molecules

Review
Development of Slow-Release Fertilizers with Function of Water
Retention Using Eco-Friendly Starch Hydrogels
Yue Song 1,2 , Litao Ma 1 , Qingfei Duan 1,3 , Huifang Xie 1 , Xinyi Dong 1 , Huaran Zhang 1 and Long Yu 1,2,3, *

1 Institute of Chemistry, Henan Academy of Sciences, Zhengzhou 450002, China; [email protected] (Y.S.);
[email protected] (L.M.); [email protected] (Q.D.); [email protected] (H.X.);
[email protected] (X.D.); [email protected] (H.Z.)
2 High & New Technology Research Center of Henan Academy of Sciences, Zhengzhou 450002, China
3 School of Food Science and Engineering, South China University of Technology, Guangzhou 510640, China
* Correspondence: [email protected]

Abstract: Over the past two decades, the development and commercialization of slow-release
fertilizers (SRFs) have significantly advanced, with the primary aim of mitigating environmental
issues associated with excessive fertilizer use. A range of methodologies, including chemical and
physical reactions, incorporation into carriers with porous and layered structures, and coating
techniques, have been explored and refined. On the other hand, global challenges such as drought
and desertification further underscore the need for SRFs that not only control nutrient release but
also improve soil moisture retention. This paper reviews the development and application of eco-
friendly starch hydrogels as fertilizer carriers and water retention for SRFs, particularly starch-based
superabsorbent polymers (SAPs) produced through grafting copolymerization with acrylamide.
This review explores both scientific issues, such as the microstructures and releasing mechanisms
of SAPs, and technical development, involving copolymerization technologies, multi-initialization
processes, methods of loading fertilizer into hydrogel, etc. Starch, as both a biodegradable and
renewable carbohydrate polymer, offers distinct advantages due to its excellent chemical stability
and high reactivity. The fabrication techniques of SAPs have been developed from traditional batch
polymerization in aqueous solutions to more efficient, solvent-free reactive extrusion. The benefits
Citation: Song, Y.; Ma, L.; Duan, Q.; of SRFs based on SAPs encompass enhanced soil aeration, the prevention of soil deterioration, the
Xie, H.; Dong, X.; Zhang, H.; Yu, L. minimization of water evaporation, environmental pollution control, reduction in plant mortality,
Development of Slow-Release and prolonged nutrient retention within soil. In this review, we summarize the current progress,
Fertilizers with Function of Water identify limitations in existing technologies, and propose future research directions to further enhance
Retention Using Eco-Friendly Starch the performance of starch-based SRFs.
Hydrogels. Molecules 2024, 29, 4835.
https://doi.org/10.3390/ Keywords: slow-release fertilizers; superabsorbent polymer; hydrogel; starch
molecules29204835

Academic Editor: Vasyl M. Haramus

Received: 13 September 2024 1. Introduction of Slow-Release Fertilizers

Revised: 5 October 2024
Data from the International Fertilizer Association (IFA) reveal a steady increase in
Accepted: 9 October 2024
Published: 12 October 2024
global fertilizer consumption, reflecting the increasing reliance on chemical inputs to en-
hance crop yields and meet the demands of a growing global population. From 2019 to
2023, fertilizer use increased by an average of 1.3% annually [1], underscoring the agricul-
tural sector’s continued dependence on these resources. Nitrogen fertilizers dominate the
Copyright: © 2024 by the authors. market due to their critical role in promoting plant growth by providing essential nutrients.
Licensee MDPI, Basel, Switzerland. However, their efficiency is undermined by significant losses—up to 70% of conventional
This article is an open access article fertilizers are wasted. This inefficiency has far-reaching environmental implications, con-
distributed under the terms and tributing to pollution through decomposition, leaching, and ammonium volatilization.
conditions of the Creative Commons These processes not only deplete the quality of water resources but also contaminate soil
Attribution (CC BY) license (https://
and air, leading to a range of environmental issues such as eutrophication, soil acidification,
creativecommons.org/licenses/by/
and the emission of greenhouse gases [2,3].
4.0/).

Molecules 2024, 29, 4835. https://doi.org/10.3390/molecules29204835 https://www.mdpi.com/journal/molecules

Molecules 2024, 29, 4835 2 of 26

To address the problems caused by overusing fertilizers, slow-release fertilizers (SRFs)

have emerged as a promising solution. These fertilizers are designed to release nutrients
gradually over an extended period, thereby enhancing nutrient uptake by plants and
reducing the environmental impact associated with conventional fertilizers [4,5]. SRFs
include a variety of products, such as controlled-release fertilizers, enhanced-efficiency
fertilizers, and smart-release fertilizers, among others. Despite differences in nomencla-
tures, all these products should be classified as SRFs, because their primary function is to
decelerate the release rate, without the ability to modulate performance based on specific
crops or environmental conditions. Evaluation standards from the EU, ISO, and GB (China)
also categorize these fertilizers as SRFs. Technically, there are two main strategies SRFs use
to supply nutrients to plants: one involves slowing down nutrient availability in soil or
reducing their solubility in water [6–8].
Various slow-release methodologies, including physical or chemical reactions, loading
into carriers, and coating techniques, have been established [9–11]. Among these, coating
is particularly favored for developing SRFs due to its simplicity, efficiency, and precise
control over coating thickness, thereby modulating the release rate [12]. A wide range of
materials have been explored as coating agents for SRFs, including petrochemical-derived
polymers and biodegradable compounds like synthetic polylactic acid (PLA) and natural
materials such as cellulose, lignin, starch, chitosan, and alginate [13–16]. Given concerns
about potential environmental impacts from non-biodegradable materials, systems derived
from biodegradable polymers, particularly those from renewable sources, have garnered
significant interest. Additionally, to address challenges such as drought and desertifica-
tion in agriculture, incorporating superabsorbent polymers (SAPs) into polymer-coated
SRF products offers benefits such as enhanced water retention in soil and reduced soil
pollution [17–19]. Recently, the use of eco-friendly hydrogels or SAPs as fertilizer carriers
for developing SRFs has attracted growing attention [20,21]. SRFs based on SAPs offer
numerous advantages, including improved soil aeration, the mitigation of soil degradation,
reduced carbon emissions, and enhanced nutrient retention in soil.
While many reviews have covered SRF development from various perspectives and
stages [9,22–32], this review focuses specifically on the use of eco-friendly hydrogels as
fertilizer carriers for SRFs, emphasizing their water retention capabilities and unique
release mechanisms. It addresses both scientific and technical developments, summarizing
current achievements, identifying limitations in existing technologies, and proposing future
research directions in this area.

2. Development of Starch-Based Hydrogels

Hydrogels, characterized by their unique capacity to absorb and retain large amounts
of water, play a crucial role in various scientific and industrial applications. These materials
are highly versatile, offering a range of properties that can be tailored to specific needs.
Hydrogels consist of a network of hydrophilic polymers that are crosslinked, allowing
them to maintain a solid structure despite their high water content [33]. This crosslinking is
critical, as it prevents the polymer chains from dissolving in water, enabling the hydrogel to
absorb water without losing its structural integrity. Both synthetic and natural polymers are
used in hydrogel composition. Synthetic polymers like polyacrylic acid (PAA), polyvinyl
alcohol (PVA), and polyacrylamide (PAM) are commonly used due to their controllable
properties and ease of synthesis [34–36]. Natural polymers, such as proteins, polysaccha-
rides, and nucleic acids, offer advantages like being bioresorbable and non-toxic, making
them ideal for biomedical applications. Polysaccharides, in particular, are favored for
their robustness and cost-effectiveness, with starch, alginate, chitosan, and hyaluronic acid
being prominent examples. Manuel and Jennifer [37] recently conducted a comprehensive
review of hydrogels, encompassing their properties, classification, synthesis mechanisms,
and applications across various industries, with an emphasis on starch and cellulose as
copolymer components in hydrogel formulation.
Molecules 2024, 29, x FOR PEER REVIEW 3 of 27
Molecules 2024, 29, 4835 3 of 26

Starch, a polysaccharide composed of amylose and amylopectin (Figure 1) [38], has

