POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. (2008)

Published online in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/pat.1163

Preparation and properties of natural rubber composites

reinforced with pretreated carbon nanotubes
G. Sui1,2*, W. H. Zhong2, X. P. Yang1, Y. H. Yu1 and S. H. Zhao1
1

The Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology,
Beijing 100029, China
2
School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164, USA
Received 18 September 2007; Revised 15 December 2007; Accepted 16 March 2008

In order to achieve dramatic improvements in the performance of rubber materials, the development
of carbon nanotube (CNT)-reinforced rubber composites was attempted. The CNT/natural rubber
(NR) nanocomposite was prepared through solvent mixing on the basis of pretreatment of CNTs.
Thermal properties, vulcanization characteristics, and physical and mechanical properties of the
CNT/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR composite.
Through the addition of the CNTs treated using acid bath followed by ball milling with HRH
(hydrated silica, resorcinol, and hexamethylene tetramine) bonding systems, the crystallization
melting peak in differential scanning calorimetry (DSC) curves of NR weakened and the curing
rate of NR slightly decreased. Meanwhile, the over-curing reversion of CNT/NR nanocomposites was
alleviated. The dispersion of the treated CNTs in the rubber matrix and interfacial bonding between
them were rather good. The mechanical properties of the CNT-reinforced NR showed a considerable
increase compared to the neat NR and traditional CB/NR composite. At the same time, the CNT/NR
nanocomposites exhibited better rebound resilience and dynamic compression properties. The
storage modulus of the CNT/NR nanocomposites greatly exceeds that of neat NR and CB/NR
composites under all temperature regions. The thermal stability of NR was also obviously improved
with the addition of the treated CNTs. Copyright # 2008 John Wiley & Sons, Ltd.
KEYWORDS: carbon nanotubes; polymer; nanocomposites; mechanical properties; pretreatment

INTRODUCTION
To further strengthen the properties of current polymer
materials, the addition of many kinds of inorganic fillers has
already been researched and applied extensively. The size
and dispersion characteristics of inorganic particles have a
great effect on the comprehensive properties of polymer
composites. The application of nanometer fillers to polymer
materials is a promising channel for property modification.
Some nano-fillers have improved polymer performance
remarkably because of their high specific surface area
compared to conventional fibers or particles.13
As an important type of polymer material, rubber is widely
used due to its high and reversible deformability. Since the
essential modulus and strength of neat rubber are low, an
additional reinforcing phase is necessary for the practical
uses of rubber materials.4 Rubber is generally reinforced with
fibers, carbon blacks (CBs), and silicates. The full reinforcing
effects from these fillers are diminished due to their large size
and agglomeration, and application of the well-dispersed

*Correspondence to: G. Sui, The Key Laboratory of Beijing City on

Preparation and Processing of Novel Polymer Materials, Beijing
University of Chemical Technology, Beijing 100029, China.
E-mail: suig2004@yahoo.com.cn

nano-fillers into rubber to obtain beneficial mechanical and

physical properties is becoming crucial.5,6
In recent years, a great deal of attention has been paid to
carbon nanotubes (CNTs), which consist of rolled-up
graphite sheets built from sp2 carbon units, because CNTs
possess outstanding electrical, thermal, and mechanical
characteristics.710 As ideal reinforcing fillers in polymer
composites, CNTs are expected to provide a better
reinforcement effect compared to other nano-fillers due to
their inherent superior properties. As a consequence, CNTs
have been widely exploited in different kinds of polymers,
and considerable enhancements of electrical conductivity
and mechanical properties have been achieved in some
instances.1116 However, very little work has been done on
incorporating CNTs into rubber1719 because a large loading
is needed for reinforcement due to material characteristics of
rubber, i.e. the framework of the reinforcement phase must
be formed in rubber for enhancing the low modulus and
strength of a neat rubber. At present, the batch production of
CNTs is available because of the progress in developing
synthetic methods.20,21 So further study and development of
CNT-reinforced rubber nanocomposites are now feasible.
Some research on the pretreatment of CNTs and interfacial
modification techniques have been reported, which is helpful
to the preparation of CNT-filled rubber composites.2224 But
Copyright # 2008 John Wiley & Sons, Ltd.

