Materials Science and Engineering A352 (2003) 344
/348

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Short communication

Reinforcement of rubbery epoxy by carbon nanofibres

P. Richard a, T. Prasse a, J.Y. Cavaille a, L. Chazeau a,*, C. Gauthier a, J. Duchet b
a
GEMPPM, INSA de Lyon, 20 av. A. Einstein, Villeurbanne Cedex 69621, France
b
LMM, INSA de Lyon, 20 av. A. Einstein, Villeurbanne Cedex 69621, France

Received 15 November 2002; received in revised form 21 November 2002

Abstract

Experimental results on the reinforcement of rubbery epoxy by carbon nanofibres (CNFs) are presented. The modulus increase,
measured above and below the glass transition temperature for nanofibre contents up to 10 wt.%, is low. The interest of CNF is in
the improvement of the ultimate stress and strain. Both are largely increased, even for very low fibre content, and are improved
compared with the reinforcement obtained with carbon blacks.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Carbon nanofibre; Rubber; Mechanical properties

1. Introduction Shaffer and Windle [1] were able to process carbon

The efficiency of fillers in polymer composites is
known to strongly depend on the aspect ratio of the
fillers and on their size. New fillers such as carbon
nanotubes (CNTs) and carbon nanofibres (CNFs)
present both advantages: their aspect ratio is extremely
high (more than 1000) and their nanoscopic scale leads
to an important interface area. CNT and CNF mainly
differ by their size and intrinsic longitudinal tensile
modulus. CNT can be both single-wall or multi-wall
nanotube, with a diameter ranging from 1 to 20 nm and
are supposed to have a modulus around 1 TPa. CNF
have a typical dimension of 100
/200 nm. Due to their
bamboo-like structure, they have a lower modulus of
only few tens of GPa but are much easier to produce
than CNT.
All these properties combined with a low density offer
scope for the development of nanotube or nanofibre-
reinforced composites materials. Some papers already
report results about nanotube-reinforced composites:
* Corresponding author. Tel.: /33-4-72-43-61-30; fax: /33-4-72-
43-85-28.
E-mail address: laurent.chazeau@insa-lyon.fr (L. Chazeau).
0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5093(02)00895-X
nanotube/polyvinyl-alcohol composites films and Qian
et al. [2] prepared composites with a polystyrene matrix.
Other matrices such as polymethylmethacrylate and
especially epoxy resin have also been evaluated [3
/5].
In the case of nanofibre, some papers report experi-
mental studies on composites with thermoplastic matrix
such as polypropylene, polyethylene and polycarbonate
[6
/9].
In a glassy or semi-crystalline matrix (whose rigidity is
relatively high), the flexibility of these nanofibres might
be a drawback as a mean to increase the modulus of the
composite, at least in the case of isotropic dispersion.
This is indeed confirmed by the low modulus increase
measured as function of fibre content in the composites
cited previously [6
/9]. But the possibility for the fibres
to be entangled could favour the formation of a network
whose efficiency should be visible at large deformation,
when this network is stretched. That is the reason why
our work is focused on a rubbery matrix, which allows
relatively large deformation at break. Here we report
experimental results of dynamic mechanical analysis
(DMA) and tensile measurements on these materials as
compared with the mechanical properties of a carbon
black composite with the same matrix.
 P. Richard et al. / Materials Science and Engineering A352 (2003) 344
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2. Materials
For this study, untreated carbon nanofibres (Pyro-
graf-IIITM) were supplied by Applied Sciences, Inc.
These nanofibres are produced by chemical vapour
deposition process. They have circular cross-sections
with diameters around 200 nm [10]. Kilogram quantities
are available from the manufacturer, enabling compo-
site development at an industrial scale. A transmission
electron microscopy image of these fibres is reported in
Fig. 1. The high aspect ratio is confirmed. The fibres
have a bamboo-like structure: they are made of an
assembly of relatively straight tubes, with variable
lengths, linked by irregular parts with structural defects.
The matrix is based on an epoxy resin (DGEBA from
CIBA-GEIGY) and a Jeffamine D2000 hardener
(HUNTSMAN). With stoichiometric conditions and
optimised curing procedure, the glass transition tem-
perature of this soft epoxy is around 238 K. The high
molecular weight of the hardener allows to achieve an
elongation at break around 22% at room temperature.
This value is small compared with that of the classical
elastomer such as natural rubber (up to 600%). How-
ever, the mechanical behaviour of this rubbery epoxy
matrix can be roughly described like that of an
elastomer.
A typical preparation of the composite is as follows: a
given weight of carbon fibre powder is sonicated a few
minutes in the hardener. Then the resin is added in
stoichiometric proportion and the system is convention-
ally mixed during 1.25 h at 323 K. The blend is then
introduced in a circular aluminium mould of 6 cm
diameter and heated 22 h at 373 K followed by 5 h at
398 K. Afterwards, the sample is removed from the oven
and cooled at room temperature.
Samples with different weight fraction of carbon
nanofibres have been prepared (1, 3, 5, 7 and 10
wt.%). The same procedure was also used to incorporate
Fig. 1. TEM observation of the nanofibres from a dried cast toluene
solution.
345
5 wt.% of carbon black (N234 from Cabot) within the
epoxy resin.
3. Structural characterisation
To check the dispersion quality of the fillers in the
matrix, scanning electron microscopy (SEM) on frac-
tured surfaces was carried out. All composites show a
good dispersion of the fillers as shown in Fig. 2 for 5
wt.% of nanofibres. This is provided by the electrostatic
stabilisation of the fibres in the resin before curing,
which can be evidenced by electrophoresis measure-
ments [11].
4. Mechanical characterisation
DMA measurements were performed in torsion mode
(Mécanalyseur from Metravib S.A.) at a fixed frequency
(0.1 Hz) from 173 to 373 K with a heating rate of 1 K
min 1. Sample dimensions were around 15/5 /1.5
mm3. The storage modulus G ? and the loss modulus G ??
are plotted as a function of temperature in Figs. 3 and 4,
respectively.
The main mechanical relaxation is not modified by
the presence of the carbon nanofibres. The temperature
of the maximum of the G ?? peak is constant and about
230 K, while its magnitude is unchanged. This relaxa-
tion process is associated to the glass transition phe-
nomenon. It has been confirmed by differential scanning
calorimetry measurement (Perkin
/Elmer DSC7 appa-
ratus with a heating rate of 10 K min 1) that the glass
transition temperature (around 238 K) is independent
on the percentage of filler.
Fig. 2. SEM photography of the fracture surface (end of a tensile test)
of a CNF-reinforced epoxy resin (5 wt.% CNF).
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Fig. 3. Elastic shear modulus G ? as a function of temperature (f /0.1 Hz) for different CNF-reinforced epoxy resins.

