Preparation of Ph/temperature Responsive Semi IPN Hydrogels Based On Sodium Alginate and Humic Acid As Slow Release and Water Retention Fertilizers

Polymer Bulletin (2024) 81:4175–4198
https://doi.org/10.1007/s00289-023-04901-7
ORIGINAL PAPER
Preparation of pH/temperature‑responsive semi‑IPN

hydrogels based on sodium alginate and humic acid
as slow‑release and water‑retention fertilizers
Bingyan Hua1 · Hongliang Wei1 · Chunwang Hu1 · Yaqi Zhang1 · Shuai Yang1 ·
Gang Wang1 · Tao Guo1 · Jingjing Li1
Received: 20 October 2022 / Revised: 23 February 2023 / Accepted: 30 June 2023 /

Published online: 11 July 2023
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023
Abstract
Herein, a semi-interpenetrating network (semi-IPN) hydrogel (SH/PNA) was pre-
pared by simple free radical polymerization using N-isopropylacrylamide and
2-acrylamide-2-methylpropanesulfonic acid as monomers, poly(ethylene glycol)
dimethacrylate as a crosslinking agent, and sodium alginate and humic acid as filled
biomolecules. Fourier transform infrared spectroscopy, scanning electron micros-
copy, X-ray diffraction, and rheometer were used to characterize the structure and
properties of the samples. The effect of feeding ratios on the gel mass fraction and
swelling properties of the SH/PNA hydrogel was explored to optimize its prepara-
tion conditions. The swelling behavior under different pH and temperatures was
investigated. The experimental result showed that the SH/PNA hydrogel had excel-
lent water absorption capacity and pH/temperature dual responsiveness. Moreover,
SH/PNA hydrogel was used as a carrier of urea to prepare slow-release and water-
retention fertilizer by in situ loading method, and slow-release properties of urea in
water and soil were measured. Taking into account its good ability for controlled
release and water retention, the WSRF was expected to be a promising low-cost,
environmentally friendly fertilizer that can be used in agriculture and horticulture.
Keywords Semi-IPN hydrogel · Fertilizer · Slow-release · Responsiveness · Water

retention
* Hongliang Wei
weihl68@126.com
* Jingjing Li
nicoleljj@tju.edu.cn
1
School of Chemistry and Chemical Engineering, Henan University of Technology,
Zhengzhou 450001, People’s Republic of China
13
Vol.:(0123456789)
4176 Polymer Bulletin (2024) 81:4175–4198
Introduction
Rapid population growth and limited arable land and water resources have led to the
food crisis becoming one of the major global concerns [1]. Plants cannot grow with-
out soil, and fertilizers can provide a lot of nutrients, such as nitrogen (N), phospho-
rus (P), and potassium (K), to improve soil fertility. Over the past 50 years, the use
of nitrogen fertilizer has increased from 32 million tons to 110 million tons to meet
the growing demand for food and agricultural products [2]. Urea is widely used in
farm land due to its high nitrogen content, low cost, simple preparation process, and
easy use. However, due to its high solubility, a large number of nitrogen nutrients
will be lost to the environment through volatilization (NH3 and NO2, etc.), deni-
trification, leaching, and other ways, which makes the utilization rate of urea only
30–50% (Fig. 1) [3, 4]. This not only causes huge economic losses, but also leads to
a sequence of major environmental pollution issues such as soil degradation, water
eutrophication, and air pollutants [5, 6]. To solve these problems, developing con-
trolled-release/slow-release fertilizers (SRF) has become the focus of people’s atten-
tion [7].
Compared with conventional fertilizers, SRF has the advantages of controlling
nutrient release rate, improving fertilizer utilization rate, lessening fertilization
frequency, and reducing nutrient loss [8]. Li et al. [6] prepared a SRF by solvent-
free semi-solid phase blending method from polybutylene succinate-butylene adi-
pate copolymer, which could extend the urea release time to 12 h in water. Ye et al.
prepared an inclusion compound SRF using a twin-screw extrusion mechanism
Fig. 1 The diagram of the fast release of pure urea and the slow release of urea-loaded SRF
13
Polymer Bulletin (2024) 81:4175–4198 4177
by blending degradable polyester with urea. The indoor plant growth experiment
showed that the SRF had a certain effect on the growth status of maize seedlings,
and all the growth indexes were better than the control [9].
On the other hand, reasonable water to fertilizer ratio plays a crucial role in
improving nutrient utilization rate, maintaining soil fertility, and promoting crop
growth [10]. Using hydrogel as a fertilizer carrier can give SRF water retention,
which is very beneficial to crop growth due to the synergistic effect of water and fer-
tilizer [11]. Therefore, a novel sustained-release strategy combining SRF and hydro-
gel has been proposed.
Hydrogel is a polymer material with excellent water absorption and water reten-
tion ability, but is insoluble in water [12]. Hydrogels can be divided into organic
hydrogels, inorganic hydrogels, and organic–inorganic composite hydrogels accord-
ing to composition, among which organic hydrogels can be subdivided into syn-
thetic and natural polymer hydrogels [13]. According to the response to environ-
mental stimuli, hydrogels can be segmented into traditional hydrogels and intelligent
hydrogels. Intelligent hydrogels can perceive subtle physical and chemical variations
(such as pH, temperature, ultraviolet light, and magnetic field.) in external surround-
ings and respond to these external stimuli through volume expansion or contraction
[14]. Hydrogel materials have considerable application prospects in water treatment
[15], food packaging [16], biomedicine [17], and tissue engineering [18], etc.
Interpenetrating network (IPN) or semi-IPN is an effective technology to improve
the properties of hydrogels. Among them, IPN is defined by IUPAC as “a poly-
mer consisting of two or more interleaved networks with no covalent bond forma-
tion between the network”; semi-IPN is defined as “a polymer consisting of one or
more networks and one or more linear or branched polymers characterized by at
least some linear or branched macromolecules that penetrate at least one network
at the molecular scale” [19]. In semi-IPN hydrogels, the molecular chains of the
linear or branched polymer are only dispersed in the network formed by the first
cross-linked polymer. The polymer and the network are physically bonded to each
other through hydrogen bond, electrostatic attraction, hydrophobic association, van
der Waals force and other interactions [20]. Compared with conventional hydrogels,
semi-IPN hydrogels exhibit good fertilizer capture and slow-release characteristics
due to their interconnected porous network structure. Furthermore, the physical
entanglement and interaction between the polymer and the network lead to higher
mechanical strength, making the hydrogel have special synergistic effects in proper-
ties or functions [21].
When SRF and hydrogel are put into one system, water-retention and slow-release
fertilizer (WSRF) is fabricated. It has a broad application prospect and represents
an important research direction of fertilizer. Liu et al. used sodium alginate, poly-
vinyl alcohol, and cellulose nanofibers to prepare a new nanocomposite hydrogel
through blending-crosslinking, and the hydrogel has excellent water retention ability
and slow-release ability [22]. However, most of the polymers used to prepare WSRF
are synthetic, which have some disadvantages such as high cost, complex synthesis
process and hard to degrade. Therefore, biopolymer has become the preferred raw
material for WSRF preparation [23, 24]. Biopolymer-based hydrogels not only have
the characteristics of traditional hydrogels, but also have excellent green, renewable
13
and degradable properties [25, 26]. Therefore, WSRF based on biopolymer hydrogel
is especially attractive.
Sodium alginate (SA) is a pH sensitive, non-toxic, anionic, natural polysaccha-
ride extracted from brown algae [27]. It is formed by connecting β-D-mannuronic
acid (M) and α-L-guluronic acid (G) via a 1–4 glucoside bond (Fig. 2). Recently,
SA has become an important raw material for preparing functional hydrogels due
to its excellent properties of flame retardancy, biodegradability, biocompatibility,
and ion exchange [28]. SA-based hydrogels are widely used in 3D printing, biologi-
cal medicine, wastewater treatment, and agriculture [29–32]. Arafa et al. prepared
a slow-release fertilizer based on sodium alginate/carboxymethyl chitosan hydrogel
with Ca2+ ion cross-linking points, and it has certain antibacterial and degradability.
The controlled release experiment of urea showed that the cumulative release rate of
this slow-release fertilizer reached 91% in 26 days [33].
Humic acid (HA) is a group of long-chain organic substances with colloidal prop-
erties and multi-spatial structure, which is formed by chemical reactions and micro-
bial decomposition of animal and plant remains [34, 35]. HA cannot be expressed
by a single chemical formula, and the structure model of HA reported in the relevant
literature is shown in Fig. 3 [36]. It exists widely in natural environments such as
soil and water, accounting for about 50% of the earth’s total carbon resources. HA is
soluble in alkaline solution, partially soluble in water, but insoluble in acidic solu-
tion. Various functional groups (phenol, quinone, amide, sulfonate group, etc.) give
it unique properties, such as ion exchange, complexation, antioxidant, adsorption,
and catalysis. [37, 38]. Therefore, HA has been widely used in water treatment, bio-
medicine, and other fields [39]. Chen et al. [38] fabricated starch-humic acid com-
posite hydrogel beads via inverse suspension crosslinking method and studied their
application in the removal of lead (II) and methylene blue. Especially in agriculture,
HA can promote the activity of protein enzymes, improve soil structure, promote
the plant for nitrogen phosphorus potassium absorption, and increase crop output
[34, 40]. Wang et al. prepared pH-responsive gel spheres for the sustained release
of HA(CSGCH) using SA and activated carbon as carriers. Soil remediation tests
showed that CSGCH had a positive effect on different types of soil. The organic
matter content and soil nutrient were significantly increased, while the pH and salt
content were decreased within 50 days of the restoration. Plant experiments showed
that CSGCH effectively promoted crop growth. As a soil amendment, CSGCH had
Fig. 2 Structural composition of repetitive units of SA
13
Fig. 3 Basic unit of HA molecular structure
huge potential value in improving soil environment and facilitating crop growth in
agriculture [41].
Based on the above context, a semi-IPN SH/PNA hydrogel was prepared by sim-
ple free radical polymerization of N-isopropylacrylamide and 2-acrylamide-2-meth-
ylpropanesulfonic acid, two commonly used monomers during preparing supera-
bsorbent, using SA and HA as filled biomolecules. Due to abundant hydrophilic
groups in SA and HA, their introduction is expected to increase the hydrophilicity
of WSRF. In addition, HA degradation can improve soil fertility. The effects of dif-
ferent feed ratios on gel mass fraction and swelling degree were studied to determine
the optimal preparation process. Its swelling behavior under different pH and tem-
peratures was investigated. WSRF was prepared using SH/PNA hydrogel as a carrier
by in situ wrapping urea into the gel, and its slow-release behavior in water and soil
was studied. Kinetic models were used to investigate the kinetic mechanism of slow
release of urea. To the best of our knowledge, there is no report on the preparation of
sodium alginate and humic acid based WSRF in this way.
Materials and methods
Materials
Sodium alginate (SA) was obtained from Tianjin Kaitong Chemical Reagent Co.,
Ltd, China. Humic acid (HA) was provided by Zhengzhou Acme Chemical Co.
Ltd, China. N-isopropylacrylamide (NIPAM) and 2-acrylamide-2-methyl-1-pro-
panesulfonic acid (AMPS) were obtained from Shanghai Saan Chemical Tech-
nology Co., Ltd, China. NaOH was purchased from Xilong Chemical Co., Ltd,
13
China. Ascorbic acid (AC) was procured from Beijing Enokai Technology Co.,
Ltd, China. Potassium persulfate (KPS) and urea were obtained from Tianjin
Kemiou Chemical Reagent Co., Ltd, China. Poly (ethylene glycol) dimethacrylate
(PEGDMA, Mw = 750) was procured from Shanghai Aladdin Biochemical Tech-
nology Co., Ltd, China. All chemicals were of analytical reagent grade, and the
water used in the experiment was deionized water.
Preparation of SH/PNA hydrogels
A series of SH/PNA hydrogels were prepared by free radical polymerization with

