Front. Chem. Sci. Eng.
DOI 10.1007/s11705-015-1546-y
RESEARCH ARTICLE
Preparation and swelling properties of a starch-g-poly(acrylic
acid)/organo-mordenite hydrogel composite
Yan Zhang1,3, Pingqiang Gao3, Lin Zhao ()1,2, Yizhong Chen2
1 School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2 School of Environment Science and Engineering, Tianjin University, Tianjin 300072, China
3 School of Chemistry and Chemical Engineering, Yulin University, Shaanxi 719000, China
Higher Education Press and Springer-Verlag Berlin Heidelberg 2016
Abstract A novel hydrogel composite was prepared via
inverse suspension polymerization using starch, acrylic
acid and organo-mordenite micropowder with the cross-
linker, N,N-methylenebisacrylamide and the initiator,
potassium persulfate. Fourier transform infrared spectro-
scopy, X-ray diffraction spectroscopy, scanning electron
microscopy, and energy dispersive spectroscopy conrmed
that the acrylic acid was grafted onto the backbone of the
corn starch, that the organo-mordenite participated in the
polymerization, and that the addition of organo-mordenite
improved the surface morphology of the hydrogel
composite. The swelling capacity of the hydrogel compo-
site was evaluated in distilled water, and solutions with
different pH values, and various salt solutions. It was found
that the incorporation of 10 wt-% organo-mordenite
enhanced the water absorbency by 144% (from 268 to
655 g$g1) and swelling was extremely sensitive to the pH
values, the concentration of the salt solution and cation
type. Swelling kinetics and water diffusion mechanism of
the hydrogel composite in distilled water were also
discussed. Moreover, the hydrogel composite showed
excellent reversibility of water absorption even after ve
repetitive cycles and the hydrogel composite exhibited
signicant environmental-responsiveness by changing the
swelling medium from distilled water to 0.1 mol$L1 NaCl
solution. In addition, the loading and release of urea by the
hydrogel composite were tested and the nutrient-slow-
release capability of this material was found to be suitable
for many potential applications.
Keywords hydrogel composite, environmental-respon-
siveness, organo-mordenite, starch, acrylic acid
Received April 20, 2015; accepted September 5, 2015
E-mail: zhaolin@tju.edu.cn
1 Introduction
Hydrogels are crosslinked hydrophilic polymers that
absorb water, salt solutions, or other liquids [1]. By virtue
of their unique three-dimensional network structure and
their various functional groups, hydrogels have become an
important polymeric material and they have been applied
to various elds, such as agriculture [2], horticulture [3],
wastewater treatment [4], and adult incontinence products
[5]. When added to soil, hydrogels help speed absorption,
prolong the retention of water, and improve the fertilizer
retention capacity, which promotes the germination of
seeds and plant growth [6,7].
The conventional methods for hydrogel synthesis are
solution polymerization [2,8] and inverse suspension
polymerization [9,10] methods. The extreme solution
viscosity generated by solution polymerization leads to
problems, such as difculties with stirring and heat
transfer. In addition, heat elimination during these
polymerization reactions is challenging. There are also
some challenges during post-treatment, and the resin that is
obtained is a lump which must be cut, dried, and
pulverized prior to use.
Inverse suspension polymerization is a widely used
method for the preparation of polymers. Here a dispersion
consisting of a water-soluble monomer in an organic
matrix is maintained by vigorous stirring during the
reaction. The advantage of an inverse suspension is that
a ne powdery product is obtained, and the particle size
can be easily modulated by controlling the reaction
conditions. The inverse-suspension polymerization
method has been successfully employed to prepare water
soluble/swellable products, such as occulating agents
[11] and superabsorbent hydrogels [12].
Most hydrogels are made with synthetic poly(acrylic
acid). These hydrogels have poor biodegradability in soil
and pose an environmental problem. In addition, the
2 Front. Chem. Sci. Eng.
increasing prices of petrochemical feedstocks, waste
disposal issues as well as the desire to use renewable and
environmentally friendly resources have fueled the search
for alternative materials. For decades, starch, which is a
natural carbohydrate biopolymer, has received much
interest from both academic and industrial groups due to
its biodegradability, low cost, and versatility of use [13]. In
addition, different monomers can be easily grafted onto the
starch backbone to increase the hydrophilicity, hydro-
phobicity or polyelectrolyte properties of the starch [14].
Much research has focused on developing starch-grafted
copolymers with specic properties such as thermal
stability, high viscosity, biodegradability, and high water
absorption capacity [1517]. These copolymers have been
applied as occulants, ion exchangers, and superabsorbent
hydrogels.
In recent years, the design and development of organic-
inorganic hydrogel composites, especially ones containing
clay minerals, have attracted increasing attention. This type
of hydrogel composite can substantially reduce the nal
cost of the product and improve its properties (e.g.,
mechanical and thermal stability). Polyethylene-g-poly
(acrylic acid) composites with 3 wt-% organo-montmor-
illonite clay exhibit better water absorbency and gel
strength than composites without organo-montmorillonite
clay. The thermal properties of hydrogel composites have
also been improved by introducing montmorillonite which
created a crosslinking effect and improved the nanostruc-
ture [18]. In addition, the inclusion of inorganic clays into
hydrogels has been shown to decrease their nutrient-
release rate in distilled water [19].
Zeolites, which have been used as a clay material, are
highly crystalline aluminosilicates represented by the
x
general formula Mn x=n AlO2 x SiO2 y  $zH2 O (where 2 Materials and methods
M is a metal cation, a proton or less frequently a charged
molecule). Zeolites are characterized by a three-dimen-
sional, regular intracrystalline array. Mordenite, which is a
natural zeolite, has been widely used in agricultural
applications due to its large surface area, large ion
exchange capability, and low cost. The unique physical
and chemical properties of mordenite makes it suitable as a
