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Department of Polymer Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
b
Institute of Applied Biochemistry, University of Tsukuba, Tsukuba, Ibaraki 305, Japan
c
National Institute of Advanced Industrial Science and Technology, Material and Chemical Process Institute, Tsukuba, Ibaraki 305-8565, Japan
d
Department of Theoretical, P.N. Lebedev Institute, Russian Academy of Science, Moscow, Leninskii prosp., 53, 117924, Russian Federation
e
Neutron Scattering Laboratory, Institute for Solid State Physics, The University of Tokyo, Tokai, Naka-gun, Ibaraki 319-1106, Japan
Received 18 January 2002; received in revised form 1 May 2002; accepted 27 May 2002
Abstract
A comparison of network structure in a solvent was made for two types of poly(N-isopropylacrylamide) gels cross-linked by chemical
reaction with N,N0 -methylenebisacrylamide (BIS) (chemical gels) and by g-ray irradiation (g-ray gels). The cross-linking density
dependence for these gels was examined by small angle neutron scattering (SANS). The SANS results indicated an increase of frozen
inhomogeneities with an introduction of cross-links for both chemical and g-ray gels. However, it was found that the effect of cross-linking is
much stronger in the chemical gels than in the g-ray gels. The differences in the structure were successfully interpreted by a statisticalmechanical theory of gels proposed by Panyukov Rabin (Phys. Rep. 269 (1996) 1). The degree of polymerization between cross-links, N,
was a decreasing function of cross-linking content for both types of gels, while that for the g-ray gels was a weak function of irradiation dose.
Quantitative analyses on BIS concentration and g-ray dose dependence led to an experimental evidence of the existence of cross-linking
saturation threshold. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Cross-linking saturation threshold; Polymer gels; Poly(N-isopropylacrylamide)
1. Introduction
A polymer gel is a three-dimensional network consisting
of long chain molecules cross-linked to each other. It
possesses both solid- and liquid-like properties [1 3]. It can
be regarded as solid because of the presence of a finite
elastic modulus and ability of shape retention. On the other
hand, it exhibits similar phenomena to those of a semi-dilute
polymer solution, such as cooperative diffusion. Gels may
be indistinguishable with the corresponding polymer
solutions on the scale at several nanometers. However, if
we zoom out the view to the distance comparable to the
inter-cross-link distance, we should observe the effects of
cross-links playing an important role in the physical
properties. It is easy to envisage that polymer chains are
* Corresponding author. Fax: 81-75-724-7853.
E-mail address: nori@ipc.kit.ac.jp (T. Norisuye).
0032-3861/01/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 3 2 - 3 8 6 1 ( 0 2 ) 0 0 3 4 3 - 9
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2. Experimental section
PNIPA gels were employed as a model system to study
the structure of gels because they are chemically stable at a
temperature much lower than the volume phase transition
temperature (< 33 8C) [28]. Two types of PNIPA gels were
prepared in deuterated water by redox polymerization and
by g-ray irradiation for comparison of the network
structures. The chemical gels having different cross-linking
densities were synthesized at 20 8C, in the presence of
N,N,N0 ,N0 -tetramethylethylenediamine (accelerator), BIS
(cross-linker), and ammonium persulfate (APS; initiator).
Molar concentration of BIS, CBIS, was varied from 0 to
35 mM while that of NIPA, CNIPA was kept to be 690 mM.
NIPA monomer, supplied by Kohjin Chemical Co., was
purified by recrystallization prior to use. Reagent grade BIS
and APS were purchased from Wakenyaku Co. Ltd and
were used without further purification. The details of sample
preparation are described elsewhere [29].
PNIPA solutions without cross-linker were prepared by
above method in advance to the g-ray irradiation. Irradiation
of g-ray was carried out by using a 60Co source, where the
sample was regulated with a thermostat bath at 20 8C. The
g-ray gels having different cross-linking densities were
obtained with different irradiation times, 0.5 16 h, at
constant dose rate of about 1 Mrad/h. All the samples
were transparent. The g-ray gels with higher irradiation
dose (i.e. 16 Mrad) exhibited volume shrinking after
irradiation.