a redox initiation system (KPS: oxidant; AC: reductant) according to different
feed ratios (Table S1). Typically, the preparation scheme under the optimal con-
ditions (sample 9) is as follows: 0.1697 g (1.5 mmol) of NIPAM and 0.1036 g
(0.5 mmol) of AMPS were weighed and placed in a tube. Subsequently, 2 mL of
deionized water was added and the mixed solution was obtained by ultrasound.
Then, 0.5 mol/L NaOH solution was used to adjust the pH to alkaline. Subse-
quently, 0.0054 g (0.02 mmol) of KPS, 0.0035 g (0.02 mmol) of AC, 0.04 g of
HA, and 0.04 g of SA were added into the mixed solution to disperse evenly by
ultrasound. Finally, after adding 0.015 g (0.02 mmol) of PEGDMA, the tube was
placed in a water bath of 30 °C, and the solution gelled within about 5 min. To
fully react, the gel was maintained in the water bath for 4 h before drying (Fig. 4).
For comparison, the single network hydrogel (PNA) without SA and HA was pre-
pared. The prepared hydrogels were vacuum-dried to constant weight at 50 °C.
Fig. 4 Synthetic process of PNA and SH/PNA hydrogel
13
Preparation of WSRF
There are two ways to load fertilizer with water-retaining materials, one is in situ
embedding method, and the other is swelling-adsorption method [42]. The former
blends the fertilizer directly with the reactant and loads the fertilizer into the gel
through in situ polymerization. The latter is to soak the dry gel in the fertilizer
solution for swelling and absorption, then dry the gel after reaching the absorp-
tion saturation. Considering that the second method is complicated and the ferti-
lizer loading rate is lower, we choose the in situ loading method to prepare SH/
PNA WSRF. Briefly, 0.7546 g of urea was dissolved in 2 mL of deionized water,
and then, the reactants were added in sequence according to the preparation steps
of the SH/PNA hydrogel. After the reaction, the prepared WSRF was vacuum-
dried to constant weight at 50 °C.
Characterization
A Fourier transform infrared spectrometer (FTIR, PerkinElmer UATR Two,

Liantrisant, UK) was used to characterize the functional groups of the samples in
the wavelength range of 400–4000 cm−1. The resolution and scanning frequency
were 4 cm−1 and 16 times, respectively. Before the measurement, the samples
were vacuum dried and ground. A scanning electron microscope (SEM, JEOL
JSM-6490A, Tokyo, Japan) was used to observe the surface micromorphology
of the samples, which were freeze-dried and sprayed with gold at an acceleration
voltage of 20 kV. An X-ray diffractometer (XRD, Rigaku Miniflex-600 ×, Japan)
was used to analyze the aggregated structure of the samples in the 2θ scanning
range of 10°–90° with a scanning speed of 10°/min. The test was operated with
Cu-Kα radiation at a voltage of 40 kV and a current of 100 mA.
Determination of gel mass fraction (GMF)
A certain amount of dry gel (W0) was weighed and soaked in deionized water for
48 h to remove impurities. During this period, the water was changed every 4 h.
The gel was then removed and placed in a vacuum oven to dry to constant weight
(W1). GMF was calculated by the following Eq. (1).
W1
GMF(% ) = × 100 (1)
W0
where W0 and W1 are, respectively, the dry weight of gel samples before and after
soaking in deionized water.
13
Swelling behavior
To investigate the effect of different feeding ratios on the swelling ratios (SR) of
gel, the dry gel (W0) was immersed in deionized water at room temperature (rt)
and then, removed after swelling at preset intervals. The extra moisture on the gel
surface was immediately removed with filter paper, and the SR was calculated
according to Eq. (2).
W t − W0
SR(% ) = × 100 (2)
W0
where Wt is the mass of wet gel sample at time t. When t = 0, Wt = W0.

