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DOI 10.1007/s11705-015-1546-y
RESEARCH ARTICLE
increasing prices of petrochemical feedstocks, waste acteristics cause poor compatibility which can affect the
disposal issues as well as the desire to use renewable and nal properties of the composite. Therefore, prior to
environmentally friendly resources have fueled the search incorporation into a polymer, zeolite need to rst be
for alternative materials. For decades, starch, which is a chemically modied.
natural carbohydrate biopolymer, has received much Surfactants are water-soluble organic molecules that
interest from both academic and industrial groups due to have hydrophilic and hydrophobic properties. Cationic
its biodegradability, low cost, and versatility of use [13]. In surfactants with positively charged head groups, such as
addition, different monomers can be easily grafted onto the alkyl ammonium compounds, attached to a hydrocarbon
starch backbone to increase the hydrophilicity, hydro- moiety have been utilized to form organic-modied clays
phobicity or polyelectrolyte properties of the starch [14]. [18].
Much research has focused on developing starch-grafted Recently, hydrogels with a slow-release property for use
copolymers with specic properties such as thermal as fertilizers have attracted much attention [26,27]. The
stability, high viscosity, biodegradability, and high water water-absorbing abilities and the slow-release properties of
absorption capacity [1517]. These copolymers have been these hydrogels may make them useful in agricultural
applied as occulants, ion exchangers, and superabsorbent applications especially in the area of water-management
hydrogels. [28]. Urea is the most widely used nitrogen fertilizer due to
In recent years, the design and development of organic- its high N content (46%) and comparatively low cost.
inorganic hydrogel composites, especially ones containing Therefore, urea is commonly used to test the release
clay minerals, have attracted increasing attention. This type properties of superabsorbents [2932].
of hydrogel composite can substantially reduce the nal In this study, a low cost starch zeolite composite was
cost of the product and improve its properties (e.g., prepared and its potential applications were studied. The
mechanical and thermal stability). Polyethylene-g-poly swelling behaviors of the hydrogel composites were
(acrylic acid) composites with 3 wt-% organo-montmor- investigated in distilled water, various cationic salt
illonite clay exhibit better water absorbency and gel solutions, and the solutions with different pH values,
strength than composites without organo-montmorillonite respectively. The kinetics of the swelling behaviors and the
clay. The thermal properties of hydrogel composites have reversibility of water absorption in distilled water were
also been improved by introducing montmorillonite which examined. In addition, the environmental-responsiveness
created a crosslinking effect and improved the nanostruc- of the hydrogel composites was tested in terms of their
ture [18]. In addition, the inclusion of inorganic clays into swelling and deswelling in distilled water and 0.1 mol$L1
hydrogels has been shown to decrease their nutrient- NaCl solutions. Finally the loading and release of urea by
release rate in distilled water [19]. the hydrogel composites were also evaluated.
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- 2.1 Materials
sional, regular intracrystalline array. Mordenite, which is a
natural zeolite, has been widely used in agricultural The starch used in this work was corn starch, which was
applications due to its large surface area, large ion obtained from Ding Yan Trading & Property Co. Ltd.
