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Abstract
Organophilic montmorillonite (OMMT) was synthesized by cationic exchange between Na-MMT and tricetadecylmethyl ammonium bromide in an aqueous solution. A new nanocomposite consisting of poly(butyl acrylate)modied chitosan and OMMT was prepared by g-ray irradiation polymerization in acetic acid aqueous solution. The
degree of dispersion and the intercalation spacing of these nanocomposites were investigated using X-ray diffraction.
The enhanced thermal stabilities of nanocomposites were characterized by the thermal gravimetric analysis. The
improved mechanical properties of nanocomposites were characterized by static tensile studies and dynamic mechanical
analysis. The nanocomposites showed improved resistance to water absorption.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: Nanocomposites; Chitosan; Butyl acrylate; g-ray irradiation
1. Introduction
Chitosan is a high molecular weight polysaccharide
composed mainly of b-(1,4)-linked 2-deoxy-2-aminod-glucopyranose units and partially of b-(1,4)-linked
2-deoxy-2-acetamido-d-glucopyranose. Because of its
biocompatibility, biodegradability and avirulence, chitosan has been used in many areas.
Interest in the modication of chitosan through graft
copolymerization has grown signicantly. The combination of natural and synthetic polymers via grafting yields
hybrid materials which may produce desirable properties. In previous studies, a number of different monomers have been grafted onto chitosan, these include
methylmethacrylate (Blair et al., 1987), acrylamide
(Yazdani-Pedram et al., 2002), 2-hydroxyethlymetha*Corresponding author. Tel.: +86-551-3601586; fax: +86551-3606763.
E-mail address: fye@ustc.edu.cn (F. Yuee).
crylate (El-Tahlawy and Hudson, 2001), N,N0 -dimethylaminoethylmethacrylate (Singh and Ray, 1997). As we
know there are no references in the literature to the
incorporation of clay into graft-modied chitosan.
Polymer/clay nanocomposites are of interest because
they combine the structure, physical and chemical
properties of both inorganic and organic materials.
Compared to the pure polymers these nanocomposites
demonstrate excellent properties such as improved
storage modulus (Yao et al., 2002), decreased thermal
expansion coefcients (Sun and Garces, 2002), reduced
gas permeability (Usuki et al., 2002), and enhanced ionic
conductivity (Wu and Lerner, 1993).
The clay that is most generally used is montmorillonite (MMT), which belongs to the 2:1 layered silicate. Its
crystal lattice consists of two silica tetrahedral sheets
fusing into an octahedral sheet. Isomorphous substitutions of Si4+ for Al3+ in the tetrahedral lattice and of
Al3+ for Mg2+ in the octahedral sheet can generate
negative charges that are counterbalanced by cations
0969-806X/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2003.10.012
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2. Experimental
2.1. Materials
Chitosan was obtained from San Huan Ocean
Biochemical Co. Ltd. (China). Its degree of deacetylation and the apparent viscosity were determined as
91.2% and 30 MPa s. Butyl acrylate was chemical grade.
Na+-MMT, with a cation exchange capacity (CEC)
value of 100 mmol/100 g, (Ling An Chemicals Co. Ltd.,
Hangzhou, China) was used without further purication. Tricetadecylmethyl ammonium bromide (TRIAB)
was supplied by Fei Xiang Chemicals Co. Ltd.,
Jiangshu, China.
The samples were irradiated at room temperature,
with the 2.22 1015 Bq 60Co g-ray source. The
irradiation doses were measured by ferrous sulfate
dosimeter.
2.2. Preparation of OMMT
The OMMT was prepared by cationic exchange
between Na+-MMT galleries and TRIAB in an aqueous
solution. The suspension solution containing 12.5 g
of Na+-MMT and 4.6 g TRIAB was mixed in
240 ml of distilled water. The suspension solution
was stirred at 75 C for 2 h, the exchanged MMT
was ltered and washed with distilled water until no
bromide ions was detected with 0.1 M AgNO3 solution.
Then the product was dried in vacuum oven at 60 C for
24 h. The OMMT obtained was ground with a mortar
and pestle and sieved through a 280 mesh copper
griddle.