To explore the influence of pH and temperature on the swelling behavior of gel, the
SR of gel at different times was measured in buffer solution with the temperature range
of 20–60 °C and pH range of 2–10, respectively (Buffer solution was prepared accord-
ing to Table S2). The measurement and calculation method was the same as above.
Water retention experiment in air
First, a certain amount of dry gel was soaked in water until it reached a swelling equi-
librium. The wet gel was wrapped in a 200-mesh nylon bag and suspended in the air
at rt to dry naturally. The wet gel mass was measured every 12 h. The water retention
index (WR) was calculated according to Eq. (3).
Mt − M
WR(% ) = × 100 (3)
M0 − M
where Mt is the total mass of wet gel and mesh bag at time t; M is the initial mass of
mesh bag. When t = 0, Mt = M0.
Slow‑release behavior of the WSRF in water and soil
Slow‑release experiment in water
A certain mass of WSRF was weighed and placed in a conical flask containing 50 mL
of deionized water. At regular intervals, 10 mL solution was aspirated from the conical
flask using a pipette gun, while the same volume of deionized water was added to keep
the volume constant. Urea content in the solution was measured by p-Dimethylamin-
obenzaldehyde coloration method (Fig. S1 and Table S3). The cumulative release rate
of urea was calculated according to Eq. (4).
∑n−1
Ci Vi + Cn V
UR(% ) = i=1 × 100 (4)
W0
13
where Ci and Cn are the concentrations of urea in the solution; i and n are the sam-
ple collection times; Vi and V are the sample volume and total volume of solution,
respectively; W0 is the mass of urea loaded in the gel.
Slow‑release experiment in soil
The urea release behavior of WSRF in soil was investigated by the intermittent soil
column leaching method [43]. Firstly, the nylon gauze and wire were used to tie
one end of a PVC pipe with a diameter of 10 cm and a height of 30 cm, and a thin
layer of cotton was spread over the gauze. Then, 100 g of dried soil (treated with 35
mesh sieve) was added to the tube, and a certain quality of WSRF was buried 4 cm
from the bottom of the PVC pipe. The PVC pipe was placed on the Buchner funnel
and fixed on the iron frame. A 50 mL volumetric bottle was placed below to receive
the leaching solution. After wetting the soil with deionized water, 50 mL water was
added every 2 h to leach the soil column for 7 times. The soil column with untreated
pure urea was used as a reference. After the collected solution reached a constant
volume of 50 mL, the concentration of urea was determined by UV spectrophotom-
eter with p-dimethylaminobenzaldehyde colorimetry.
Release kinetics
To further analyze the mechanism of fertilizer release, Korsmeyer–Peppas, Higuchi,

zero-order kinetics, and first-order kinetics models were used to fit the experimental
data linearly [44].
(1) Korsmeyer–Peppas model
Mt
= kkp tn (5)
M∞
(2) Higuchi model

Mt
= kH t1∕2 (6)
M∞
(3) Zero-order kinetics model

Mt
= k0 (7)
M∞
(4) First-order kinetics model

Mt
= 1 − e−k1 t (8)
M∞
where Mt/M∞ is fertilizer release fraction at time t; t is the release time; Kkp and n
are release constant and diffusion exponent, respectively. KH is Higuchi dissolution
constant; K0 and K1 are the release constants each model, respectively.
13
The Korsmeyer–Peppas model describes the Fickian and non-Fickian release

behavior of fertilizer in the expansion and release system. The release mechanism of
WSRF can be inferred based on the diffusion exponent n. If n < 0.45, the diffusion is
Fickian diffusion; if 0.45 < n < 0.89, the diffusion is a non-Fickian transport process;
when n > 0.89, it is the most basic dissolution process. The zero-order model is used
to account for the release behavior that occurs at a constant rate over a specific time
interval and is not controlled by fertilizer concentration. In contrast, the first-order
model is used to account for the release behavior in which the release rate is con-
stant over a specific time interval and controlled by fertilizer concentration [33, 45].
Results and discussions
FTIR analysis
FTIR is an important technique to determine the functional groups and molecular

structures of polymers. The FTIR spectra of NIPAM, AMPS, and PNA hydrogel
Fig. 5 a FTIR spectra of NIPAM, AMPS, and PNA hydrogel; b FTIR spectra of SA, HA, PNA hydrogel,
and SH/PNA hydrogel; SEM images of c PNA hydrogel and d SH/PNA hydrogel
13
are shown in Fig. 5a. In the spectrum of NIPAM, the peaks at about 3296 cm−1 and
2876 cm−1 are attributed to the stretching vibration of the N–H bond the C–H bond,
respectively. A series of bands associated with conformational regularity or crystal-
linity appear between 1400 and 1040 cm−1, which can be used to distinguish differ-
ent polyamides [46]. The peaks at 1653, 1545, and 1365 cm−1 are assigned to the
amide I, amide II, and isopropyl, respectively [47]. In the spectrum of AMPS, the
peak at 3225 cm−1 is due to the symmetric stretching vibration of the amine (NH)
group, and the stretching vibration peak at 2990 cm−1 is assigned to the C–H in the
methyl group [48]. The peaks at 1657 cm−1 and 1608 cm−1 correspond to the stretch-
ing vibration of C=O and C=C, respectively [49]. Symmetrical and asymmetric
characteristic absorption peaks of the sulfonic group (–SO3H) appear at 1238 cm−1,
1073 cm−1, and 629 cm−1, respectively [50]. In the spectrum of PNA hydrogel, the
characteristic vibration of N–H, C=O, C–N, and isopropyl appears at 2975, 1644,
1545, and 1365 cm−1, respectively. Meanwhile, the characteristic absorption peaks
of the sulfonic group exhibit at 1035 cm−1 and 619 cm−1, indicating that the PNA
gel network was successfully prepared.
The FTIR spectra of SA, HA, and SH/PNA hydrogel are shown in Fig. 5b. For
SA, the peak at 3302 cm−1 is attributed to –OH, and the peaks at 1594, 1410, and
1029 cm−1 are assigned to the asymmetric and symmetric stretching vibration of
COO− and the bending vibration of C–O, respectively [51, 52]. For HA, the stretch-
ing vibration peak of –OH is shown at 3307 cm−1 [35]. Similarly, the symmetric and
asymmetric stretching vibrations of C OO− appear at 1583 and 1391 cm−1, respec-
tively [53, 54]. In addition, the characteristic peaks of S=O and C–O–S on the sul-
fonic group present at 1042 and 659 c m−1, respectively.
For the spectrum of SH/PNA hydrogel, the characteristic peaks of SA, HA, and
PNA hydrogel can be observed, and their positions are approximately the same.
Nevertheless, the peak at 1648 cm−1 is significantly enhanced, resulting from the
combination of C=O stretching vibration on NIPAM/AMPS units and the C=O
stretching vibration of the carboxylic acid group on SA and HA [55]. Therefore,
SA and HA were successfully introduced into the polymer network, and SH/PNA
hydrogel was successfully prepared.
SEM analysis
As shown in Fig. 5c and d, both of the gels have a three-dimensional network porous
structure, which enable the gel to accommodate urea molecules, and delay the diffu-
sion and release of urea. Furthermore, it can be observed that the introduction of SA
and HA makes the gel surface smoother and the pore structure more orderly.
XRD analysis
Figure 6 shows XRD patterns of SA, HA, PNA, and SH/PNA. A flat and broad dif-
fraction peak at 20.90° can be observed for SA, PNA, and SH/PNA, which is due to
the low crystallinity of the polymer, mainly amorphous periodic parallel structure
[56, 57]. Sharp characteristic diffraction peaks can be observed for HA at 11.45° and
13
Fig. 6 XRD patterns of SA, HA,