exchange capability, and low cost. The unique physical (Tianjin, China). Mordenite obtained from Nankai Uni-
and chemical properties of mordenite makes it suitable as a versity Catalyst Company (Tianjin, China) was milled
fertilizer carrier to promote efcient nutrient use [20], as a through a 320-mesh screen. The cationic surfactant,
soil additive to increase crop yields [21], and as an hexadecyltrimethyl ammonium bromide (CTAB), and the
absorbent in the removal of heavy metals from soil [22]. initiator potassium persulfate, were obtained from the Ke
The controlled release of ammonium, potassium, and Wei Chemical Reagent Company (Tianjin, China). Potas-
calcium has been achieved using mordenite as an additive sium persulfate was puried by recrystallization in distilled
to attract, retain, and slowly release critical plant nutrients water and dried at 50 C in a vacuum oven. The reactive
[23]. However, little information on the effect of mordenite monomer, acrylic acid (AA) and hydrochloric acid were
on the water absorption of hydrogel composites has been purchased from the Da Mao Chemical Reagent Factory
reported. (Tianjin, China). Acrylic acid was puried with distilled
Due to their surface structures and surface interactions, water under vacuum. The crosslinker N,N-methylenebi-
nanosized zeolite has a strong tendency to aggregate sacrylamide (MBA), sodium hydroxide, acetone, and
[24,25]. Therefore, when zeolite is directly added to a anhydrous ethanol were supplied by Kermel Chemical
polymer system, it tends to irregularly disperse. The Reagent Company (Tianjin, China). Polyglyceryl fatty acid
differences in the zeolite and polymer interfacial char- ester (PGFE), a suspension stabilizer, was purchased from
Yan Zhang et al. Preparation and swelling properties of a hydrogel composite 3
the Da He Foods and Technologies Co., Ltd. (Zhengzhou, temperature. The hydrogels (0.1 g) were immersed in
China). distilled water (400 mL) for 24 h to reach swelling
equilibrium. Residual water was removed by placing the
2.2 Organo-mordenite water-saturated hydrogel on a 200-mesh screen and
allowing the excess water to drip off for 5 min. The
Organo-mordenite was prepared using the procedure water absorbencies for the hydrogels were determined
reported by Zhang et al. [33]. Briey, 2 g of mordenite from:
and 25 mL of CTAB aqueous solution (31 mmol$L1) were m m0
placed in a 100-mL conical ask. The ask was kept in a W , (1)
m0
water bath at 70 C while sonicating for 60 min. The
reaction product was then ltered and washed several where W is the mass of the gained water (g) per gram of
times with anhydrous ethanol to ensure the complete hydrogel, m is the mass of the swollen absorbent, and m0 is
removal of the Br. The product was then dried to a the mass of the dry material. All of the procedures were
constant weight at 60 C. performed in triplicate, and the reported value is the
average of the three replicates.
2.3 Synthesis of starch-g-poly(acrylic acid)/organo- The water absorbencies of the samples in various salt
mordenite hydrogel composite 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
The starch-g-poly(acrylic acid)/organo-mordenite hydro- also tested using the same procedure.
gel composite was prepared by inverse suspension The water absorbencies of the hydrogels in the solutions
polymerization according to the following steps. First of different pH values were analyzed. The solutions with
4.8 g of starch was solubilized in 50 mL of distilled water acidic and basic pH were prepared by dilution of
at 95 C for 30 min using a 500-mL four-neck ask hydrochloric acid (pH 1.0) and sodium hydroxide solution
equipped with a condenser, stirrer, thermometer, and (pH 13.0), respectively, to get pH levels of 1.0, 2.0, 3.0,
nitrogen line. Next, the ask was cooled to 3540 C, 7.0, 9.0, 11.0, and 12.0. The water absorbencies of the
and 300 mL of cyclohexane and 0.12 g of suspension hydrogels were measured in each case according to Eq. (1).
stabilizer (PGFE) were added to the system. The slurry was Kinetic swelling behaviors of hydrogel composite in
stirred for 15 min, and 8.7 mL of the potassium persulfate distilled water were measured by the following procedure:
initiator (5 g$L1) was added. This solution was then stirred 0.1 g sample was immersed in 400 mL of distilled water for
for 15 min. After that 80% neutralization degrees of AA set period of time. Then, the swollen gels was ltered using
solution (14.4 g of AA was pre-neutralized using 32 mL of a 200-mesh screen, and the water absorption (Wt) of
20 wt-% NaOH solution in an ice bath) , organo-mordenite hydrogel composite at a given time (t) can be measured by
(the mass ratio of organo-mordenite to AA were 5 and 10 weighing in the swollen and dry sample, and calculated
wt-%, respectively) , and 2.5 mL of the MBA crosslinking according to Eq. (1). In all cased three parallel samples
agent (5 g$L1) were successively added to the system. The were used and the average are reported in the paper.