G. Sui et al.

the dispersion of CNTs into rubber materials is still

problematic due to possible entanglement of the high
aspect ratio CNTs and the high viscosity of rubbers.
Although some studies on CNT-reinforced rubbers have
been performed, presently the overall performance of these
rubber nanocomposites has not reached the expected
potential.1719,2527
In our previous work, the powder CNT-reinforced rubber
composites were prepared using rubber suspension by
means of the spray drying process,28,29 and the overall
performance of these powder rubber nanocomposites was
increased. For further exploring the preparation and properties of solid rubber nanocomposites in bulk, the solvent
mixing assisted with a two-roll mill was adopted in this
study. After a great deal of exploratory experiments, some
good properties of the resulting rubber composites and
valuable results were obtained. The effects of the treated
CNTs on thermal properties, vulcanization characteristics,
and physical and mechanical properties of the natural rubber
(NR) composites were characterized in contrast to the
traditional CB/NR composites.

EXPERIMENTAL
Materials
The CNTs used in the experiments were prepared by
chemical vapor deposition (CVD) of propylene gas at 7008C
using Ni as a catalyst. The diameters of raw nanotubes vary
from 20 to 50 nm, and lengths vary from 100 to 1 mm. The
transmission electron microscope (TEM) image of raw CNTs
is shown in Fig. 1. The raw CNTs were purified in
hydrofluoric acid (HF) for 24 hr, and then cleaned them
continuously with de-ionized water until chemically neutral.
The purified CNTs were obtained after drying for 24 hr in a
vacuum oven to remove moisture. To create some functional
groups on the surface of the CNTs and improve the bonding
between the CNTs and NR matrix, the purified CNTs were
further treated with blended acid and HRH (hydrated silica,
resorcinol, and hexamethylene tetramine with a weight ratio
15:10:6) bonding systems. The dry tri-component system

Figure 1. TEM micrographs of raw CNTs.

Copyright # 2008 John Wiley & Sons, Ltd.

Figure 2. SEM micrographs of ball-milled CNTs.

comprising hydrated silica, resorcinol, and hexamethylene

tetramine, popularly known as HRH, was used as the
bonding system to achieve improved bonding between the
fillers and the rubber matrix.30,31 This effective and economical silica-containing bonding system was introduced in
CNT/NR nanocomposites in this study. The dry HRH
bonding system was prepared in the experiment. The
purified CNTs were dipped in a blended acid solution with
a volume ratio between nitric acid and sulfuric acid of 1:3.
The loading of CNTs was 1 g for 10 ml of blended acid
solution. The mixing solution was boiled and refluxed for
0.5 hr, and then the CNTs were carefully washed and
filtrated with de-ionized water until chemically neutral.
According to the analyzing results of previous infrared
spectroscopy,32,33 some functional groups such as hydroxyl,
carboxyl, and carbonyl were loaded on the CNT surface after
the blended acid treatment. The dry acid-treated CNTs were
blended with the HRH bonding systems with a weight ratio
of 25:3. To untie the entanglement of CNTs and facilitate the
co-mixing of CNTs and HRH bonding systems, the mixture
was milled for 0.5 hr in a ball-milling machine. Dry ball
milling was undertaken in a purified argon protect
atmosphere on a planetary ball mill. Steel balls with
diameters of 4 and 6 mm were used as a grinding medium.
Ball milling was conducted with the disk revolution speed of
180 rpm. The scanning electron microscope (SEM) image of
the ball-milled CNTs is shown in Fig. 2. It can be found that
after the ball-milling treatment, the CNTs were loose in bulk,
which was beneficial to the dispersion and penetration of
CNTs inside the rubber macromolecular chains. Furthermore, there was no drastic decrease in the aspect ratio of the
CNTs due to the short milling time (0.5 hr), which can insure
stress transfer ability in the composites. The chemical
properties of the ball-milled CNTs and the interaction
between the CNTs and NR are reported in another of our
papers.34 CB (N326) was supplied by Tianjin Carbon Black
Factory, China. The NR used in this study was a Standard
Malaysian Rubber 5, and provided by Beijing Academy of
Rubber Industry, China. The ball-milled CNTs and CB were
mixed with NR in experiment, respectively.
Polym. Adv. Technol. (2008)
DOI: 10.1002/pat