Starch, a polysaccharide
high hydrophilicity, makingcomposed of amylose
it an attractive and amylopectin
precursor for hydrogel(Figure 1) [38], has
synthesis. Starch-
high hydrophilicity, making it an attractive precursor for hydrogel synthesis.
based hydrogels have garnered significant attention in agriculture due to their inherent Starch-based
hydrogels have garnered significant attention in agriculture due to their inherent properties
properties such as biodegradability and eco-friendliness. However, native starch-based
such as biodegradability and eco-friendliness. However, native starch-based hydrogels face
hydrogels face limitations, including inadequate water absorption capacity, poor mechan-
limitations, including inadequate water absorption capacity, poor mechanical stability, and
ical stability, and limited salt tolerance [39]. To address these challenges, researchers have
limited salt tolerance [39]. To address these challenges, researchers have explored various
explored various modification techniques to enhance the properties of starch-based hy-
modification techniques to enhance the properties of starch-based hydrogels [40–42]. One of
drogels
the most [40–42].
effective One of the
methods most effective
is grafting, in whichmethods is grafting,
hydrophilic in which hydrophilic
vinyl monomers such as acrylicvinyl
acid (AA) and acrylamide (AM) are covalently attached to the starch backbone [43–46]. the
monomers such as acrylic acid (AA) and acrylamide (AM) are covalently attached to
starch
This backbone
grafting [43–46].
process This grafting
introduces process
additional introduces
hydrophilic additional
groups into the hydrophilic groups
starch matrix,
into the starch
significantly matrix,the
boosting significantly
hydrogel’s boosting the hydrogel’s
water absorption capacitywater
and absorption
mechanicalcapacity
strength.and
mechanical
Grafting strength.
is typically Grafting
initiated is typically
through initiated
free radical through free
polymerization, radical
using polymerization,
chemical initiators
using
like chemical cerium
ammonium initiators like persulfate,
nitrate, ammonium cerium
and redox nitrate,
systems persulfate, and redoxis systems
[47,48]. Crosslinking also
a[47,48].
criticalCrosslinking is also
step in hydrogel a critical
synthesis, asstep in hydrogel
it determines thesynthesis,
structural as it determines
integrity the struc-
and swelling
behavior of the and
tural integrity hydrogel.
swellingVarious crosslinking
behavior methodsVarious
of the hydrogel. have been employed,methods
crosslinking includinghave
irradiation with ultraviolet
been employed, including(UV) light, microwave
irradiation irradiation,
with ultraviolet (UV)orlight,
gamma (γ) radiation,
microwave and
irradiation,
chemical crosslinking agents [49,50].
or gamma (γ) radiation, and chemical crosslinking agents [49,50].

Figure1.1.Chemical
Figure Chemicalcomposition
compositionofof starch
starch featuring
featuring units
units of amylose
of amylose andand amylopectin.
amylopectin.

Starch-based
Starch-basedsuperabsorbent
superabsorbentpolymers
polymers(SAPs),
(SAPs),known
knownforfor their
their exceptional
exceptional water
water ab-
absorption capability, are often synthesized via graft polymerization onto starch substrates.
sorption capability, are often synthesized via graft polymerization onto starch substrates.
These
These SAPs
SAPs can absorb several
can absorb several hundred
hundred to
tothousands
thousandsofoftimes
timestheir
theirweight
weightinin water,
water, mak-
making them ideal for applications such as agriculture, where they help retain
ing them ideal for applications such as agriculture, where they help retain water in water in soil
soil
andand improve
improve plantgrowth
plant growth conditions.
conditions. Additionally,
Additionally,SAPs
SAPscan encapsulate
can nutrients
encapsulate nutrients
through physicochemical interactions, allowing for controlled nutrient release, which is
through physicochemical interactions, allowing for controlled nutrient release, which is
beneficial in slow-release fertilizer (SRF) formulations. Recent studies by Supare and
beneficial in slow-release fertilizer (SRF) formulations. Recent studies by Supare and
Mhanwar [49] have extensively reviewed the role of SAPs in agriculture, focusing on starch-
Mhanwar [49] have extensively reviewed the role of SAPs in agriculture, focusing on
derived SAPs, crosslinking, and graft copolymerization methods used in their synthesis.
starch-derived SAPs, crosslinking, and graft copolymerization methods used in their syn-
This chapter delves into the methods of synthesizing starch-based SAPs under various
thesis. This
process chapter delves into the methods of synthesizing starch-based SAPs under var-
conditions.
ious process conditions.
2.1. Grafting Copolymerization with Starches
2.1. Grafting Copolymerization
Starch-grafted PAM and PAA withare
Starches
among the most effective superabsorbent materials
due toStarch-grafted
their superior water
PAM absorption
and PAA arecapabilities.
among the These
mostmaterials
effectiveare synthesized through
superabsorbent materials
graft polymerization, which typically takes place in an aqueous medium
due to their superior water absorption capabilities. These materials are synthesized using batch
processing techniques. This process enables the production of starch-based
through graft polymerization, which typically takes place in an aqueous medium SAPs that
using
are highly
batch efficienttechniques.
processing in retainingThis
water and can
process be used
enables theinproduction
various fields, ranging from
of starch-based SAPs
agriculture to personal care products [51–53]. A schematic diagram of the process
that are highly efficient in retaining water and can be used in various fields, ranging from for
agriculture to personal care products [51–53]. A schematic diagram of the process for pre-
paring a hydrogel through starch graft polymerization in aqueous solution is shown in
Molecules 2024,
Molecules 2024, 29,
29,4835
x FOR PEER REVIEW 4 of 426of 27

preparing a hydrogel through starch graft polymerization in aqueous solution is shown

Figure 2. The starch is first gelatinized at a certain temperature, which destroys the crys-
in Figure 2. The starch is first gelatinized at a certain temperature, which destroys the
talline structure
crystalline structure ofofthe
thestarch
starchand
and promotes
promotes itsitsuniform
uniformdissolution.
dissolution. This
This stepstep is essential,
is essential,
as it enhances the accessibility of starch molecules to the chemical reactions involved in in
as it enhances the accessibility of starch molecules to the chemical reactions involved
grafting.Subsequently,
grafting. Subsequently, a chemical
a chemical initiator,
initiator, suchsuch
as aasredox
a redox system,
system, is then
is then introduced
introduced to to
generatefree
generate freeradicals
radicals required
required to to initiate
initiate thethe grafting
grafting reaction.
reaction. Monomers
Monomers andand crosslinkers
crosslinkers
are subsequently added to the solution, and the grafting polymerization
are subsequently added to the solution, and the grafting polymerization process proceeds process proceeds
until the desired degree of polymerization is achieved. The resulting starch-based SAPsSAPs
until the desired degree of polymerization is achieved. The resulting starch-based
areisolated
are isolatedfromfromthethereaction
reaction mixture
mixture through
through filtration
filtration or centrifugation,
or centrifugation, followed
followed by by
washing
washingand anddrying
dryingtoto remove
remove anyany residual monomers,
residual monomers, initiators, andand
initiators, by-products.
by-products. The The
final
finalproduct
productisisa ahighly
highly absorbent
absorbent material
materialcapable
capable of retaining large
of retaining amounts
large amounts of water,
of water,
making it suitable for a wide range of applications
making it suitable for a wide range of applications [54,55]. [54,55].

Figure2.2.Schematic
Figure Schematicdiagram
diagramofof process
process of of preparing
preparing hydrogel
hydrogel by starch
by starch graftgraft polymerization
polymerization in in
aqueous solution.
aqueous solution.