SANS experiments were carried out on the research
reactor, SANS-U, at Institute for Solid State Physics, The
University of Tokyo, located at Japan Atomic Energy
Research Institute, Tokai, Japan. A flux of cold neutrons
was irradiated to the sample, and
with a wavelength of 7.0 A
the scattered intensity profile was collected with an area
detector of 128 128 pixels. The sample-to-detector
distance was set to be 4 m, which covered the accessible q
21, where q is the scattering
range being 0.01 0.078 A
vector. The sample was placed in a brass chamber with
quartz windows and the chamber was thermo-regulated
within an error of ^ 0.1 8C at the sample position with a
NESLAB 110 water circulating bath. The sample thicknesses were in the range of 2.28 and 4.0 mm, depending on
the samples. Scattered intensities were circularly averaged
by taking into account the detector inhomogeneities,
corrected for cell scattering, fast neutrons, transmission,
and incoherent scattering, and then scaled to the absolute
intensities with a polyethylene standard sample (Lupolen).
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3. Theoretical background
gq
Sq Gq Cq
fNgq
1 wgq
1
2
2 21
2
2
Q =2 4Q 1
1 Q f0 =f2=3
2
8
l3
1 wgq2 1 Q2 2
where l and S0 q are the linear swelling ratio, and the
structure factor at gel preparation, respectively, which are
given by
f0 1=3
l
the mean field
9
f
and
S0 q
f0 N
Na2 q2
w0 2 1
12
10
12
w0 f0 N
13
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14
fN
w Q2 =2
1 2 2x f
Gq
G0
1 j 2 q2
15
Gq
a2 q2
12f
16
17
5293
Fig. 2. Iqs for the PNIPA solution obtained with different sample to
detector distances, i.e. 4 and 1 m. The accessible q range was 0.01
21. The solid line indicates the result fitted with Eq. (17).
0.20 A
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Now, we discuss the critical cross-linking density. Crosslinks are formed between monomer units whose chains are
actually contacting during the process of gelation. Therefore, the number of cross-linking points does not exceed that
of the binary contact points in the corresponding semi-dilute
solution. This fact leads to the following statement. There
should be a limiting value of cross-linking density or degree
of polymerization between cross-links. This limiting value
is called the CST as described in the original paper of the PR
theory [21]. The location of CST is determined by the
balance of the numbers of such contacts and cross-links and
is defined where the reduced excluded volume parameter is
unity at q 0 (Eq. (10)). By substituting w0 1 into
Eqs. (12) and (13), we obtained the limiting value for CST
for the case of mean field approach,
NCST
1
1 2 2x0 f0 f0
19
25=4
NCST f0
20
Fig. 5. CBIS and irradiation dose dependence of the inhomogeneitycorrelation length at sample preparation, J, for the chemical gels (W) and
the g-ray gels () calculated with Eq. (14).
"
B JN!1 2
A
CBIS; CST
22
5295
!g #
24
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5. Conclusions
Structural analyses for two types of PNIPA gels, i.e.
chemical gels and g-ray gels, have been investigated by
SANS. In addition to scattering described by a Lorentz-type
function corresponding to PNIPA solutions, an excess
scattering was observed for the chemical gels at low q
region, which became dominant with increasing crosslinking density. As reported in literature [18], this excess
scattering was explained as appearance of built-in inhomogeneities introduced by cross-links. On the other hand, the
scattering functions for the g-ray gels were found to be
unchanged irrespective of irradiation dose. In order to
elucidate these phenomena, a quantitative SANS analysis
was carried out by the PR theory. The observed scattering
intensity functions were successfully reproduced with the
PR theory, from which the degree of polymerization
between cross-links, N, and the inhomogeneity correlation
length, J, were evaluated as a function of degree of crosslinking.
The following facts are disclosed in this work. (1) The
g-ray gels have very different microscopic structures
compared with those of the chemically cross-linked gels.
The inhomogeneities increase with increasing cross-linker
concentration for the case of chemical gels, while less
irradiation dose dependence was observed for the inhomogeneities in the g-ray gels. (2) The weak irradiation-dose
dependence of the g-ray gels is deduced to be due to random
cross-linking and absence of the micro-gel cluster formation
during gelation process. (3) This lower cross-linking density
may lead to a rapid shrinking capability of g-ray gels
reported in the literature because of generation of long intercross-linking chains and many dangling chains in the
polymer network. (4) There exists a limiting value of N
below which the value of N does not decrease with
increasing cross-linking density, CBIS, for CBIS . CBIS, CST.
Acknowledgments
This work is supported by Grant-in-Aid, nos. 12450388
and 13750832, and Grant-in-Aid for Scientific Research on
Priority Areas (A), Dynamic Control of Strongly Correlated Soft Materials (no. 413/13031019) from the Ministry
of Education, Science, Sports, Culture, and Technology.
This work was performed with the approval of Institute for
Solid State Physics, The University of Tokyo (Proposal no.
00-0586 and 01-1591), at Japan Atomic Energy Research
Institute, Tokai, Japan.
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