Science of the Total Environment 843 (2022) 157050

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Multicomponent biodegradable hydrogels based on natural biopolymers as

environmentally coating membrane for slow-release fertilizers: Effect of
crosslinker type
Patchareepon Jungsinyatam a, Pitchayaporn Suwanakood b, Sayant Saengsuwan a,
⁎
a
Laboratory of Advanced Polymer and Rubber Materials (APRM), Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon
Ratchathani University, Warin Chamrap, Ubon Ratchathani 34190, Thailand
b
Department of Bioscience, Faculty of Science, Ubon Ratchathani University, Warin Chamrap, Ubon Ratchathani 34190, Thailand

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Effect of different crosslinker types on the

properties of CSt-g-PAA/NR/PVA semi-
IPN (CSB) hydrogel was evaluated.
• Water swelling, water-retention, and bio-
degradability of CSB hydrogels were
strongly affected by crosslinker types.
• Glutaraldehyde (GA) crosslinker was the
suitable crosslinker for coating membrane.
• The UCSBw-G2 fertilizer reduced soil pol-
lution and increased soil water-retention
and plant growth.

A R T I C L E I N F O A B S T R A C T

Editor: Baoliang Chen This work aims to explore the suitable crosslinker type for synthesizing multicomponent biodegradable hydrogels of cas-
sava starch (CSt) grafted with acrylic acid (AA) semi-interpenetrated by natural rubber (NR)/polyvinyl alcohol (PVA)
Keywords: blend (CSt-g-PAA/NR/PVA, CSB semi-IPN hydrogel) as coating membranes for slow-release urea fertilizers. Three
Starch crosslinker types (ethylene glycol dimethacrylate (EGDMA), glutaraldehyde (GA) and N,N′- methylene-bis-acrylamide
Natural rubber
(MBA)) were employed to investigate their influences on the properties of CSB semi-IPN hydrogels. The results revealed
PVA
AA
that the different crosslinkers clearly exhibited different water-retention capacity, biodegradation, slow release and
Kinetics plant growth performance of the CSB semi-IPN hydrogels. The CSB-G2 hydrogel (crosslinked with GA at 2 wt%) re-
Biosafety mained higher water-retention at 30 days (20.2 %), greater rate of degradation (1.37 %/day) and better biosafety
(OD600 = 2.26) compared to CSB-M2 and CSB-E2 hydrogels. After urea pellets were coated by CSB hydrogels and
wax layers (UCSBw formulation), the urea release rates from the UCSBw-M2, UCSBw-E2 and UCSBw-G2 formulations
in 30 days were 67.7 %, 68.7 % and 78.3 %, respectively, corresponding well with swelling ratio and pore size. Besides,
the UCSBw-G2 formulation yielded the greater plant growth performance (height, leaf length and product weight) than
other two formulations and commercial fertilizer. In conclusion, GA is the suitable crosslinker for synthesizing the CSB-
g-PAA/NR/PVA hydrogels with high water-retention, excellent biodegradation, less negative impact on environments,
acceptable slow-release rate, good biosafety and reasonable price for slow-release fertilizers.

⁎ Corresponding author.
E-mail address: sayant.s@ubu.ac.th (S. Saengsuwan).