fertilizer carrier to promote efcient nutrient use [20], as a
soil additive to increase crop yields [21], and as an
absorbent in the removal of heavy metals from soil [22].
The controlled release of ammonium, potassium, and
calcium has been achieved using mordenite as an additive
to attract, retain, and slowly release critical plant nutrients
[23]. However, little information on the effect of mordenite
on the water absorption of hydrogel composites has been
reported.
Due to their surface structures and surface interactions,
nanosized zeolite has a strong tendency to aggregate
[24,25]. Therefore, when zeolite is directly added to a
polymer system, it tends to irregularly disperse. The
differences in the zeolite and polymer interfacial char-
acteristics cause poor compatibility which can affect the
nal properties of the composite. Therefore, prior to
incorporation into a polymer, zeolite need to rst be
chemically modied.
Surfactants are water-soluble organic molecules that
have hydrophilic and hydrophobic properties. Cationic
surfactants with positively charged head groups, such as
alkyl ammonium compounds, attached to a hydrocarbon
moiety have been utilized to form organic-modied clays
[18].
Recently, hydrogels with a slow-release property for use
as fertilizers have attracted much attention [26,27]. The
water-absorbing abilities and the slow-release properties of
these hydrogels may make them useful in agricultural
applications especially in the area of water-management
[28]. Urea is the most widely used nitrogen fertilizer due to
its high N content (46%) and comparatively low cost.
Therefore, urea is commonly used to test the release
properties of superabsorbents [2932].
In this study, a low cost starch zeolite composite was
prepared and its potential applications were studied. The
swelling behaviors of the hydrogel composites were
investigated in distilled water, various cationic salt
solutions, and the solutions with different pH values,
respectively. The kinetics of the swelling behaviors and the
reversibility of water absorption in distilled water were
examined. In addition, the environmental-responsiveness
of the hydrogel composites was tested in terms of their
swelling and deswelling in distilled water and 0.1 mol$L1
NaCl solutions. Finally the loading and release of urea by
the hydrogel composites were also evaluated.
2.1 Materials
The starch used in this work was corn starch, which was
obtained from Ding Yan Trading & Property Co. Ltd.
(Tianjin, China). Mordenite obtained from Nankai Uni-
versity Catalyst Company (Tianjin, China) was milled
through a 320-mesh screen. The cationic surfactant,
hexadecyltrimethyl ammonium bromide (CTAB), and the
initiator potassium persulfate, were obtained from the Ke
Wei Chemical Reagent Company (Tianjin, China). Potas-
sium persulfate was puried by recrystallization in distilled
water and dried at 50 C in a vacuum oven. The reactive
monomer, acrylic acid (AA) and hydrochloric acid were
purchased from the Da Mao Chemical Reagent Factory
(Tianjin, China). Acrylic acid was puried with distilled
water under vacuum. The crosslinker N,N-methylenebi-
sacrylamide (MBA), sodium hydroxide, acetone, and
anhydrous ethanol were supplied by Kermel Chemical
Reagent Company (Tianjin, China). Polyglyceryl fatty acid
ester (PGFE), a suspension stabilizer, was purchased from
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite
the Da He Foods and Technologies Co., Ltd. (Zhengzhou,
China).
2.2 Organo-mordenite
Organo-mordenite was prepared using the procedure
reported by Zhang et al. [33]. Briey, 2 g of mordenite
and 25 mL of CTAB aqueous solution (31 mmol$L1) were
placed in a 100-mL conical ask. The ask was kept in a
water bath at 70 C while sonicating for 60 min. The
reaction product was then ltered and washed several
times with anhydrous ethanol to ensure the complete
removal of the Br. The product was then dried to a
constant weight at 60 C.
2.3 Synthesis of starch-g-poly(acrylic acid)/organo-
mordenite hydrogel composite
The starch-g-poly(acrylic acid)/organo-mordenite hydro-
gel composite was prepared by inverse suspension
polymerization according to the following steps. First
4.8 g of starch was solubilized in 50 mL of distilled water
at 95 C for 30 min using a 500-mL four-neck ask
equipped with a condenser, stirrer, thermometer, and
nitrogen line. Next, the ask was cooled to 3540 C,
and 300 mL of cyclohexane and 0.12 g of suspension
stabilizer (PGFE) were added to the system. The slurry was
stirred for 15 min, and 8.7 mL of the potassium persulfate
initiator (5 g$L1) was added. This solution was then stirred
for 15 min. After that 80% neutralization degrees of AA
solution (14.4 g of AA was pre-neutralized using 32 mL of
20 wt-% NaOH solution in an ice bath) , organo-mordenite
(the mass ratio of organo-mordenite to AA were 5 and 10
wt-%, respectively) , and 2.5 mL of the MBA crosslinking
agent (5 g$L1) were successively added to the system. The
water bath was heated slowly to 70 C and the ask was
maintained at this temperature for 3 h to carry out the
polymerization reaction. The system was mechanically
stirred (400600 r$min1) throughout the entire process.
After the polymerization was complete, the reaction
mixture was rst immersed in anhydrous ethanol to
remove the residual reactants. Next, the product was
fully washed with distilled water. In the end, the crude
products were then oven-dried at 70 C to a constant
weight. The starch-g-polymer composite was extracted
from the crude products with acetone for 10 h to obtain the
pure hydrogels. A control sample with no organo-
mordenite was also prepared according the above
procedure. This sample is referred to as starch-g-poly
(acrylic acid) hydrogel.
2.4 Evaluation of the water absorbency and swelling
kinetics of the hydrogels
The water absorbency was determined at ambient
3
temperature. The hydrogels (0.1 g) were immersed in
distilled water (400 mL) for 24 h to reach swelling
equilibrium. Residual water was removed by placing the
water-saturated hydrogel on a 200-mesh screen and
allowing the excess water to drip off for 5 min. The
water absorbencies for the hydrogels were determined
from:
m m0
W , (1)
m0
where W is the mass of the gained water (g) per gram of
hydrogel, m is the mass of the swollen absorbent, and m0 is
the mass of the dry material. All of the procedures were
performed in triplicate, and the reported value is the
average of the three replicates.