Preparation and properties of natural rubber composites

Table 1. The composition of NR composites

Constituent

Neat NR

CNT/NR

CB/NR

100phr
5.0phr
3.0phr
2.8phr
1.3phr
0.1phr
25phr

25phr

NR
Zinc oxide
Stearic acid
Sulfur
N-Cyclohexyl-2-benzothiazole-sulfenamide
2-Mercaptobenzothiazole
Ball-milled CNTs
CB

Preparation of the CNT/NR nanocomposites

The formulation of NR composites used in experiments is
shown in Table 1. The incorporation of treated CNTs into NR
was carried out by a solvent mixing method. Firstly, a certain
quantity of CNTs and NR was added into the toluene
solution, respectively. The solution of CNTs was sonicated
using a Brasonic1 Ultrasonic cleaner 1210 (Branson Ultrasonics Corporation) for 2 hr. Meanwhile, the solution of NR
was stirred and kept for certain duration until the rubber was
uniformly dissolved in the toluene. The toluene solution of
CNTs was subsequently dispersed into the solution of NR
with stirrer and ultrasonication simultaneously for 2 hr. Then
the dry CNT/NR mixture was obtained by evaporating the
solvent off at 808C under vacuum. Subsequently, the
preparation of CNT/NR nanocomposites was accomplished
by adding other ingredients including vulcanizing agent in
the formulation of composites in an open two-roll mill
(160
320 mm2) at room temperature with the nip gap of
about 1 mm. At the same time, the neat NR and CB/NR
composites were prepared in an open two-roll mill
(160
320 mm2) at room temperature by the traditional
mechanical mixing method.

Characterizations of the materials

Differential scanning calorimetry (DSC) analysis was performed using TA Instruments DSC 2910 in a nitrogen
atmosphere. The measurement was performed at temperature varying from 100 to 2008C with a heating rate of 108C/
min. The vulcanization behavior of neat NR and NR
composites were determined at the processing temperature
of 1508C using non-rotor rheometer with a model of
MM4130C2 produced by Beijing Huanfeng Mechanical
Factory, China. The microstructures of raw CNTs were
observed using JEM-200CX TEM produced by NEC
Company, Japan. The microstructures of treated CNTs and
the fracture surface morphologies of the cured NR composites were observed using S-3500N model SEM produced by
Hitachi Company, Japan. The neat NR and NR composites
were pressed using a hot press, and then cut into standard
specimens. The tests of all mechanical properties of NR
vulcanizates were carried out according to the ASTM
standards. Five specimens were measured for every case
and the average values were taken. The dynamic mechanical
performances of neat NR and NR nanocomposites were
studied using a Perkin-Elmer 7 dynamic mechanical
analyzer in the pressing mode at a frequency of 11 Hz.
The specimens were heated from 80 to 1008C at a heating
rate of 58C/min. The thermal stability of specimens was
Copyright # 2008 John Wiley & Sons, Ltd.

tested using a TGA 2050 thermogravimetric analyzer from

room temperature to 5008C at a heating rate of 108C/min
under nitrogen purge.