http://dx.doi.org/10.1016/j.scitotenv.2022.157050
Received 18 March 2022; Received in revised form 24 May 2022; Accepted 25 June 2022
Available online 30 June 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
P. Jungsinyatam et al.
1. Introduction
Fundamentally, water and fertilizers are known as the most essential
factors in agricultural production systems (Sarmah and Karak, 2020).To
date, urea fertilizer is vastly used in agricultural sectors due to its high ni-
trogen (N) contents (46 %), simple application and low cost. However,
urea fertilizer suffers from the high N loss via volatilization, denitrification,
nitrogen leaching and ammonia emission, causing various seriously envi-
ronmental pollutions such as soil degradation, water eutrophication and
large economic loss (Azeem et al., 2014; Tanan et al., 2021a). Thus, to im-
prove the N nutrient use efficiency, controlled/slow-release fertilizers
(CRF/SRF) have been intensively developed (Azeem et al., 2014; Wu
et al., 2020; Lawrencia et al., 2021a). These CRF/SRFs are normally fabri-
cated by coating traditional fertilizers with various organic/inorganic or
polymeric materials to slowly supply the nutrient amounts matching with
the plant requirement and reducing fertilizer loss to the environments
(Mikula et al., 2020). However, such coating materials are usually made
from synthetic polymers with high cost and non-biodegradability, prevent-
ing their wide applications (Wu et al., 2020). To overcome these draw-
backs, biodegradable coating materials have thus attracted much research
attention (Sarmah and Karak, 2020; Tanan et al., 2021a; Mikula et al.,
2020; Ramli, 2019).
The hydrogels are hydrophilic polymers having three-dimensional net-
work structures, yielding high-water absorption property without dissolving
(Tanan et al., 2019; Dragan, 2014; Tanan and Saengsuwan, 2020). Its excel-
lent swelling properties can control the released nutrients, reduce the water
run-off and improve the soil permeability and infiltration rate (Narayanan
and Dhamodharan, 2015). Thus, many biopolymeric hydrogels based on
starches and celluloses have been used as biodegradable and low-cost coating
materials in the SRFs (Tanan et al., 2021a; Wu et al., 2020; Lawrencia et al.,
2021a; Vudjung and Saengsuwan, 2018). However, these materials suffer
from low mechanical strength, limiting their wide applications especially in
agricultural fields. To resolve this limitation, semi-interpenetrating polymer
network (semi-IPN) technology has been introduced to prepare the biode-
gradable hydrogels requiring both enhanced mechanical properties and com-
patibility (Dragan, 2014; Panpinit et al., 2020; Vudjung and Saengsuwan,
2017). Moreover, it allows to create multicomponent semi-IPN hydrogels
from various polymers like biopolymers and synthetic polymers. Hence, sev-
eral biodegradable hydrogels based on semi-IPN structures have been inves-
tigated extensively (Tanan et al., 2019; Dragan, 2014; Vudjung and
Saengsuwan, 2017).
To produce the low-cost, environment-friendly, and biodegradable
coating materials, the starting materials must be biodegradable and renew-
able natural materials. Cassava starch (CSt) and natural rubber (NR) are
both classified as renewable, biodegradable and cheap natural polymers
abundantly available in Thailand (Tanan et al., 2021a). The CSt contains
much -OH groups in their chemical structures serving to absorb large
amount of waters, while the NR returns high flexibility, excellent resilience
and acceptable mechanical strength (Vudjung and Saengsuwan, 2018;
Vudjung and Saengsuwan, 2017; Zhou et al., 2009). Recently, our research
group has thus developed the novel, low-cost and biodegradable hydrogels
based on CSt, NR, polyacrylic acid (PAA) and polyvinyl alcohol (PVA) by
using N,N′-methylene bis-acrylamide (MBA) as a crosslinker with variation
of the CSt/PAA (Tanan et al., 2019) and NR/PVA compositions (Tanan
et al., 2021a) for applying as urea coating materials. The synthesized CSt-
g-PAA/NR/PVA semi-IPN hydrogels exhibited good water-retention,
water swelling, and biodegradability. Then, these hydrogels were used as
coating membrane on urea fertilizers called BHWCU and it was found
that the BHWCU/9:1 formulation revealed an excellent slow-release N
nutrient in both water (47.5 % at 168 h) and soil (38.5 % at 30 day) and
promoted the effective growth of chili plants (Tanan et al., 2021a). Impor-
tantly, it is known that various factors can affect significantly the hydrogel
properties such as types and concentrations of crosslinker, initiators, poly-
mers/monomers, and operating conditions (Ismail et al., 2013; Bialik-Wąs
et al., 2021; Maitra and Shukla, 2014; Wong et al., 2015). In the view of
crosslinkers, most literatures usually reported only the effect of crosslinker
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Science of the Total Environment 843 (2022) 157050
contents resulting in the lower swelling ratio and also the smaller pore size
of hydrogels due to the higher crosslinking density (Wong et al., 2015;
Chavda and Patel, 2011). To the best of our knowledge, the effect of
crosslinker types on the physical properties and slow-release characteristics
of hydrogel systems has rarely been investigated, especially in the CSt-g-
PAA/NR/PVA systems (Tanan et al., 2021a; Tanan et al., 2019).
In this work, we attempted to deeply explore the effect of crosslinker
types on the properties and release characteristics of the CSt-g-PAA/
NR/PVA systems, aiming to identify the suitable crosslinker. Three
crosslinkers including MBA, ethylene glycol dimethacrylate (EGDMA)
and glutaraldehyde (GA) were employed. The properties, swelling
behavior, water-retention, and biodegradation of the synthesized
hydrogels were characterized and compared. Then, the slow-release be-
havior, plant growth, and biosafety were also performed to realize their
potential usages in agricultural and horticultural applications. This work
could provide the valuable reference for producing the slow-release fertil-
izers with improving soil water retention, enhancing nutrient release and
less negative impacting on the soil, air and water environments.
2. Experimental
2.1. Materials
High ammonia concentrated NR latex (HA latex, 60 % dry rubber con-
tent) was obtained from Thai Rubber Latex Corporation. Cassava starch
(CSt, 19 wt% amylose) was purchased from Bigtree Intertrade Co. Ltd.
Ammonium persulfate (APS) was obtained from Sigma-Aldrich. Polyvinyl
alcohol (PVA, average MW = 85,000-120,000) and acrylic acid (AA)
were purchased from Acros. Emulvin WA was obtained from Lanxess Com-
pany. Three crosslinkers consist of N,N-methylenebisacrylamide (MBA),
ethylene glycol dimethacrylate (EGDMA) and glutaraldehyde (GA). Urea
(46 % of N) was obtained from Chia Tai Co., Ltd. (Bangkok, Thailand).
Gram-negative bacterium Escherichia coli (E. coli, ATCC25922) was
obtained from Department of Medical Science, Ministry of Public Health,
Thailand.
2.2. Preparation of CSt-g-PAA/PVA/NR semi-IPN hydrogels
The synthesis procedure was slightly adapted from previous reports
(Tanan et al., 2021a; Tanan et al., 2019). Firstly, CSt powder (7.5 g), dis-
tilled water (40 mL) and 40 % NaOH (1.0 mL) as H-bonding breaking
agent were mixed in round-bottom flask and heated at 40 °C for gelatiniza-
tion. Then, APS (0.3 wt% of AA) was added under N2 atmosphere to initiate
the reaction. After 30 min vigorous magnetic stirring, the AA monomer
(60 % neutralized with 20 wt% NaOH to improve the swelling properties
(Wang et al., 2020)) and the three different crosslinkers (MBA, EGDMA
and GA) at 1–5 wt% were added and stirred at 50 °C for 1 h to produce
the crosslinked CSt-g-PAA solutions. Simultaneously, PVA (5 g) was dis-
