Swelling behavior of polyacrylamide/laponite clay nanocomposite hydrogels:

pH-sensitive property
Peng Li
a
, Nam Hoon Kim
c
, Siddaramaiah
a,b
, Joong Hee Lee
a,c,
*
a
BIN Fusion Research Team, Department of Polymer/Nano Engineering, Chonbuk National University, Duckjin-dong 1Ga 664-14, Jeonju, Jeonbuk 561-756, Republic of Korea
b
Department of Polymer Science and Technology, Sri Jayachamarajendra College of Engineering, Mysore 570 006, India
c
Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University, Jeonju, Jeonbuk 561-756, Republic of Korea
a r t i c l e i n f o
Article history:
Received 23 September 2008
Received in revised form 19 January 2009
Accepted 19 January 2009
Available online 27 January 2009
Keywords:
A. Nano-structures
A. Hydrogels
B. Swelling behavior
B. Physical properties
a b s t r a c t
In this study, an investigation is carried out on the inuence of varying clay contents (2543%), pH values
(211 buffer solutions), heat treatment, temperatures (2560 C) and ionic strengths (saline solution,
10
7
0.1 M) on the water absorbency of polyacrylamide (PAAm)/laponite nanocomposite (NC) hydrogels
in the absence of polyelectrolyte. For the inuence of pH value on swelling behaviors, a maximum swell-
ing ratio occurs at pH 11. Heat treatment of the hydrogels signicantly improved the swelling capacity
and created an obvious pH sensitive area (pH 34). The swelling capacity of the hydrogels was enhanced
by increasing the temperature of the absorbing media. The results of swelling at different ionic strengths
also indicate that the ionic strength can considerably weaken the swelling abilities of the NC hydrogels.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Stimuli-responsive hydrogels have been produced that exhibit
dramatic changes in their swelling behavior, network structure,
permeability and mechanical strength in response to a number of
external stimuli, including pH, ionic strength of the surrounding
uid, temperature, presence of specic solutes and applied electri-
cal or magnetic elds [13]. Because of their environmental sensi-
tivity and unique structure, these polymeric hydrogels have been
investigated for many biomedical and pharmaceutical applications
including drug delivery systems, separation techniques, muscle-
like actuators, and construction of sensors [48]. Among these
intelligent polymers, pH- and temperature-sensitive hydrogels
are the most widely investigated. PH-sensitive polymer hydrogels
are produced by adding pendant acidic or basic functional groups
to the polymer backbone; these either accept or release protons
in response to appropriate pH and ionic strength changes in aque-
ous media [7].
The synthesis of new super-absorbents and the development of
their applications are still interesting research areas. Recently, the
preparation of organicinorganic super-absorbent composites
[9,10] and polymer/clay nanocomposite (NC) hydrogels [11,12]
has attracted a great deal of attention because of their relatively
low production cost, high water absorbency, high mechanical
resistance, and their broad spectrum of applications such as agri-
culture, horticulture, etc., where water absorbency in saline solu-
tions and water retention ability of super-absorbents is critically
important. Therefore, it is necessary to investigate the swelling
behavior of polymer hydrogels in various saline solutions as well
as their water retention ability.
Recently, Haraguchi et al. [1315] have reported a novel NC
hydrogel consisting of N-isopropylacrylamide (PNIPA) and inor-
ganic clay, which is prepared without using any organic cross-lin-
ker. This type of NC hydrogel exhibited high transparency, a high
deswelling rate and outstanding mechanical properties with high
strength and elongation at break in excess of 1000%. Haraguchi
et al. considered that a unique organic/inorganic network structure
was formed by in situ free-radical polymerization, in which the
PNIPA chains were attached to the surface of clay sheets, which
acted as effective multifunctional cross-linkers through ionic or
polar interactions. Furthermore, Li et al. have recently reported
the swelling behaviors of clay based super-absorbent composites
[16].
Depending on the type of monomers (i.e., ionic or neutral)
incorporated in the gels, they can be made to respond to a variety
of external environmental changes such as pH, ionic strength, tem-
perature or specic chemical compounds [1719]. Therefore, a sig-
nicant number of acidic or basic monomers were incorporated
1359-8368/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2009.01.001
* Corresponding author. Address: BIN Fusion Research Team, Department of
Polymer/Nano Engineering, Chonbuk National University, Duckjin-dong 1Ga 664-
14, Jeonju, Jeonbuk 561-756, Republic of Korea. Tel.: +82 63 270 2342; fax: +82 63
270 2341.
E-mail address: jhl@chonbuk.ac.kr (J.H. Lee).
Composites: Part B 40 (2009) 275283
Contents lists available at ScienceDirect
Composites: Part B
j our nal homepage: www. el sevi er. com/ l ocat e/ composi t esb
into a hydrogel network in order to improve the environmental
response behaviors. Until now, almost all pH-sensitive hydrogels
that have been studied with at least one monomer is of acidic or
basic groups. The present study focuses on the swelling behavior
of laponite clay cross-linked polyacrylamide (PAAm) hydrogels.
Though there is no acidic or basic group in the monomer, there
are a number of negative charges on the clay surface and the poly-
acrylamide can hydrolyze in either acidic or basic solutions. The
Table 1
Formulations of the initial solutions and the resulting NC hydrogels.
Hydrogel Composition (g) Water/Hydrogel (wt.%) Clay/composite (wt.%)
Clay AAm
NC15 1.5 3.0 87.0 33.3
NC20 2.0 3.0 85.7 40.0
NC25 2.5 3.0 84.5 45.5
Fig. 1. FT-IR spectra of NC15 hydrogel.
0 50 100 150 200 0 50 100 150 200
0 50 100 150 200
0
20
40
60
80
100
W