RESULTS AND DISCUSSION

Thermal properties of uncured rubber
To study the effect of the different fillers on the material
characteristics of NR, the uncured neat NR and NR
composites were subjected to DSC analyses. The DSC curves
are shown in Fig. 3. From these DSC curves, the thermal
properties of specimens were analyzed. The glass transition
region of NR occurred below 608C, and the exotherm peaks
between 160 and 2008C can be attributed to the vulcanization
reaction. The glass transition temperatures (Tg), the onset
temperature of curing (the temperature at the intersection of
the baseline and the tangent of the low temperature side
of the exotherm peak resulting from curing, Tc), and the peak
temperature of exothermal peak (Tp) were obtained and
listed in Table 2. Because functional groups introduced on
the surface of CNTs through the treatment with acid and ball
mill could result in physical adsorption and chemical
interaction between CNTs and rubber molecules, the
molecular mobilization of the rubber matrix in composites
was restricted. A slight increase in the Tg of NR with the
addition of fillers is indicated. At the same time, the
crystalline structure of NR was also affected by the activity
of the macromolecular chains. As NR is a type of semicrystalline material, the heat absorption peak appeared
around 308C in the curves due to the melting of the crystals.

Figure 3. DSC curves of neat NR and NR composites.

Polym. Adv. Technol. (2008)
DOI: 10.1002/pat

G. Sui et al.

Table 2. Thermal property parameters of NR and NR composites

NR
CNT/NR
CB/NR

Tg (8C)

Tc (8C)

Tp (8C)

TpTc (8C)

64.22
62.55
62.78

168.85
164.68
163.66

177.25
179.48
174.96

8.40
14.80
11.30

The fillers can obstruct the mobilization of the rubber

macromolecular chains, and prevent macromolecular segments from obtaining ordered alignment of the crystal
lattices. Moreover, the percentage of the rubber matrix in the
composites decreased because of the addition of the fillers.
Therefore, the degree of crystallinity of the NR composite
specimens decreased accordingly and the heat absorption
peaks in DSC curves weakened after the addition of the
fillers. After adding fillers, the value of TpTc of NR
composites showed an increasing tendency which indicated
that the vulcanizing rate of the NR matrix was decreasing.
Some studies indicated that the addition of CNTs could
absorb the basic accelerator species and delay vulcanization.17,35 Therefore, the vulcanizing rate of the NR matrix
decreased owing to the addition of CNTs in this study.

Vulcanization characteristics
Vulcanization curves of the neat NR and NR composites are
shown in Fig. 4. It can be seen that the scorch time of NR,
which is the measurement of premature vulcanization of
rubber, showed a slight reduction after the addition of the
fillers. Although some studies indicated that the addition of
CNTs could delay the onset of vulcanization,17,27 the
addition of the CNTs could improve the thermal conductivity of the NR material because of the superior thermal
conductivity of the CNTs, and could promote occurrence of
the vulcanization. Therefore, the effect of CNTs on the scorch
time might depend on the composition and microstructure of
rubber composites. During the curing reaction period, the
torque of rubber specimens gradually increased. The time for
reaching the maximum torque of the nanocomposite
containing treated CNTs was a little longer than the other
two specimens, which reflected that the vulcanizing rate of
CNT/NR nanocomposites is lower. This is consistent with
the results of DSC analyses. Meanwhile, the maximum
torque of the CNT/NR nanocomposite specimen was the
highest among the materials. This is because the CNTs with
ultra-high modulus effectively restricted the changes in
polymer molecular configuration, and then enhanced the
modulus of the rubber composites. In the last region of the
vulcanization process, the over-curing reversion of NR

reduced due to the addition of CNTs, when compared to

the neat NR and CB/NR composites. It would be an
advantage to eliminate the difference of crosslinking degree
between the surface and inside the thick rubber product
arising from the low thermal conductivity of the rubber
materials.

Physical and mechanical properties of NR

vulcanizates
Several important physical and mechanical properties of the
neat NR and NR composites are tested and listed in Table 3.
Compared to the neat NR and CB/NR composites, the
addition of the CNTs brought about remarkable increase in
hardness, tensile modulus, and tensile strength to the rubber
material. The rebound resilience and dynamic compression
properties of the CNT/NR nanocomposites are better than
that of CB-filled NR composites, which is beneficial for the
actual application such as tire, etc., under a dynamic
condition. The fracture morphology of the cured CNT/NR
nanocomposites is shown in Fig. 5. It is noted that no obvious
aggregates of treated CNTs in rubber matrix were found. A
few outcrops of the CNTs existed on the fracture surface,
which indicated that the strong interaction between the
CNTs and the rubber macromolecules in the NR composites

Figure 4. Vulcanizing curves of neat NR and NR composites.

