Swelling and mechanical behaviors of carbon nanotube/poly

(vinyl alcohol) hybrid hydrogels

Xin Tong
a,

, Jingjing Zheng
a
, Yancheng Lu
a
, Zhenfang Zhang
a
, Huiming Cheng
b
a
Materials Science and Engineering College, Shenyang Ligong University, Shenyang 110168, China
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Science, Shenyang 110016, China
Received 28 March 2006; accepted 22 July 2006
Available online 14 August 2006
Abstract
In this paper, carbon nanotubes (CNTs) were added into poly(vinyl alcohol) (PVA) hydrogels to modify their mechanical properties. A series of
CNT/PVA hybrid hydrogels were prepared by freezing/thawing method. The mechanical and swelling properties of all hybrid hydrogels are better
than those of the original PVA hydrogel. Especially, for CNTP-0.5 specimen with 0.5% w/w CNTs, its tensile modulus, tensile strength and strain
at break are increased by 78.2%, 94.3% and 12.7%, respectively. And its swelling behavior is different from that of the pure PVA hydrogel. Its
final swelling ratios at room temperature and 310 K are increased by 35.7% and 44.9%, respectively.
2006 Elsevier B.V. All rights reserved.
Keywords: Carbon nanotubes; Nanocomposites; Swelling; Mechanical properties
1. Introduction
The research on the application of carbon nanotubes (CNTs)
has been carried out for more than ten years due to their unique
mechanical and electrical properties. Since CNTs was success-
fully made soluble in both organic solvents [1] and in aqueous
solutions [2], their application in the biological field has gained
more and more attention. Bianoco and Prato's group demon-
strated that CNTs can serve as useful scaffolds for new
nanobiotechnological applications [3]. Especially, bioactive
materials endowed with immunological properties can be
prepared by conjugating bioactive peptides to the external
walls of the CNTs. Also, CNTs are considered as an ideal
candidate for drug delivery [4] and biochemical sensing [5]. Li
et al. added CNTs into gelatin and finally found that the hybrid
hydrogels with CNTs had the ability to separate protein [6].
Except for these, it was found that CNTs had the actuator
property and could be used as artificial muscles [79]. Koerner
et al. filled thermoplastic elastomers with CNTs. The results
show the resulting nanocomposites have the remote actuator
and good shape-recovery properties [10]. In this paper, CNT/
poly(vinyl alcohol) (PVA) hybrid hydrogels were prepared and
their swelling and mechanical properties were investigated as
the basis of the application of CNTs in the field of biomaterials.
Hydrogels have potential applications as biomaterials in
artificial muscle and tissue engineering. However, poor
mechanical properties limit their application as structural
biomaterials. Crosslinking by chemical agents [11] or physical
method (e.g. freezing/thaw cycles [12]) is often used to
reinforce the hydrogels. Its shortcoming is that a large amount
of crosslinkers will result in the reduction of swelling capability.
Some results [13,14] show that layered silicates can solve this
problem by strengthening the hydrogels with retaining or
increasing the swelling properties. Here the influence of CNTs
on the swelling and mechanical behavior of the PVA hydrogels
will be investigated.
2. Materials and methods
PVA with Mw 146,000186,000 and hydrolysis 98%99%
was purchased from Aldrich. CNTs were prepared by a floating
catalyst method with an outer diameter of about 50 nm. Before
use, the CNTs were stirred in the mixed acid of concentrated
HNO
3
/H
2
SO
4
(1:3, v/v) for 4 h in order to further get rid of the
amorphous carbon and metal catalysts. Meanwhile, this process
Materials Letters 61 (2007) 17041706
www.elsevier.com/locate/matlet

Corresponding author.
E-mail address: xtong@imr.ac.cn (X. Tong).
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.07.115
will be helpful for the CNTs to disperse in the water. The
distilled water was used.