PNA hydrogel, and SH/PNA
hydrogel
26.67°, indicating that HA has a relatively regular lattice and exists in the form of a
semi-crystalline [35]. Comparing the XRD patterns of PNA hydrogel with SH/PNA
hydrogel, it can be seen that the peak intensity of the latter increases at 20.90°, and
the peak is relatively sharp. A new small diffraction peak appears at 26.67°, which is
consistent with the characteristic diffraction peak of HA, indicating that SA and HA
are successfully involved in the SH/PNA hydrogel. The above results suggest that
the aggregated structure of the gel gradually changed when introducing SA and HA.
Rheological behavior
The dynamic rheological behavior of hydrogels under different strains and fre-
quencies is shown in Fig. 7. In dynamic strain scanning test (Fig. 7a), the G val-
ues of the two hydrogels were not affected by the applied strain within the range of
Fig. 7 a The strain sweep curves of PNA hydrogel and SH/PNA hydrogel at a frequency of 1 Hz and a
temperature of 25 °C and b the oscillatory frequency sweep curves of PNA and SH/PNA hydrogel at s at
a strain of 1%
13
LVR, indicating that the network structure of hydrogels was relatively stable [58].
As shown in Fig. 7b, when the strain is 1% and the frequency scanning range is
0.01 ~ 10 Hz, the Gʺ value is always greater than Gʺ, indicating that the sample is
a viscoelastic solid. The G value of the SH/PNA hydrogel increases with frequency,
showing typical elastic deformation and a certain frequency dependence [59]. In
addition, the Gʹ and Gʺ values of SH/PNA hydrogel were higher than those of PNA
hydrogel at the same strain and frequency, indicating that the introduction of SA and
HA increased the mechanical strength and elasticity of the gel [60].
Gel mass fraction (GMF) analysis
The effects of SA/HA content, monomer concentration, monomer molar ratio, and
crosslinking agent dosage on GMF were investigated by the gravimetric method
(Fig. 8). It can be seen from Fig. 8a that the addition of SA/HA has no significant
effect on GMF. Figure 8b and d shows that the GMF value is proportional to mono-
mer concentration and crosslinking agent dosage. Higher monomer concentration
and crosslinking agent dosage will increase the probability of monomer collision,
forming more crosslinking points and denser gel network, which will increase
GMF value. As shown in Fig. 8c, excessive NIPAM may generate more chain
Fig. 8 GMF of hydrogels at rt under different a SA/HA content, b monomer concentration, c monomer
molar ratio (NIPAM: AMPS), and d crosslinking agent dosage
13
entanglement to increase the degree of crosslinking, thus improving GMF value and
enhancing gel structural stability.
Swelling behavior
Swelling is an essential property of WSRF. The expansion/contraction rate and ratio

of WSRF are determined mainly by the micro- and macro-characteristics of the pol-
ymer network, including many parameters such as crosslinked density, components,
and macropores [61]. Herein, we studied the influence of different factors on the
swelling ratio of SH/PNA hydrogel, including the content of SA/HA, the concen-
tration of monomer, the molar ratio of monomers, and the amount of crosslinking
agent. The effect of different pH values and temperatures on the SR of SH/PNA
hydrogel was also studied.
Effect of feed ratios on SR
As depicted in Fig. 9a, the SR of the SH/PNA hydrogel is significantly higher

than that of the SNA hydrogel after the introduction of SA/HA with a mass frac-
tion of 2 wt%, which is due to the existence of dense hydrophilic groups such as
Fig. 9 Swelling curves of gels at rt under different a SA/HA content, b monomer concentration, c mono-
mer molar ratio (NIPAM: AMPS), and d crosslinking agent dosage
13
–COOH and –OH on the molecular chain of SA/HA. However, as SA/HA content
increased to a certain extent, intramolecular hydrogen bonds were formed, resulting
in the decrease in the diffusion rate of water penetration into WSRF. Therefore, an
appropriate amount of SA/HA content is beneficial for promoting swelling, while an
excessive amount of SA/HA reduces swelling. According to Fig. 9b, d, both mono-
mer concentration and cross-linker dosage are negatively correlated with SR. This
is because high cross-linker concentration or monomer concentration will lead to
the increase in high crosslinking points and crosslinking density, resulting in the
formation of dense networks. Dense networks will hinder the absorption of water,
thus reducing SR. However, the excessive low monomer concentration (0.75 mol/L)
resulted in structural instability of the hydrogel, which partially degraded during
the measurement, causing the SR to drop sharply after 90 min. Figure 9c shows
that the SR is maximal when the molar ratio of monomer (NIPAM: AMPS) is 1:1.
Combined with the analysis of GMF results, the network is relatively dense and the
water absorption is relatively small when NIPAM is excessive. In addition, it is well
known that the number of hydrophilic groups on the polymer chain is a vital factor
affecting the water absorption performance of the hydrogel, which can be controlled
by changing the molar ratio of NIPAM/AMPS in the PNA system. When AMPS is
excessive, the reaction degree of the monomer is low (The GMF is 47%). The num-
ber of sulfonic groups (strong hydrophilic groups) on the polymer molecular chain
is far less than that of the polymer chain with an equal molar ratio, and thus, the SR
is lower.
After comprehensively considering SR and GMF, we chose the SH/PNA hydro-
gel prepared under the following conditions to proceed the below experiments: SA/
HA content is 2%; the concentration of monomers is 1 mol/L; the molar ratio of
NIPAM to AMPS is 3:1; the molar ratio of monomers to cross-linker is 100:1. The
GMF and SR of the SH/PNA hydrogel under the above conditions is 62.09% and
31,388%, respectively.
Effect of pH on SR
The pH sensitivity of hydrogels is controlled by various factors, such as the nature

of ionizable groups, the composition of the polymer, and ionic strength. Hydrogel
materials with pH responsiveness are mainly prepared from monomers containing
ionizable functional groups or by introducing ionizable groups into the polymer. The
weakly acidic or basic groups contained in the polymer backbone will undergo pro-
tonation or deprotonation under the influence of the pH value to provide pH sensi-
tivity. As shown in Fig. 10a, SH/PNA hydrogel has a certain response to the change
of pH of the solution, and its swelling degree decreases first and then, increases
with the rise of pH value. In acidic conditions, carboxylic acid ions and sulfonate
ions were protonated to exist in the form of –COOH and –SO3H, which favored the
formation of hydrogen bonds with water molecules. The stronger the acidity of the
solution medium was, the more obvious the protonation effect was. Therefore, the
swelling degree of SH/PNA hydrogel decreased successively from pH 2 to 6. In
alkaline conditions, carboxylic acid and sulfonic acid groups were deprotonated to
13
Fig. 10 a Swelling curves and b the tendency of equilibrium swelling of SH/PNA hydrogel at pH = 2–10;
c the swelling cycle curve of SH/PNA hydrogel at pH = 2 and pH = 6; d Swelling curves and e the ten-
dency of equilibrium swelling of SH/PNA hydrogel at 20–60 °C; f the swelling cycle curve of SH/PNA
hydrogel at 20 °C and 60 °C
form COO− and S O3− anions, increasing the charge density of the molecular chain.
The electrostatic repulsion between ions stretched the polymer molecular chain,
which raised the three-dimensional network space of the gel and enhanced the water
storage capacity of the gel. Moreover, the ionization degree of the gel increased with
pH value, resulting in a gradual increase in the swelling degree of the gel [62].
Effect of temperatures on SR
Figure 10d shows the effect of temperatures on the SR of the SH/PNA hydrogel.
The SR of SH/PNA hydrogel decreases with the rise in temperature. It is known
that poly(N-isopropyl acrylamide) contains hydrophobic isopropyl groups and
hydrophilic amide groups, and their interactions with water vary with temperature,
resulting in SR changing with temperature. When the temperature is lower than the
low critical solution temperature (LCST), the hydrogen-bond interaction between
polar amide groups and water dominates [63]. The polymer chains can dissolve in
water, and the gel shows a transparent phase with a strong water absorption capac-
ity. However, when the temperature is above LCST, the hydrogen bond collapses,
the hydrophobic effect is enhanced, and the solubility of the polymer plummets.
The agglomerated molecular chain causes the gel to present an opaque phase with
volume shrinks, and the water absorption capacity decreases gradually [57]. This
transformation is reversible. Therefore, the higher the temperature is, the weaker
the water absorption capacity of hydrogel is, which is manifested as the decrease in
swelling degree [64].
13
Swelling cycling of SH/PNA hydrogel
As shown in Fig. 10 c, f, the swelling cycling of SH/PNA hydrogel was studied in