Table 3. The mechanical properties of NR composites

Samples
Hardness (Shore A)
Modulus at 300% (MPa)
Tensile strength (MPa)
Elongation at break (%)
Rebound degree (%)
Goodrich compression permanent set (%)
Goodrich compression heat accumulation (8C)
Copyright # 2008 John Wiley & Sons, Ltd.

NR

CNT/NR

CB/NR

41  2
1.8  0.2
7.2  0.6
680  20

63  2
12.5  0.3
24.8  2.0
495  15
73  2
12.5  0.3
3.2  0.3

54  2
9.5  0.3
22.5  1.8
480  20
54  3
13.5  0.5
4.4  0.3
Polym. Adv. Technol. (2008)
DOI: 10.1002/pat

Preparation and properties of natural rubber composites

The effect of the fillers on the dynamic mechanical property

of NR material was analyzed by DMA in this work. The
elastic modulus (E0 ) and the loss factor (tan d) of the neat NR
and NR composites were characterized as functions of
temperature. Under an oscillating force, the resultant strain
in specimen depends upon both elastic and viscous behavior
of materials. The storage modulus reflects the elastic
modulus of the rubber materials which measures the

recoverable strain energy in a deformed specimen, and the

loss factor is related to the energy damped due to energy
dissipation as heat.
The storage modulus of the neat NR and NR composites
versus temperature curves is shown in Fig. 6. It is found from
Fig. 6(a) that the storage modulus of the CNT/NR
nanocomposites is higher than that of the neat NR and
CB/NR composites from low temperature to high temperature regions. The high modulus and specific surface areas of
CNTs enhance the stiffness of the NR, which results in an
increment of storage modulus of the CNT/NR nanocomposite. At low temperature, the modulus of the neat
NR exhibits a high value due to the semi-crystalline
characteristic of NR, and a small variation of modulus of
NR appeared after the addition of fillers. With the increase in
temperature, although the E0 of all specimens manifested
declining trends, it is evident that stiffness of NR increases as
a result of addition of fillers. A shift of rapid decreasing
region of E0 towards higher temperature can be seen for NR
after adding the CNTs and the reinforcing effect is more
obvious above the Tg of NR. The storage modulus of CNT/
NR nanocomposite in the rubbery region is the highest
among all specimens and keeps the steady value within the
testing temperature.
Figure 7 shows the temperature dependence of tan d of
neat NR and NR composites. The position of tan d peak in tan
dtemperature curve can also be used to identify the Tg of the
rubber materials. It can be seen that the peak of tan d of the NR
composite slightly shifts to a higher temperature compared to
that of the neat NR. It denotes that the mobilization of rubber
macromolecules is restricted due to the addition of fillers. The
enhancement of tan d peak position of NR composites
corresponds to the DSC experiment results. The tan d value of
NR composites is related to both NR and fillers material
characteristics. The adding of CNTs reduces the percentage
of the NR in composites, which lowers hysteresis loss of
the rubber under an oscillating force. Therefore, the height of
the tan d peak of NR decreases after the adding of fillers. In
general, the higher tan d value of a rubber from 20 to 108C
can be used to predict the preferable anti-skid properties of
rubber material under wet conditions, and the small tan d

Figure 6. The dynamic storage modulus as a function of

temperature for neat NR and NR composites.

Figure 7. The loss factor as a function of temperature for

neat NR and NR composites.

Figure 5. SEM micrograph of CNT/NR nanocomposites.

was formed. Therefore, the CNTs could carry stress
throughout the rubber matrix, and play an effective
reinforcement role in the resulting nanocomposites. Predictably, the NR composites containing the CNTs possessed
the best mechanical properties among these specimens. This
CNT/NR nanocomposite exhibited great enhancements in
Shore A hardness, tensile modulus, and tensile strength by
16, 32, and 10%, respectively, compared to NR composites
reinforced with the same loading level of CB. The theoretical
modeling studies on the mechanical properties of CNT/NR
composites will be the subject of a future work.

