Composite Structures 75 (2006) 496–500

www.elsevier.com/locate/compstruct

Effect of multi-wall carbon nanotubes on the mechanical

properties of natural rubber
A. Fakhru’l-Razi a, M.A. Atieh a,*, N. Girun a, T.G. Chuah a,
M. El-Sadig b, D.R.A. Biak a
a
Department of Chemical and Environmental Engineering, University Putra Malaysia, 43400 UPM, Serdang, Malaysia
b
Department of Aerospace Engineering, University Putra Malaysia, 43400 UPM, Serdang, Malaysia

Available online 27 June 2006

Abstract

Multi-walled carbon nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first effort to achieve
nanostructures in MWNTs/NR nanocomposites were formed by incorporating carbonnanotubes in a polymer solution and subsequently
evaporating the solvent. Using this technique, nanotubess can be dispersed homogeneously in the NR matrix in an attempt to increase
the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, tear
strength, elongation at break and hardness were studied. Mechanical test results show an increase in the initial modulus for up to 12
times in relation to pure NR. In addition to mechanical testing, the dispersion state of the MWNTs into NR was studied by transmission
electron microscopy (TEM) in order to understand the morphology of the resulting system. According to the present study, application
of the physical and mechanical properties of carbon nanotubes to NR can result in rubber products which have improved mechanical,
physical and chemical properties, compared with existing rubber products reinforced with carbon black or silicone.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Carbon nanotubes; Natural rubber; Nanocomposite; Young’s modulus

1. Introduction
Research on new materials technology is attracting the
attention of researchers all over the world. Developments
are being made to improve the properties of the materials
and also to find alternative precursors that can bestow
desirable properties on the materials. Great interest has
recently developed in the area of nanostructured carbon
materials. Carbon nanostructures are becoming commer-
cially important with interest growing rapidly over the dec-
ade or so since the discovery of buckminsterfullerene,
carbon nanotubes, and carbon nanofibers. Carbon nano-
tubes (CNTs) exhibit unique mechanical, electronic and
magnetic properties, which have caused them to be widely
studied [1–3]. CNTs are probably the strongest substances
*
Corresponding author. Tel.: +60 3 89466185.
E-mail address: fakhrul@eng.upm.edu.my (M.A. Atieh).
that will ever exist with a tensile strength greater than steel,
but only one sixth the weight of steel [4]. Iijima (1991) first
discovered carbon nanotubes (CNTs) using the arc dis-
charge method [5,6]. Following this discovery, a number
of scientific researches have been initiated and variable
methods have been used to synthesis CNTs namely, arc dis-
charge, laser vaporization [7] and catalytic chemical vapor
deposition of hydrocarbons [8–10]. Since carbon–carbon
covalent bonds are one of the strongest in nature, a struc-
ture based on a perfect arrangement of these bonds oriented
along the axis of nanotubes would produce an exceedingly
strong material. Nanotubes are strong and resilient struc-
tures that can be bent and stretched into shapes without cat-
astrophic structural failure in the nanotube [11,12]. The
Young’s modulus and tensile strength rival that of diamond
(1 TPa  200 GPa, respectively) [13–16]. This fantastic
property of mechanical strength allows for these structures
to be used as possible reinforcing materials. Just like current

0263-8223/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compstruct.2006.04.035
 A. Fakhru’l-Razi et al. / Composite Structures 75 (2006) 496–500 497

carbon fiber technology, these nanotubes reinforcement
would allow for very strong and light materials to be pro-
duced. These properties of CNTs attracted the attention
of scientists all over the world because of their high ability
for absorbing load applied to nanocomposite materials
[17,18].
Multi-walled carbon nanotubes (MWNTs) will be used
to prepare natural rubber (NR) nanocomposites. Our first
effort to achieve nanostructures in MWNTs/NR nanocom-
posites was by incorporating nanotubes in a polymer solu-
tion and subsequently evaporating the solvent. Using this
technique, nanotubes will be dispersed homogeneously in
the NR matrix in an attempt to increase the mechanical
properties of these nanocomposites. The properties of the
composites such as tensile strength, tensile modulus and
elongation at break were studied.
• Mixing of rubber with nanotube solution: This is the final
step in the melt preparation process and basically
involves thorough mixing of the solutions prepared in
the first and second stages, resulting in a solution that
consists of a good blend of nanotubes in the rubber.
• Pressing and testing the sample: The nanocomposite
material (rubber with CNTs) was pressed using hot
press and cut into standard shape. Finally instron
machine was used to characterize the mechanical prop-
erties of the sample.
3. Results and discussion
Carbon nanotubes have been produced by using floating
catalyst chemical vapour deposition (FC–CVD). The