the buffer solutions of pH = 2 and pH = 6, and the distilled water of 20 °C and 60 °C,
respectively. It was evident that the SH/PNA hydrogel had no reversible swelling
behavior when it was alternately put in the buffer solutions of pH = 2 and pH = 6.
However, the SH/PNA hydrogel had a good swelling cycle in the water at 20 °C and
60 °C, and water absorption did not change significantly after 5 cycles.
Water retention of SH/PNA hydrogel in air
Water retention is one of the significant characteristics of WSRF. WSRF can absorb
agricultural irrigation water or natural rainfall and then, slowly release water for
plant growth to improve water efficiency, especially in arid regions. Figure 11 shows
the water loss curve of SH/PNA hydrogel in air. At 12 h, 36 h, and 60 h, the water
retention rate of SH/PNA hydrogel decreased to 71.53%, 40.69%, and 24.06%,
respectively, and the water retention rate was maintained at 0.43% at 144 h. The
results indicated that the SH/PNA hydrogel prepared had certain water retention.
Study on urea release behavior
Cumulative release of urea in water
p-Dimethylaminobenzaldehyde coloration method was used to measure the con-

centration of urea in water (The spectral scanning curve and standard curve of
urea are shown in Fig. S1). Figure 12a and b shows the cumulative release curves
of pure urea and SRF at different temperatures. It can be seen that pure urea was
almost released completely after 10 min. When T = 298 K, the release rate of urea
decreased significantly when loaded in WSRF, releasing about 35% after 10 min.
The release process reached equilibrium at 240 min, and the maximum release
Fig. 11 Water retention behavior

of SH/PNA hydrogel in air
13
Fig. 12 Cumulative release rates of a pure urea and b SRF in water at 298 K, 308 K, and 318 K, pH = 7;
Cumulative release rates of c pure urea and d WSRF in water at 35 °C, pH = 4, 6, and 8
rate reached 94%. The release process lasted for about 4 h, indicating that the
release rate could be reduced by about 24 times. Furthermore, the release rate
of slow-release fertilizers was fast in the initial stage and then, increased slowly
until it reached dynamic equilibrium. It may be that in the initial stage, the rapid
dissolution of urea accumulated on the surface of WSRF led to a rapid increase
in the release rate. In contrast, urea molecules embedded in the WSRF needed to
diffuse slowly to the surface of the WSRF through pore structure before diffusing
to water phase, so the release rate of urea slowed down significantly in the later
stage [11, 65]. Meanwhile, at 298 K, 308 K, and 318 K, the cumulative release of
pure urea at 10 min was 96.54%, 98.79%, and 100%, respectively. Nevertheless,
the cumulative release rates of urea in WSRF at 240 min were 93.43%, 96.13%,
and 100%, respectively. The results showed that WSRF could effectively control
the release rate of urea and delay the release time of urea. In addition, pure urea
and SRF had higher release rates and cumulative release amounts at higher tem-
peratures due to the increase in molecular diffusion rates [66].
Figure 12c and d shows the cumulative release curves of pure urea and WSRF in
buffer solutions with different pH values. At 10 min, urea was completely released in
the buffer solution, while the release rate of WSRF in the buffer solutions of pH = 6
reached 55%. Similarly, in the buffer solution with pH = 4 and pH = 8, the urea
13
release in WSRF was 55.36% and 49.28%, respectively. Furthermore, the change
trend of the cumulative release rate of WSRF with pH was consistent with that of
swelling with pH, indicating swelling degree played an important role in the release
of fertilizer. The above consequences showed that WSRF could effectively slow the
release rate of urea and the release rate was related to pH and temperature [24].
Cumulative release of urea in soil
The soil leaching method was used to study the release kinetics of urea from
WSRF in soil. The cumulative release curves of pure urea and WSRF in the soil
are shown in Fig. 13. It can be observed that the cumulative release rate in the
soil is obviously lower than that in the water. The relatively less free water con-
tent in soil reduced the exchange rate of water and fertilizer. Pure urea without
carrier in the soil was close to the release equilibrium within one hour. Compara-
tively speaking, WSRF had a better slow-release performance in the soil, and the
release amount of urea in one hour was 43.71%. This was because that the SRF
had a high specific surface area and complex pore structure, and urea in WSRF
network needed to break through WSRF into soil. The moisture from the soil dif-
fused into the WSRF, resulting in the expansion of the WSRF, and the embedded
urea slowly dissolves and then, gradually diffuses from the inside of the WSRF
to the outside under the action of osmotic pressure. Therefore, the release rate of
urea can decrease greatly by loading urea in a hydrogel network [67, 68].
Release kinetics model analysis
The Korsmeyer–Peppas, Higuchi, zero-order, and first-order mathematical mod-

els were used to explore the release mechanism of slow release of urea in WSRF
in water and soil. The kinetic parameters are shown in Table 1. By comparing the
Fig. 13 Cumulative release rates

of pure urea and SRF in the
soil at rt
13
Table 1 Release kinetics model Kinetic models Parameter Water Soil