solved in 50 mL deionized water and later mixed with NR latex (5 g) and
emulvin at room temperature. Subsequently, the PVA/NR blend solution
was added into the crosslinked CSt-g-PAA hydrogel solutions and heated
at 50 °C (3 h) to archive the semi-IPN hydrogel solution. The CSt-g-PAA/
NR/PVA semi-IPN hydrogels with EGDMA, GA and MBA crosslinkers at
various contents (1–5 wt%) were prepared and labeled as CSB-Ex, CSB-Gx
Table 1
Chemical compositions of CSt-g PAA/NR/PVA (CSB) semi-IPN hydrogels
crosslinked by three crosslinkers at various contents (1–5 wt%).
Sample codes Crosslinker types Crosslinker content (wt%) CSt AA NR PVA
(g) (mL) (g) (g)
CSB-Ex EGDMA 1–5 7.5 6.0 5.0 5.00
CSB-Gx GA 1–5 7.5 6.0 5.0 5.00
CSB-Mx MBA 1–5 7.5 6.0 5.0 5.00
*Note: x means wt% of crosslinker with respect to AA; APS (0.5 M) = 150 μL.
P. Jungsinyatam et al.
and CSB-Mx, respectively, where x means wt% of crosslinker (see Table 1)
to investigate their influences on the slow-release properties.
Moreover, the final homogeneous solutions of CSB-Mx, CSB-Ex and
CSB-Gx semi-IPN hydrogels with good dispersion were cast on a round
glass plate, dried at 50 °C and immersed overnight in distilled water.
Finally, all the CSB film samples (~150–250 μm) were dried in an oven
at 40 °C for 24 h and stored in a desiccator for further evaluating their prop-
erties by various methods.
2.3. Characterization of CSB semi-IPN hydrogels
The chemical structure of the CSB semi-IPN hydrogel films was con-
ducted through the attenuated total reflection Fourier transform infrared
spectroscopy (ATR-FTIR, Spectrum RX1, Perkin Elmer) recorded in the
range of 4000–650 cm−1. The amorphous/crystalline structure of raw ma-
terials and CSB hydrogels were analyzed by X-rays diffractometer (X'Pert,
MPD, Phillips) in range of 10° - 60°. The morphology of hydrogels and
urea-coated fertilizer was observed by field emission scanning electron mi-
croscope (FESEM, JEOL-JSM 5410 LV) at a voltage of 15 kV (Zhou et al.,
2009; Huang and Yang, 2007). Tensile tests of the hydrogel films (50 mm
× 10 mm × 250 μm) were performed on universal test machine (Lloyds,
LR Series) with deformation rate of 10 mm/min at room temperature.
The thermal stability of the hydrogel films (3.0–5.0 mg) was performed
by a thermogravimetric analyzer (TGA, Thermo Plus TG8120, Rigaku)
from 25 to 650 °C at a heating rate of 10 °C/min under N2 atmosphere.
2.4. Swelling ratio of CSB semi-IPN hydrogels
The weighing technique was used to study the swelling behavior of the
CSB hydrogels with different crosslinkers. About 0.01 g of dried hydrogel
films (5 mm × 5 mm) was immersed in distilled water at room temperature
(27–28 °C). At equilibrium (30 min), the hydrogel sample was taken out
from the water and weighed after wiping the surface water with filter
paper. The percentage of swelling ratio was finally calculated as follows
(Tanan and Saengsuwan, 2020; Tanan et al., 2021b).
W s −W d
Swelling ratio ð%Þ ¼  100%
Wd
where, Wd and Ws are the weight of the dry and swollen samples, respec-
tively. The reported data were the averaged values from triplicate.
2.5. Zero-point charge of CSB semi-IPN hydrogels
The pH of zero-point charge (pHzpc) of CSB semi-IPN hydrogels was
evaluated by using a pH drift method. NaCl solution (0.1 M) was adjusted
to different pH values from 2 to 10 (pHi) by adding drops of 0.1 M HCl
and 0.1 M NaOH. Next, CSB semi IPN hydrogels (0.1 g) was added to
each vial solution (50 mL). These solutions were then shaken at room tem-
perature for 24 h. Subsequently, the final pH value (pHf) was measured.
The value of pHzpc is the intersection of the curve pHi and pHf versus pHi.
All the measurements were performed in triplicate.
2.6. Water-retention behavior of CSB semi-IPN hydrogels in soil
The dried CSB-E2, CSB-G2 and CSB-M2 hydrogels were chosen to pres-
ent the effect of crosslinkers on the water-retention. Each hydrogel film
sample (1.0 g) was mixed with 200 g of dried loamy sand soil (below
200-mesh) in a plastic cup (W0). Besides, loamy sand soil without hydrogel
sample was prepared as a control sample. Then, 50 mL of distilled water
was slowly added into the plastic cup and weight (Wd). The plastic cup
was kept at room temperature and weighted (Wt) at various times (1–30
Science of the Total Environment 843 (2022) 157050
days). The water-retention behavior (WR, %) of the soil was calculated by
Eq. (2) (Tanan et al., 2021a; Wen et al., 2017).
Wi  W0
WR ð%Þ ¼  100% (2)
Wd  W0
2.7. Biodegradation test
Biodegradation test of CSB hydrogels was carried in the soil for 120
days. The CSB hydrogel samples (3 cm × 3 cm) was buried under the soil
surface (10 cm) in plastic cup. After that, the plastic cup was drenched
with 50 mL distilled water every three days. Each 15 days, the samples
were taken out from the soil and washed with distilled water for removing
soil as much as possible. The samples were dried in an oven at 50 °C to a
constant weight and weighed. The biodegradation (%) of the CSB hydrogels
was calculated by the following equation (Tanan et al., 2021a; Nguyen
et al., 2016):
W o −W d
Biodegradation ð%Þ ¼  100% ð3Þ
Wo
where W0 and W1 is weight of sample before and after degradation,
respectively.
2.8. Preparation of coated urea fertilizers
To prepare the hydrogel coated urea fertilizer granules, the coating
method (rotary drum) is selected in our laboratory due to the simple oper-
ation (Tanan et al., 2021a). The three different CSB semi-IPN hydrogels
with 2 wt% crosslinkers (CSB-E2, CSB-G2 and CSB-M2) were selected as
coating materials to represent the influence of different crosslinkers on
the slow-release properties and plant growths. The coating process and dig-
ital photographs of UCSBw-E2 fertilizers are illustrated in Fig. 1. Briefly,
commercial pure urea prills (45 g, ~4 mm in diameter) were loaded into
a rotating drum and preheated at 70 ± 2 °C for 10 min. Then, 15.0 g of
CSB semi-IPN hydrogel solution obtained from Section 2.2 (viscosity
ð1Þ
~513 ± 16 cP at room temperature) was gradually injected by plastic sy-
ringe onto the surface of pure urea within 1 min to minimize the dissolution
of urea pellets. The curing process of coating material was then finished in
the rotating drum at 35 rpm and temperature of 70 ± 2 °C for 10 min to fab-
ricate the urea prills coated with CSB semi-IPN hydrogel (UCSB).
In the final step, any cracks or flaws on the UCSB coating surfaces were
further sealed by wax solution as outer coating layers in rotating drum at
room temperature to yield UCSBw sample. The UCSBw samples coated
with CSB-E2, CSB-G2, and CSB-M2 were assigned as UCSBw-M2, UCSBw-
E2 and UCSBw-G2, respectively. It should be noted that some part of urea
pellets will be dissolved when contact with hydrogel solution and thus, to
minimize this effect, the dropping time was done at short period of time
and the temperature of rotating drum was kept at 70 ± 2 °C with a suitable
rotating rate of 35 rpm.
2.9. Release behaviors of UCSBw in water and soil environments
The slow-release behavior of urea fertilizer from UCSBw in water was
evaluated by adding UCSBw (0.25 ± 0.01 g) into a beaker containing dis-
tilled water (100 mL) at room temperature without stirring. At a given time,
2.0 mL sample solution was withdrawn and mixed with 2.0 mL of color re-
agent (2.0 g of p-dimethyl aminobenzaldehyde +10 mL of concentrated
HCl, and 100 mL of 95 % ethanol). Then, 2 mL of distilled water was also
filled to keep a constant volume of solvent.
The release of urea fertilizer in aqua solution was analyzed by UV–Vis
spectrophotometer (UV-2600, Perkin Elmer) at wavelength of 420 nm
(Tanan et al., 2021a; Bortolin et al., 2013). All experiments were done in
3
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