For pure PVAhydrogels, a 10% w/wsolution was prepared by
heating and mixing with the use of a reflux column/flask com-
bination. The PVA solution was poured into an aluminium mold
with dimensions of 100501 mm. The PVA in the mold was
processed through freezing and thawing cycles between 20 and
20 Cin a heated/refrigerated circulator with the freezing/thawing
rate of 0.2 C/min and holding time of 1 h at 20 and 20 C. For
CNT/PVA (2%, w/w) hybrid hydrogels, CNTs were dispersed in
water in advance. Then the PVA was dissolved in this solution.
Other hybrid hydrogels were prepared by diluting the CNT/PVA
(2%, w/w) solution using the 10% w/w PVA solution. For all
solutions, the concentration of PVA in water was always kept in
10% w/w. Other steps were the same as that of the PVA hydrogel.
Different cycle numbers of 7 and 10 were chosen to prepare pure
PVA hydrogels. The cycle number of all hybrid hydrogels was 7.
After the freeze/thaw cycles, the PVA sheet was extracted and
punched into dumbbell-shaped specimens for the tensile test.
Tensile tests were performed at room temperature on a
Hounsfield H5K-S electronic testing machine at a crosshead
speed of 10 mm/min. An average value of five specimens was
taken. Before the swelling test, the specimens were dehydrated
in alcohol (95 wt.%), then dried in a vacuum oven at 30 C for
48 h. The swelling behavior of the hydrogel was measured in
distilled water at room temperature and 310 K. At particular
time points, the hydrogels were removed from the water and
weighted after quick blotting with filter paper. Results were
expressed at swelling ratio (S) and were calculated by using the
following equation: S=[(W
t
W
0
) / W
0
], where W
0
is the weight
of dry gel at time 0 and W
t
is the weight of the hydrated or
swollen gel at time t. Each swelling value was the average value
of three specimens at the same time t. The final curves were
gained by the Sigmoidal fit tool in the OriginPro 7.0 software.
3. Results and discussion
Tensile test results are summarized in Table 1. From the data, it can
be seen that with the increase in the cycle numbers, the mechanical
properties of hydrogels are improved. These results are the same as
other reports [15]. For all specimens prepared by 7 freeze/thaw cycles,
the mechanical properties of the hybrid hydrogels are better than the
pure PVA hydrogels. It is to say that adding the CNTs to the hydrogel
matrix is helpful to the mechanical properties. Among them, the CNTP-
0.5 specimen with 0.5% w/w CNT loadings is the best, whose tensile
modulus and strength are even higher than those of PVA10 by 10
freeze/thaw cycles. For CNTP-0.5 specimen, compared to its matrix, its
tensile modulus, tensile strength and strain at break are increased by
78.2%, 94.3% and 12.7%, respectively. Except for these, from the
results, it can be found that the increase in the mechanical properties is
not proportionate to the CNT loadings. With the increase of CNT
loading, the mechanical properties of the hybrid hydrogels are not
increased, but on the contrary decreased. Therefore, in order to obtain
the excellent mechanical performance, the CNT contents in the hybrid
hydrogels had to be adjusted.
From the microstructure point of view, there are three different
regions within the PVA hydrogel: crystalline, amorphous and water.
The more the number of freeze/thaw cycles, the more crystalline region
is formed, so the mechanical properties are modified. From the above
results, it can be seen that adding the CNTs to the hydrogel is another
effective way to modify the mechanical properties. Especially, adding
only 0.5% w/w CNTs, the properties of the hybrid hydrogel has already
been close to that of pure hydrogels by 10 cycles. The reinforcing role
Table 1
Tensile test results of all specimens
Specimens Numbers
of cycles
Loading of
CNTs (%)
Tensile
modulus
(MPa)
Tensile
strength
(MPa)
Strain at
break (%)
PVA7
a
7 0.0 0.320.07 1.060.35 237.547.7
CNTP-0.5 7 0.5 0.570.03 2.060.12 267.613.30
CNTP-1.0 7 1.0 0.370.06 1.480.25 243.810.60
CNTP-2.0 7 2.0 0.350.04 1.300.19 269.819.50
PVA10 10 0.0 0.430.10 1.890.48 303.845.70
a
The number denotes the cycle numbers.