water bath was heated slowly to 70 C and the ask was
maintained at this temperature for 3 h to carry out the 2.5 Environmental-responsiveness of the hydrogel
polymerization reaction. The system was mechanically
stirred (400600 r$min1) throughout the entire process. The environmental-responsiveness of the hydrogel com-
After the polymerization was complete, the reaction posites were tested in terms of their swelling and
mixture was rst immersed in anhydrous ethanol to deswelling in distilled water and 0.1 mol$L1 NaCl
remove the residual reactants. Next, the product was solutions. Typically, the hydrogel composites (0.1 g)
fully washed with distilled water. In the end, the crude were immersed in 400 mL of distilled water for a set
products were then oven-dried at 70 C to a constant period of time intervals until reaching equilibrium. Then,
weight. The starch-g-polymer composite was extracted the swollen samples were soaked in 0.1 mol$L1 NaCl
from the crude products with acetone for 10 h to obtain the solutions for set time intervals. Finally, the swollen
pure hydrogels. A control sample with no organo- samples were ltered, weighted and then calculated to
mordenite was also prepared according the above the mass change of samples before and after swelling. The
procedure. This sample is referred to as starch-g-poly same procedure was repeated for three cycles. After every
(acrylic acid) hydrogel. cycle, each solution was renewed.
2.4 Evaluation of the water absorbency and swelling 2.6 Reversibility of the absorption by the hydrogels
kinetics of the hydrogels
The reversibility of the water absorption was determined
The water absorbency was determined at ambient 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 samples after the samples were coated with a gold lm.
re-immersed in distilled water until the gel reverted to its Energy-dispersive spectroscopy (EDS) combined with
swollen state. The wn (where n is the nth absorption/drying scanning electron microscopy (SEM) was used to analyze
cycle) were calculated using Eq. (1). All the procedures the elements in the samples. The applied voltage was
were performed in triplicate, and the reported value is the 15.0 kV with a current of 20.0 A.
average of the three replicates.
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 824 and 453 cm1 respectively although with weakened
stretching mode of glucomannan [41]. The broad band at intensities. These results prove that the organo-mordenite
3421 cm1 is due to polysaccharide hydroxyl group participated in the grafted copolymerization through its
stretches. The C O C stretching bands are at 1158 and active silanol groups [4345].
1080 cm1. After grafting acrylic acid onto the starch
(starch-g-poly(acrylic acid), new peaks appeared in the 3.1.3 X-ray diffraction (XRD) analysis
spectrum, as shown in Fig. 2(c). These include a C = O
stretching band at 1710 cm1, symmetric and asymmetric XRD was employed to investigate the structure and
COO bands at 1415 and 1560 cm1, respectively, and a crystallinity of the samples. Figure 3 shows the XRD
medium peak at 3512 cm1 which is due to water patterns of starch-g-poly(acrylic acid), organo-mordenite,
molecules. The peak at 2934 cm1 is due to C H and starch-g-poly(acrylic acid)/organo-mordenite. The
symmetric stretching. These results conrm that acrylic XRD pattern of the starch-g-poly(acrylic acid) hydrogel
acid was grafted onto the starch. Earlier studies on the (Fig. 3(a)) exhibits a weak broad peak at 2 = 22. This
copolymerization of starch with acrylic acid support this peak indicates an amorphous structure with low crystal-
result [42]. linity. Similar results have been previously reported by
The spectrum for starch-g-poly(acrylic acid)/oragno- Kaur et al. [42].