(
%
)
Time (hours)
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
a b
c
0
20
40
60
80
100
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
Time (hours)
W

(
%
)
0
20
40
60
80
100
W

(
%
)
Time (hours)
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
Fig. 2. Swelling isotherm of NC hydrogels with different clay content in different pH solutions (0.01 M) (a) NC15, (b) NC20, and (c) NC25.
276 P. Li et al. / Composites: Part B 40 (2009) 275283
inuence of the amount of clay content and heat treatment of NC
hydrogel on the water absorbent properties (i.e., their capacity
and rate of absorption) at different pH value solutions has been
discussed in this article.
2. Experimental
2.1. Materials
Acrylamide (AAm) and synthetic hectorite, laponite XLS (Lap)
(cation exchange capacity = 104 mequiv/100 g), were obtained
from KanTo Chemical industries, Ltd., Japan, and from Rockwood
Co., USA, respectively. The composition of laponite XLS is
92.32 wt.% Mg
5.34
Li
0.66
Si
8
O
20
(OH)
4
Na
0.66
and 7.68 wt.% Na
4
P
2
O
7
.
Potassium persulfate (initiator) and N,N,N
0
,N
0
-tetramethylene dia-
mine (TEMED) (accelerator) were obtained from Tokyo Chemical
Industry Co. Ltd., Japan, and were used without further purica-
tion. Distilled water was used for all experiments including the
swelling experiments. For the preparation of the hydrogels, nitro-
gen gas was bubbled through the distilled water for more than
3 h prior to use.
2.2. Preparation of polyacrylamide/laponite nanocomposite hydrogels
(PAAm/Lap NC hydrogels)
Nanocomposite hydrogels were prepared using initial solutions
consisting of a monomer (AAm), a cross-linker (clay), a solvent
(water), an initiator (potassium persulfate), and an accelerator
(TEMED). The molar ratio between the monomer, initiator and
accelerator used was 100:0.426:0.735. The NC hydrogels were pre-
pared by the in situ free radical polymerization of AAm in the pres-
ence of the water-swollen inorganic clay without using any organic
cross-linker [17,18]. First, a transparent aqueous solution consist-
ing of water (28.5 mL), AAm (3 g), and various amounts of inor-
ganic clay content (12.5 g) were prepared. Thus, the obtained
NC hydrogels are referred to herein as NC15NC25. The formula-
tions of the prepared NC hydrogels are shown in Table 1. The accel-
erator (TEMED, 24 lL), and subsequently the aqueous solution of
the initiator (0.03 g KPS in 1.5 mL H
2
O), were added to the former
solution with constant stirring at iced-water temperature. The NC
hydrogels were synthesized in airtight glass tubes (interior size:
7.8 mm diameter and 60 mm long). The polymerization of AAm
was then allowed to continue in a water bath at 30 C for 48 h. A
number of hydrogels were heat treated in an incubator at 60 C
for different durations (06 days). The heat treated hydrogels were
named as NC15Hn, where n is the days of heat treatment. During
the polymerization, oxygen was excluded from the reaction mix-
ture by purging it with nitrogen gas.
2.3. Characterization of swelling behavior
To determine the effect of the pH on swelling behaviors of dif-
ferent NC hydrogels, different pH solutions were prepared. The
pH was changed by adding HCl or NaOH and the ionic strength
of all solutions was 0.01 M, which was controlled by adding NaCl.
The wet samples (approximately 0.4 g) were immersed in 200 mL
of the buffer solution at 25 C, and were taken out at regular
intervals of time in order to monitor the changes in weight. All
2 4 6 8 10 12
0.08
0.12
0.16
0.20
0.24
0.28
NC15
NC20
NC25
K