Fig. 1. Fabrication routes of urea coating process (UCSBw) and digital photographs of urea pills, UCSB-E2 and UCSBw-E2 samples.

triplicate and reported as average values. The % urea release rate was cal- where Ccu,t and Cuc present the urea concentration (ppm) in solution re-
culated by the following equation: leased from coated urea at different time intervals and from the uncoated
urea sample.
Abs420 −Y intercept To study the slow-release behavior of UCSBw in soil environment, the
Urea concentration ðppmÞ ¼ ð4Þ
slope of calibration curve home-made apparatus was setup as shown in Scheme 1. Then, 1.0 kg of
dried loamy sand soil (below mesh-18) was placed as first layer in PVC
Ccu;t tube (5.25 cm dimeter and 45 cm length). Later, the UCSBw fertilizer
Urea release ð%Þ ¼  100% ð5Þ
Cuc (5.0 g) was mixed with 100 g of dried loamy sand soil and 200 g of

Scheme 1. The system used to study the urea release behavior.

4
P. Jungsinyatam et al.
loamy sand soil was placed as the second and third layers, respectively.
Then, distilled water (70 mL) was firstly added into PVC tube to keep the
soil moisture at 30 % (Stahl et al., 2000). At interval times, each 10 mL of
leachate sample was determined by UV-VIS spectrophotometer and
10 mL of distilled water was also added into the PVC tube to replace the
loss water in the system.
2.10. Plant growth experiments
The chili young plants (Jinda, age 25 day with similar height, an eco-
nomic plant mostly cultivated by farmers in Ubon Ratchathani, Thailand)
were transplanted in the plastic pots (24 cm diameter and 18 cm height)
with 1.8 kg of loamy soil. The chili plants were treated with 4.0 g of differ-
ent fertilizers; urea coated fertilizers (UCSBw-M2, UCSBw-E2 and UCSBw-
G2), commercial urea fertilizer, and without urea fertilizers (control sam-
ples). Each condition was done in five replicates under the same condition
and the plants were watered with 400 mL every day. The plant growths; the
plant height, the leaves length, and weight of chili balls were recorded at
15, 30 and 45 days for comparison. The data were recorded and the average
of five experiments was reported. The statistical analysis for all measure-
ments were also carried out by using one-way ANOVA (Vudjung and
Saengsuwan, 2018). The significant difference between any means and cor-
relation coefficients were considered, when P < 0.05.
2.11. Biosafety and cost evaluation
The biosafety of UCSBw and CSB semi-IPN hydrogel coating solution at
2 wt% of different crosslinkers was also evaluated to monitor their safety.
The experimental procedures followed the method described by Ref.
(Tanan et al., 2021a; Xiang et al., 2018). Briefly, E. coli (ATCC25922) was
cultured in LB culture medium without sample (control) and with the solu-
tions (104 ppm concentration) of native commercial urea, UCSBw and CSB
solutions at 37 °C for 24 h. UV–visible spectrophotometer at 600 nm (optical
density (OD) 600) was used to analyze the concentrations of E. coli viability
(Xiang et al., 2018). The obtained values were recorded, compared and dis-
cussed. Finally, cost evaluation of UCSBw fertilizers using different
crosslinker types was estimated to relate their prices with the commercial
products.
3. Results and discussion
3.1. Synthesis of CSB semi-IPNs hydrogels with different crosslinking agents
This work aims to fabricate the cassava starch-graft-polyacrylic acid/
polyvinyl alcohol/natural rubber (CSt-g-PAA/PVA/NR) semi-IPN biode-
gradable (CSB) hydrogels by using three different crosslinkers; EGDMA,
GA, and MBA, aiming to investigate the suitable crosslinker providing the
good properties, acceptable slow-release characteristics and better plant
growth performance of the CSB semi-IPN hydrogels having less negative
impact on environments. The CSB hydrogels were synthesized via grafting
copolymerization and semi-IPN technology using the optimum conditions
reported by Tanan et.al (see Table 1) (Tanan et al., 2019). In this work, a
series of three crosslinkers (EGDMA, GA and MBA) at 1–5 wt% of AA
composition were optimized to obtain the suitable crosslinker contents
(see Fig. 2).
Finally, the PVA/NR blend solution was thoroughly mixed and semi-
interpenetrated into the CSt-g-PAA networks to form the CSt-g-PAA/PVA/
NR semi-IPN (CSB) hydrogels with enhanced mechanical strength and flex-
ibility (Huang and Yang, 2007). The CSB hydrogels crosslinked by EGDMA,
GA and MBA crosslinkers (1–5 wt%) are labeled as CSB-Ex, CSB-Gx and
CSB-Mx, respectively, where x means wt% of crosslinker with respect to
AA weight (see Table 1). Thus, it was predicted that the different
crosslinkers could affect distinctly the swelling behavior and the physical
properties of the final CSB hydrogels.
5
Science of the Total Environment 843 (2022) 157050
3.2. Characterization
3.2.1. Chemical structure by FTIR spectra
FTIR spectra of the CSB hydrogels and raw materials are presented in
Fig. 3a. CSt spectrum shows a broad peak at 3297, 1150 and 1020 cm−1 at-
tributing to O\\H stretching of the CSt, C\\O and C-O-H stretching of am-
ylose, respectively (Parvathy and Jyothi, 2012). For AA monomer
spectrum, the peaks at 1695, 1626, and 1440 cm−1 relates to C_O and
C_C stretching and O\\H bending of carboxylic group, respectively (Li
et al., 2015). PVA spectrum exhibits a broad peak at 3307 cm−1 (O\\H
stretching), attributing to the inter/intramolecular interactions of PVA
molecules (Mansur et al., 2008). For NR spectrum, two peaks at 1614 and
1560 cm−1 correspond to C_C stretching and peaks at 2962, 2921 and
2856 cm−1 are associated with C\\H stretching of NR molecule (Vudjung
and Saengsuwan, 2018).
The FTIR spectra of CSB hydrogels crosslinked with different
crosslinkers (MBA, EGDMA and GA) are also presented in Fig. 3b which
are similar to spectra reported by Tanan et al. (Tanan et al., 2021a). All
CSB semi-IPNs hydrogels present a broad peak around 3330 cm−1 (O\\H
stretching) with less intensity and slightly shifts to lower wavenumbers
compared to CSt and AA molecules. Moreover, a peak around 1700 cm−1
assigning to C_O stretching of -COOH in AA molecules is also observed.
The peak around 2925 cm−1 corresponds to C\\H stretching of the PVA/
NR polymer blend (Tanan et al., 2021a).
To gain more insight into the chemical structure of CSB hydrogels
crosslinked with three different crosslinkers (EGDMA, GA, and MBA), the
FTIR spectra of CSB-E2, CSB-G2 and CSB-M2 hydrogels as representative
samples are shown in Fig. 3b. The CSB-E2 spectrum shows the important
peaks at 1722, 1151 and 1017 cm−1, corresponding to the C_O, C\\O
and C-O-C stretching of the EGDMA crosslinked with PAA, respectively
(Urbano-Juan et al., 2019). For CSB-G2 spectrum, the peaks at 1723 and
1018 cm−1 are attributed to C_O and C-O-C stretching of the GA mole-
cules (Panpinit et al., 2020; Saikia et al., 2016). In addition, the CSB-M2
spectrum shows peaks at 1664, 1551 and 1021 cm−1 assigning to C_O
stretching, N\\H stretching and C-O-C stretching of the CSt-g-PAA chains
crosslinked with MBA (Tanan et al., 2019; Fajardo et al., 2013). Hence,
these results could suggest that the CSB semi-IPN hydrogels were success-
fully crosslinked by three different crosslinkers.
3.2.2. SEM morphology
The SEM morphology of the CSB hydrogels at various contents of differ-
ent crosslinkers is presented in Fig. S1. It is seen that all CSB semi-IPN
hydrogels exhibit homogeneous porous structures with some wrinkles, fa-
cilitating the water fluid permeation into the polymer networks (Tanan
et al., 2021a). By increasing crosslinker contents, the porous structures
tend to increase while the pore size is decreased due to the higher
crosslinking density, resulting in the lower water swelling (see Fig. 8).
Also, the CSB-Mx and CSB-Ex hydrogels display numerous porous struc-
tures with a smaller pore size and uniform distribution, compared to the
CSB-Gx one.
To investigate the effect of crosslinkers on the pore size of CSB
hydrogels, the SEM images of CSB-M2, CSB-E2 and CSB-G2 hydrogels as
representative samples are compared in Fig. 4. By using ImageJ program,
the average pore sizes of CSB-M2, CSB-E2 and CSB-G2 hydrogels are calcu-
lated to be 9.9 ± 1.7, 16.4 ± 0.3 and 34.9 ± 0.3 μm, respectively. This in-
dicates that the CSB-G2 hydrogel has the larger pore size, permitting more
diffusion of water molecules into the three-dimensional hydrogel networks,
and resulting in the higher swelling ratio and the more water-retention
(Chang et al., 2010).
Besides, the equilibrium water swelling (Seq) of CSB hydrogels relates lin-
early with the pore size (ϕ), describing by the equation: Seq (%) = 35.66 ϕ +
4.93, R2 = 0.987, as shown in Fig. 4d. These pore morphologies also corre-
late very well to biodegradation rates (see Fig. 10) and release kinetics (see
Fig. 11) of the CSB hydrogels.
The SEM micrographs of urea fertilizer, UCSBw-E2 (an example) and its
cross-section are presented in Fig. 5. The surface of urea pellet is smooth
P. Jungsinyatam et al.
Fig. 2. Possible mechanism for synthesis of CSt-g-PAA/NR/PVA semi-IPN (CSB) hydrogels crosslinked with MBA, EGDMA and GA crosslinkers; (A) crosslinked CSt-g-PAA and
(B) schematic diagram of CSB-hydrogel synthesis.
containing a layer superposition phenomenon (see Fig. 5a). After the urea
pellet was coated by the CSB-E2 hydrogel solution, the surface of coated
urea (UCSB-E2) is smoother than that of uncoated urea (see Fig. 5b). This
implies that the urea was successfully coated by the CSB hydrogel as
inner layer (see Fig. 1). However, such coating surfaces still exhibit some
pinholes/pores (see green circles, Fig. 5b). These pinholes/pores may
promote the water molecules to get easily into the urea pellet, leading to
quick dissolution of urea. When the wax was added, it can change the
porosity and therefore the swelling properties.
To close such pinholes and to improve the stability of coating mem-
brane when encounters with moisture and water in soil, the coated urea
fertilizers were further modified by wax solution as an outer coating
layer (UCSBw-E2, see Fig. 5c and Fig. 1). It is seen that the surface of
UCSBw-E2 has no pinholes and is relatively smoother than UCSB-E2.
Fig. 5d presents the cross-sectional area of UCSBw-E2 shell containing
three main regions: urea pellet, hydrogel layer, and wax layer. Accord-
ing to the Fig. 5d, the thickness of the wax is higher than UCSBw-E2.
Additionally, the help of wax can not only retain the structure of coating
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Science of the Total Environment 843 (2022) 157050
membrane but also improves the controlled-release performance (Tanan
et al., 2021a; Qiao et al., 2016).
3.2.3. Microstructure and thermal stability of CSB semi-IPN hydrogels
X-ray diffraction (XRD) patterns of pure CSt powder, pure PVA film
and the selected CSB semi-IPN hydrogels are measured to evaluate
their microstructures as illustrated in Fig. 6a. It is seen that CSt show
the diffraction peak at 2θ = 15.1°, 17.4° and 23.2°, indicating the
semi-crystalline nature (Chen et al., 2011). The PVA film shows the
characteristic semi-crystalline nature of PVA at 2θ = 19.4°, attributing
to (101) crystalline reflection (Mahendia et al., 2011). For the CSB
hydrogels at similar crosslinker content (2 wt%), a considerable
broad peak at 2θ = 20.2° with low intensity is observed for all CSB
hydrogels, signifying the amorphous nature of CSB hydrogels which
is beneficial to improve the water swelling and water-retention in soil
(Likhitha et al., 2014).
To get more insight into the thermal stability of CSB hydrogels affected by
different crosslinkers, the representative CSB hydrogel samples (CSB-E2, CSB-
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

Fig. 3. FTIR spectra of (a) pure CSt, PVA, AA, and NR films, and (b) CSB-E2, CSB-G2 and CSB-M2 hydrogels.