mordenite is shown in Fig. 2(d). Compared with the The XRD spectrum for organo-mordenite is shown in
spectrum for starch-g-poly(acrylic acid), the C = O Fig. 3(b). The spectrum contains diffraction peaks at 2 =
stretching band at 1710 cm1 shifted to 1720 cm1, and 6.5, 8.6, 9.7, 13.5, 15.1, 21.5, 24.6, 26.1, 27.8,
the asymmetrical stretching band at 1560 cm1 shifted to and 30.3 which correspond to Miller indices of [110],
1566 cm1. The organo-mordenite Si O stretching band at [020], [200], [111], [310], [330], [420], [202], [350], and
1093 cm1 became much weaker and shifted to 1027 cm1 [511], respectively [46]. Figure 3(c) shows the XRD
for the composite. In addition, the external and internal (Si, patterns of the starch-g-poly(acrylic acid)/organo-morde-
Al) O vibrational peaks are also seen in the composite at nite hydrogel composite. This spectrum contains the same
6 Front. Chem. Sci. Eng.
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- 10 wt-%, the maximum water absorbency (655 g$g1) was
sites with and without attapulgite. In addition, when obtained.
organo-mordenite is below 10 wt-%, water absorbency
increased with the increase in organo-mordenite content. 3.3 Swelling kinetics of the hydrogels
The repulsive forces between the COO groups of the
hydrogel and the negative surface charges of mordenite The swelling behavior of a hydrogel is inuenced by
results in an expansion of the hydrogel network which in various factors, such as the composition of the absorbent,
turn results in higher water absorbency [49]. However, the the size, and the surface area [51]. Therefore, the effect of
water absorbency of the hydrogel composite decreased for introduction of organo-mordenite into the polymeric
higher organo-mordenite. This is probably due to some system on the swelling behavior in distilled water was
reasons. On the one hand, the generation of more studied and the results are shown in Fig. 7.
crosslinking points may produce fewer network voids It was observed that the synthesized hydrogels reached
[50], which could restrict the movement of the polymer their equilibrium swelling values after 150 min and 300
chains. On another hand, excessive organo-mordenite may min for hydrogel and hydrogel composite. Also, it can be
physically stack inside the network voids which plug them seen that the water absorbency for the hydrogel composite
[44]. Besides that, starch-g-poly(acrylic acid) is respon- was always higher than that of pure hydrogel without
sible for the water absorbency of the hydrogel composites, organo-mordenite.
so a higher zeolite content results in less starch-g-poly The swelling curves were used to evaluate the swelling
(acrylic acid) which decreases the water absorbency. mechanism and the effect of incorporating organo-
Finally, when the amount of the organo-mordenite was 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
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 )$min1]; e) diffusion parameters (gwater gabsorbent
1
)
10 Front. Chem. Sci. Eng.
Fig. 10 Absorption of various salt solutions by hydrogels (a) starch-g-poly(acrylic acid)/organo-mordenite hydrogel composite
(10 wt-% organo-mordenite) and (b) starch-g-poly(acrylic acid)
Yan Zhang et al. Preparation and swelling properties of a hydrogel composite 11
the concentrations of 0.02, 0.04, 0.08, and 0.12 mol$L1, 3.9 Release of urea from loaded hydrogel composite in
respectively. As shown in Fig. 13, the swelling capacity of distilled water
the hydrogel composite is dependent on the concentration
of the urea solution. The swelling absorbency increases Figure 14 depicts the releasing proles of urea from loaded
with the concentration of urea solution increasing from hydrogel composite with 10 wt-% organo-mordenite (urea
0.02 to 0.04 mol$L1, but slightly decreases when this loading percentage: 46.5%) in distilled water. In the case of
concentration further increases from 0.04 to 0.12 mol$L1. the hydrogel composite, the releasing rate is initially high
A possible reason for the behavior might be as follows. (up to 24 h), and then gradually decreases. The releasing
When the concentration of the urea solution was less than percentage of urea in the starch-g-poly(acrylic acid)/
0.04 mol$L1, urea does not affect the electrostatic organo-mordenite is 93% for 48 h.
repulsion force of COO on the polymer chain and has
hydrophilic sites, such as NH2, which may improve the
interaction between water and the polymer network.
Therefore, with the concentration of the urea solution
increasing, the swelling absorbency of the hydrogel
composite increases. However, when concentration of the
urea solution is greater than 0.04 mol$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.
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