Mahmoodi-Babolan
Mahmoodi-Babolan et et
al. al.
[56][56]
synthesized
synthesized starch-based
starch-basedSAPsSAPs
via solution polymeriza-
via solution polymeri-
tion by incorporating
zation by incorporating AA and AM.AM.
AA and The material’s performance
The material’s was improved
performance was improvedby grafting
by graft-
catecholamine
ing catecholamine functional groupsgroups
functional onto itsonto
poreits
surfaces through through
pore surfaces dopamine oxidationoxidation
dopamine poly-
merization.
polymerization.The resultant bimodal
The resultant mesoporous
bimodal adsorbent
mesoporous demonstrated
adsorbent a swellinga ratio
demonstrated swelling
of 5914.66%. SAPs have also shown high efficacy as adsorbents
ratio of 5914.66%. SAPs have also shown high efficacy as adsorbents for pollutant for pollutant removal, re-
particularly dyes, withdyes,
moval, particularly a maximum
with a adsorption
maximum capacity
adsorption of 2276 mg/goffor2276
capacity methylene
mg/g for blue.
meth-
Various starches from different resources with different microstructures have been
ylene blue.
evaluated to be used as raw materials. Zhang et al. [57] developed three types of rice starch-
Various starches from different resources with different microstructures have been
based superabsorbent materials (SPAMs). The findings indicated that there was a minimal
evaluated to be used as raw materials. Zhang et al. [57] developed three types of rice
occurrence of side reactions, resulting in an exceptionally high acrylic grafting efficiency of
starch-based
93–94%. superabsorbent
Substantial materials
amylose content (SPAMs).
enhances polymerThe chain
findings indicated
interactions that
and there was a
structural
minimal occurrence of side reactions, resulting in an exceptionally
integrity through hydrogen bonding. The structured rigidity of amylopectin’s branched high acrylic grafting
efficiency of 93–94%. Substantial amylose content enhances polymer
chains in glutinous rice starch contributes to the SPAM’s favorable water absorption prop- chain interactions
and structural
erties. Siyamak et integrity through hydrogen
al. [58] reported bonding.
on the grafting The structured
of acrylamide monomers rigidity of amylopec-
through free
tin’s branched
radical chains inonto
copolymerization glutinous rice starch
four distinct starchescontributes to ammonium
as potential the SPAM’ssorbents.
favorable Thewater
absorption properties. Siyamak et al. [58] reported on the grafting
findings indicated that there was no significant difference in the average monomer conver- of acrylamide mono-
mers
sion and through free radical
graft efficiency among copolymerization
the different types ontoof four distinct
starch. Zou etstarches as potential
al. [59] performed an am-
extensive
monium investigation
sorbents. Theinto the impact
findings of the that
indicated amylose–amylopectin ratio in corn-derived
there was no significant difference in the
starches
averageon the grafting
monomer reactionsand
conversion andgraft
the resultant
efficiencyproperties
among the of different
starch-basedtypesSAPs. Their Zou
of starch.
results demonstrated that, under consistent reaction conditions, both
et al. [59] performed an extensive investigation into the impact of the amylose–amylopec- the grafting ratio
and efficiency increased with higher amylose content, correlating with
tin ratio in corn-derived starches on the grafting reactions and the resultant properties ofthe water absorp-
tion capacity. The
starch-based SAPs. high molecular
Their results weight and branched
demonstrated structure
that, under of amylopectin
consistent reduce
reaction conditions,
polymer
both thechain mobility,
grafting ratio thereby increasing
and efficiency viscositywith
increased andhigher
potentially affecting
amylose the grafting
content, correlating
reactions and performance attributes of starch-based SAPs. Bao et al. [60,61] investigated
with the water absorption capacity. The high molecular weight and branched structure of
amylopectin reduce polymer chain mobility, thereby increasing viscosity and potentially
affecting the grafting reactions and performance attributes of starch-based SAPs. Bao et
Molecules 2024, 29, x FOR PEER REVIEW 5 of 27

Molecules 2024, 29, 4835 al. [60,61] investigated the relationship between molecular structures, viscoelastic proper- 5 of 26
ties, graft polymerization, and hydrogel microstructures using cornstarch models with
varying amylose–amylopectin ratios. They found that an increase in amylose content re-
the relationship
sulted in a higher between molecular
viscoelastic structures,
modulus viscoelastic
in starch melts, properties,
which wasgraft polymerization,
associated with a re-
and hydrogel microstructures using cornstarch models with varying
duced degree of micro-mixing at lower rheological dynamic rates. Although monomer amylose–amylopectin
ratios. Theyremained
conversion found thatnearly
an increase in amylose
constant content resulted
with increasing amylosein acontent,
higher viscoelastic
the graftingmod- effi-
ulus in starch melts, which was associated with a reduced degree of micro-mixing at lower
ciency decreased. This decrease was attributed to the higher tendency of high-amylose
rheological dynamic rates. Although monomer conversion remained nearly constant with
starch to form crosslinks with grafted components.
increasing amylose content, the grafting efficiency decreased. This decrease was attributed
In order to enhance the performance of hydrogels, particularly in terms of gel
to the higher tendency of high-amylose starch to form crosslinks with grafted components.
strength and water
In order absorption
to enhance capacity, researchers
the performance of hydrogels, have been exploring
particularly in termsthe
of synthesis
gel strength and
application of composite hydrogels. One of the primary strategies
and water absorption capacity, researchers have been exploring the synthesis and appli- in enhancing gel
strength involves the introduction of reinforcing agents into the hydrogel
cation of composite hydrogels. One of the primary strategies in enhancing gel strength matrix. These
agents
involvescanthe
include various of
introduction types of fibers,agents
reinforcing nanoparticles, and other
into the hydrogel polymers
matrix. that
These can in-
agents
crease the structural
can include various integrity of the hydrogel
types of fibers, [62–64].
nanoparticles, andLi et al.polymers
other [65] synthesized
that can aincrease
starch-g-
PAA–attapulgite superabsorbent
the structural integrity composite
of the hydrogel [62–64].byLiincorporating attapulgite
et al. [65] synthesized micropowder
a starch-g-PAA–
into an aqueous
attapulgite reaction medium.
superabsorbent composite Thebyoptimal synthesis
incorporating conditions,
attapulgite which included
micropowder into an10
w%aqueous reaction
attapulgite, medium.
resulted in The optimal synthesis
a composite with a waterconditions, which
absorption included
capacity 10 w%
of 1077 gHatta-
2O/g
pulgite,inresulted
sample in water
distilled a composite
and 61withg Ha2O/g
water absorption
sample capacity
in a 0.9 w% NaCl of 1077 g H2 O/g
solution. sample
This biode-
in distilled
gradable, water and 61and
cost-effective, g Henvironmentally
2 O/g sample in a friendly
0.9 w% NaCl solution. This
superabsorbent biodegradable,
composite demon-
cost-effective, and environmentally friendly superabsorbent composite
strates superior water absorbency and water retention capabilities under load, making demonstrates supe- it
rior water absorbency and water retention capabilities under
particularly suitable for agricultural and horticultural applications. load, making it particularly
suitable for agricultural and horticultural applications.
2.2. Radiation In Situ Polymerization
2.2. Radiation In Situ Polymerization
Radiation
Radiation technology
technology has hasbeen
been extensively
extensively employed
employed in theinmodification
the modification of starch,
of starch, with
with numerous radiation techniques being utilized to produce starch-based
numerous radiation techniques being utilized to produce starch-based hydrogels [66–69]. hydrogels
[66–69].
RadiationsRadiations are typically
are typically classifiedclassified into and
into ionizing ionizing and nonionizing
nonionizing categoriescategories based
based on their
on their to
ability ability
ionizetomaterials.
ionize materials.
IonizingIonizing
radiationradiation has the capability
has the capability to ionizeto ionize
the mediumthe me-
it
dium
passesit through,
passes through, either through
either through direct or direct
indirectorinteraction
indirect interaction with theInmaterial.
with the material. contrast,In
contrast,
nonionizing nonionizing
radiation, radiation, dueionizing
due to its low to its low ionizing
potential, potential,
is incapable of is incapable
ionizing of ionizing
materials [70].
materials [70]. Among
Among ionizing radiationionizing radiation
techniques, gammatechniques,
radiation andgamma
electronradiation
beams are and electron
extensively
utilized
beams are forextensively
hydrogel synthesis. Nonionizing
utilized for hydrogelradiation
synthesis. has been explored
Nonionizing for the microwave-
radiation has been ex-
assisted
plored forsynthesis of hydrogels [71]. synthesis
the microwave-assisted As depicted ofin Figure 3, the
hydrogels [71].radiation-induced ionization
As depicted in Figure 3, the
process of starch generally involves two stages. First, covalent bonds are
radiation-induced ionization process of starch generally involves two stages. First, cova- disrupted, leading
to the
lent formation
bonds of free radicals.
are disrupted, leading These
to theradicals
formation thenofinitiate chemicalThese
free radicals. reactions among
radicals then
molecules at varying concentrations [72].
initiate chemical reactions among molecules at varying concentrations [72].