G2 and CSB-M2) are evaluated by TGA and DTG techniques as shown in
Fig. 6b. All samples display a similar four weight-loss step which agrees
very well with the previous work (Tanan et al., 2019). Also, the thermal sta-
bility of CSB-E2 and CSB-M2 hydrogels is comparable and slightly higher
than that of the CSB-G2 hydrogel, associating with the mechanical properties.
By increasing the crosslinker contents, the thermal stability of all CSB
hydrogels is more stable (see Fig. S3), resulting from the higher crosslink den-
sity of CSt-g-PAA networks. The more details of thermal stability of all CSB
hydrogels at various types and contents of crosslinkers are presented in S1
and Fig. S2–3.
This is due to the higher crosslinking density, relating well with the lower
swelling ratio of CSB hydrogels (see Fig. 8a) (Sarmah and Karak, 2020;
Wong et al., 2015). From Fig. 7d, the highest values of TS and YM are
found in CSB-E2 hydrogel while the lowest values of TS and YM are found
in CSB-G2 hydrogel, agreeing well with the SEM morphology and %mass
swelling values. Thus, this result implies that the different crosslinkers
cause the distinctly mechanical properties of CSB hydrogels. Also, it suggests
that the proper crosslinker type should be carefully selected to meet the
desired requirements of hydrogel productions with suitable properties and
effective prices.

3.2.4. Mechanical properties of CSB semi-IPN hydrogels
The tensile properties of CSB semi-IPN hydrogels were performed as
shown in Fig. 7. It is observed that tensile strength (TS) and Young's modulus
(YM) of CSB hydrogels tend to significantly increase with increasing
crosslinker content, while the elongation at break tends to markedly decrease.
3.3. Water swelling behavior of CSB semi-IPN hydrogels
It is generally known that the swelling behavior is one of the significant
properties of hydrogels. Thus, the swelling behavior of CSB hydrogels in
different environments or conditions should be discovered to identify

Fig. 4. SEM images of (a) CSB-M2, (b) CSB-E2 and (c) CSB-G2 semi-IPN hydrogels and (d) the relationship between equilibrium swelling and pore size of the CSB hydrogels.

7
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

Fig. 5. SEM images of (a) urea pills, (b) UCSB-E2, (c) UCSBw-E2 and (d) cross-section of UCSBw-E2.

their characteristics and its potential applications. In this work, various ef-
fects such as crosslinker type and content, saline solutions and pH of solu-
tion on the swelling properties of CSB hydrogels were thus investigated.
3.3.1. Effect of content and type of crosslinker
Fundamentally, the different crosslinker types could modify the differ-
ent functional groups in the molecular structures of hydrogel, resulting in
the different swelling abilities of hydrogels (Saraydin et al., 2004). There-
fore, it is interesting to evaluate their influences on the swelling behavior
of the CSB hydrogels crosslinked by different crosslinkers (MBA, EGDMA
and GA) (see Table 1). Fig. 8a presents the water swelling of CSB-Ex, CSB-
Gx and CSB-Mx hydrogels at various crosslinker contents (0.5–5.0 wt%).
As seen, the swelling ratios of all CSB hydrogels increase significantly
with increasing crosslinker content at low concentration range and after
reaching the maximum value, their swelling ratios tend to rapidly decrease.
The maximum swelling ratios of CSB-Mx, CSB-Ex and CSB-Gx
hydrogels are found to be 445 %, 556 % and 1432 % at crosslinker
content of 2, 2 and 1 wt%, respectively. The decrease in swelling ratio
could attribute to the greater crosslink density which also reduces the
flexibility of hydrogel networks (Sarmah and Karak, 2020; Wong
et al., 2015), matching well with the mechanical properties of the CSB
hydrogels. Also, the CSB hydrogels crosslinked by GA (CSB-Gx) exhibit
the significantly higher swelling capacity than CSB-Ex and CSB-Mx
hydrogels. This could be due to the higher network flexibility and the
greater pore size (ϕ) of CSB-Gx hydrogels (see Fig. S1), facilitating the
more penetration of water molecules into the hydrogel networks.
Thus, this result indicates that the GA crosslinker would be the best
choice for synthesizing the hydrogels requiring high swelling capacity.
To verify the effect of crosslinker types on other properties of CSB
hydrogels, the suitable content was selected to fix at 2 wt%, yielding both
the good mechanical properties and high swelling ratios. Therefore, the

(a) (b) CSB-M2

0 CSB-E2
CSB-G2

-20
Intensity (a.u.)

TG (%)

-40
PVA film
Zone I Zone IV
0 Zone II

CSB-E2 Zone III

-2
-60
CSB-M2
DTG (%/min)

-4

CSB-G2 -6

-80
-8

-10
CSt powder 100 200 300 400 500 600

-100 Temperature ( C)

10 20 30 40 50 100 200 300 400 500 600

2 Theta (degree) Temperature (oC)

Fig. 6. (a) XRD patterns and (b) TG and DTG thermograms of CSB-E2, CSB-G2 and CSB-M2 hydrogels.

8
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

Fig. 7. The mechanical properties of CSB hydrogels crosslinked by (a) MBA, (b) EGDMA, and (c) GA at various contents, and (d) comparison of the mechanical properties of
CSB hydrogels at the same content of crosslinkers (2 wt%).

CSB-E2, CSB-G2 and CSB-M2 hydrogels will be used further as representa- crosslinking density in the hydrogel, consequently leading to the
tive samples for comparing the effects of crosslinker type. decrease of water absorption (Tanan et al., 2019; Xu et al., 2015).

3.3.2. Effect of salt solution
Fig. 8b presents the swelling ratio of the CSB-E2, CSB-G2 and CSB-
M2 hydrogels in distilled water and 0.9 wt% NaCl solution. The swelling
ratios of CSB-M2, CSB-E2 and CSB-G2 hydrogels are 445 %, 556 %,
1261 % and 323 %, 356 %, 532 %, in distilled water and 0.9 wt%
NaCl solution, respectively. This means that the swelling of the CSB-
M2, CSB-E2 and CSB-G2 hydrogels in salt solution decreases drastically
about −27 %, −36 % and − 58 %, respectively, compared to distilled
water. This behavior derives from the shielding effect of cations on the
carboxylate anions (COO-), resulting in the shrinkage of hydrogel
networks and the reduction of swelling ratio. In other words, the
complexity of cation and carboxylate anions can cause the higher ion-
3.3.3. Effect of pH on the swelling ratio and PZC of CSB hydrogels
To validate the effect of pH on the swelling behavior of CSB
hydrogels, the pH of swelling medium was varied from 2.0 to 10.0 as
shown in Fig. 9a. The swelling ratio of all CSB hydrogels seems to line-
arly increase with increasing pH (2.0–6.0) and reaches the maximum
value at pH ~ 6.0. Subsequently, the swelling ratio decreases gradually
when pH > 6.0. At lower pH (< 5.0), the carboxylate groups (-COO-)
from PAA chains are protonated to be -COOH groups, eliminating the
main anion-anion repulsive interactions and then reducing the water
absorbency (Tanan et al., 2019). Besides, the hydrogen bonds on
-COOH groups are strengthen, leading to the decrease in water swelling
of the CSB hydrogels (Dai et al., 2018). At pH = 5.0–6.0, the hydrogen

1500 1400
(a) Swelling in DI water (b)
1400 Swelling in 0.9 wt% NaCl solution
1200
Equilibrium swelling (Seq, %)

1300

1000
900
-58%
800 800
Seq (%)

700
600
600
CSB-Gx -36%
500 400 -27%

400 CSB-Mx
200
300
CSB-Ex
200 0
0 1 2 3 4 5 CSB-M2 CSB-E2 CSB-G2
Crosslinking content (wt%)

Fig. 8. The swelling behavior of CSB hydrogels at (a) various crosslinker contents and (b) different swelling mediums (distilled water and 0.9 wt% NaCl solution).