parameters of WSRF in water
(25 °C, pH = 7) and soil Korsmeyer–Peppas R2 0.8549 0.9336
N 0.4568 0.3514
kkP 0.1017 0.1114
Higuchi R2 0.8452 0.8775
kH 0.0601 0.0310
Zero-order R2 0.6709 0.7360
k0 0.0030 8.5676
First-order R2 0.9916 0.9862
k1 0.0250 0.0085
correlation coefficients (R2), the release mechanism of urea in water was more in
line with the first-order model (R2298K = 0.9916,), indicating that urea was released
in an exponential decreasing manner, and the released urea maintained a certain pro-
portion with the remaining urea in the WSRF. The release mechanism of urea from
WSRF in the soil was consistent with both the first-order and Korsmeyer–Peppas
models (R2FO = 0.9862, R2KP = 0.9336). The diffusion exponent n value is 0.3514
(n < 0.45), indicating that the urea release process of WSRF in the soil is consistent
with Fickian diffusion [69].
Conclusions
In this study, a SH/PNA hydrogel based on SA and HA with semi-IPN structure was
synthesized by rapid and simple free radical polymerization. The optimal synthesis
parameters were as follows: the SA/HA (1:1) concentration was 4 wt%, the mono-
mer concentration was 1 mol/L, the molar ratio of monomer to crosslinking agent
was 100:1, and the molar ratio of NIPAM/AMPS was 3:1. The water absorption
of the semi-IPN gel reached 31,388% under the optimal conditions. The results of
FTIR and XRD showed that the PNA hydrogel was successfully synthesized and
SA/HA were introduced into the gel. The SEM morphology showed that SH/PNA
hydrogel had a typical three-dimensional porous network structure, which was con-
ducive to water absorption and controlled release of urea. The rheological study
showed that the gel was a viscoelastic solid and the addition of SA/HA increased the
mechanical strength of PNA hydrogel. The swelling behavior of SH/PNA hydrogel
showed that it was responsive to both temperature and pH, and had a good swelling
reversibility at 20–60 °C. In addition, the WSRF prepared from SH/PNA hydrogel
can control urea release in water and soil. Due to its low-cost raw material and sim-
ple preparation process, the WSRF has great application potential in agriculture.
Supplementary Information The online version contains supplementary material available at https://doi.
org/10.1007/s00289-023-04901-7.
13
Author contribution All authors contributed to conception and design of the study. BH, CH and YZ per-
formed material preparation, data collection, and analysis. SY, GW and TG prepared figures. The first
draft of the manuscript was written by BH, HW and JL reviewed and edited the manuscript. All authors
reviewed the manuscript.
Funding The work was supported by Natural Science Project of Zhengzhou Science and Technology
Bureau [Grant number 21ZZXTCX14]; the Innovative Funds Plan of Henan University of Technol-
ogy [Grant number: 2021ZKCJ08]; the National Natural Science Foundation of China [Grant number:
U1904171].
Declarations
Conflict of interest The authors declare that they have no conflict of interest.
Consent for publication All authors agreed to publish.
References
1. Sim DHH, Tan IAW, Lim LLP, Hameed BH (2021) Encapsulated biochar-based sustained release
fertilizer for precision agriculture: a review. J Clean Prod 303:127018. https://doi.org/10.1016/j.
jclepro.2021.127018
2. Rudmin M, Banerjee S, Yakich T et al (2020) Formulation of a slow-release fertilizer by mechanical
activation of smectite/glauconite and urea mixtures. Appl Clay Sci 196:105775. https://doi.org/10.
1016/j.clay.2020.105775
3. Abd El-Aziz ME, Salama DM, Morsi SMM, Youssef AM, El-Sakhawy M (2021) Development
of polymer composites and encapsulation technology for slow-release fertilizers. Rev Chem Eng
38:603–616. https://doi.org/10.1515/revce-2020-0044
4. Saha BK, Rose MT, Wong VNL, Cavagnaro TR, Patti AF (2019) A slow release brown coal-urea
fertiliser reduced gaseous N loss from soil and increased silver beet yield and N uptake. Sci Total
Environ 649:793–800. https://doi.org/10.1016/j.scitotenv.2018.08.145
5. Dong G, Mu Z, Liu D et al (2021) Starch phosphate carbamate hydrogel based slow-release urea
formulation with good water retentivity. Int J Biol Macromol 190:189–197. https://doi.org/10.
1016/j.ijbiomac.2021.08.234
6. Li HF, An SD, Zhang LY et al (2021) Urea fertilizer with precisely regulable slow-release perfor-
mance by complexing with random copolyester. J Environ Chem Eng 9:105120. https://doi.org/10.
1016/j.jece.2021.105120
7. Tanan W, Panichpakdee J, Suwanakood P, Saengsuwan S (2021) Biodegradable hydrogels of cas-
sava starch-g-polyacrylic acid/natural rubber/polyvinyl alcohol as environmentally friendly and
highly efficient coating material for slow-release urea fertilizers. J Ind Eng Chem 101:237–252.
https://doi.org/10.1016/j.jiec.2021.06.008
8. Xiang Y, Ru X, Shi J et al (2017) Preparation and properties of a novel semi-IPN slow-release fer-
tilizer with the function of water retention. J Agric Food Chem 65:10851–10858. https://doi.org/10.
1021/acs.jafc.7b03827
9. Ye HM, Li HF, Wang CS et al (2020) Degradable polyester/urea inclusion complex applied as a fac-
ile and environment-friendly strategy for slow-release fertilizer: performance and mechanism. Chem
Eng J 381:122704. https://doi.org/10.1016/j.cej.2019.122704
10. Guo X, Wang Y, Qin Y, Shen P, Peng Q (2020) Structures, properties and application of alginic
acid: a review. Int J Biol Macromol 162:618–628. https://doi.org/10.1016/j.ijbiomac.2020.06.180
11. Guo L, Wang Y, Wang M et al (2021) Synthesis of bio-based MIL-100(Fe)@CNF-SA composite
hydrogel and its application in slow-release N-fertilizer. J Clean Prod 324:129274. https://doi.org/
10.1016/j.jclepro.2021.129274
12. Bashir S, Hina M, Iqbal J et al (2020) Fundamental concepts of hydrogels: synthesis, properties, and
their applications. Polymers (Basel) 12:2702. https://doi.org/10.3390/polym12112702
13. Huang X, Li J, Luo J et al (2021) Research progress on double-network hydrogels. Mater Today
Commun. 29:102757. https://doi.org/10.1016/j.mtcomm.2021.102757
13
14. Hu S, Zhi Y, Shan S, Ni Y (2022) Research progress of smart response composite hydrogels based
on nanocellulose. Carbohydr Polym 275:118741. https://doi.org/10.1016/j.carbpol.2021.118741
15. Wu Z, Zhang P, Zhang H et al (2022) Tough porous nanocomposite hydrogel for water treatment. J
Hazard Mater 421:126754. https://doi.org/10.1016/j.jhazmat.2021.126754
16. Li J, Jia X, Yin L (2021) Hydrogel: diversity of structures and applications in food science. Food
Rev Int 37(3):313–372. https://doi.org/10.1080/87559129.2020.1858313
17. Pourjavadi A, Heydarpour R, Tehrani ZM (2021) Multi-stimuli-responsive hydrogels and their med-
ical applications. New J Chem 45:15705–15717. https://doi.org/10.1039/d1nj02260a
18. Maiz-Fernandez S, Perez-Alvarez L, Ruiz-Rubio L, Vilas-Vilela JL, Lanceros-Mendez S (2020)
Polysaccharide-based in situ self-healing hydrogels for tissue engineering applications. Polymers
12:2261. https://doi.org/10.3390/polym12102261
19. Zenoozi S, Mohamad Sadeghi GM, Rafiee M (2020) Synthesis and characterization of biocompat-
ible semi-interpenetrating polymer networks based on polyurethane and cross-linked poly (acrylic
acid). Eur Polym J 140:109974. https://doi.org/10.1016/j.eurpolymj.2020.109974
20. Chen J, Liu M, Liu H et al (2010) Synthesis and properties of thermo- and pH-sensitive
poly(diallyldimethylammonium chloride)/poly(N, N-diethylacrylamide) semi-IPN hydrogel. Chem
Eng J 159:247–256. https://doi.org/10.1016/j.cej.2010.02.034
21. Rungrod A, Kapanya A, Punyodom W et al (2022) Synthesis and characterization of semi-IPN
hydrogels composed of sodium 2-acrylamido-2-methylpropanesulfonate and poly(ε-caprolactone)
diol for controlled drug delivery. Eur Polym J 164:110978. https://doi.org/10.1016/j.eurpolymj.
2021.110978
22. Liu S, Wu Q, Sun X et al (2021) Novel alginate-cellulose nanofiber-poly(vinyl alcohol) hydrogels
for carrying and delivering nitrogen, phosphorus and potassium chemicals. Int J Biol Macromol
172:330–340. https://doi.org/10.1016/j.ijbiomac.2021.01.063
23. Vo PT, Nguyen HT, Trinh HT et al (2021) The nitrogen slow-release fertilizer based on urea incor-
porating chitosan and poly(vinyl alcohol) blend. Environ Technol Innov 22:101528. https://doi.org/
10.1016/j.eti.2021.101528
24. Lin X, Guo L, Shaghaleh H et al (2021) A TEMPO-oxidized cellulose nanofibers/MOFs hydrogel
with temperature and pH responsiveness for fertilizers slow-release. Int J Biol Macromol 191:483–
491. https://doi.org/10.1016/j.ijbiomac.2021.09.075
25. Khattab TA, Kamel S (2022) Advances in polysaccharide-based hydrogels: Self-healing and electri-
cal conductivity. J Mol Liq 352:118712. https://doi.org/10.1016/j.molliq.2022.118712
26. Guilherme MR, Aouada FA, Fajardo AR et al (2015) Superabsorbent hydrogels based on polysac-
charides for application in agriculture as soil conditioner and nutrient carrier: a review. Eur Polym J
72:365–385. https://doi.org/10.1016/j.eurpolymj.2015.04.017
27. Zhu B, Ni F, Xiong Q, Yao Z (2021) Marine oligosaccharides originated from seaweeds: source,
preparation, structure, physiological activity and applications. Crit Rev Food Sci Nutr 61:60–74.
https://doi.org/10.1080/10408398.2020.1716207
28. Lakouraj MM, Rezaei M, Hasantabar V (2021) Synthesis, characterization and in-vitro prolonged
release of L-DOPA using a novel amphiphilic hydrogel based on sodium alginate-polypyrrole. Int J
Biol Macromol 193:609–618. https://doi.org/10.1016/j.ijbiomac.2021.10.171
29. Xiao G, Li F, Li Y et al (2022) A novel biomass material composite hydrogel based on sodium algi-
nate. Colloids Surf A Physicochem Eng Asp 648:129383. https://doi.org/10.1016/j.colsurfa.2022.
129383r
30. Shang W, Liu Y, Wan W et al (2017) Hybrid 3D printing and electrodeposition approach for con-
