite is still insulator. The 1
and 4 wt.% composites are conductor with conductivity
as high as respectively 103 and 6102 S/cm. The
addition of 1 wt.% of CNTs into the matrix is sufficient
to obtain a composite suitable for applications requiring
electrostatic discharge. From the electrical properties
measurements, the threshold of a conducting or inter-
connected network of the CNTs was reached at 1 wt.%.
In putting 4 wt.% CNTs, the conductivity was
improved only an order of magnitude compared to 1
Fig. 9. AC conductivity as a function of the frequency.
1997
wt.% samples. Same phenomenon was noticed on the
mechanical properties. There is some kind ‘‘saturation
effect’’. The results of this study suggest that it would
not be helpful to use high CNTs concentrations to
improve the mechanical properties of composites if they
are in random distribution. The upper limit is governed
by the distribution and the morphology (aspect ratio) of
the CNTs. The higher the alignment degree of CNTs,
the higher this value. The lower limit of the CNTs con-
centration can be determined easily by conductivity
measurement. The full domain of reinforcement and/or
improvement of the mechanical and electrical properties
is boarded by these two limit values. This kind of full-
courage models have been proposed in the case of duc-
tile-to-brittle fracture transition in the metal matrix
composites [28].
The CNTs, like conventional carbon fibers, carbon
black and graphite can reinforce the polymer matrix to
form advanced nanocomposites. Qian et al. [17] have
reported that by adding 1% of nanotubes into poly-
styrene matrices resulted in increasing of ever-all tensile
modulus and strength by approximately 42 and 25%,
respectively. Kymakis et al. [29] presented a percolation
threshold of approximately 11 wt.% SWNTs in a P3OT
polymer. As the nanotubes concentration increases
from 0 to 20 wt.%, the conductivity of the resulting
films increases by five orders of magnitude. Ezquerra et
al. [30] concluded that lower percolation thresholds and
higher conductivity values are observed upon compar-
ing carbon black (at 1.1 wt.%) and graphite (at 12
wt.%) composites due to the differences in particle sizes.
A very different picture emerges when studying carbon
fibers composites, the high fiber orientation gives rise to
materials with higher electric conductivity levels than
those found for particulate composites. Considering the
fact that the MWNTs in our work are in random
orientation and often in agglomeration (Fig. 7b), good
results have been obtained, both on the mechanical
reinforcement effect and on the electric conductivity
improvement. The preparation is simple, easy and at
low cost. The further work should be aimed at improv-
ing the dispersion and the alignment of the CNTs in the
matrix and the interfacial bonding between the CNTs
and the matrix.
4. Conclusion
This study has demonstrated the intrinsic potential of
the CNT. Small quantity addition can modify con-
siderably the mechanical and electrical behavior of a
soft polymer matrix. The exceptional mechanical prop-
erties, the high aspect ratio and the good conductivity of
MWNT have been used to improve the performance of
a rubbery epoxy matrix nanocomposites. Considerable
enhancement has been obtained with CVD MWNT and
1998 A. Allaoui et al. / Composites Science and Technology 62 (2002) 1993–1998
simple process. The addition of 1 and 4 wt.% of CNT
into the epoxy matrix has a remarkable effect on the
mechanical properties. The Young’s modulus and the
yield strength of the 1 wt.% composite have been
increased by respectively 100 and 200% compared to
the pure matrix. On the other hand, the CNTs confer
conductivity to the insulator matrix. An increase in the
conductivity by nine orders of magnitude was observed
in the range of 0–4 wt.% CNTs, as a result of a perco-
lation phenomenon. The critical wt.% threshold was
estimated to be between 0.5 and 1 wt.% CNTs. The
decrease of the slope of the normalized Young’s modulus
versus CNT wt.% curve between 1 and 4 wt.% has
confirmed that the homogeneity of the composite is a
critical point for mechanical behavior of the nano-
composites. The non-homogeneity of CNTs may have a
less effect on their electrical properties. The results of this
study suggest that it would not be helpful to use high
CNTs concentrations to improve the mechanical prop-
erties of composites if they are in random distribution.
Acknowledgements
The authors would like to thank the contribution of
Mr. R. Merle during his PPL training at ECP, Dr. Th.
Fournier of Lab. SPMS for Raman spectroscopy ana-
lyses, Mrs. S. Konate and Mrs. S. Bourgeois for sample
preparation and mechanical tests, Dr. N. Rieux and
Mrs. M. Marugan of Alstom at Massy for the electrical
AC measurements.
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