9
P. Jungsinyatam et al.
Fig. 9. (a) The effect of pH on swelling ratio and (b) point of zero charge (pHpzc) of CSB-E2, CSB-G2 and CSB-M2 hydrogels.
bonding interactions and electrostatic repulsions between -COOH
groups are weakened progressively, resulting from some of -COOH
groups are turned to -COO−. Thus, the physical crosslinking of CSB net-
works is decreased progressively, enhancing the swelling ratio to reach
value at pH = 6.0 for each CSB hydrogel. Moreover, it should be noted
that the maximum swelling of CSB hydrogels was archived at around its
point of zero charge (pH ~6–7, see Fig. 9b), which the interactions be-
tween the negative and positive charges on hydrogel surfaces are al-
most balanced. Nevertheless, the swelling ratio is significantly
decreased at pH > 7.0, because a charged screening effect of counter-
ions (Na+) would generate and subsequently hinder the swelling capac-
ity (Mikula et al., 2020; Maitra and Shukla, 2014). This result indicates
that the swelling behavior of CSB hydrogels is pH-dependent.
Moreover, the point of zero charge (pHpzc) was also measured by using a
pH drift method to define the surface electro-kinetic nature of CSB
hydrogels, affecting the surface adsorption capability and type of surface
active sites (Zhang et al., 2021). The pHpzc values of CSB-M2, CSB-E2 and
CSB-G2 are found to be 6.15, 6.20 and 6.85, respectively (see Fig. 9b). At
pH < pHpzc, the main surface of CSB hydrogels becomes protonated carbox-
ylic groups, yielding positive surface charges (Rizzi et al., 2021). On the
other hand, at pH > pHpzc, the carboxylic groups (–COOH) from PAA struc-
ture are deprotonated to form carboxylate (–COO−) groups, resulting in
negative surface charges (Chen et al., 2021). Therefore, the hydrogel net-
work structures can suffer damage upon experience to excess H+ or OH−
ions, leading to the reduction of its performances.
3.4. Water-retention behavior of CSB hydrogels
Generally, water-retention of soil is one of the vital properties of the
compound fertilizers for applying in the agriculture and horticulture. It im-
proves not only the soil quality and survival rate of seedling but also the
plant growth (Tanan et al., 2019; Wen et al., 2016). The water-retention ca-
pacity of soil mixed with different CSB hydrogels (0–1.5 g) was thus exam-
ined as shown in Fig. S4. It is seen that the water-retention capacity of soil
without and with CSB hydrogels decreases with increasing time (day) due
to the water evaporation from the soil. Fortunately, the water-retention ca-
pacity of soil mixed with CSB hydrogels is significantly higher than that of
control soil (0 g of hydrogel) and increases with increasing amounts of CSB
hydrogels (see Fig. S4a-c). This behavior is in good agreement with the pre-
vious reports (Tanan et al., 2021a; Mikula et al., 2020; Ramli, 2019). Be-
sides, this result suggests that the addition of CSB hydrogels into soil can
improve the water-retention, moisture, and quality of the soil which is ben-
eficial in the semi-arid farmland. Hence, plants could be supplied with more
moisture and nutrition rather than traditional fertilizers (Wen et al., 2017;
Wen et al., 2016).
To investigate the effect of crosslinker types on the water-retention ca-
pacity of soil, the water-retention of soil mixed with CSB-E2, CSB-M2 and
CSB-G2 hydrogels (1.5 g) was compared in Fig. 10a. It is observed that
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Science of the Total Environment 843 (2022) 157050
the water-retention capacity of control soil at 7 and 30 days reaches
50.3 % and only 0.2 %, respectively, while that of the soils mixed with
CSB-M2, CSB-E2, and CSB-G2 hydrogels at 7 and 30 days remains at
68.2 %, 70.2 %, 76.9 % and 12.6 %, 14.5 %, 20.2 %, respectively.
This result exhibits that the soil quality and soil moisture can be im-
proved by addition of CSB hydrogels with different types and weights
(Tanan et al., 2021a). Thus, by comparison between the water-retention
capacities of soils, it suggests that GA crosslinker is more suitable than MBA
and EGDMA ones to synthesize the CSt-g-PAA/NR/PVA hydrogel systems.
3.5. Biodegradation test
To fabricate the coated fertilizers with less pollution and safety to the
environments, the degradation property of coating materials is also desired
(Tanan et al., 2021a). Fig. 10b illustrates the time-dependent degradation
of CSB-M2, CSB-E2, and CSB-G2 hydrogels at ambient temperature. It is
seen that all CSB samples exhibit an excellent degradation with similar be-
havior, increasing with exposure time. The degradation of CSB hydrogels in
the studied range may be divided into two phases; 0–60 % and >60 %. In
the first phase, the degradation rates of CSB-M2, CSB-E2, and CSB-G2
hydrogels are calculated to be 0.95, 1.05, and 1.37 %/day, respectively,
by a linear fitting with R2 > 0.99. This demonstrates that the degradation
of CSB-G2 hydrogel is significantly higher than that of the CSB-E2 and
CSB-M2 ones.
Interestingly, the biodegradation rates (BR, %/day) of CSB hydrogels in
the first stage correlate very well with the equilibrium swelling (Seq, %) and
pore size (ϕ, μm) of CSB hydrogels, describing by two linear relationships:
BR (%/day) = 4.9 × 10−4 Seq (%) + 0.75, R2 = 0.989 and BR (%/day) =
1.69 × 10−2 ϕ (μm) + 0.78, R2 = 0.999, respectively (see Fig. 10c and d).
This suggests that the biodegradation of CSB hydrogels is simultaneously
governed by both the pore size and swelling capacity of CSB hydrogels.
Moreover, other factors such as microbial population and extensive envi-
ronments (temperature, pH, moisture, and nutrition) generally influence
the biodegradation of hydrogels and the higher swelling capacity supports
more growth of the microbial biodegradation (Yang et al., 2013; Salimi
et al., 2020). At >60 % degradation (the second phase), the degradation
rate was slower due to the addition of NR molecules into hydrogel making
it more difficult to degrade (Tanan et al., 2021a; Vudjung et al., 2014). At
90 days, the weight loss of CSB-M2, CSB-E2 and CSB-G2 hydrogels is
about 78.8 %, 84.5 % and 90.9 %, respectively. These results indicate the
excellent biodegradation of CSB semi-IPN hydrogels which could be ap-
plied as environmentally friendly and less polluted coating membrane for
slow-release fertilizer applications.
3.6. Slow-release behavior of UCSBw fertilizer
The release behavior and release kinetics of slow-release fertilizers are
the important parameters for identifying their potential applications in
P. Jungsinyatam et al.
Fig. 10. (a) Water-retention capacity of soil mixed with the CSB-M2, CSB-E2 and CSB-G2 hydrogels and (b) the biodegradation of different CSB hydrogels at different times.
the agricultural fields. Generally, the release mechanism of slow-release fer-
tilizers consists of three stages; lag period, steady release and decay phase,
respectively (Lawrencia et al., 2021b). The urea release profiles as a func-
tion of time for pure urea, UCSBw-E2, UCSBw-G2 and UCSBw-M2 coated
fertilizers in distilled water and soil environments are presented in
Fig. 11a and b, respectively. From Fig. 11a, it is found that the uncoated
urea fertilizer releases quickly (98.2 %) within 1 h and nearly completes
(99.6 %) at 2 h. In contrast, the urea release from all UCSBw formulations
represents three stages of release behavior with slower initial release
rates. The cumulative releases of UCSBw-M2, UCSBw-E2 and UCSBw-G2
formulations at 24 h are just only 26.2 %, 35.2 %, and 38.9 %, respectively,
indicating the good slow-release property of the UCSBw formulations. This
result could be correlated to the barrier properties of CSB semi-IPN net-
works, the hydrophilic/hydrophobic properties of polymers and the help
of wax (Wu et al., 2020; El Assimi et al., 2020).
Furthermore, it is seen that the urea release of all UCSBw formulations
in water is linearly increased as a function of time (h) up to 72 h and then
increases very slowly, reaching equilibrium point. At 72 h, the cumulative
release rates of UCSBw-M2, UCSBw-E2 and UCSBw-G2 formulations are
81.9 %, 83.3 % and 89.6 %, respectively, matching well with their swelling
ratios and the average pore sizes (see Fig. 11e). Besides, Tanan et al. also
suggested that the urea release profiles of the hydrogel coated fertilizers
in water were markedly influenced by the NR/PVA ratios and the surface
area and pore volume of the coated membranes (Tanan et al., 2021a).
To examine the practical use of UCSBw fertilizers in the agriculture and
horticulture, the slow-release profiles of UCSBw fertilizers in soil were thus
also studied as depicted in Fig. 11b. It is found that the release of uncoated
urea increases suddenly up to 70.8 % in the first 7 days due to the high dis-
solution of urea fertilizer in water/moisture environments. After that, it
gradually increases and reaches 93.7 % at 30 days. However, the urea re-
lease behaviors of UCSBw fertilizers are gradually increased with the
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Science of the Total Environment 843 (2022) 157050
buried time. The urea release rates from the UCSBw-M2, UCSBw-E2 and
UCSBw-G2 formulations in 7 and 30 days are 19.6 %, 24.3 %, 29.8 %,
and 67.7 %, 68.7 %, 77.3 %, respectively. A similar release behavior was
also found in the system of biochar embedded-bentonite based semi-IPN
SRF (BiBe-SRF), exhibiting the N release rate of around 65 % in 30 days
which was reported by An et al. (An et al., 2020). They also concluded
that the superior slow-release performance for BiBe-SRF resulted from the
desirable porous structure, the stable formation of N-and P- related chemi-
cal bonds and the good interactions between functional groups in the BeBi-
SRF.
In addition, the slow-release characters of all UCSBw fertilizers agree
with the standard of slow release fertilizers (<15 % and <75 % at 24 h
and 28 days, respectively) of the Committee of European Normalization
(CEN) (Rashidzadeh and Olad, 2014; Wang et al., 2021). Again, the release
rate of UCSBw-G2 is gradually higher than that of the UCSBw-M2 and
UCSBw-E2 hydrogels, matching well with the higher water absorbency
(see Fig. 8) and larger pore size (see Fig. 4) (Tanan et al., 2021a; Chang
et al., 2010). This result indicates that the swelling property and porous
structure play a vital role in the release of coated urea fertilizer as shown
in Fig. 11f (Tanan et al., 2021a; Yang et al., 2013; Salimi et al., 2020).
3.7. Release kinetics of urea release in water and soil environments
To gain more insight into the release mechanism from the coated fertil-
izers (UCSBw) in water and soil environments, the well-known empirical
(Higuchi) and semi-empirical (Korsmeyer-Peppas) kinetic models (Tanan
et al., 2021a; Lawrencia et al., 2021b) were applied to fit the release data
by using OriginPro 2018® program as shown in Fig. 11c-d and the kinetic
parameters of the release behavior are listed in Table 2. As presented, the
Korsmeyer-Peppas model is a suitable model with high correlation (R2)
for describing the urea release mechanism from all UCSBw fertilizers in
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