100:
BuA used g
Wg W W0
100;
W0
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469
M1 M0
;
M0
Intensity
Intensity
a: 0% OMMT
b: 3% OMMT
c: 5% OMMT
d: 7% OMMT
e: pure OMMT
e
OMMT
+
Na -MMT
c
b
a
3
2
2 (degrees)
Fig. 1. XRD patterns of Na+-MMT and OMMT.
2 (degrees)
Fig. 2. XRD patterns of pure OMMT and nanocomposites
with different OMMT contents.
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L. Yu et al. / Radiation Physics and Chemistry 69 (2004) 467471
470
100
60
40
0% OMMT
7% OMMT
20
0
0
10
11
12
a: 0%
b: 3%
c: 5%
d: 7%
d
100
80
60
a
40
20
0
100
200
300
400
Temperature (C)
Fig. 4. TGA thermograms of CTS-PBuA and CTS-PBuA
nanocomposites with the different OMMT contents.
Fig. 5 shows the storage modulus, E0 of the CTSPBuA and CTS-PBuA nanocomposites with different
OMMT contents. Compared with the CTS-PBuA, the
CTS-PBuA nanocomposite with 3 wt% OMMT exhibited an enhanced E0 . The CTS-PBuA nanocomposites
with more than 3 wt% OMMT did not show an increase
in E0 , and in fact the E0 decreased below the glass
transition temperature of PBuA. A similar phenomenon
was also observed in the tensile testing results (Table 1).
This may be explained as follows: the introduction of
OMMT can form many cross-linking points which
strengthen the interaction of the MMT and PBuA;
when the concentration of OMMT is higher, some
MMT forms clusters in the composites and these clusters
may act as stress concentrating points resulting in a
decrease in E0 .
The loss tangent tan y for these nanocomposites is
shown in Fig. 6. CTS-PBuA shows a narrow peak
around 50 C and a broad peak at 100 C. The former
peak corresponds to the glass transition temperature
(Tg) of PBuA. The second peak may be due to some
transition of chitosan. With the increase of OMMT
concentration, two peaks of CTS-PBuA nanocomposites
800
a: 0%
b: 3%
c: 5%
d: 7%
1000
E' (mPa)
conversion
80
600
400
The TGA thermograms of CTS-PBuA and CTSPBuA nanocomposites with different OMMT contents
are presented in Fig. 4. The thermal degradation prole
of CTS-PBuA exhibit two main decomposition stages
with one starting at around 270 C and another starting
at around 350 C. The rst stage is attributed to the
degradation of chitosan. The second stage is the
0
-50
50
100
150
200
Temperature (C)
Fig. 5. The trend of the storage modulus E0 of CTS-PBuA
and CTS-PBuA nanocomposites with the different OMMT
contents.
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Table 1
Tensile testing of CTS-PBuA nanocomposites
4. Conclusion
0.40
a: 0%
b: 3%
c: 5%
d: 7%
0.35
tan
0.30
a
b
0.25
0.20
0.15
a
0.10
471
0.05
-50
50
100
150
200
Acknowledgements
Temperature (C)
Fig. 6. The tan y vs. temperature of CTS-PBuA and CTSPBuA nanocomposites with the different OMMT contents.
Table 2
Water absorption of CTS-PBuA nanocomposites
References
0
133.2
3
82.2
5
80.5
7
75.6
are shifted to higher temperature, compared to CTSPBuA. The Tg of PBuA in the nanocomposite with
7 wt% OMMT is about 10 C more than that in the pure
CTS-PBuA. It means the interaction between the MMT
and PBuA limits the segmental movement of the PBuA.
We do not at present understand the origin of the second
peak, but according to the result of a previous report
(Ratto et al., 1996), it may be due to the signicant
rearrangement of bond structure taking place within the
acetamide and amine bond regions of chitosan. The
introduction of OMMT may inhibit the rearrangement
of bond structure. Hence, the transition temperature of
chitosan is increased.
3.6. Water absorption studies
Table 2 shows the percentage of water absorption for
the CTS-PBuA nanocomposites. It shows an decreasing
trend of water absorption percentage with the increase
of OMMT concentration. This is probably because that
OMMT can form large numbers of cross-linking points
which results in a crosslinking network structure. As a
consequence the water absorption is reduced.