Figure 3. Schematic diagram of hydrogels prepared by starch irradiation graft polymerization.

Figure 3. Schematic diagram of hydrogels prepared by starch irradiation graft polymerization.

Gamma
Gamma irradiation hasproven
irradiation has proven
to to
be be particularly
particularly effective
effective in forming
in forming three-dimen-
three-dimensional
sional polymeric
polymeric networks
networks in superabsorbent
in superabsorbent materials,
materials, showcasing
showcasing high efficiency
high efficiency [73].
[73]. This
This method
method offers
offers several
several advantages
advantages over over conventional
conventional hydrogel
hydrogel fabrication
fabrication techniques.
techniques. Tra-
Molecules 2024, 29, x FOR PEER REVIEW 6 of 27

Molecules 2024, 29, 4835 6 of 26

Traditional techniques often require toxic initiators and crosslinking agents, which pose
risks to both human health and the environment [74]. In contrast, gamma irradiation elim-
ditional techniques often require toxic initiators and crosslinking agents, which pose risks
inates the need for these chemicals, making the process safer and more environmentally
to both human health and the environment [74]. In contrast, gamma irradiation eliminates
friendly.
the need forAdditionally,
these chemicals, it allows
making forthe
reactions underand
process safer milder
more conditions,
environmentally reducing energy
friendly.
consumption and operational costs [75]. The formation of minimal
Additionally, it allows for reactions under milder conditions, reducing energy consumption by-products further
enhances
and the sustainability
operational costs [75]. The of the processof
formation byminimal
reducing waste generation
by-products furtherand simplifies
enhances the the
purification steps.
sustainability of the The irradiation
process by reducingprocess
wasteis highly
generationcontrollable,
and simplifiesallowing for precise ad-
the purification
justments in radiation dose to achieve the desired degree of polymerization
steps. The irradiation process is highly controllable, allowing for precise adjustments and crosslink-
in
ing [76,77]. This flexibility enables the production of starch
radiation dose to achieve the desired degree of polymerization and crosslinking hydrogels with tailored prop-
[76,77].
erties,
This such asenables
flexibility absorption capacity, mechanical
the production strength,with
of starch hydrogels andtailored
biodegradability
properties,[78].
suchSimilar
as
to gammacapacity,
absorption ray irradiation,
mechanical electron
strength,beamandcrosslinking
biodegradability represents a clean
[78]. Similar and safe
to gamma raytech-
irradiation,
nique that electron
requiresbeam crosslinking
no external represents
initiators a clean and
or crosslinking safe technique
agents. Electron beam that requires
irradiation
no external initiators or crosslinking agents. Electron beam irradiation
surpasses gamma irradiation techniques in hydrogel production, primarily due to its surpasses gamma
irradiation techniques
faster processing in hydrogel
speed and precise production, primarily
beam control [79].due to its faster processing speed
and precise beam control
Starch-based [79]. were synthesized at ambient temperature using gamma ra-
hydrogels
Starch-based hydrogels
diation [80–82], as shown in were synthesized
Figure 4. This at ambient
study temperature
reveals that, withinusing gamma range,
a certain radia- in-
tion [80–82], as shown in Figure 4. This study reveals that, within a certain range, increasing
creasing radiation dosage leads to a higher gel fraction. Higher doses generate more per-
radiation dosage leads to a higher gel fraction. Higher doses generate more persistent
sistent free radicals, which enhances the probability of homopolymerization and the for-
free radicals, which enhances the probability of homopolymerization and the formation
mation of an entangled network. As the radiation dose escalates, so does the concentration
of an entangled network. As the radiation dose escalates, so does the concentration of
of free radicals, leading to a higher degree of conversion and crosslinking. However, at
free radicals, leading to a higher degree of conversion and crosslinking. However, at
higherdoses,
higher doses,intramolecular
intramolecularfree freeradical
radicalrecombination
recombinationbecomes becomesmore moredominant
dominantthan than in-
termolecular recombination,
intermolecular particularlyatatsufficiently
recombination, particularly sufficiently high
high absorbed
absorbed doses,
doses, whichwhich
can can
inhibit further crosslinking and initiate the degradation of
inhibit further crosslinking and initiate the degradation of the polymer network. Whenthe polymer network. When
superabsorbent polymers (SAPs) were synthesized via the
superabsorbent polymers (SAPs) were synthesized via the gamma irradiation of aqueousgamma irradiation of aqueous
mixturescontaining
mixtures containing carboxymethylcellulose
carboxymethylcellulose (CMC) (CMC) and the
and starch, starch, the incorporation
incorporation of starch of
starch significantly
significantly increasedincreased
both the gelboth the gel
fraction andfraction and water capacity
water absorption absorption capacitylow
at relatively at rela-
tively low doses
irradiation irradiation dosesHowever,
of 20 kGy. of 20 kGy. However,
excessive excessive
starch contentstarch
hindered content hindered gel
gel formation,
reducing
formation,thereducing
gel fraction.
theStarch is inherently
gel fraction. Starchprone to radiation-induced
is inherently degradation, butdeg-
prone to radiation-induced
in the presence
radation, but inofthe CMC, radicals
presence of formed on starch
CMC, radicals molecules
formed interact
on starch with those
molecules on thewith
interact
CMC
thosechains,
on thepromoting
CMC chains, crosslinking
promoting rather than degradation
crosslinking rather than[83].degradation [83].

Figure4.4.Schematic
Figure Schematic representation
representation of procedure
of procedure and and principle
principle of polyacrylamide
of polyacrylamide graftedgrafted starch us-
starch using
ing γ-ray
γ-ray [82]. [82].
 Molecules 2024, 29, x FOR PEER REVIEW 7 of 27
Molecules 2024, 29, 4835 7 of 26

2.3. Application of Reactive Extrusion Technology

2.3. Application of Reactive Extrusion Technology
Traditional methods of producing starch-based SAPs often rely on batch processes
that Traditional methods of
are solvent-intensive and producing
inefficientstarch-based SAPs often
in terms of energy rely on batch
consumption processes
and waste gen-
that are solvent-intensive
eration. The shift towardsand inefficient
reactive in terms
extrusion (REX) ofrepresents
energy consumption
a significantand waste gen-
advancement,
eration.
offeringThe shift towards
a more reactive
sustainable extrusionapproach
and efficient (REX) represents
to SAP amanufacturing
significant advancement,
[84–88]. As
offering a more sustainable and efficient approach to SAP manufacturing
shown in Figure 5, REX is a continuous process that uses extruders as chemical [84–88]. As
reactors
shown
to facilitate the grafting and polymerization of starch-based materials [58]. This methodtois
in Figure 5, REX is a continuous process that uses extruders as chemical reactors
facilitate the advantageous
particularly grafting and polymerization of starch-based
for handling high-viscosity materials
polymers, [58].are
which This method
often is
difficult
particularly advantageous for handling high-viscosity polymers, which are
to process using conventional batch techniques [89]. By reducing solvent use, REX mini- often difficult to
process using conventional
mizes environmental impactbatch techniques
while improving [89].the
Bysafety
reducing
and solvent use,ofREX
efficiency minimizes
the production
environmental
process. impact while improving the safety and efficiency of the production process.

Figure5.5.Schematic
Figure Schematicdiagram
diagramof
ofreactive
reactiveextrusion
extrusiontotoprepare
preparestarch-based
starch-basedmaterials.
materials.