trollable 3D alginate hydrogel formation. Biofabrication 9:025032. https://doi.org/10.1088/1758-
5090/aa6ed8
31. Pashaei-Fakhri S, Peighambardoust SJ, Foroutan R, Arsalani N, Ramavandi B (2021) Crystal vio-
let dye sorption over acrylamide/graphene oxide bonded sodium alginate nanocomposite hydrogel.
Chemosphere 270:129419. https://doi.org/10.1016/j.chemosphere.2020.129419
32. Afshar M, Dini G, Vaezifar S, Mehdikhani M, Movahedi B (2020) Preparation and characteriza-
tion of sodium alginate/polyvinyl alcohol hydrogel containing drug-loaded chitosan nanoparti-
cles as a drug delivery system. J Drug Deliv Sci Tec 56:101530. https://doi.org/10.1016/j.jddst.
2020.101530
33. Arafa EG, Sabaa MW, Mohamed RR, Elzanaty AM, Abdel-Gawad OF (2022) Preparation of
biodegradable sodium alginate/carboxymethylchitosan hydrogels for the slow-release of urea fer-
tilizer and their antimicrobial activity. React Funct Polym 174:105243. https://doi.org/10.1016/j.
reactfunctpolym.2022.105243
13
34. Miao ZH, LiK LPY et al (2018) Natural humic-acid-based phototheranostic agent. Adv Healthc
Mater 7(7):1701202. https://doi.org/10.1002/adhm.201701202
35. Sirousazar M, Khodamoradi P (2020) Freeze-thawed humic acid/polyvinyl alcohol supramolecu-
lar hydrogels. Mater Today Commun 22:100719. https://doi.org/10.1016/j.mtcomm.2019.100719
36. Yang F, Antonietti M (2020) Artificial humic acids: sustainable materials against climate change.
Adv Sci (Weinh) 7:1902992. https://doi.org/10.1002/advs.201902992
37. Yalman V, Laçin NT (2019) Development of humic acid and alginate-based wound dressing and
evaluation on inflammation. Mater Technol 34:705–717. https://doi.org/10.1080/10667857.2019.
1619961
38. Chen R, Zhang Y, Shen L et al (2015) Lead(II) and methylene blue removal using a fully biode-
gradable hydrogel based on starch immobilized humic acid. Chem Eng J 268:348–355. https://
doi.org/10.1016/j.cej.2015.01.081
39. Afzal MZ, Yue R, Sun X-F, Song C, Wang S-G (2019) Enhanced removal of ciprofloxacin using
humic acid modified hydrogel beads. J Colloid Interface Sci 543:76–83. https://doi.org/10.
1016/j.jcis.2019.01.083
40. Li H, Li Y, Li C (2013) Characterization of humic acids and fulvic acids derived from sewage
sludge. Asian J Chem 25:10087–10091. https://doi.org/10.14233/ajchem.2013.15162
41. Wang W, Qu K, Zhang X, Teng M, Huang Z (2021) Integrated instillation technology for the
synthesis of a pH-responsive sodium alginate/biomass charcoal soil conditioner for controlled
release of humic acid and soil remediation. J Agric Food Chem 69:13386–13397. https://doi.org/
10.1021/acs.jafc.1c04121
42. Ramli RA (2019) Slow release fertilizer hydrogels: a review. Polym Chem 10:6073–6090.
https://doi.org/10.1039/c9py01036j
43. Wang L, Xin J, Nai H, Zheng X (2021) Effects of different fertilizer applications on nitrogen
leaching losses and the response in soil microbial community structure. Environ Technol Innov
23:101608. https://doi.org/10.1016/j.eti.2021.101608
44. Huanbutta K, Sriamornsak P, Limmatvapirat S et al (2011) Swelling kinetics of spray-dried chi-
tosan acetate assessed by magnetic resonance imaging and their relation to drug release kinet-
ics of chitosan matrix tablets. Eur J Pharm Biopharm 77:320–326. https://doi.org/10.1016/j.ejpb.
2010.11.019
45. Wei H, Wang H, Chu H, Li J (2019) Preparation and characterization of slow-release and water-
retention fertilizer based on starch and halloysite. Int J Biol Macromol 133:1210–1218. https://
doi.org/10.1016/j.ijbiomac.2019.04.183
46. Kamoun EA, Fahmy A, Taha TH et al (2018) Thermo-and pH-sensitive hydrogel membranes
composed of poly(N-isopropylacrylamide)-hyaluronan for biomedical applications: Influence
of hyaluronan incorporation on the membrane properties. Int J Biol Macromol 106:158–167.
https://doi.org/10.1016/j.ijbiomac.2017.08.011
47. Zheng D, Bai B, He Y, Hu N, Wang H (2020) Synthesis and characterization of dopamine-
modified Ca-alginate/poly(N-isopropylacrylamide) microspheres for water retention and multi-
responsive controlled release of agrochemicals. Int J Biol Macromol 160:518–530. https://doi.
org/10.1016/j.ijbiomac.2020.05.234
48. Khalid I, Ahmad M, Usman Minhas M, Barkat K (2018) Synthesis and evaluation of chondroitin
sulfate based hydrogels of loxoprofen with adjustable properties as controlled release carriers.
Carbohydr Polym 181:1169–1179. https://doi.org/10.1016/j.carbpol.2017.10.092
49. Khanum H, Ullah K, Murtaza G, Khan SA (2018) Fabrication and in vitro characteriza-
tion of HPMC-g-poly(AMPS) hydrogels loaded with loxoprofen sodium. Int J Biol Macromol
50. Ghobashy MM, Elbarbary AM, Hegazy DE (2021) Gamma radiation synthesis of a novel amphi-
philic terpolymer hydrogel pH-responsive based chitosan for colon cancer drug delivery. Carbo-
hydr Polym 263:117975. https://doi.org/10.1016/j.carbpol.2021.117975
51. Zhao D, Feng M, Zhang L et al (2021) Facile synthesis of self-healing and layered sodium
alginate/polyacrylamide hydrogel promoted by dynamic hydrogen bond. Carbohydr Polym
256:117580. https://doi.org/10.1016/j.carbpol.2020.117580
52. Kiti K, Suwantong O (2020) Bilayer wound dressing based on sodium alginate incorporated
with curcumin-beta-cyclodextrin inclusion complex/chitosan hydrogel. Int J Biol Macromol
53. Li W, Wang J, Zou L, Zhu S (2008) Synthesis and characterization of potassium humate–acrylic
acid–acrylamide hydrogel. J Polym Res 15:435–445. https://doi.org/10.1007/s10965-008-9189-z
13
54. Chen H, Li Q, Wang M, Ji D, Tan W (2020) XPS and two-dimensional FTIR correlation
analysis on the binding characteristics of humic acid onto kaolinite surface. Sci Total Environ
724:138154. https://doi.org/10.1016/j.scitotenv.2020.138154
55. Yu NN, Li GY, Gao YR, Jiang H, Tao Q (2016) Thermo-sensitive complex micelles from sodium
alginate-graft-poly(N-isopropylacrylamide) for drug release. Int J Biol Macromol 86:296–301.
https://doi.org/10.1016/j.ijbiomac.2016.01.066
56. Sinha V, Chakma S (2020) Synthesis and evaluation of CMC-g-AMPS/Fe/Al/AC compos-
ite hydrogel and their use in fluoride removal from aqueous solution. Environ Technol Innov
17:100620. https://doi.org/10.1016/j.eti.2020.100620
57. Choe SR, Haldorai Y, Jang S-C et al (2018) Fabrication of alginate/humic acid/Fe-aminoclay
hydrogel composed of a grafted-network for the efficient removal of strontium ions from aqueous
solution. Environ Technol Innov 9:285–293. https://doi.org/10.1016/j.eti.2017.12.008
58. Wang W, Shen M, Jiang L et al (2019) Rheological behavior, microstructure characterization
and formation mechanism of Mesona blumes polysaccharide gels induced by calcium ions. Food
Hydrocoll 94:136–143. https://doi.org/10.1016/j.foodhyd.2019.03.014
59. Huang T, Tu ZC, Wang H et al (2017) Pectin and enzyme complex modified fish scales gelatin:
rheological behavior, gel properties and nanostructure. Carbohydr Polym 156:294–302. https://
doi.org/10.1016/j.carbpol.2016.09.040
60. Qu RJ, Wang Y, Li D, Wang LJ (2021) Rheological behavior of nanocellulose gels at various
calcium chloride concentrations. Carbohydr Polym 274:118660. https://doi.org/10.1016/j.carbp
ol.2021.118660
61. Tang L, Wang L, Yang X et al (2021) Poly(N-isopropylacrylamide)-based smart hydrogels:
design, properties and applications. Prog Mater Sci 115:100702. https://doi.org/10.1016/j.pmats
ci.2020.100702
62. Wang Y, Zhu Y, Liu Y, Mu B, Wang A (2021) Research on preparation and properties of a mul-
tifunctional superabsorbent based on semicoke and humic acid. Eur Polym J 159:110750. https://
doi.org/10.1016/j.eurpolymj.2021.110750
63. Jayaramudu T, Varaprasad K, Sadiku ER, Amalraj J (2019) Temperature-sensitive semi-IPN
composite hydrogels for antibacterial applications. Colloids Surf A Physicochem Eng Asp
572:307–316. https://doi.org/10.1016/j.colsur fa.2019.04.012
64. Zakerikhoob M, Abbasi S, Yousefi G, Mokhtari M, Noorbakhsh MS (2021) Curcumin-incorpo-
rated crosslinked sodium alginate-g-poly (N-isopropyl acrylamide) thermo-responsive hydrogel
as an in-situ forming injectable dressing for wound healing: in vitro characterization and in vivo
evaluation. Carbohydr Polym 271:118434. https://doi.org/10.1016/j.carbpol.2021.1184344
65. Cheng D, Liu Y, Yang G, Zhang A (2018) Water- and fertilizer-integrated hydrogel derived from
the polymerization of acrylic acid and urea as a slow-release N fertilizer and water retention in
agriculture. J Agric Food Chem 66:5762–5769. https://doi.org/10.1021/acs.jafc.8b00872
66. Li J, Liu Y, Liu J et al (2022) A novel synthetic slow release fertilizer with low energy produc-
tion for efficient nutrient management. Sci Total Environ 831:154844. https://doi.org/10.1016/j.
scitotenv.2022.154844
67. Wang Y, Shaghaleh H, Hamoud YA et al (2021) Synthesis of a pH-responsive nano-cellulose/
sodium alginate/MOFs hydrogel and its application in the regulation of water and N-fertilizer.
Int J Biol Macromol 187:262–271. https://doi.org/10.1016/j.ijbiomac.2021.07.154
68. Kong W, Li Q, Li X et al (2019) A biodegradable biomass-based polymeric composite for slow
release and water retention. J Environ Manage 230:190–198. https://doi.org/10.1016/j.jenvman.
2018.09.086
69. Andelkovic IB, Kabiri S, Tavakkoli E et al (2018) Graphene oxide-Fe(III) composite containing
phosphate – a novel slow release fertilizer for improved agriculture management. J Clean Prod
185:97–104. https://doi.org/10.1016/j.jclepro.2018.03.050
Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published maps
and institutional affiliations.
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under
a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted
manuscript version of this article is solely governed by the terms of such publishing agreement and
applicable law.
13