Dynamic mechanical properties of NR

vulcanizates

Copyright # 2008 John Wiley & Sons, Ltd.

Polym. Adv. Technol. (2008)

DOI: 10.1002/pat

G. Sui et al.

process of polymer materials affects the thermal stability

of CNTs composites.

CONCLUSIONS

Figure 8. TGA curves of neat NR and NR composites.

value of a rubber in the region of 50608C implies the low

rolling resistance of rubber material.36,37 Therefore, it can be
deduced from Fig. 6(b) that compared to CB, the CNTs can
offer rubber materials significantly better anti-skid properties and low rolling resistance, which is of great value for
ideal tire materials.

Thermal stability of NR vulcanizates

Figure 8 shows TGA curves of the neat NR and NR
composites. By comparing the weight loss as a function of
temperature, the effect of CNTs on the thermal stability of
NR can be analyzed. Although there is no obvious variation
at the onset temperature of thermal degradation for different
specimens, a shift of rapid degradation region towards
higher temperature can be seen for NR after adding the
fillers, especially adding the CNTs. Meanwhile, the weight
loss of CNT/NR nanocomposites at the same temperature is
the smallest among all studied specimens. The reason is that
CNTs can impose the restriction on the mobilization of
rubber macromolecules and conduct heat homogeneously
and avoid the heat concentration. Therefore, the thermal
stability of NR was further improved by adding CNTs
compared to CB/NR composites.
However, inconsistent results had been reported by Puglia
et al.,38 where they found the thermal degradation rate
increased and the onset temperature of thermal degradation
decreased for epoxy resin after the addition of CNTs. It was
attributed to the high thermal conductivity and specific
surface areas of CNTs which can accelerate the transfer of
heat. This interpretation is not completely substantiated. The
improved thermal stability of PMMA was also proved in
thermal degradation experiment of CNT/PMMA.39 The
study of Troitskii et al. indicated that C60 can combine with
free radicals produced in the thermal degradation process of
PMMA, and form relative steady macro-free radicals.40
Therefore, the CNTs can also combine with free radicals
produced in the thermal degradation process of NR, forming
relative steady-free radicals, which then delay the progression of thermal degradation. Because the thermal
degradation of epoxy usually proceeds according to a cation
mechanism and the thermal degradation of PMMA and NR
proceeds according to a free radical reaction, the different
chemical mechanism during the thermal degradation
Copyright # 2008 John Wiley & Sons, Ltd.

The CNT/NR nanocomposites were fabricated through

solvent mixing assisted with a two-roll mill. With the
addition of the treated CNTs, Tg of the resulting composites
increased slightly. At the same time, the area of crystallization melting peak of NR in DSC curves and curing rate of
NR decreased. Compared to the neat NR and traditional CB/
NR composite, the over-curing reversion of CNT/NR
nanocomposite abated. The dispersion of the treated CNTs
in the rubber matrix and interfacial bonding between them
were satisfactory. The mechanical properties of the CNT/NR
nanocomposites showed a great enhancement compared to
the neat NR and CB/NR composite. The rebound resilience
and dynamic compression properties of NR loaded with
CNTs are better than that of CB/NR composites. The storage
modulus and thermal stability of NR were also markedly
improved by adding treated CNTs. In conclusion, the NR
nanocomposites loaded with the treated CNTs exhibited
excellent overall performance improvements due to the
reinforcement effect of the high aspect ratio functionalized
CNTs. Furthermore, advanced rubber nanocomposites with
improved comprehensive performance have demonstrated
the potential for expanded future industrial applications in
bulk scenarios through a facile technique which improves the
industrial processing, a requirement for high quality
industrial-scale production. In summary the results indicate
(1) improved performance for the eventual NR products, and
(2) improved processing for production (less complicated
procedures, higher quality, new manufacturing efficiencies).

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Polym. Adv. Technol. (2008)

DOI: 10.1002/pat