2.5 Blank SMR CV60

2. Experimental 1% CNT
3% CNT
The carbon nanotubes were added to natural rubber as 5% CNT
2 7% CNT
filler. The natural rubber was used in this study is a Stan- 10% CNT
dard Malaysian Rubber Constant Viscosity 60 (SMR
CV60). The preparation of the nanocomposites was carried
Stress (MPa)

out by a solvent casting method using toluene as a solvent. 1.5

The added amounts of the carbon nanotubes were 1%, 3%,
5%, 7% and 10% of 10 g of the total weight.
The process of making natural rubber/nanotubes as 1
nanompcosite material can be divided into the following
four processes;
0.5
• Dispersion of nanotubes: This phase involves the dissolu-
tion/dispersion of CNTs in a solvent (in this case, tolu-
ene) in order to disentangle the nanotubes that typically 0
0 1 2 3 4 5 6 7 8
tend to cling together and form lumps, making it diffi- Strain (mm/mm)
cult to process. For this, a certain quantity of carbon
nanotubes was added to a specific amount of toluene Fig. 3.1. Stress–strain of SMR CV60 with different percentage of CNTs.
solution after carefully weighing it using a weighing bal-
ance (in order to maintain a specific weight ratio of
nanotubes in the solution). This solution was further 2.6
sonicated using a mechanical probe sonicator (Branson 2.4
sonifier), capable of vibrating at ultrasonic frequencies 2.2
in order to induce an efficient dispersion of nanotubes. 2
For this study, different CNT solutions were prepared
Young modulus (MPa)

1.8
(containing CNTs in various weight ratios): (i) 1 wt%
1.6
CNTs containing in 10 ml of toluene solution, (ii)
3 wt% CNTs in 10 ml of toluene solution, (iii) 5 wt% 1.4
of CNTs in 10 ml of toluene solution, and (iv) 7 wt% 1.2
CNTs in 10 ml of toluene solution and 10% of CNTs 1
in 10 ml of toluene solution. 0.8
• Dissolution of the rubber: This stage involves the dissolu-
0.6
tion of the Rubber in a suitable organic solvent (tolu-
0.4
ene). A specific amount of rubber (in this case, 10 g)
was added to a certain quantity of organic solvent 0.2

(500 ml of toluene) thereby maintaining a desired rubber 0

0 1 2 3 4 5 6 7 8 9 10 11
weight ratio. This mixture was stirred and kept for cer-
% of CNT IN SMRCV60
tain duration of time until the rubber gets uniformly dis-
solved in the solvent. Fig. 3.2. Young modulus of SMR CV60 at different percentage of CNTs.
498 A. Fakhru’l-Razi et al. / Composite Structures 75 (2006) 496–500

production conditions of pure CNTs have been fixed at
reaction temperature 850 C, Hydrogen flow rate 300 ml/
min and reaction time 45 min. The diameters of the CNTs
were varied from 2 to 30 nm and the average length was at
70 lm.
3.1. Effect of CNTs on the stress–strain value of natural
rubber
The stress–strain curve of different percentages of pure
carbon nanotube (1, 3, 5, 7 and 10 wt% of CNTs) with