Oneofofthe
One theprimary
primary advantages
advantages of REX
of REX is itsisoperational
its operational flexibility.
flexibility. Various Various pro-
processing
cessing parameters,
parameters, such as temperature
such as temperature and pressure,
and pressure, can be controlled,
can be precisely precisely controlled, allow-
allowing manu-
ing manufacturers
facturers to tailor the topolymer’s
tailor the polymer’s
propertiesproperties
to specificto specific requirements
requirements [90–94]. Ad-
[90–94]. Additionally,
ditionally,
REX REX offers
offers precise precise
control overcontrol over thetime
the residence residence time of
of reactants reactants
within within the
the extruder, ex-
opti-
truder,reaction
mizing optimizing reaction
kinetics andkinetics
enhancing and product
enhancing product performance.
performance. The continuous The continuous
nature of
REX leads
nature to higher
of REX leadsthroughput rates compared
to higher throughput to batch processes,
rates compared significantly
to batch processes, reducing
significantly
production time and associated
reducing production time andcosts. This increased
associated costs. This efficiency also enables
increased efficiency manufacturers
also enables
to respond moretoquickly
manufacturers respondtomore market demands
quickly [92]. Furthermore,
to market demands [92].the reduced need
Furthermore, thefor
re-
solvents
duced needand the associated
for solvents anddecrease in wastedecrease
the associated treatmentincontribute to a more
waste treatment sustainable
contribute to a
manufacturing
more sustainable approach. Siyamakapproach.
manufacturing et al. [95] Siyamak
demonstrated et al. the
[95]use of REX to synthesize
demonstrated the use of
starch-g-PAM copolymers, utilizing a screw configuration
REX to synthesize starch-g-PAM copolymers, utilizing a screw configuration with various elements. The
with various
solvent-free graft copolymerization of starch was performed at
elements. The solvent-free graft copolymerization of starch was performed at high solid high solid concentrations,
with the reactionwith
concentrations, reaching completion
the reaction reachingwithin 5 min. This
completion process
within 5 min.resulted in an average
This process resulted
monomer conversion
in an average monomer rateconversion
of 80% andrate a grafting
of 80% efficiency
and a grafting of approximately 74%. Another
efficiency of approximately
key
74%.advantage
Another key of REX is its modular
advantage of REX isdesign,
its modularwhich allowswhich
design, for easy
allowsmodifications and
for easy modifi-
optimization of the system for different types of starch-based materials
cations and optimization of the system for different types of starch-based materials and and desired product
characteristics
desired product [96]. This adaptability
characteristics is crucial
[96]. This for ongoing
adaptability research
is crucial and development,
for ongoing research and
where
development, where continuous improvements are being made to enhance and
continuous improvements are being made to enhance SAP performance SAPexpand
perfor-
their applications.
mance and expand their applications.
Jiang
Jiangetetal.
al.[97]
[97]developed
developeda aREX REX system
system (illustrated
(illustrated in in
Figure
Figure6) for thethe
6) for production
productionof
starch-g-PAM hydrogels, utilizing a dual-initiation mechanism.
of starch-g-PAM hydrogels, utilizing a dual-initiation mechanism. The REX system, The REX system, equipped
with a twin-screw
equipped co-extruder,
with a twin-screw a solid feeder,
co-extruder, a solid and four injection
feeder, and four ports,
injectionfacilitated the
ports, facili-
separate addition of an acrylamide solution, initiator-1, initiator-2, and
tated the separate addition of an acrylamide solution, initiator-1, initiator-2, and a sapon- a saponifying agent.
The dual-initiation approach was found to enhance the homogeneity of the hydrogel’s
ifying agent. The dual-initiation approach was found to enhance the homogeneity of the
network microstructure and augment its gel strength.
hydrogel’s network microstructure and augment its gel strength.
Molecules 2024,29,
Molecules2024, 29,4835
x FOR PEER REVIEW 8 of
8 of2726

Figure6.6.Schematic
Figure Schematic representation
representation of
of dual-stage
dual-stage and
and dual-initiator
dual-initiator reactive
reactive extrusion
extrusionsystems
systems[97].
[97].

2.4.
2.4.Characterization
Characterization Techniques
Techniques for for Hydrogel
Hydrogel Network Structure
Rheological
Rheological Characterization
Characterization of of Hydrogels.
Hydrogels. Rheology
Rheologyisisthe thescience
scienceof ofstudying
studyingthe the
flow
flowandanddeformation
deformationbehaviorbehaviorof ofmaterials,
materials,aimingaimingto toinvestigate
investigatethe theresponse
responseofofmaterials
materi-
under external
als under externalforces [98,99].
forces [98,99]. It It
covers
coversbothboththe thehydrodynamic
hydrodynamic theory theory of fluidsfluidsand andthe the
elasticity
elasticity theory
theory of of elastomers.
elastomers. For For simple
simple Newtonian
Newtonianfluids fluidsand andelastomers,
elastomers,their theirrheo-
rheo-
logical
logical properties
properties can can bebe described
described by simple simple continuity
continuity equations
equationssuch suchas asHooke’s
Hooke’slaw law
and
andNewton’s
Newton’slaw lawof ofviscosity.
viscosity.However,
However,the therheological
rheologicalproperties
propertiesof ofcomplex
complexviscoelastic
viscoelas-
materials
tic materials likelike
hydrogels
hydrogels are are
much much more moreintricate [100].
intricate Hydrogels
[100]. Hydrogels exhibit
exhibitboth viscous
both viscous and
elastic properties,
and elastic and their
properties, behavior
and their behavior is influenced
is influencedby stress, strain,
by stress, strain
strain, rate,rate,
strain and even
and
deformation
even deformation history, displaying
history, displaying notable nonlinear
notable nonlinearcharacteristics
characteristics [101,102].
[101,102]. AsAs a typical
a typ-
complex
ical complex viscoelastic material, the rheological characterization of starch-based hydro-is
viscoelastic material, the rheological characterization of starch-based hydrogels
crucial
gels is for understanding
crucial for understanding the relationship between
the relationship their microstructure
between their microstructure and macroscopic
and mac-
mechanical properties.properties.
roscopic mechanical Dynamic Dynamic shear testing shear using a rotational
testing rheometer,rheometer,
using a rotational known for
its operational
known simplicity and
for its operational clear demonstration
simplicity and clear demonstrationof viscoelastic characteristics,
of viscoelastic is the
characteris-
preferred
tics, is thetechnique
preferredfor evaluating
technique the viscoelastic
for evaluating behavior ofbehavior
the viscoelastic starch-based hydrogels. hy-
of starch-based This
method
drogels.applies
This methodperiodic sinusoidal
applies periodic displacements and torque, measuring
sinusoidal displacements and torque,the response
measuring
torque or strain
the response and its
torque phase and
or strain difference
its phase from the applied
difference fromaction, effectively
the applied action, revealing
effectively the
material’s viscoelastic characteristics, including storage modulus (G ′ ), loss modulus (G′′ ),
revealing the material’s viscoelastic characteristics, including storage modulus (G′), loss
and complex
modulus viscosity
(G″), and complex(η*). These
viscosity rheological
(η*). These parameters
rheological notparameters
only help in not understanding
only help in
the interactions between
understanding starch molecular
the interactions between chains starch and the influence
molecular chains of and crosslinking
the influence densityof
on material performance
crosslinking density on materialbut alsoperformance
guide the optimization
but also guide of the
formulations
optimization andofprocessing
formula-
conditions to ensure product
tions and processing conditionsquality and meet
to ensure specific
product application
quality and meet needs. (1) Strain
specific Sweep:
application
The linear
needs. viscoelastic
(1) Strain Sweep:region (LVR)
The linear of hydrogels
viscoelastic can(LVR)
region be identified
of hydrogels through can strain sweeps
be identified
at constant
through frequency.
strain sweepsIn atthe low strain
constant range,In
frequency. viscoelastic
the low strain moduli range, remain independent
viscoelastic moduliof
strain but exceed the critical strain, and the gel structure begins
remain independent of strain but exceed the critical strain, and the gel structure begins to to break down. Chemically
crosslinked
break down. gels typically have
Chemically larger critical
crosslinked strain values
gels typically than physical
have larger gels, with
critical strain values thethan
LVR
depending
physical gels, on chain
with the interactions
LVR depending and crosslinking density. (2) and
on chain interactions Frequency
crosslinkingSweep:density.
Frequency (2)
sweep
Frequencyis essential
Sweep:for probingsweep
Frequency the molecular
is essential structure
for probingof gel thenetworks.
molecularBy analyzing
structure vis-
of gel
coelastic
networks. moduli versus frequency
By analyzing viscoelasticinmoduli a log–log plot,frequency
versus the relaxation behavior
in a log–log plot,of the
gel relax-
chains
isation
revealed.
behavior Physical crosslinking
of gel chains is revealed. systems formed
Physical by hydrogen
crosslinking systemsbonds, double
formed helices,
by hydro-
and
gen ionic
bonds, bonds
double show varied
helices, andgel ionicstrengths
bonds show and relaxation spectra. In
varied gel strengths and highly crosslinked
relaxation spec-
gels, the storage modulus (G ′ ) is significantly higher than the loss modulus (G′′ ) over the
tra. In highly crosslinked gels, the storage modulus (G′) is significantly higher than the
entire frequency
loss modulus range,
(G″) overindicating
the entireelastic frequencybehavior.
range, (3)indicating
Time Sweep: Time
elastic sweep at(3)
behavior. constant
Time
amplitude
Sweep: Time andsweep
frequency monitors
at constant the real-time
amplitude changes monitors
and frequency in the hydrogel network.
the real-time It can
changes
reveal molecularnetwork.
in the hydrogel structure changes
It can revealand the kinetics
molecular of gel
structure formation,
changes and the with viscoelastic
kinetics of gel
moduli
formation, increasing significantly
with viscoelastic moduliduring the process.
increasing (4) Temperature
significantly during the Sweep: Temperature
process. (4) Tem-
sweeps
perature involve
Sweep:heating or cooling
Temperature sweeps gelsinvolve
while keeping
heating or strain
coolingandgelsfrequency constant.
while keeping The
strain
intersection of G ′ and G′′ indicates the sol–gel transition temperature, providing insights
and frequency constant. The intersection of G′ and G″ indicates the sol–gel transition tem-
into gel thermal
perature, providingstability andinto
insights crosslinking
gel thermal strength.
stability and crosslinking strength.
Molecules 2024, 29, 4835 9 of 26