The water absorbencies of the samples in various salt
solutions (i.e., NaCl, CaCl2, and AlCl3) with different
concentrations (0.1, 0.3, 0.5, 0.7, 0.9, and 1.2 wt-%) were
also tested using the same procedure.
The water absorbencies of the hydrogels in the solutions
of different pH values were analyzed. The solutions with
acidic and basic pH were prepared by dilution of
hydrochloric acid (pH 1.0) and sodium hydroxide solution
(pH 13.0), respectively, to get pH levels of 1.0, 2.0, 3.0,
7.0, 9.0, 11.0, and 12.0. The water absorbencies of the
hydrogels were measured in each case according to Eq. (1).
Kinetic swelling behaviors of hydrogel composite in
distilled water were measured by the following procedure:
0.1 g sample was immersed in 400 mL of distilled water for
set period of time. Then, the swollen gels was ltered using
a 200-mesh screen, and the water absorption (Wt) of
hydrogel composite at a given time (t) can be measured by
weighing in the swollen and dry sample, and calculated
according to Eq. (1). In all cased three parallel samples
were used and the average are reported in the paper.
2.5 Environmental-responsiveness of the hydrogel
The environmental-responsiveness of the hydrogel com-
posites were tested in terms of their swelling and
deswelling in distilled water and 0.1 mol$L1 NaCl
solutions. Typically, the hydrogel composites (0.1 g)
were immersed in 400 mL of distilled water for a set
period of time intervals until reaching equilibrium. Then,
the swollen samples were soaked in 0.1 mol$L1 NaCl
solutions for set time intervals. Finally, the swollen
samples were ltered, weighted and then calculated to
the mass change of samples before and after swelling. The
same procedure was repeated for three cycles. After every
cycle, each solution was renewed.
2.6 Reversibility of the absorption by the hydrogels
The reversibility of the water absorption was determined
by repeatedly swelling and drying the hydrogels. The
4 Front. Chem. Sci. Eng.
swollen samples were dried in an oven at 80 C and then
re-immersed in distilled water until the gel reverted to its
swollen state. The wn (where n is the nth absorption/drying
cycle) were calculated using Eq. (1). All the procedures
were performed in triplicate, and the reported value is the
average of the three replicates.
2.7 Loading of urea
Urea was loaded onto the hydrogels by immersing the dry
gels (1.0 g) in various urea solutions for 20 h to achieve
swelling equilibrium. Thereafter, the mixture was washed
with distilled water to remove any unloaded and free urea.
Then the swollen gels were dried at 60 C for 6 days.
Finally, the dried products were milled and screened [34].
The loading percentage was calculated using:
m2 m1
Loading%  100% (2)
m2
where m1 and m2 are the weights of the unloaded and
loaded dry gels respectively. All of the procedures were
performed in triplicate, and the reported value is the mean
of the three replicates.
2.8 Release of urea from samples in water
A Unico Model UV-2800 spectrophotometer with matched
Corex cells was used to measure the transmittance of the
samples. A loaded dry hydrogel (0.1 g) was placed in a
tapered bottle, which was lled with 400 mL of distilled
water (release medium). The amount of urea in the aqueous
solution was then determined at 3, 6, 15, 24, and 48 h, and
a urea release curve was then prepared from this data. The
amount of urea released was determined by a spectro-
photometric method using p-dimethylaminobenzaldehyde
in a hydro-alcoholic medium with hydrochloric acid as the
reagent [35]. The percent release was calculated using:
Mt
Re lease%  100% (3)
Me
where Mt is the weight of urea released into distilled water
at time t (min), and Me is the weight of the urea loaded onto
the hydrogel.
2.9 Characterization of the hydrogels
Fourier transform infrared (FTIR) spectra of the hydrogels
pressed into KBr pellets were recorded on a NICOLET-
6770 FTIR instrument from 4004000 cm1. Powder X-ray
diffraction spectra of the samples was performed on a
Bruker X-ray diffractometer with Cu K radiation ( =
0.15406 nm). A FEI (USA) Nanosem 430 Scanning
electron microscope operated at an acceleration voltage
of 10.0 kV was used to obtain surface micrographs of the
samples after the samples were coated with a gold lm.
Energy-dispersive spectroscopy (EDS) combined with
scanning electron microscopy (SEM) was used to analyze
the elements in the samples. The applied voltage was
15.0 kV with a current of 20.0 A.
3 Results and discussion
3.1 Preparation and characterization of the hydrogels
3.1.1 Hydrogel preparation
The hydrogel samples were prepared by the inverse
suspension polymerization of acrylic acid onto corn starch
with organo-mordenite as an inorganic clay using MBA as
a crosslinker. The proposed mechanism for the formation
of starch-g-poly(acrylic acid)/organo-mordenite is shown
in Fig. 1. In the rst step, potassium persulfate, a free
radical initiator, was decomposed by heating to generate
sulfate anion-radicals. The anion-radicals then abstracted
hydrogen from the starch hydroxyl groups to form macro
radicals. These macro radicals were on the starch backbone
chains and can initiate the grafting of the acrylic acid
monomer molecules. Then, the monomer molecular
became free radical donors to neighboring molecules,
resulting in the growth of polymer chains. After that, MBA
as a bi-functional crosslinker [36] reacted with the polymer
chains during chain progagation. In this way, a cross-
linked structure was formed. Finally, the organo-mordenite
was then dispersed throughout the polymeric system.
3.1.2 FTIR analysis
FTIR spectroscopy is an important technique for exploring
intermolecular interactions between certain functional
groups [37]. The formation of hydrogen bonds in a
copolymer hydrogel, such as starch-g-poly(acrylic acid), is
one kind of molecular interaction that can be studied using
FTIR spectroscopy. The FTIR spectra of the organo-
mordenite, starch, starch-g-poly(acrylic acid) and starch-g-
poly(acrylic acid)/organo-mordenite (10 wt-% organo-
mordenite) are shown in Fig. 2.
Figure 2(a) displays a broad peak at 3473 cm1 which is
due to the mordenite (Al OH Al) and (Si OH Si)
hydroxyl stretching vibrations [38]. The peaks at 1643 and
1034 cm1 correspond to H O H bending vibrations and
Si O (Si) or Si O (Al) stretches, respectively. The peak
at 453 cm1 is due to internal (Si, Al) O vibrations [39].
The absorption bands at 2922 and 2848 cm1 correspond to