Preparation of Ph/temperature Responsive Semi IPN Hydrogels Based On Sodium Alginate and Humic Acid As Slow Release and Water Retention Fertilizers

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Preparation of Ph/temperature Responsive Semi IPN Hydrogels Based On Sodium Alginate and Humic Acid As Slow Release and Water Retention Fertilizers

Uploaded by

Copyright:

Available Formats

Polymer Bulletin (2024) 81:4175–4198

Preparation of pH/temperature‑responsive semi‑IPN

Received: 20 October 2022 / Revised: 23 February 2023 / Accepted: 30 June 2023 /

Keywords Semi-IPN hydrogel · Fertilizer · Slow-release · Responsiveness · Water

Fig. 2 Structural composition of repetitive units of SA

Fig. 3 Basic unit of HA molecular structure

Materials and methods

Preparation of SH/PNA hydrogels

A series of SH/PNA hydrogels were prepared by free radical polymerization with

Fig. 4 Synthetic process of PNA and SH/PNA hydrogel

A Fourier transform infrared spectrometer (FTIR, PerkinElmer UATR Two,

Determination of gel mass fraction (GMF)

where Wt is the mass of wet gel sample at time t. When t = 0, Wt = W0.

Water retention experiment in air

Slow‑release behavior of the WSRF in water and soil

Slow‑release experiment in water

Slow‑release experiment in soil

To further analyze the mechanism of fertilizer release, Korsmeyer–Peppas, Higuchi,

(2) Higuchi model

(3) Zero-order kinetics model

(4) First-order kinetics model

The Korsmeyer–Peppas model describes the Fickian and non-Fickian release

Results and discussions

FTIR is an important technique to determine the functional groups and molecular

Fig. 6 XRD patterns of SA, HA,

Gel mass fraction (GMF) analysis

Swelling is an essential property of WSRF. The expansion/contraction rate and ratio

Effect of feed ratios on SR

As depicted in Fig. 9a, the SR of the SH/PNA hydrogel is significantly higher

The pH sensitivity of hydrogels is controlled by various factors, such as the nature

Swelling cycling of SH/PNA hydrogel

As shown in Fig. 10 c, f, the swelling cycling of SH/PNA hydrogel was studied in

Water retention of SH/PNA hydrogel in air

Study on urea release behavior

Cumulative release of urea in water

p-Dimethylaminobenzaldehyde coloration method was used to measure the con-

Fig. 11 Water retention behavior

Cumulative release of urea in soil

Release kinetics model analysis

The Korsmeyer–Peppas, Higuchi, zero-order, and first-order mathematical mod-

Fig. 13 Cumulative release rates

Table 1 Release kinetics model Kinetic models Parameter Water Soil

Consent for publication All authors agreed to publish.

You might also like