(
h
o
u
r
-
1
)
pH value
a b
c
2 4 6 8 10 12
76
80
84
88
92
96
W

(
%
)
pH value
NC15
NC20
NC25
2 4 6 8 10 12
0
5
10
15
20
25
30
35
40
pH value
Q

(
g
/
g
)
NC15
NC20
NC25
Fig. 3. Effects of clay content of NC hydrogel on its (a) swelling rate constant, (b) equilibrium water content, and (c) equilibrium swelling degree in different pH solutions.
P. Li et al. / Composites: Part B 40 (2009) 275283 277
hydrogels were kept in solutions until equilibrium swelling was
reached. The aqueous solution content of the swollen gel was ex-
pressed as:
Wt
mt m
0
mt
1
where, m(t) and m
0
are the weights of the hydrogel at time t and the
original hydrogel, respectively. The function W(t) is a relative value
and the swelling percentage (Q(t)) is used to compare the swelling
degree. The swelling percentage was calculated using the following
equation;
Qt
mt m
0
m
0
2
where m(t) and m
0
are the same as in Eq. (1). Based on Eqs. (1) and
(2), we can obtain Eq. (3);
Qt
Wt
1 Wt
3
In order to investigate the effect of temperature and ionic strength
on the swelling behavior of NC hydrogels, the experiments were
conducted similarly to the previous experiments. To study the effect
of temperature, the NC15 samples (approximately 0.4 g) were
Fig. 4. FT-IR spectra of NC15 hydrogel after exposed to different buffer solutions: (a) pH 2, (b) pH3, (c) pH 4, and (d) pH 11.
0
20
40
60
80
100
W

(
%
)
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
0
20
40
60
80
100
W

(
%
)
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
0 50 100 150 200
0
20
40
60
80
100
pH2
pH3
pH4
pH5
pH6
pH7
pH8
pH9
pH10
pH11
W