the asymmetric and symmetric stretching vibration of the
CTAB methylene groups [39,40], which conrm the
modication of mordenite.
Figure 2(b) shows the characteristic spectrum of
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite
Fig. 1 Proposed mechanism for the synthesis of the starch-g-poly(acrylic acid)/organo-mordenite hydrogel composite
cornstarch. The peak at 1647 cm1 is due to the carbonyl
stretching mode of glucomannan [41]. The broad band at
3421 cm1 is due to polysaccharide hydroxyl group
stretches. The C O C stretching bands are at 1158 and
1080 cm1. After grafting acrylic acid onto the starch
(starch-g-poly(acrylic acid), new peaks appeared in the
spectrum, as shown in Fig. 2(c). These include a C = O
stretching band at 1710 cm1, symmetric and asymmetric
COO bands at 1415 and 1560 cm1, respectively, and a
medium peak at 3512 cm1 which is due to water
molecules. The peak at 2934 cm1 is due to C H
symmetric stretching. These results conrm that acrylic
acid was grafted onto the starch. Earlier studies on the
copolymerization of starch with acrylic acid support this
result [42].
The spectrum for starch-g-poly(acrylic acid)/oragno-
mordenite is shown in Fig. 2(d). Compared with the
spectrum for starch-g-poly(acrylic acid), the C = O
stretching band at 1710 cm1 shifted to 1720 cm1, and
the asymmetrical stretching band at 1560 cm1 shifted to
1566 cm1. The organo-mordenite Si O stretching band at
1093 cm1 became much weaker and shifted to 1027 cm1
for the composite. In addition, the external and internal (Si,
Al) O vibrational peaks are also seen in the composite at
5
824 and 453 cm1 respectively although with weakened
intensities. These results prove that the organo-mordenite
participated in the grafted copolymerization through its
active silanol groups [4345].
3.1.3 X-ray diffraction (XRD) analysis
XRD was employed to investigate the structure and
crystallinity of the samples. Figure 3 shows the XRD
patterns of starch-g-poly(acrylic acid), organo-mordenite,
and starch-g-poly(acrylic acid)/organo-mordenite. The
XRD pattern of the starch-g-poly(acrylic acid) hydrogel
(Fig. 3(a)) exhibits a weak broad peak at 2 = 22. This
peak indicates an amorphous structure with low crystal-
linity. Similar results have been previously reported by
Kaur et al. [42].
The XRD spectrum for organo-mordenite is shown in
Fig. 3(b). The spectrum contains diffraction peaks at 2 =
6.5, 8.6, 9.7, 13.5, 15.1, 21.5, 24.6, 26.1, 27.8,
and 30.3 which correspond to Miller indices of [110],
[020], [200], [111], [310], [330], [420], [202], [350], and
[511], respectively [46]. Figure 3(c) shows the XRD
patterns of the starch-g-poly(acrylic acid)/organo-morde-
nite hydrogel composite. This spectrum contains the same
6 Front. Chem. Sci. Eng.
Fig. 2 FTIR spectra of (a) organo-mordenite, (b) starch,
(c) starch-g-poly(acrylic acid) and (d) starch-g-poly(acrylic acid)/
organo-mordenite hydrogel composite with 10 wt-% of organo-
mordenite
Fig. 3 XRD spectra of (a) starch-g-poly(acrylic acid) hydrogel,
(b) organo-mordenite, and (c) starch-g-poly(acrylic acid)/organo-
mordenite with 10 wt-% organo-mordenite
crystallite peaks as the mordenite spectrum conrming the
presence of mordenite in the hydrogel composite. Due to
the existence of the starch-g-poly(acrylic acid) hydrogel on
the outer and inner surfaces of the mordenite lattice
channels, the intensity of the peaks associated with
mordenite decreased.
3.1.4 SEM and EDS analysis
The SEM micrographs of the starch-g-poly(acrylic acid)
hydrogel, the organo-mordenite and the starch-g-poly
(acrylic acid)/organo-mordenite hydrogel composites (5
and 10 wt-%) are shown in Fig. 4. The starch-g-poly
(acrylic acid) hydrogel microspheres (Fig. 4(a)) had a
diameter of less than 0.8 m and the surface morphologies
are compact and smooth. The organo-mordenite showed a
correspondingly coarse and sheet surface morphology
(Fig. 4(b)). After doping organo-mordenite into the starch-
g-poly(acrylic acid), the surface roughness and the particle
size were obviously increased and some folds can be
observed (Fig. 4(c)). As the amount of organo-mordenite
in the composite increased, the number of surface folds
also increased (compare Fig. 4(c) (5 wt-%) with Fig. 4(d)
(10 wt-%)). When the surface of the hydrogel composite is
folded, the material has a higher specic surface area.
These folds may be regions where water or other external
stimuli can permeate and interact with the hydrophilic
groups of the grafted copolymers, which facilitated the
permeation of water into the polymeric network [47]. In
addition, it should be pointed out no bulk mordenite was
observed in the hydrogel composites, indicating that the
organo-mordenite was well dispersed in the hydrogel
composite.
Figure 5 shows the EDS spectra of starch-g-poly(acrylic
acid), organo-mordenite, and starch-g-poly(acrylic acid)/
organo-mordenite (5 and 10 wt-%), corresponding to the
surface of samples shown in (Figs. 4(a)4(d)). In the EDS
spectrum of starch-g-poly(acrylic acid) (Fig. 5(a)), only
peaks for C, O and Na are observed and the weight
percentage of these elements were 68.1%, 27.7%, and
3.31%, respectively. The organo-mordenite (Fig. 5(b)) was
consisted of C, O, Si, Al, and Na. The weight percentages
of these elements were 14.8 %, 37.9%, 39.05%, 2.7%, and
5.3%, respectively. The spectra of the starch-g-poly(acrylic
acid)/organo-mordentie composites (Figs. 5(c)5(d)),
showed peaks for C, O, Si, Al, and Na. Here, Si and Al
can all be attributed to the presence of organo-mordenite
(Fig. 5(b)). The C, O, and Na of the hydrogel composites
(with 5 and 10 wt-% organo-mordnite) were attributed to
the hydrogel and the organo-mordenite. The C, O, and Na
of the hydrogel composites (with 5 wt-% organo-mordnite)
were 48.6%, 24.7%, and 24.6%, respectively. The C, O,
and Na of the hydrogel composites (with 10 wt-% organo-
mordnite) were 49.4%, 26.2%, and 20.51%, respectively.
This indicated that organo-mordenite was distributed in the
polymer matrix.
3.2 Effect of the amount of organo-mordenite on the water
absorbency of the hydrogel composites
The effect of the amount of organo-mordenite on the water
absorbency of the hydrogel composite is shown in Fig. 6.
The addition of any amount of mordenite increased the
amount of water absorbed by the hydrogel composite. This
phenomenon could be attributed to the organo-mordenite,
which participates in the polymerization reaction. Zhang
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite 7