Fig. 11. The release behavior (a,b), kinetics of release (c,d) and correlation between kKP versus swelling and pore size (e,f) of UCSBw-M2, UCSBw-E2 and UCSBw-G2 in water
(left column) and soil environments (right column).

both water (R2 ~ 0.97) and soil environments (R2 > 0.98). The n values in means that urea diffuses partially through a swollen matrix and water filled
both environments are higher than 0.5 and in the range of 0.62–0.99 pores in the hydrogel membranes. In other words, the mechanism of urea
(Salimi et al., 2020), indicating a non-Fickian diffusion mechanism. This release from all UCSBw formulations is regulated simultaneously by both

Table 2
Kinetic parameters for urea release data from UCSBw-E2, UCSBw-G2, and UCSBw-M2 formulations in water and soil.
Kinetic model Equation Parameter Formulation

UCSBw-E2 UCSBw-G2 UCSBw-M2

Water Soil Water Soil Water Soil

Higuchi CR = kHt0.5 kH 7.53 10.80 8.15 12.21 6.04 10.14

R2 0.866 0.876 0.891 0.914 0.865 0.873
Korsmeyer-Peppas CR = kKPtn kKP 1.50 4.09 2.17 5.20 1.12 3.71
n 0.97 0.84 0.89 0.84 0.99 0.86
R2 0.998 0.982 0.997 0.990 0.994 0.985

Note: Cr = (Mt/M ) represents the fractional nutrient release at time t. Mt is the cumulative release rate in time t, M∞ is the total amount of urea released at the longest time of
∞
the experiment. k is a kinetic constant, n is a diffusional exponent characterizing the release mechanism.

12
P. Jungsinyatam et al.
water diffusion and polymer relaxation (Tanan et al., 2021a; Rozo et al.,
2019).
To elucidate the effect of crosslinker types on the rate constant (kKP) of
urea release, the kKP values in water and soil are also compared. From
Table 2, the kKP values for the UCSBw-M2, UCSBw-E2, and UCSBw-G2 for-
mulations in water and soil are 1.12, 1.50, 2.17 %/h, and 3.71, 4.09, 5.20
%/day, respectively. This implies that the kKP values in soil are about
7.2–10.0 times lower than those in water because the exchange rates be-
tween water/vapor and fertilizer in soil are markedly reduced/restricted,
resulting in the marked decrease of the release rate. Besides, the kKP is in
the following order: UCSBw-G2 > UCSBw-E2 > UCSBw-M2, corresponding
well to the equilibrium swelling (Seq) and the average pore size (ϕ) of the
CSB hydrogels as shown in Fig. 10e-f. Therefore, this denotes that pore
sizes or network structures and water absorbency properties of the CSB
hydrogels could be the critical parameters for administering the nutrient re-
lease behaviors of slow-release fertilizer (Wei et al., 2019).
3.8. Effect of UCSBw on plant growth performance
To further demonstrate the possible effectiveness of UCSBw formula-
tions on plant growth, pot culture experiments of red chili plants (Jinda
breed) treated with USBw-M2, UCSBw-E2 and UCSBw-G2 formulations
were performed by recording the evolution of the plant height, leaf length
and weight of products for 45 days as shown in Fig. 12a-d. It is found that
the plant height, leaf length and product weight of plants promoted by
three UCSBw formulations are much higher than those of plants treated
with pure urea fertilizer and control (no fertilizer) (P < 0.05). In addition,
Fig. 12. Effect of different UCSBw fertilizers on the chili plant growth (Jinda breed); (a) plant height, (b) plant length and (c) product weight harvested at 45 day and
(d) photographs of the chili plants treated with different fertilizers taken at 45 day after a single fertilizer application and its products.
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Science of the Total Environment 843 (2022) 157050
the green leaves of chili plants treated with UCSBw fertilizers are darker
than those of uncoated urea and control (see Fig. 12d). The products of
chili obtained from USCBw fertilizers was about two times higher than
from pure urea fertilizer, resulting from the improved soil quality and
enough nutrients and high water-retention. These results accord well to
the previous works reporting that the plant height, root length, seed germi-
nation rate, plant growth, the size of leaves and stems treated with SRFs
were greater than those of plant treated with the traditional urea fertilizer
(Tanan et al., 2021a; Wen et al., 2016; Gao et al., 2018).
To gain greater insight into the effect of crosslinker types on the plant
performances, the plant height, leaves length and product weight of chili
plant are considered as presented in Fig. 12a-c. By careful comparison in
all three parameters, it could be concluded that the UCSBw-G2 formulation
exhibits the best overall performances rather than other two ones. This
means that the GA crosslinking agent could be the suitable crosslinker for
the preparation of CSB semi-IPN hydrogels with higher water-retention ca-
pacity and higher biodegradation rate.
From these data, it can be stated that the UCSBw fertilizers could effi-
ciently control the release of fertilizer nutrients and significantly improve
the retaining ability of nutrients. Moreover, it could supply enough nutri-
ents to the requirement of chili plant, contributing to the good growth of
chili and better yield of chili products.
3.9. Economic and biosafety evaluation of UCSBw fertilizers
It is well known that the cost of UCSBw fertilizers is a key parameter for
widely practical use in agricultural and horticultural sectors. Thus, the
P. Jungsinyatam et al. Science of the Total Environment 843 (2022) 157050