(
%
)
Time (hours)
0 50 100 150 200
Time (hours)
0 50 100 150 200
Time (hours)
a b
c
Fig. 5. Swelling isotherm of NC15 hydrogels with different heat treatment time in different pH solutions (0.01 M); (a) NC15H2, (b) NC15H4, and (c) NC15H6.
278 P. Li et al. / Composites: Part B 40 (2009) 275283
immersed in 200 mL of the buffer solution (pH 7, ionic strength =
0.1 M) at different temperatures viz., 25, 35, and 60 C for 7 days.
Finally, neutral solutions with different ionic strengths viz., 10
7
,
0.01, 0.05, and 0.1 M were used to probe the effect of ion strength
on the swelling behaviors of NC hydrogels at 25 C.
3. Results and discussion
The characteristic phenomenon of pH-sensitive hydrogels is the
dynamic swelling corresponding to different pH values of the sur-
rounding medium. The transfer of water molecules from the sur-
roundings into the hydrogels is the primary reason for swelling.
Most applications of hydrogels in biotechnology and controlled-re-
lease systems are intimately related to water or solute mass trans-
port characteristics of gels. The swelling behavior of hydrogels is
considerably dependent on the ionization of the gel as well as on
the ionic strength of the surrounding solution [19,20].
3.1. Chemical structure characterization
Fig. 1 shows the FTIR spectra of PAAm/Lap NC15 hydrogel. The
characteristic absorptions of both PAAm (2928, 2788, 1678, 1550,
and 1455 cm
1
) and clay (1010 and 652 cm
1
) were shown in
the spectra. In the FTIR spectra, the peak at 1678 cm
1
corresponds
to the carbonyl moiety of the AAm unit, the peak at 1455 cm
1
cor-
responds to the CN stretching of the AAm unit, and the peak at
1010 cm
1
corresponds to the SiO stretching of clay [21,22].
3.2. Effect of pH value
The swelling behaviors of the NC hydrogels were studied at
room temperature in various pH-solutions between 2 and 11 with
the same ion strength. The water content W, as a function of time,
is plotted in Fig. 2(a)(c) for NC hydrogels with different clay
contents and in different pH-solutions. Polyacrylamide is a non-
ionic polymer, which cannot ionize in an aqueous solution yet
can undergo hydrolysis in acidic and basic solutions, which induces
the appearance of the carboxylic acids group. Therefore, the swell-
ing behavior may change according to the pH of the environment.
At the same time, NC hydrogel was cross-linked by laponite XLS, in
which the surface has a number of anionic groups (OH

). The anio-
nic groups in the network of hydrogel may also affect the swelling
behaviors of NC hydrogels in different pH solutions. Moreover, a
literature search indicates a lack of reporting on this area of
investigation.
Fig. 2 shows that the rate of water uptake sharply increases, and
then begins to level off. In all cases, the equilibrium water uptake
value is high at pH 11 and 2, while it is low around pH 3 and 4. The
swelling process of hydrogels commonly follows second-order
kinetics with respect to the unrealized swelling capacity and the
swelling rate at any time may be expressed as:
2 4 6 8 10 12
0.0
0.2
0.4
0.6
0.8
1.0
pH value pH value
NC15
NC15H2
NC15H4
NC15H6 K

(
h
o
u
r
-
1
)
76
80
84
88
92
96
NC15
NC15H2
NC15H4
NC15H6
W

(
%
)
2 4 6 8 10 12
2 4 6 8 10 12
0
10
20
30
40
pH value
NC15
NC15H2
NC15H4
NC15H6
Q

(
g
/
g
)
a b
c
Fig. 6. Effects of heat treatment of NC15 hydrogel on: (a) swelling rate constant, (b) equilibrium water content, and (c) equilibrium swelling degree in different pH solutions.
P. Li et al. / Composites: Part B 40 (2009) 275283 279
dW
dt
KW
1
W
2
4
where W is the water content of the gel at time t, W
1
is the maxi-
mum or equilibrium water content, and K is the rate constant for
the swelling process. By integrating and rearranging the equation,
the following expression can be obtained:
t
W

1
KW
2
1

1
W
1
t
1
W
1
1
KW
1
t

5
According to this equation, the experimental data must t a straight
line with a slope of 1/W
1
and an ordinate of 1=KW
2
1
. For any of the
hydrogels studied, the experimental data ts the above equation
over the whole range of values, suggesting that the swelling process
of the studied hydrogels follows second-order kinetics. The values
of W
1
and K were obtained from the slope and ordinate of the
experimental straight line for all hydrogels and the R
2
values ob-
tained from the linear regression analysis were above 0.999.
The swelling behavior of the NC hydrogels was characterized
by measuring their rate constant (K), steady-state swelling
(W
1
) and swelling percentage (Q) for the swelling process and
by measuring their plots as a function of pH, as shown in
Fig. 3(a)(c), respectively. Fig. 3(a) shows that the swelling rate
constant values of NC hydrogels are small in pH 2 and 3 solu-
tions. There are two factors we should consider: the hydrolysis
of PAAm and the ionic groups (OH