Dynamic mechanical thermal analysis (DMTA) of hydrogels. DMTA is a key tech-

nique used to study the mechanical properties of materials under dynamic stress as a
function of temperature or frequency [103,104]. By applying a periodic sinusoidal load to
polymer-based composites and precisely recording their response, it is possible to observe
a phase lag between the deformation and the applied load due to the viscoelastic nature
of the material. As the temperature increases, molecular segments within the material
are activated, leading to significant changes in the stiffness of the matrix. These changes
can be reflected through parameters such as the storage modulus (E′ ), loss modulus (E′′ ),
and the loss factor (tan δ = E′′ /E′ ), which provide valuable insights for understanding and
predicting the material’s performance in practical applications, particularly in assessing its
viscoelasticity and energy dissipation capabilities [105].
Microstructural parameters, such as molecular weight, molecular orientation, crys-
tallinity, the degree of crosslinking, and the nature of copolymers, significantly influence
the macroscopic mechanical properties of materials. DMTA determines the glass transition
temperature (Tg ) and secondary relaxation transitions by analyzing how E′ , E′′ , and tan
δ change with temperature. These transitions reflect changes in the material’s internal
structure. For example, the glass transition temperature is the point at which a polymer
transitions from a glassy state to a rubbery state, associated with the increased mobility of
molecular chains. This transition directly illustrates the relationship between the material’s
microstructure and its macroscopic mechanical properties. In reality, the glass transition
does not occur at a single, specific temperature but over a range of temperatures where the
material’s characteristics change. Various methods are used to determine Tg , including the
peak of the tan δ curve, the peak of the E′′ curve, and the inflection point of the E’ curve.
Each method has its advantages and disadvantages, and they may yield slightly different
results. Typically, the temperature corresponding to the peak of the tan δ curve is taken as
the Tg of the material.

3. Loading Fertilizer into Hydrogels

3.1. Coating by Starch
Among the various methods for creating SRFs, the coated and matrix types have gar-
nered considerable attention [106]. Coated-type SRFs, in particular, have been extensively
researched for their capacity to modulate nutrient release through the manipulation of
coating materials [11,107,108]. These SRFs are typically prepared by applying a layer of
inert material onto solid fertilizers to reduce their dissolution rate. The effectiveness of
this approach heavily relies on the intrinsic physical attributes of the coating material,
including its hydrophobic/hydrophilic nature and porosity. Starch granules have emerged
as a promising coating material due to their ability to enhance the adhesion on fertilizer
surfaces. For instance, Khan et al. [109] demonstrated a process where starch was incorpo-
rated into NPK fertilizers as a binder, ensuring the uniform coating of the NPK granules
with starch particles. However, native starch has limitations such as poor film-forming
ability, low water resistance, and susceptibility to damage in humid environments. To
overcome these challenges, starch is often chemically modified through processes like ester-
ification, crosslinking, and graft copolymerization to enhance its water resistance [110–113].
Modified starch as a coating material has been extensively reviewed [38], and this chapter
specifically delves into the novel application of starch-based hydrogel coatings in SRFs.
Qiao et al. [114] introduced an innovative double-coated SRF design, utilizing ethyl
cellulose (EC) as the inner layer and a starch-based SAP as the outer layer, with urea as the
core, accounting for 55% w/w (Figure 7). The release of nutrients from the double-coated
SRF occurs in three distinct phases: (1) the absorption of water by the starch-based SAP
and its subsequent permeation through the EC layer, (2) the dissolution of the urea core’s
nutrients by water, and (3) nutrient delivery into soil through the dual-layered system.
The release dynamics of the fertilizer are primarily influenced by the properties of the
starch–SAP layer. This double-coating technique significantly augments the controlled
release of nutrients and improves the overall efficiency and sustainability of fertilizer
 Molecules 2024, 29, x FOR PEER REVIEW 10 of 27

Molecules 2024, 29, 4835 10 of 26

the starch–SAP layer. This double-coating technique significantly augments the controlled
release of nutrients and improves the overall efficiency and sustainability of fertilizer ap-
application. Similarly,Lü
plication. Similarly, Lüet
etal.
al. [115]
[115] developed
developed another
another dual-coated
dual-coated SRF
SRFthat
thatincorporated
incorporated
starch
starch acetate and a combination of carboxymethyl starch and xanthan gum.By
acetate and a combination of carboxymethyl starch and xanthan gum. Bycarefully
carefully
selecting and modifying coating materials, researchers cancustomize the
selecting and modifying coating materials, researchers cancustomize the releaserelease profiles of
profiles
SRFs to meet specific agricultural requirements„ ultimately leading to more effective
of SRFs to meet specific agricultural requirements,, ultimately leading to more effective and
environmentally friendly
and environmentally farming
friendly practices.
farming practices.

Figure7.7.AAschematic
Figure schematicrepresentation
representationofofthe
therelationship
relationshipbetween
betweenstarch-based
starch-basedSAP
SAPcharacteristics
characteristics
and the slow-release behaviors of the double-coated fertilizer [114].
and the slow-release behaviors of the double-coated fertilizer [114].

Polyvinylalcohol
Polyvinyl alcohol(PVA),
(PVA), a biodegradable
a biodegradable polymer,
polymer, can can
formform a strong
a strong and environ-
and environmen-
mentally friendly coating matrix when combined with starch. The
tally friendly coating matrix when combined with starch. The enhancement in interactions enhancement in inter-
actions
and and crosslinking
crosslinking within PVA–starch
within PVA–starch blends not blends
only not only augments
augments the and
the strength strength
densityand
ofdensity of the resulting
the resulting films butfilms
also but also impedes
impedes the swelling
the swelling of thestructure
of the starch starch structure by re-
by reducing
ducing accessible
accessible regions,increasing
regions, thereby thereby increasing their to
their resistance resistance to dissolution.
dissolution. Zafarused
Zafar et al. [111] et al.
[111] used starch and PVA coatings, acrylic acid, citric acid, and maleic
starch and PVA coatings, acrylic acid, citric acid, and maleic acid as crosslinking agents and acid as crosslink-
ing agents
prepared and type
a new prepared a new
of coated type
urea SRFof through
coated urea SRF through a granulator/fluidized
a granulator/fluidized bed coater. The
bed coater. The
incorporation incorporation
of clay of clay
nanoparticles, nanoparticles,
such as bentonite,such as bentonite,
further augmentsfurther augments
the mechanical
the mechanical
properties of theproperties
coating film,of the coating
making film, durable
it more making and it more durable
effective and effective
in controlling thein
controlling
release the release
of nutrients. of nutrients.
Sarkar Sarkar
et al. [116] et al. [116] demonstrated
demonstrated a novel approach a novel approach to
to encapsulate
encapsulate diammonium
diammonium phosphate (DAP) phosphate
using(DAP)
a blend using a blend
of wheat of wheat
starch, PVA,starch, PVA, andclay,
and bentonite ben-
tonite to
aiming clay, aimingthe
optimize to release
optimize the release
kinetics kineticsthe
and improve and improve
overall the overall
performance performance
of the fertilizer.
The resulting
of the coated
fertilizer. DAP particles
The resulting coatedexhibited controlled
DAP particles release
exhibited characteristics,
controlled with the
release character-
release rate influenced
istics, with by the
the release rate concentration
influenced by theof bentonite clay.
concentration Higher concentrations
of bentonite clay. Higher con- of
bentonite
centrations resulted in slower
of bentonite releaseinrates,
resulted sloweras the clay rates,
release nanoparticles
as the clayincreased the film’s
nanoparticles in-
barrier
creased properties
the film’s and reduced
barrier permeability.
properties This controlled
and reduced release mechanism
permeability. This controlledis beneficial
release
for optimizing
mechanism is nutrient
beneficial availability for plants
for optimizing andavailability
nutrient minimizingfor environmental impact by re-
plants and minimizing en-
ducing nutrient leaching. This approach holds promise for the development
vironmental impact by reducing nutrient leaching. This approach holds promise for the of sustainable
and efficient slow-release
development of sustainablefertilizers, contributing
and efficient to improved
slow-release agricultural
fertilizers, practicestoand
contributing im-
environmental sustainability.
proved agricultural practices and environmental sustainability.