Fig. 4 SEM micrographs of (a) starch-g-poly(acrylic acid), magnication 50000, (b) organo-mordenite, magnication 6000, (c) starch-
g-polyacrylic aicd)/organo-mordenite (5 wt-%), magnication 5000, and (d) starch-g-polyacrylic aicd)/organo-mordenite (10 wt-% ),
magnication 5000

et al. [48] observed similar proles for hydrogel compo-
sites with and without attapulgite. In addition, when
organo-mordenite is below 10 wt-%, water absorbency
increased with the increase in organo-mordenite content.
The repulsive forces between the COO groups of the
hydrogel and the negative surface charges of mordenite
results in an expansion of the hydrogel network which in
turn results in higher water absorbency [49]. However, the
water absorbency of the hydrogel composite decreased for
higher organo-mordenite. This is probably due to some
reasons. On the one hand, the generation of more
crosslinking points may produce fewer network voids
[50], which could restrict the movement of the polymer
chains. On another hand, excessive organo-mordenite may
physically stack inside the network voids which plug them
[44]. Besides that, starch-g-poly(acrylic acid) is respon-
sible for the water absorbency of the hydrogel composites,
so a higher zeolite content results in less starch-g-poly
(acrylic acid) which decreases the water absorbency.
Finally, when the amount of the organo-mordenite was
10 wt-%, the maximum water absorbency (655 g$g1) was
obtained.
3.3 Swelling kinetics of the hydrogels
The swelling behavior of a hydrogel is inuenced by
various factors, such as the composition of the absorbent,
the size, and the surface area [51]. Therefore, the effect of
introduction of organo-mordenite into the polymeric
system on the swelling behavior in distilled water was
studied and the results are shown in Fig. 7.
It was observed that the synthesized hydrogels reached
their equilibrium swelling values after 150 min and 300
min for hydrogel and hydrogel composite. Also, it can be
seen that the water absorbency for the hydrogel composite
was always higher than that of pure hydrogel without
organo-mordenite.
The swelling curves were used to evaluate the swelling
mechanism and the effect of incorporating organo-
mordenite on the swelling kinetics of hydrogels. The
8 Front. Chem. Sci. Eng.