) on the clay surface. Firstly,

the hydrolysis of amide groups of PAAm is closely related to
the pH value of the medium and temperature. In strong acidic
or basic environments at high temperature, hydrogels are easy
to hydrolyze. Secondly, in acidic solutions H
+
interacted with
hydrolyzed OH

groups which induce the decrease of ionic con-

centration in the network, the swelling rate constant and the
equilibrium swelling degree of NC hydrogels. The two factors
have opposite effects on the swelling behaviors of NC hydrogels.
Because the solutions were placed at room temperature, the
hydrolysis rate of NC hydrogel was very low, and the rate con-
stant of NC hydrogel is small in pH 2 and 3 solutions. In pH 2
solutions, the hydrolysis of PAAm (rst factor) plays the domi-
nant role, while in pH 3 the ionic groups (second factor) are also
important. The swelling rate constant of hydrogel in pH 3 was
thus smaller, due to the lower ion concentration in the hydrogels
network.
According to the obtained data of the equilibrium water content
W
1
, the curve can be divided into three parts: pH 24, 410, and
1011. The water absorbency for PAAm composites remains
roughly constant in a pH value range from 4 to 10. This behavior
was attributed to the buffer action on the CONH
2
groups of PAAm,
as previously reported by Lee and Wu [23]. Maximum swelling
absorption values were noticed at pH 11 for all NC hydrogels.
When the pH value is increased to 11, the hydrolysis of CONH
groups of PAAm increases and the electrostatic repulsion between
the molecular chains predominates, which results in further
expanding of the network. At the same time, the OH

groups in
the network were not changed in the basic condition.
In order to analyze the hydrolysis of CONH groups, FT-IR spec-
tra of the hydrogels exposed to different pH solutions were ob-
served as shown in Fig. 4. In the spectra, the peak of COO was
not observed, because the hydrolysis of PAAm in weak acidic and
basic environments at room temperature was still too low to be
observed. A very weak peak around 1560 cm
1
was only observed
in the spectrum for pH 11, which was the typical peak of COO.
3.3. Effect of clay content
The swelling capacity of pure PAAm hydrogel is very poor since
it is a nonionic polymer [24]. However, the PAAm/Lap NC hydro-
gels showed a higher swelling capacity. Haraguchi [25] theoreti-
cally claried that the polymer chains between the cross-linking
points in the hydrogels that were cross-linked by clay were long
and exible, and that the distribution of chain lengths was fairly
narrow. Therefore, it is reasonable to infer that the hydrogels
cross-linked by clay have lower cross-linking densities than those
of the hydrogels that are cross-linked by an organic cross-linker,
thus resulting in higher swelling ratios.
Fig. 7. FT-IR spectra of NC15 hydrogel after heat treatment different durations in neutral solutions: (a) 0 days, (b) 4 days, and (c) 6 days.
0 50 100 150 200
0
20
40
60
80
100
25
o
C
35
o
C
60
o
C
Time (hour)
W