Fig. 1. The swelling behavior of some specimens at different testing temperature.
Table 2
Swelling ratios of some specimens at 400 min
Testing temperature PVA 7 CNTP-0.5 CNTP-1.0 CNTP-2.0
Room temperature 3.75 5.09 5.49 4.91
310 K 3.16 4.58 4.73 4.44
1705 X. Tong et al. / Materials Letters 61 (2007) 17041706
of the CNTs may be caused by their remarkable mechanical properties.
It has been indicated that the theoretical and experimental elastic
modulus of CNTs is in the range of 0.11 TPa, and the axial strength is
in the range of 10150 GPa [16], which make them ideal as rein-
forcement elements. Up to now, most commercially available polymers
have been as the matrices to investigate the reinforcing role of the
CNTs [17]. Most of the results show that the CNTs played a very good
role in the reinforcement. In order to effectively transfer the load to the
CNTs, good dispersion and interfacial adhesion are necessary. Some
research [18] on CNT/PVA composites showed that it was possible for
PVA to form a crystalline coating around the nanotubes, maximizing
interfacial stress transfer. This may be one of the reasons why the
mechanical properties of the hybrid hydrogels are better than the pure
PVA hydrogels. The CNTs used in our experiments have been treated
with the HNO
3
/H
2
SO
4
(1:3, v/v) for 4 h. Shi's studies show that the
CNTs can be evenly dispersed in the water after reacting with the
concentrated mixed acid for 4 h [19]. And many carboxyl, carbonyl and
phenol groups were added on the surface of the CNTs. These groups
are helpful to establish a good interaction between the CNTs and PVA
molecules. When the content of the CNTs is low, the interaction among
the CNTs is weaker than that between the PVA molecules and the
CNTs, so the CNTs can homogeneously disperse in the PVA matrix.
With the increase in the CNT loadings, the distance between two CNTs
is shortened and the interaction becomes strong. The aggregation
happened so that the reinforcing role of the CNTs was weakened.
Therefore, the amount of the CNTs should be controlled in a suitable
range.
To understand the influence of the CNTs on the swelling behavior
of the hydrogels, the swelling behavior of some specimens at different
testing temperatures was investigated (seen in Fig. 1). The results show
that the swelling behavior of hybrid hydrogels is obviously different
from that of pure hydrogels. Firstly, at the early stage of swelling, the
swelling rate of the CNTP-0.5 specimen is slower than that of the pure
hydrogels, whereas other hybrid hydrogels' is quicker. Secondly, the
swelling ratio of all hybrid hydrogels at 400 min is higher than that of
pure PVA hydrogel. The detail values are shown in Table 2.
Additionally, when the testing temperature is increased, the swelling
ratio of all specimens is reduced. But relatively, the reduction of hybrid
hydrogels is less.
About the swelling behavior, generally, when the crosslinkage
between the PVA molecules is increased, the swelling capability of the
hydrogels will be reduced. This contradiction has to be faced if modi-
fying the mechanical properties by increasing the crosslinkage. Some
researchers [20,21] solved this problem by adding the layered silicates
into the hydrogels. The results showed that retaining or increasing the
swelling properties occurred with the improvement of the mechanical
properties. From Fig. 1, it is found that the CNTs play the same role.
This result is different from Li's results [6]. Their experiments show
that the swelling ratio is decreased due to the addition of CNTs into the
gelatin. This may be caused by different hydrogel matrices, CNTs'
loadings and dispersion. From our results, it can be seen that when the
CNT loadings are different, the influence of the CNTs on the swelling
behavior is different. The accurate mechanism is unclear now, which
should be studied in a forthcoming research. The influence of the
temperature on the swelling ratio of the hydrogels is because that part
of the hydrogels will be dissolved in the warm water. When the CNTs
are added, the effect becomes weak. It is analyzed that the strong
interaction between PVA molecules and CNTs prevents the PVA
molecules from moving into the water.