Fig. 5 EDS spectra of (a) starch-g-poly(acrylic acid), (b) organo-mordenite, (c) starch-g-polyacrylic aicd)/organo-mordenite (5 wt-%),
and (d) starch-g-polyacrylic aicd)/organo-mordenite (10 wt-%)

Fig. 6 Effect of the amount of organo-mordenite on the swelling Fig. 7 Swelling behavior of starch-g-poly(acrylic acid) hydrogel
capacity of starch-g-poly(acrylic acid)/organo-mordenite hydrogel and starch-g-poly(acrylic acid)/organo-mordenite hydrogel com-
composite (10 wt-%) in distilled water posite (10 wt-%) as a function of time in distilled water

experimental data was tted using Schotts pseudo second t 1 t

, (6)
order swelling kinetic model [52]. The model can be Wt ks W12 W1
expressed as:
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite 9

where Wt is the swelling absorbency (g$g1) at swelling Wt

time t (min), W1 is the theoretical equilibrium swelling kt n , (5)
W1
absorbency, and ks is the swelling rate constant ((g$g1)
$min1). Since  
Wt
ln lnk nlnt, (6)
kis ks W1
2
, (7) W1

where kis is the initial swelling rate constant ((g$g1) where Wt and W1 are the quantities of equilibrium water
$min1) The equation can be also be expressed as: uptake and maximum water uptake at time t, respectively, k
is a proportionality constant, and the exponent n describes
t 1 t the type of diffusion mechanism. For Fickian diffusion, n is
: (8)
Wt kis W1 less than 0.5 [36], and for non-Fickian or anomalous
diffusion, n is between 0.5 and 1.0. For case-II diffusion
The plots of t/Wt versus t are shown in Fig. 8(a). The
(relaxation-controlled transport), n = 1.0 and for supercase-
slopes and intercepts of the best t lines were determined
II diffusion, n is greater than 1.0 [54]. A plot of ln (Wt/W1)
and are shown in the gure. The theoretical swelling value
as a function of lnt was used to obtain the values of n for
(W1), the rate constant for swelling (ks), the initial
the hydrogel and hydrogel composite samples in distilled
swelling rate constant (kis), and the kinetic tting
water and is shown in Fig. 8(b). The swelling exponents
parameters are given in Table 1. As shown in Fig. 8(a),
(n) are equal to the slope of the lines. As shown in Table 1,
the plot of t/Wt versus t for both starch-g-poly(acrylic acid)
the n values were 0.30 and 0.38 for the hydrogel and
and starch-g-poly(acrylic acid)/organo-mordenite gave
hydrogel composite, respectively. Since these values are
straight lines with high linear correlation coefcients
less than 0.5, this indicates that the transport mechanism
(R2 > 0.98). The theoretical values for W1 are in good
followed Fickian diffusion.
agreement with the experimental data, which indicates that
the swelling process followed Schotts swelling kinetic
3.4 Effect of pH values on the water absorbencies of the
model.
hydrogels
To determine the nature of the diffusion of the water into
the hydrogels, the following equation was used for the rst The pH sensitivity of hydrogels has gained much attention
60% of the fractional liquid uptake [53]. on various applications in the biomedical elds [55].

Fig. 8 Swelling behavior of the starch-g-poly(acrylic acid) hydrogel and the starch-g-poly(acrylic acid)/organo-mordenite hydrogel
composite (10 wt-%) in distilled water (a) t/Wt versus t and (b) ln(Wt/W1) versus lnt.

Table 1 Swelling kinetics and diffusion parameters for starch-g-poly(acrylic acid) and starch-g-poly(acrylic acid)/organo-mordenite (10 wt-%)
Kinetics parameters Diffusion parameters
Sample a
We
b
W1
c
ks
d
kis R 2 ne) R2