2.5
impacts of production costs of slow-release fertilizer on various economic
indicators was analyzed following the previous work (Tanan et al.,
2021a). The economic evaluation of three UCSBw fertilizers developed in
this work is thus presented in Table S1. The cost for production of
UCSBw-M2, UCSBw-E2 and UCSBw-G2 formulations was about 97.04,
91.87 and 94.53 Baht/kg, respectively, which was 76 %–77 % cheaper 2.0
than that of commercial SRF (Osmocoat®, 400 Baht/kg). Furthermore,

OD600
many profits could be gained from the UCSBw fertilizers compared to the
commercial fertilizers such as higher longevity of nutrient release, effective
reduction of irrigation times, improvement of soil moisture, profiting in
arid regions. Moreover, they are easily biodegradable by microorganisms 0.5

and no secondary pollution is generated in soil after application of the

UCSBw fertilizers, leading to less negative impact to environments. Conse-
quently, the application of UCSBw fertilizer not only profits for efficient
plant growth and yield, but also the good soil environments, which could
appropriate to compensate the cost. 0.0
To gain more information about the biosafety of UCSBw formulations,

ea

E2

2
2

2
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-G

-G
-E

-M

-M
ur

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SB

SB
SB

SB
SB

SB
the effects of UCSBw fertilizers (UCSBw-M2, UCSBw-E2, UCSBw-G2),

re
C

C
C

C
C

C
Pu

U
CSB solutions (CSB-M2, CSB-E2, CSB-G2), and pure urea at the same 5 ×
103 ppm concentrations on bacteria (E. coli) were examined by using the Fig. 13. Biosafety evaluation of control, pure urea, CSB solutions and UCSBw
optical density (OD600) method and compared (Tanan et al., 2021a). fertilizers on the growth of E. coli.
Fig. 13 reveals that the OD600s of E. coli treated with pure urea (0.27)
are slightly lower than those of all three UCSBw fertilizers (0.32–0.35)
but the OD600s values of pure urea and UCSBw fertilizers are clearly with increasing crosslinker contents, respectively. The equilibrium swelling
lower than that of untreated control (0.41). These results suggest that of CSB hydrogels corresponded well with pore sizes and mechanical prop-
pure urea and UCSBw fertilizers have gradually influence on the growth erties of hydrogels. Moreover, the CSB-G2 hydrogel (crosslinked by GA at
and metabolism of E. coli. However, in the case of CSB solutions, the 2 wt%) showed a higher water-retention capacity at 30 days (20.2 %),
OD600 values of E. coli is evidently increased to 1.83–2.26. grater rate of degradation (1.37 %/day) and better biosafety compared to
This implies that the inherent properties of CSB hydrogels have a high CSB-M2 and CSB-E2 hydrogels. The urea release rates from the UCSBw-
level of safety and could be a favored nutrient for E. coli growth (Tanan G2 formulations in 30 days was 77.3 %. Finally, the UCSBw-G2 formulation
et al., 2021a), agreeing well with the excellent biodegradation (see also exhibited the greater plant growth performance (height, leaf length
Fig. 10). By comparison between the biosafety data of UCSBw fertilizers and product weight) than other two formulations (UCSBw-M2 and
and CSB solutions, it could be stated that the UCSBw-G2 fertilizer has UCSBw-E2) and commercial fertilizer. Therefore, it could be concluded
more biosafety than UCSBw-E2 and UCSBw-M2 ones. Furthermore, the that GA is the suitable crosslinker for synthesizing the CSt-g-PAA/NR/
use of slow-released fertilizers is also found not only to improve the plant PVA semi-IPN hydrogel with high water-retention, excellent biodegrada-
growth and crop yield, but also reduce the total greenhouse gas emissions tion, less negative impact on environments, acceptable slow-release rate,
and fertilizer emissions, water eutrophication and soil degradation good biosafety and reasonable price for slow-release fertilizers. These find-
(Mikula et al., 2020; Sikora et al., 2020). ings could offer good references for the selection of suitable crosslinkers to
synthesize the biodegradable hydrogels requiring high values of swelling
3.10. Comparison between the properties of CSB hydrogels water-retention and excellent biodegradation with acceptable release rate
as well as less negative impact on water, soil and air environments.
Finally, to distinguish and compare which crosslinkers would be a suit-
able crosslinker for fabricating the CSt-g-PAA/NR/PVA semi-IPN hydrogels CRediT authorship contribution statement
(CSB hydrogels) as an environmentally friendly coating membrane with
high water-retention and excellent biodegradable properties, acceptable Patchareepon Jungsinyatam: Methodology, Experiment, Investigation,
urea-release rate and high plant growth performance, the properties and ex- and Writing- Review
periment results obtained from the CSB-M2, CSB-E2, and CSB-G2 semi-IPN Pitchayaporn Suwanakood: Biosafety evaluation and supervision
hydrogels are summarized in Table 3 for consideration. From the swelling Sayant Saengsuwan: Conceptualization, Visualization, Writing - Review
capacity, water-retention, biodegradation in soil, release rate, total plant & Editing,
growth performance and biosafety points of view, it is believed that the Supervision and Project Administration.
CSB-G2 hydrogels is a suitable coating membrane for encapsulating the fer-
tilizer prills in the production of slow-release fertilizers. This means that GA
crosslinker should be selected as an appropriate crosslinker for the prepara- Table 3
tion of biodegradable hydrogels comprising of CSt and NR as the main com- Comparison of the properties of CSB-M2, CSB-E3 and CSB-G2 semi-IPN hydrogels.
positions. This is because it provides the high water-retention, excellent Properties Hydrogel formulations
biodegradability, efficient slow-release rate, high plant growth perfor- CSB-M2 CSB-E2 CSB-G2
mance and great biosafety with an acceptable price.
1. Pore size (μm) 9.9 ± 1.7 16.4 ± 0.3 34.9 ± 0.3
2. Yung's modulus (GPa) 0.65 ± 0.35 0.72 ± 0.02 0.29 ± 0.03
4. Conclusions 3. Equilibrium swelling (Seq, %) 445 ± 21 559 ± 11 1261 ± 13
4. Point of zero charge (pH) 6.15 6.20 6.85
5. Water-retention at 30 days (%) 12.6 14.5 20.2
In this study, a suitable crosslinkers for synthesizing the CSt-g-PAA/NR/
6. Biodegradation in soil at 90 days (%) 78.8 84.5 90.9
PVA semi-IPN (CSB) multicomponent hydrogels as an environmentally 7. Release rate in soil at 30 days (%) 67.7 68.7 77.3
friendly coating membrane for slow-release fertilizers has been investi- 8. n parameter 0.84 0.84 0.86
gated. Three crosslinkers including MBA, EGDMA and GA were selected 9. Total plant growth performance 90.75 89.26 96.32
to compare their influences. Results revealed that mechanical properties 10. Biosafety (OD600s) 1.83 1.9 2.26
11. Price/1 kg (Baht) 97.04 91.87 94.53
and swelling capacity of all CSB hydrogels tended to increase and reduce

14
P. Jungsinyatam et al.
Declaration of competing interest
The authors declare that they have no conflict of interest or personal
relationships that could have appeared to influence the work reported in
this paper.
Acknowledgements
Financial support from the center of excellent for innovation in
chemistry (PERCH-CIC), Ministry of Higher Education, Science, Research
and Innovation, and a research fund for graduate student (academic year
2019) from Ubon Ratchathani University are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2022.157050.
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