Fig. 3.3. Tem image of CNTs in SMR CV60 (a) 1 wt% of CNTs (b) 3 wt% of CNTs (c) 5 wt% of CNTs (d) 7 wt% of CNTs and (e) 10 wt% of CNTs.
 A. Fakhru’l-Razi et al. / Composite Structures 75 (2006) 496–500
SMR CV60 is presented in Fig. 3.1. The tensile strength
radically increases as the amount of CNTs concentration
increases. The general tendency is that the stress level is
increased by the addition of CNTs which play the role of
reinforcement. From these results, it is deduced that the
reinforcing effect of CNTs is very marked. As the CNTs
content in the rubber increases, the stress level gradually
increases but at the same time the strain of the nanocom-
posites decreased.
The increment of stress level was due to the interaction
between the CNTs and the rubber. A good interface
between the CNTs and the rubber is very important for a
material to stand the stress. As described above CNTs
are highly strong materials compared to other types of
fillers thus making them good candidate as nanofillers.
Under load, the matrix distributes the force to the CNTs
which carry most of the applied load.
3.2. Effect of CNTs on the Young’s modulus
of SMR CV60
The same phenomenon was observed for Young’s mod-
ulus. The Young’s modulus of the composites normalized
with that of the pure matrix is presented in Fig. 3.2. The
result indicated that the Young’s modulus increased with
increase in the amount of the CNTs. However, at 1 and
3 wt% of CNTs, the increment of the modulus is not as
high as that of the tensile strength. The same value of the
modulus and the tensile strength were observed at 5 wt%
of CNTs. While at 7 and 10 wt% the modulus was higher
than the tensile strength. At 1 wt% of CNTs the young
modulus increased by 25.95% compared to the pure SMR
CV60. At 3 wt% CNTs the increase in the young’s Modu-
lus was 141.92%. Further increase in the amount of CNTs
from 5, 7 to 10 wt% increased the young Modulus by
305.55%, 679.85% and 850.375% respectively compared
to the pure SMR CV60.
3.3. Tem observations
The dispersion of CNTs in the SMR CV60 was charac-
terized by using Transmission Electron Microscopy
(TEM). A thin section of about 100 nm was cut with a dia-
mond knife at 120 C to observe the dispersion of CNT
inside the rubber. In Fig. 3.3(a) short and long CNTs are
seen. It was shown in this figure that the CNTs are homog-
enously distributed in the SMR CV60. However the CNTs
are open at both ends during the dispersion of the CNTs
into the toluene, using ultrasonic frequency vibration and
during the mixing of CNTs in the SMR CV60 by mechan-
ical stirring. The distance between the CNTs in the matrix
is wide and that make them well oriented with little inter-
face interaction between them. The size of the CNTs in
the TEM shows varying diameter from 2–20 nm and vary-
ing length which can be either short or long. Fig. 3.3(b)
shows the image of a 3% CNTs, dispersed in the matrix,
the orientations of the CNTs in the SMR CV60 had
499
become less oriented and more randomize. The figure also
shows that the CNTs are open at the end. Fig. 3.3(c)–(e)
shows the CNTs in the SMR CV60 at 5%, 7%, and 10%
respectively. The images show that by increasing the
amount of the CNTs in the SMR CV60 the orientations
of the CNTs become more randomize. The figures also
indicate that the orientation of the CNTs plays a very
important role to stress and strain of the matrix. Another
factor considered important on the mechanical properties
is the aspect ratio; if the aspect ratio is high the strength
of the material will increase.
4. Conclusion
In summary, we have demonstrated the successful fabri-
cations of nanocomposite consisting of Natural Rubber
matrix with 1–10 wt% multi walled carbon nanotubes
(MWCNTs). Carbon nanotubes were applied for interface
nano-reinforcement in advanced commercial carbon/rub-
ber composite and this is the first attempt such a work is
reported. The preparation of the nanocomposites was car-
ried out by a solvent casting method using toluene as a sol-
vent. It is clear from the figure that the maximum stress of
pure SMR CV60 is 0.2839 MPa. When 1 wt% of CNTs
were added to the rubber the stress level for the nanocom-
posite material increased from 0.2839 to 0.56413 MPa.
Addition of the wt% CNTs to the natural rubber increased
the stress level gradually as shown in the Fig. 3.1. At
10 wt% of CNTs the stress value obtained reached
2.55 MPa which is 9 times that of pure natural rubber.
The result indicates that, by increasing the amount of
CNTs into the rubber the ductility decreased and the mate-
rial become stronger and tougher but at the same time
more brittle. The clear trend observed here is that as nano-
tube load increases, the fiber breaking strain decreases. It
also shows that the highest strain value was obtained for
the nanocomposite at 1 wt% of the CNTs. This composite
at this percentage is more ductile and more elastic com-
pared to other percentages of CNTs. The strain value at
1% was almost the same as for pure rubber. Minimum
strain value was obtained at 10% of CNTs; the strain value
decreased almost 2.5 times, i.e., 2.94 compared to pure rub-
ber which was 7.34.
Acknowledgements
The authors gratefully acknowledge the National Inten-
sification of Research in Priority Areas (IRPA) for their
financial support and Universiti Putra Malaysia for their
support of this research.
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