Starch-g-ploy (acrylic acid) 268 278 2.9104 22.5 0.9993 0.30 0.8158
5
Starch-g-poly(acrylic acid)/ organo-mordenite 655 943 1.310 11.5 0.9801 0.38 0.9325
1 1 1 1
a) Equilibrium swelling (gwater gabsorbent ); b) equilibrium theoretical swelling (gwater gabsorbent ); c) constant rate for swelling [(gwater gabsorbent )$min ]; d) initial swelling
1
constant [(gwater gabsorbent )$min1]; e) diffusion parameters (gwater gabsorbent
1
)
10
Fig. 9 Effect of pH values on the water absorption of hydrogels
Figure 9 shows the swelling prole for the hydrogel
composite (with 10 wt-% organo-mordenite) and the pure
hydrogel in all pH solutions ranging from 1 to 12. From
this investigation, it was shown that the swelling behavior
of the hydrogels was dependent on the pH value. The
swelling behavior of the hydrogels was increased with
increasing pH from 1 to 7, and further increasing of pH
from 7 to 12 signicantly decreased the swelling
absorbency. When the pH value of the swelling medium
increased from pH 2, the COOH groups dissociated into
COO anions that caused the enhancement of the anion-
anion repulsive. This in turn led to relaxation of the
network and then more water could diffuse into the
network, thereby could increment the swelling absorbency.
When the pH values of the swelling medium was greater
than 7, the Na+ cations from NaOH solutions shielded the
COO groups and prevented perfect anion-anion repul-
sion in the cross-link hydrogels. This resulted in a
reduction in the expansion of the network and a decrease
in the swelling absorbency. A similar pH-dependent
Fig. 10 Absorption of various salt solutions by hydrogels (a) starch-g-poly(acrylic acid)/organo-mordenite hydrogel composite
(10 wt-% organo-mordenite) and (b) starch-g-poly(acrylic acid)
Front. Chem. Sci. Eng.
swelling behavior has been observed in another ionic
hydrogel system [56].
The water absorbency of the hydrogel composite was
higher than that of the pure hydrogel at pH 7. On the one
hand, most of the COOH groups were tend to converted
to COO at this pH value, and this resulted in high
electrostatic repulsion that may cause an enhancement in
the swelling absorbency. On another hand, the deprotona-
tion of surface silanols and disruption of hydrogen bonds
occur at pH values close to neutral. The repulsion of the
SiO centers and COO groups resulted in the high
absorbency ability of the hydrogel composite [57]. There-
fore, the introduction of mordenite into the polymeric
network improved the pH sensitivity of the hydrogel
composite.
3.5 Effect of salt solution on water absorbency of the
hydrogels
Salinity is an inuence on the swelling properties of
hydrogels. When hydrogels are used in hygienic products
or agricultural applications, the liquid that interacts with
the hydrogel contains a variety of electrolyte ions or salts.
Therefore, the effect of the samples to absorbing different
concentrations of different salt solutions has to be known.
The effect of the concentration of the chloride salt
solutions (NaCl, CaCl2, and AlCl3 aqueous solutions) on
the swelling behavior of the hydrogel composite (with 10
wt-% organo-mordenite) and the pure hydrogel were
investigated. As shown in Fig. 10, respectively, the
experimental results indicated that the water absorbencies
decreased with increasing the concentration of the salt
solutions for all the samples. A screening effect of the
additional cations from the salt solutions caused a non
efcient anion-anion electrostatic repulsion. This led to the
reduction of the osmotic pressure difference between the
hydrogel network and external solution [41,58]. And then,
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite 11

the decreasing swelling driving force induced a decrease in

the water absorbency.
The absorbencies of the hydrogels in various salt
solutions were measured to determine the resistance to
salts. For a given conectration of salt solution from the Fig.
10, the water absorbency in NaCl solution was higher than
that in CaCl2 and AlCl3 solutions. This result may due to
the ability of carboxylate groups in the hydrogels to form
complexes with the cations from the salt solutions. Based
on their formation constants with ethylenediaminetetraa-
cetic acid, the ability of the hydrogel carboxylate group to
complex with the three studied cations should be in the
order Na+ < Ca2 + < Al3+ [43] and this order is in good
agreement with the absorption results.
The introduction of the organo-mordenite also affected
the water absorbencies of the hydrogels in salt solutions.
Fig. 11 Environmental-responsiveness of starch-g-poly(acrylic
Because The long alkyl chains of CTAB can interfere with
acid)/mordenite hydrogel composite: swelling in distilled water
the formation of a complex between the carboxylate and deswelling in NaCl (0.1 mol$L1)
groups and the cations, which weakens the screening effect
of the cations [59]. Therefore, the introduction of
in Fig. 12. For the pure hydrogel, the water retention
mordenite into the polymeric network was apt to the
signicantly decreased with repetitive absorptions. The
generate a salt-resistant hydrogel composite.
water absorbency was only 145 g$g1 in the fth repetitive
cycle. In comparison, the hydrogel composite had a water
3.6 Environmental-responsiveness of the hydrogel
absorbency of 580 g$g1 even after the fth cycle. This
composite
improvement may be due to the presence of organo-
mordenite in the hydrogel composite which is responsible
Figure 11 depicts the circular swelling-deswelling beha-
for the better network of the hydrogel composite. The
vior of the hydrogel composite (with 10 wt-% organo-
better network prevented the decrease of the water
mordenite ) in distilled water and a 0.1 mol$L1 NaCl
absorption during the repeated swellings of the hydrogel
solution. As can be seen, the water-swollen hydrogel
composite [61].
composite can shrink and loss the absorbed water when it
was soaked into the NaCl solution, but the shrunken gel
can be recovered in distilled water. The switching salt
stimuli-responsive property was achieved. The dramatic
decrease of water absorbency in NaCl solution could be
due to the fact that Na+ ions from the NaCl solution and the
carboxylate groups from the hydrogel composite could
form the intra- and intermolecular complexes, leading to
deswelling of the hydrogel composite. After three circles
of swelling (On)-deswelling (Off), the hydrogel composite
still keeps excellent water absorbency, indicating the
swelling is switched and reversible. This environmental-
responsiveness (i.e., reversible swelling and deswelling)
has been reported for other hydrogels [60]. The sharp
swelling-deswelling behavior of the hydrogel composite
makes it suitable candidates for controlled systems.