3.2.
3.2.Swelling
Swellingand
andAbsorption
AbsorptionEquilibrium
EquilibriumMethod
Method
When
When hydrogels are immersed in a fertilizersolution,
hydrogels are immersed in a fertilizer solution,they
theyabsorb
absorbnutrients
nutrientsand
andswell
swell
as they take up liquid. This process continues until the hydrogels reach an equilibrium
as they take up liquid. This process continues until the hydrogels reach an equilibrium
state, where they have absorbed as much fertilizer solution as they can hold. These nutrient-
state, where they have absorbed as much fertilizer solution as they can hold. These nutri-
loaded hydrogels can then be applied to soil, where they gradually release the absorbed
ent-loaded hydrogels can then be applied to soil, where they gradually release the ab-
fertilizers over time as the liquid is released (Figure 8). This method allows for the controlled
sorbed fertilizers over time as the liquid is released (Figure 8). This method allows for the
and sustained release of fertilizers, improving nutrient uptake by plants and reducing the
risk of nutrient leaching into the environment.
Molecules 2024, 29, x FOR PEER REVIEW 11 of 27

Molecules 2024, 29, 4835 11 of 26

controlled and sustained release of fertilizers, improving nutrient uptake by plants and
reducing the risk of nutrient leaching into the environment.

Figure 8. Schematic diagram of hydrogel absorption swelling and fertilizer release process.
Figure 8. Schematic diagram of hydrogel absorption swelling and fertilizer release process.

Leόn et
León et al.
al.[117]
[117]explored
exploredthe thegraft
graft copolymerization
copolymerization of starch
of starch with
with itaconic
itaconic acidacid to
to pro-
produce
duce SAPs.
SAPs. TheThe findings
findings indicated
indicated thatthat increasing
increasing the fertilizer
the fertilizer concentration
concentration fromfrom 0.5
0.5 g/L
g/L10tog/L
to 10 g/L enhanced
enhanced urea
urea absorption
absorption butbut reduced
reduced theadsorption
the adsorptionofofKNO KNO3 3andand NHNH44NO
NO33..
The release behavior of fertilizers also varied, with higher fertilizer concentrations
behavior of fertilizers also varied, with higher fertilizer concentrations lead- leading
to slower
ing release
to slower rates.rates.
release Similarly, PerezPerez
Similarly, et al.et[118] studied
al. [118] macrospheres
studied fabricated
macrospheres from
fabricated
chitosan
from and chitosan–starch
chitosan and chitosan–starch blends. The dry
blends. The polymer matrices
dry polymer were immersed
matrices were immersedin a ferti-
in
alizer-enriched solution
fertilizer-enriched for 4 hfor
solution at 4ambient temperature,
h at ambient then dried
temperature, then at 40 °C
dried 40 ◦48
at for C h.
forAnal-
48 h.
yses revealed
Analyses that that
revealed the bead structure
the bead significantly
structure significantly influenced
influenced swelling behavior,
swelling behavior, which
whichin
turn
in affected
turn affected their
theirfertilizer
fertilizerloading
loadingcapacity
capacityand andrelease
releasekinetics.
kinetics. Although
Although the the swelling
and absorption equilibrium
equilibrium methodmethod is simple, it has certain limitations. Drying the loaded
hydrogels requires
hydrogels requiressubstantial
substantialenergy,
energy,and and thethe fertilizer
fertilizer loading
loading capacity
capacity is restricted
is restricted by
by the
hydrogel’s
the hydrogel’s swelling
swellingcapability.
capability.Furthermore,
Furthermore, the the
swelling
swelling andandabsorption
absorption capacity
capacityof all
of
SAPs is significantly
all SAPs is significantly reduced
reduced in ionic solutions,
in ionic solutions, such as as
such those
thosefound in in
found various
various fertilizers.
fertiliz-
As
ers.aAs
result, the concentration
a result, the concentration of fertilizer within
of fertilizer SAPsSAPs
within is typically modest.
is typically modest.

3.3. In Situ
3.3. In Situ Polymerization
Polymerization Technology
Technology
The in situ
The in situpolymerization
polymerizationofofstarch
starchisisa method
a method of of directly
directly initiating
initiating thethe polymer-
polymeriza-
ization of monomers in the presence of starch, which enables the formation
tion of monomers in the presence of starch, which enables the formation of polymers on of polymers
on
thethe surface
surface or inside
or inside starch
starch granules,
granules, thus
thus improving
improving thethe physicochemical
physicochemical properties
properties of
of starch or giving it new functions [119,120]. Salimi et al. [121] fabricated
starch or giving it new functions [119,120]. Salimi et al. [121] fabricated a novel slow-re- a novel slow-
release
lease ureaureafertilizer
fertilizerusing
usingan anin
in situ
situ polymerization
polymerization process.
process. This
This method
method integrated
integrated
acrylic monomers with starch in the presence of urea, achieving a
acrylic monomers with starch in the presence of urea, achieving a homogeneous blend. homogeneous blend.
The innovation was further enhanced by incorporating natural char nanoparticles as nano-
The innovation was further enhanced by incorporating natural char nanoparticles as
fillers, which uniformly dispersed within the polymer matrix. This uniform distribution
nano-fillers, which uniformly dispersed within the polymer matrix. This uniform distri-
significantly improved the interfacial interactions between the polymer and the fillers,
bution significantly improved the interfacial interactions between the polymer and the
effectively retarding nitrogen diffusion and reducing the release rate in both aqueous and
fillers, effectively retarding nitrogen diffusion and reducing the release rate in both aque-
soil conditions.
ous and soil conditions.
Chen et al. [82] developed an approach for synthesizing SRFs through the in situ
Chen et al. [82] developed an approach for synthesizing SRFs through the in situ ra-
radiation-induced polymerization of monolithic hydrogels. This method involves embed-
diation-induced polymerization of monolithic hydrogels. This method involves embed-
ding urea within a starch-based matrix and grafting it with polyacrylamide. The analysis
ding urea within a starch-based matrix and grafting it with polyacrylamide. The analysis
demonstrated distinct microstructures in hydrogels prepared under different conditions
demonstrated distinct microstructures in hydrogels prepared under different conditions
(Figure 9). Low irradiation intensities preserved some honeycomb structures with weaker
(Figure 9). Low irradiation intensities preserved some honeycomb structures with weaker
fibers, but higher intensities resulted in the disappearance of these structures, replaced by
fibers, holes
larger but higher
and a intensities
denser, moreresulted in the disappearance
homogeneous of these structures,
crosslinked network. replaced by
Higher concentrations
larger holes and a denser, more homogeneous crosslinked network.
led to porous structures, whereas lower concentrations produced less dense networks Higher concentra-
and
tions led to porous structures, whereas lower concentrations produced
thinner cell walls. The presence of porous or cottony structures was primarily attributed less dense net-
works
to and thinner
the grafted starchcell walls.emphasizing
matrix, The presencethe of significant
porous or cottony
influencestructures was primarily
of irradiation intensity,
attributed to the grafted starch matrix, emphasizing the significant influence
concentration, and the AM–starch ratio on the hydrogel microstructure. An increase in of irradiation
radiation intensity and concentration enhanced grafting efficiency and monomer conver-
sion. Enhanced gel strength, associated with higher radiation levels, AM content, and
Molecules 2024, 29, x FOR PEER REVIEW 12 of 27