(
%
)
Fig. 8. Swelling isotherm of NC15 hydrogel at different temperatures (0.01 M).
280 P. Li et al. / Composites: Part B 40 (2009) 275283
In Fig. 3(a)(c), it can be observed that the rate of water uptake
increases signicantly with an increase in the clay content if the
clay content was not very high (NC15 and NC20). This is because
as the clay content increases, the amount of negative charges in
the hydrogels increases and, hence the interaction between the
water molecules and anionic groups of the hydrogels is enhanced.
At the same time, as the clay content in the hydrogel increases, the
degree of cross-linking also increases, which would inhibit the
water adsorption capacity. Therefore, the swelling rate constants
of NC20 and NC25 are almost the same. Though the swelling rate
constants are similar, the equilibrium swelling degree of NC25 is
higher than that of NC20 and NC15, and this mainly depends on
the negative charges in the hydrogels.
3.4. Effect of heat treatment
Zhang, et al. showed that the swelling ratio of NC hydrogel in
pure water can be signicantly improved by heat treatment of
the gel [26]. However, the mechanism is still not very clear and
the swelling behaviors of heat treated NC hydrogel in different
pH solutions are still unknown. The NC hydrogels were heat trea-
ted at 60 C for different lengths of time viz. 2, 4, and 6 days, and
their inuence on the swelling behavior at different pH solutions
was investigated in this study.
The effect of duration of heat treatment on swelling isotherms
of NC15 hydrogels with different durations of heat treatment,
obtained in different pH solutions are shown in Fig. 5(a)(c). By
comparing these swelling isotherms with those of the original
NC15 hydrogel obtained at 25 C (Fig. 2), it was found that there
was a signicant improvement in the values of water absorption
capacity. The experimental data tted a straight line according to
Eq. (3) and the R
2
values obtained from the linear regression
analysis were higher than 0.999. In Fig. 6(a)(c), a comparison is
shown of the K, W
1
and Q of NC15 hydrogels for different dura-
tions of heat treatments and in different pH solutions. In most
cases, an increase in heat treatment duration signicantly in-
creases the K, W
1
and Q values. However, minimum values of
W
1
and Q were noticed at pH 3. The increase in W
1
values after
heat treatment of NC hydrogels between pH 4 and 11 is much
higher compared to the increase in W
1
values at pH 3. According
to Eq. (3), the difference in the absolute swelling degree value of
NC15 hydrogel after heat treatment for 2 days and 6 days from
pH 3 to pH 4 increases drastically from 0.05 g/g to 11.29 and
24.43 g/g, respectively. Therefore, after heat treatment, a new
pH sensitive area (pH 34) was formed. The FTIR (Fig. 7) results
show that the chemical components of the NC hydrogels are not al-
tered by the heat treatment and consequently a remarkable
improvement of the water swelling capacity values of the gels
should result from the change in the physical structure of the
hydrogel network [26,27]. Although the precise nature of the inter-
action between the PAAm and laponite clays is still not completely
understood, it is generally regarded as being a combination of ionic
interaction and hydrogen bonding [21]. It is assumed that a num-
ber of repeat units of the PAAm that interacted with the clay plate-
lets became detached from the clay surface during the heat
treatment. Thus, the number of repeat units of every PAAm chain
that interacts with the clay platelets decreases after heat treatment
and the free volume of the NC hydrogels increases. This reduces the
limitation of the network for water molecules and endows the NC
hydrogels with larger water absorbency [22]. However, in pH 3
solution, though the limitation of the network was reduced for
heat treated NC hydrogels, the driving force of water molecules
moving from the solution to the network was also reduced due
to the interaction between the OH and H
+
. However, for heat trea-
ted NC hydrogels in other pH solutions, the limitation was reduced
when the driving force was kept constant. By combining the above
0
20
40
Q

(
g
/
g
)
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
K

(
h
o
u
r
-
1
)
Temperature (C)
25 35 60
Temperature (C)
25 35 60
Temperature (C)
25 35 60
0
20
40
60
80
100
W

(
%
)
a b
c
Fig. 9. Effects of temperature on (a) swelling rate constant, (b) equilibrium water content, and (c) equilibrium swelling degree of NC15 hydrogel (0.01 M).
P. Li et al. / Composites: Part B 40 (2009) 275283 281
two factors, a pH-sensitive area was created by heat treatment
without changing the chemical structure of NC hydrogels. At the
same time, the sensitive degree (differences of equilibrium swell-
ing degree of heat treated NC hydrogels in pH 3 and 4) can be con-
trolled by the duration of heat treatment. It is also noted that the
equilibrium swelling degree of heat treated NC hydrogel in pH
11 is almost the same as that in pH 410. This might be because,
after heat treatment, the molecules of AAm were totally extended
in equilibrium swelling states, whereby the NC hydrogels reached
saturated states. Therefore, the NC hydrogels cannot adsorb more
water even after hydrolysis.
3.5. Effect of temperature
The inuence of temperature on the swelling behavior of NC
hydrogels is shown in Fig. 8 The pH and ionic strength of the solu-
tion are 7 and 0.01 M, respectively. The K, W
1
and Q values were
calculated according to the data from Fig. 8 and are shown in
Fig. 9(a)(c), respectively. From the gure it was found that with
an increase in temperature, the K, W
1
and Q values noticeably in-
creased. The increase of K, W
1
and Q with an increase of test tem-
perature, occurs because the water molecules have more kinetic
energy, which will accelerate its motion from outside into the NC
hydrogel network, specically increasing the rate constant K of
the swelling process. We have previously demonstrated that after
heat treatment the values of K, W
1
and Q increase. Therefore,
the NC hydrogel at higher temperatures (35 and 60 C) undergo a
similar heat treatment process during the test, which increases
the values of K and W
1
.
3.6. Effect of ion strength
It is important to identify the swelling behavior of hydrogels in
salt solutions in order to expand their applications especially for
hygienic products and agriculture. Fig. 10 shows the effect of the
ionic strength of NaCl solution on the water absorbency of the
NC15 hydrogels. K, W
1
, and Q were calculated and are shown in
Fig. 11(a)(c), respectively. It is well known that the water absor-
bency decreased with an increase in the ionic strength of the salt
solutions. This result may be attributed to the reduction in the
osmotic pressure difference between the hydrogel and the
external salt solution with increasing ionic strength. In addition,
the penetration of counterions (Li
+
, Na
+
, K
+
) into the network re-
sults in a more evident screening effect of counterions on the anio-
nic groups (COO

