Professional Documents
Culture Documents
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
G. Sui et al.
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
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
G. Sui et al.
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
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
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
G. Sui et al.
CONCLUSIONS
REFERENCES
1. Osman MA, Atallah A, Muller M, Suter UW. Reinforcement
of poly(dimethylsiloxane) networks by mica flakes. Polymer
2001; 42: 65456556.
2. Cooper CA, Ravich D, Lips D, Mayer J, Wagner HD. Distribution and alignment of carbon nanotubes and nanofibrils in
a polymer matrix. Compos. Sci. Technol. 2002; 62: 11051112.
3. Kim JS, Reneker DH. Mechanical properties of composites
using ultrafine electrospun fibers. Polym. Compos. 1999; 20:
124131.
4. Frogley MD, Ravich D, Wagner HD. Mechanical properties
of carbon nanoparticle-reinforced elastomers. Compos. Sci.
Technol. 2003; 63: 16471654.
5. Yatsuyanagi F, Suzuki N, Ito M, Kaidou H. Effects of secondary structure of fillers on the mechanical properties of
silica filled rubber systems. Polymer 2001; 42: 95239529.
6. Alberola ND, Benzarti K, Bas C, Bomal Y. Interface effects in
elastomers reinforced by modified precipitated silica. Polym.
Compos. 2001; 22: 312325.
7. Iijima S. Helical microtubules of graphic carbon. Nature 1991;
354: 5658.
8. Bower C, Rosen R, Jin L, Han J, Zhou O. Deformation of
carbon nanotubes in nanotube-polymer composites. Appl.
Phys. Lett. 1999; 74: 33173319.
9. Ajayan PM, Schadler LS, Giannaris C, Rubio A. Singlewalled carbon nanotube-polymer composites: strength
and weakness. Adv. Mater. 2000; 12: 750753.
10. Lourie O, Wagner HD. Evaluation of Youngs modulus of
carbon nanotubes by micro-Raman spectroscopy. J. Mater.
Res. 1998; 13: 24182422.
11. Stephan C, Nguyen TP, Chapell ML, Lefrant S, Journet C,
Bernier P. Characterization of singlewalled carbon nanotubes-PMMA composites. Synthetic Met. 2000; 108: 139149.
Polym. Adv. Technol. (2008)
DOI: 10.1002/pat
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.