3.7 Reversibility of water absorption

Many practical elds, such as architecture and agriculture,
require hydrogels with good repeated absorbencies after
they are used a few times for economic purpose. In this
work, the reversibilities of water absorption for the
hydrogel composite (with 10 wt-%) and the pure hydrogel
were investigated and their experimental results are given
Fig. 12 Reversibility of the hydrogels in distilled water
3.8 Swelling of the hydrogel composite in aqueous
solutions of urea
To load urea, the hydrogel composite (10 wt-% organo-
mordenite) was swollen in aqueous solutions of urea with
12 Front. Chem. Sci. Eng.
the concentrations of 0.02, 0.04, 0.08, and 0.12 mol$L1,
respectively. As shown in Fig. 13, the swelling capacity of
the hydrogel composite is dependent on the concentration
of the urea solution. The swelling absorbency increases
with the concentration of urea solution increasing from
0.02 to 0.04 mol$L1, but slightly decreases when this
concentration further increases from 0.04 to 0.12 mol$L1.
A possible reason for the behavior might be as follows.
When the concentration of the urea solution was less than
0.04 mol$L1, urea does not affect the electrostatic
repulsion force of COO on the polymer chain and has
hydrophilic sites, such as NH2, which may improve the
interaction between water and the polymer network.
Therefore, with the concentration of the urea solution
increasing, the swelling absorbency of the hydrogel
composite increases. However, when concentration of the
urea solution is greater than 0.04 mol$L1, the existence of
the excessive urea leads to osmotic pressure differentials in
the hydrogel composite, which may facilitate water
molecules to move in the direction of the electrolyte
dilution concentration [62]. Thus, a decrease in the
swelling absorbency with increasing the concentration of
the urea solution was observed.
Fig. 13 The equilibrium swelling capacity of the hydrogel
composites (10 wt-% organo-mordenite) in urea solutions with
different concentrations (0.02, 0.04, 0.08, and 0.12 mol$L1)
The loading percentages of urea are 17.2%, 36.5%,
46.5%, and 48.6% for aqueous urea of the hydrogel
composite with various concentrations of 0.02, 0.04, 0.08,
and 0.12 mol$L1, respectively, indicating that the con-
centration of the urea solution affects the urea loading
percentage of the hydrogel composite. This may be
because when hydrogels are in the urea solution with a
high concentration, more urea molecules enter into the
polymer network and remain in the three-dimensional
network after drying, leading to the high loading
percentage of urea [56].
3.9 Release of urea from loaded hydrogel composite in
distilled water
Figure 14 depicts the releasing proles of urea from loaded
hydrogel composite with 10 wt-% organo-mordenite (urea
loading percentage: 46.5%) in distilled water. In the case of
the hydrogel composite, the releasing rate is initially high
(up to 24 h), and then gradually decreases. The releasing
percentage of urea in the starch-g-poly(acrylic acid)/
organo-mordenite is 93% for 48 h.
Fig. 14 Release of urea from loaded starch-g-poly(acrylic acid)/
organo-mordenite (with 10 wt-% organo-mordenite)
The release mechanism of urea from the loaded hydrogel
composite can be explained as follows. The slow release of
urea may be due to the signicant dissolution of urea in the
distilled water. When the hydrogel composites swell in
distilled water, the soluble urea dissolved into the distilled
water from the hydrogel composite network. The encap-
sulated urea in the network of the hydrogel composite is
released quickly. Then, a relatively quick increase of the
urea content was initially observed. When this process
ends, the soluble urea chemically bonded to the chains of
the composite hydrogel is slowly released from the
network of the hydrogel composite, resulting in a slow
increase in the urea content. This result indicates that the
hydrogel composite is endowed with an additional slow-
release property for fertilizer.
4 Conclusions
A novel hydrogel composite (starch-g-poly(acrylic acid)/
organo-mordenite) was synthesized by inverse suspension
copolymerization. The analyses by FTIR, XRD, SEM, and
EDS conrm that the organo-mordenite has been incorpo-
rated into the polymeric matrix of the hydrogel. The
incorporation of the organo-mordenite increases the
 Yan Zhang et al. Preparation and swelling properties of a hydrogel composite
swelling capabilities of the novel hydrogel composite (the
maximum water absorbency is 655 g$g1 when 10 wt-%
organo-mordenite is incorporated). The water absorbency
of the hydrogel composite is affected by the pH, species
and concentration of the salt solutions. The swelling
behavior of the hydrogel composite is Fickian transport,
and the swelling process ts the Schotts model. In
addition, the hydrogel composite exhibits excellent
environmental-responsiveness between distilled water
and 0.1 mol$L1 NaCl solutions and signicant water
absorbency (580 g$g1) even in the fth repetition cycle.
The ability to release urea renders the hydrogel composite
designed in this work an interesting potentiality in
agricultural applications.
Acknowledgements The authors would like to acknowledge National Key
Technology R&D Program of the Ministry of Science and Technology, China
(No. 2012BAC07B02) for support and for providing the funds to make this
study possible.
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