). This will also decrease the water absorbency

of the PAAm composite [23]. It can be seen from Fig. 11(a) and
(c) that the absorbency curves become atter as the ionic strength
of the saline solution increases.
Na
+
has no effect on COO

and CONH
2
groups, and the de-
crease of water absorbency for PAAm composite is mainly due to
the decrease of osmotic pressure and the screening effect. These re-
sults are all consistent with the decreasing of water absorbency for
0 50 100 150 200
0
20
40
60
80
100
W

(
%
)
Time (hour)
Pure water
0.01M
0.05M
0.1M
Fig. 10. Swelling isotherm of NC15 hydrogels in solutions with different ion
strengths.
0
20
40
60
Q

(
g
/
g
)
Ion strength (M)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
K

(
h
o
u
r
-
1
)
Ion strength (M)
1E-7 0.01 0.05 0.1
1E-7 0.01 0.05 0.1
1E-7 0.01 0.05 0.1
80
85
90
95
100
W

(
%
)
Ion strength (M)
a b
c
Fig. 11. Effects of ionic strength of solution on (a) swelling rate constant, (b) equilibrium water content, and (c) equilibrium swelling degree of NC15 hydrogel.
282 P. Li et al. / Composites: Part B 40 (2009) 275283
PAAm composite and the corresponding interpretation reported
elsewhere [28].
The well-known relationship between the swelling and salt
solution concentration is stated in Eq. (6);
Swelling kSalt
n
6
where k and n are constants for an individual super-absorbent. The
k value is the swelling at a high concentration of salt, and the value
of n is a measure of the salt sensitivity. The n value changes with the
cation valence enhancement. Based on our data, for NC15 hydrogel
in NaCl solution, n is 0.00642 and k is 0.892. The k values were <1
and were the same for all systems. Here, the ionic cross-linking fac-
tor was effective against swelling than the charge-screening effect
of the cation.
4. Conclusions
The pH values of external solutions have a signicant inuence
on the swelling behaviors of the NC hydrogels. The degree of
hydrolysis of the composite also plays a part in the swelling of
the NC hydrogels in various pH solutions. The effects of clay con-
tent (3345 by wt.%), temperature and heat treatment of NC
hydrogels on the swelling behavior at different pH values, are eval-
uated. The equilibrium water content (W
1
) and swelling percent-
age (Q) are markedly increased as increase in clay content and
temperature of swelling process. Heat treated hydrogels showed
signicant improvement in the swelling capacity, because the net-
work structure of the hydrogels cross-linked by the clay platelets is
more exible and homogeneous and is easy to change by heat
treatment. The heat treated NC hydrogels exhibited a pH sensitive
area between pH 3 to pH 4. A signicant reduction in water absor-
bency of hydrogels with an increase in the ionic strength of the
environment was noticed. This is due to the screening effect.
Acknowledgments
This research was supported by the 2nd Phase BK-21 program
and the National Space Laboratory (NSL) program
(S108A01003210), funded by the Ministry of Education, Science
and Technology of Korea. The authors are grateful for the nancial
support of the Korea Industrial Technology Foundation (KOTEF)
through the Human Resource Training Project for Regional
Innovation.
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