4. Conclusion
The CNT/PVA hybrid hydrogels were prepared by a
freezing/thawing method. It is found that CNTs can effectively
improve the mechanical properties of the PVA hydrogels, while
the swelling capability is also enhanced. The influence of CNTs
on the mechanical and swelling behavior is related to the CNT
loadings. Likewise, the addition of CNTs is helpful to keep the
good swelling capability of the hydrogels at a higher tem-
perature. All these results show that CNTs can be an ideal
candidate to modify the performance of the hydrogels.
Acknowledgments
This work was funded by the Doctor Funding of Shenyang
Ligong University.
References
[1] J. Chen, M.A. Hamon, H. Hu, Y.S. Chen, A.M. Rao, P.C. Eklund, R.C.
Haddon, Science 282 (1998) 9598.
[2] M.J. O'Connell, P. Boul, L.M. Ericson, C. Huffman, Y.H. Wang, E. Haroz,
C. Kuper, et al., Chem. Phys. Lett. 342 (2001) 265271.
[3] A. Bianco, M. Prato, Adv. Mater. 15 (2003) 17651768.
[4] A. Bianco, K. Kostarelos, M. Prato, Curr. Opin. Chem. Biol. 9 (2005)
674679.
[5] J.J. Davis, K.S. Coleman, B.R. Azamian, C.B. Bagshaw, M.L.H. Green,
Chem. Eur. J. 9 (2003) 37323739.
[6] H. Li, D.Q. Wang, H.L. Chen, B.L. Liu, L.Z. Gao, Macromol. Biosci. 3
(2003) 720724.
[7] R.H. Baughman, C.X. Cui, A.A. Zakhidov, Z. Iqbal, J.N. Barisci, G.M.
Spinks, G.G. Wallace, et al., Science 284 (1999) 13401344.
[8] A. Minett, J. Frysse, G. Gang, G.T. Kim, S. Roth, Curr. Appl. Phys. 2
(2002) 6164.
[9] U. Vohrer, I. Kolaric, M.H. Haque, S. Roth, U. Deltaff-Weglikowska,
Carbon 42 (2004) 11591164.
[10] H.K. Koerner, G. Price, N.A. Perace, M. Alexander, R.A. Vaia, Nat. Mater.
3 (2004) 115120.
[11] N.A. Peppas, in: B.D. Ratner, A.S. Hoffman, F.J. Schoen, J.E. Lemons
(Eds.), Biomaterials Science: An Introduction to Materials in Medicine,
Academic, Toronto, 1996, p. 62.
[12] L.G. Wu, Y.T. Zhang, L.S. Cai, S.H. Hu, New Chem. Mater. 29 (2001)
1821.
[13] X.H. Xia, J. Yih, N.A. D'Souza, Z.B. Hu, Polymer 44 (2003) 33893393.
[14] S.H. Zhou, J.G. Yang, C.P. Wu, Acta Polym. Sin. (2003) 326329.
[15] W.K. Wan, G. Campbell, Z.F. Zhang, A.J. Hui, D.R. Boughner, J. Biomed.
Mater. Res. 63 (2002) 854861.
[16] E.T. Thostenson, C.Y. Li, T.W. Chou, Comput. Sci. Technol. 65 (2005)
491516.
[17] O. Breuer, U. Sundararaj, Polym. Compos. 25 (2004) 630645.
[18] J.N. Coleman, M. Cadek, R. Blake, V. Nicolosi, K.P. Ryan, C. Belton,
A. Fonseca, et al., Adv. Funct. Mater. 14 (2004) 791798.
[19] Z.J. Shi, Y.F. Lian, X.H. Zhou, Z.N. Gu, Y.G. Zhang, S. Iijima, Q.H. Gong,
et al., Chem. Commun. (2000) 461462.
[20] X.H. Xia, J. Yih, N.A. D'Souza, Z.B. Hu, Polymer 44 (2003) 33893393.
[21] S.H. Zhou, J.G. Yang, C.P. Wu, Acta Polym. Sin. 3 (2003) 326329.
1706 X. Tong et al. / Materials Letters 61 (2007) 17041706