In the glassy state, considering the range of filler
concentration studied, the increase of the elastic mod-
ulus is quasi-linear with a slope of 2.2Gm (Gm being the
matrix modulus) as shown in Fig. 5a. At T /296 K, in
the rubbery plateau, the evolution is still linear but this
time with a slope of 6Gm (cf. Fig. 5b).
Tensile tests were performed at ambient temperature
on an MTS device (MTS 1/ME) with a constant cross-
head speed equal to 5 mm min 1. The samples were cut
in normalised H4 shape. The deduced stress
/strain
curves are presented in Fig. 6. Each curve of Fig. 6
corresponds to the average of five measurements. The
increase of modulus is consistent with the measurements
from DMA. Below Tg, the reinforcement in terms of
modulus is low. These results are comparable with that
obtained with polycarbonate composites [8]. In both
cases, the increase of modulus for 10% of fibre content is
about 40%. It is not surprising due to the amount of
added fillers. The flexibility of the fibres and the bad
interface with the matrix may also be involved. More-
over, it has already been observed that the nanoscopic
size of the fillers does not lead to an increase of modulus
higher than that obtained with micro-size fillers, when
the matrix is in the glassy state [12,13]. The reinforce-
ment in the rubbery plateau is more important, due to
the larger contrast of modulus between the fibres and
the matrix, combined to a large aspect ratio. It is,
however, difficult to conclude on the effect of the
nanoscopic size of these fibres.
The addition of nanofibres also increases elongation
and stress at break. For only 5% wt. of nanofibres,
elongation at break increases of about 100% while a
270% increase is found for stress. Such significant
improvement could be the consequence of strong filler/
matrix interaction. However, SEM photography of the
fracture surface obtained after a tensile test shows fibres

Fig. 4. Loss modulus G ?? as a function of temperature (f /0.1 Hz) for different CNF-reinforced epoxy resins.
 P. Richard et al. / Materials Science and Engineering A352 (2003) 344
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Fig. 5. (a) Elastic shear modulus G ? of CNF-reinforced epoxy resins as a function of CNF weight fraction, at 200 K (below Tg); (b) elastic shear
modulus G ? of CNF-reinforced epoxy resins as a function of CNF weight fraction, at 296 K (in the rubbery plateau).

pulled out the matrix (cf. Fig. 2). This is an indication of

a weak adhesion at the interface.
As a comparison, tensile measurements have been
performed on a carbon black filled composite (see Fig.
6). Actually, the surface chemistry of the carbon black
and the carbon nanofibres are similar enough to assume
that they led to the same interactions with the matrix.
Compared with the matrix, the carbon black filled
composites display an increase of the elongation and
the stress at break of 20 and 75%, respectively. This
increase of elongation at break is five times less than
what is found with carbon nanofibres. It clearly shows
that carbon nanofibres are more efficient reinforcing
fillers than CB.

5. Conclusion

CNF/rubbery epoxy matrix composites have been

processed with different CNF contents, up to 10 wt.%.
The good stabilisation of the CNF in the Jeffamine leads
to a good dispersion of the CNF in the final composite.
The increase of modulus with CNF content is low, in
particular below the glass transition temperature. The
Fig. 6. Tensile tests performed on CNF-reinforced epoxy resins with
different CNF weight content. Comparison with a carbon black-
reinforced epoxy resin (T/296 K).
348 P. Richard et al. / Materials Science and Engineering A352 (2003) 344
/348
interest of CNF seems to be in the improvement of the
ultimate properties. The ultimate strain and stress are
largely increased, even for very low fibre content, and
are much higher than those obtained with carbon blacks
(with the same concentration). For nanofibres, like for
carbon blacks, the reasons for this improvement are not
clear. The better efficiency of the nanofibres could be
due to some ‘‘entanglement’’ effects, but this point has
to be confirmed by complementary studies. For in-
stance, it could be interesting to compare these materials
with nanotube composites made with the same matrix
and the same process. This could also address the
question of the existence of a ‘‘nano’’ effect.
Acknowledgements
This work is made in the frame of the European CNT-
Network. We are indebted to Prof. D. Wagner and Prof.
K. Schulte who provided us the CNF. We thank C.
Menissez, J. Ramier and B. Van de Moortele for their
technical support.
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