Molecules 2024, 29, 4835

intensity, concentration, and the AM–starch ratio on the hydrogel microstructure. 12 Anofin-
26
crease in radiation intensity and concentration enhanced grafting efficiency and monomer
conversion. Enhanced gel strength, associated with higher radiation levels, AM content,
concentration, was correlated
and concentration, withwith
was correlated a reduced urea urea
a reduced release rate. rate.
release For example, the release
For example, the re-
rates of samples U-1~U-7 were only about 26.2%, 14.9%, 20.2%, 11.6%, 33.5%,
lease rates of samples U-1~U-7 were only about 26.2%, 14.9%, 20.2%, 11.6%, 33.5%, 9.5%,9.5%, and
30.2% in 2 h, respectively. After 42 h, the release rate of urea remained above 80%,
and 30.2% in 2 h, respectively. After 42 h, the release rate of urea remained above 80%, and the
difference was not significant.
and the difference was not significant.

Figure 9.
Figure 9. SEM
SEM images
imagesof radiation-induced
of radiation-inducedin situ
in synthesis of starch-based
situ synthesis hydrogels
of starch-based under diverse
hydrogels under
conditions. S-1–S-4, S-8: AM–starch = 1:2, water–starch = 10:1, irradiation doses
diverse conditions. S-1–S-4, S-8: AM–starch = 1:2, water–starch = 10:1, irradiation are 3 kGy, 6 kGy,
doses are9
kGy, 12 kGy, and 24 kGy, respectively. S-9: AM–starch = 1:2, water–starch = 6:1; S-15: AM–starch =
3 kGy, 6 kGy, 9 kGy, 12 kGy, and 24 kGy, respectively. S-9: AM–starch = 1:2, water–starch = 6:1;
1:2, water–starch = 15:1; S-16: AM–starch = 2:1, water–starch = 10:1; S-17: AM–starch = 2:2, water–
S-15: AM–starch = 1:2, water–starch = 15:1; S-16: AM–starch = 2:1, water–starch = 10:1; S-17:
starch = 10:1; S-20: AM–starch = 2:6, water–starch = 10:1, irradiation dose is similarly 12 kGy [82].
AM–starch = 2:2, water–starch = 10:1; S-20: AM–starch = 2:6, water–starch = 10:1, irradiation dose is
similarly 12 kGy
3.4. Reactive [82].
Extrusion Technology
REX is Extrusion
3.4. Reactive a continuous process that involves the mixing and chemical modification of
Technology
polymers
REX isinathe molten state
continuous within
process thatan extruder.
involves theThe extruder
mixing is a long,modification
and chemical cylindrical ma- of
chine equipped with a screw that rotates and conveys the polymer
polymers in the molten state within an extruder. The extruder is a long, cylindrical forward whilemachine
mixing
it with other
equipped withcomponents
a screw that[122]. The
rotates andREX process
conveys theforpolymer
loadingforward
fertilizerwhile
into hydrogels typ-
mixing it with
ically involves the following steps: (1) Preparation of hydrogel precursors.
other components [122]. The REX process for loading fertilizer into hydrogels typically The first step
is the preparation
involves of hydrogel
the following steps: (1)precursors,
Preparation which are usually
of hydrogel hydrophilic
precursors. polymers
The first step issuch
the
as PVA, PAA,
preparation PAM, starch,
of hydrogel cellulose,
precursors, whichetc.are
(2)usually
Incorporation of fertilizer.
hydrophilic polymersThe suchfertilizer,
as PVA,
whichPAM,
PAA, can be in thecellulose,
starch, form of etc.
solid(2)particles or a liquid
Incorporation solution,The
of fertilizer. is introduced into the
fertilizer, which can ex-
be
truder
in along
the form of with
solid the hydrogel
particles precursors.
or a liquid Theis extruder
solution, introduced is into
designed to provide
the extruder alonga with
con-
trolled
the environment
hydrogel for the
precursors. Themixing
extruder and
is encapsulation
designed to provide of the afertilizer within
controlled the polymer
environment for
matrix. (3) Crosslinking reaction. As the mixture moves along the extruder,
the mixing and encapsulation of the fertilizer within the polymer matrix. (3) Crosslinking a crosslinking
reaction isAs
reaction. initiated, typically
the mixture through
moves alongthe addition
the extruder, of aacrosslinking
crosslinkingagent or byisusing
reaction heat
initiated,
or radiation.
typically This the
through reaction leads
addition ofto the formationagent
a crosslinking of theorhydrogel
by usingnetwork, with the ferti-
heat or radiation. This
lizer particles
reaction leads or molecules
to the being
formation trapped
of the within
hydrogel the polymer
network, with thematrix. (4) Formation
fertilizer particles or of
hydrogel beads.
molecules The hydrogel–fertilizer
being trapped within the polymer mixture is then
matrix. extruded through
(4) Formation of hydrogela die, typically
beads. The
hydrogel–fertilizer
in the form of smallmixture
beads orispellets.
then extruded
These beadsthrough a die, typically
are rapidly cooled toinsolidify
the form theofhydro-
small
beads or pellets.
gel structure and These beads
stabilize are rapidly cooled
the encapsulated to solidify the hydrogel structure and
fertilizer.
stabilize the encapsulated fertilizer.
REX research encompasses a broad spectrum of disciplines, such as chemical reaction
engineering, rheology, polymer processing, and mechanics, involving numerous intricate
reaction processes. Given the complexity of these processes, the utilization of reactive
extrusion in the production of starch-based SRFs remains relatively constrained. A modi-
fied Hakke internal mixer was employed as a reactor to synthesize SAPs, mimicking the
operation of a twin-screw extruder [60,61,123–125]; Under a high-viscosity system, the
 REX research encompasses a broad spectrum of disciplines, such as chemical reaction
engineering, rheology, polymer processing, and mechanics, involving numerous intricate
reaction processes. Given the complexity of these processes, the utilization of reactive ex-
trusion in the production of starch-based SRFs remains relatively constrained. A modified
Molecules 2024, 29, 4835
Hakke internal mixer was employed as a reactor to synthesize SAPs, mimicking the oper-
13 of 26
ation of a twin-screw extruder [60,61,123–125]; Under a high-viscosity system, the ferti-
lizer loading rate can be increased to over 37 w% [126]. The REX process, while efficient
for many polymer processing applications, presents a unique challenge when it comes to
fertilizer loading rate can be increased to over 37 w% [126]. The REX process, while efficient
the preservation of the crosslinked structure of hydrogels. The crosslinking in hydrogels
for many polymer processing applications, presents a unique challenge when it comes to
is a critical factor that determines their mechanical strength, swelling behavior, and deg-
the preservation of the crosslinked structure of hydrogels. The crosslinking in hydrogels is
radation rate. During the reaction extrusion process, which involves the extrusion of a
a critical factor that determines their mechanical strength, swelling behavior, and degrada-
polymer melt through a die, the high shear forces and thermal conditions can potentially
tion rate. During the reaction extrusion process, which involves the extrusion of a polymer
disrupt the delicate crosslinked structure of the hydrogel. This disruption can lead to a
melt through a die, the high shear forces and thermal conditions can potentially disrupt the
decrease
delicate in the mechanical
crosslinked structureintegrity of the hydrogel,
of the hydrogel. affectingcan
This disruption itslead
performance in practical
to a decrease in the
applications.
mechanical To circumvent
integrity the potential
of the hydrogel, degradation
affecting of the crosslinked
its performance structure
in practical during
applications.
Tothe reaction extrusion
circumvent process,
the potential an alternative
degradation of theapproach known
crosslinked as post-crosslinking
structure can be
during the reaction
employed. Post-crosslinking involves the formation of crosslinks in a polymer
extrusion process, an alternative approach known as post-crosslinking can be employed. matrix after
the initial processing steps. This method allows for the preparation of hydrogels
Post-crosslinking involves the formation of crosslinks in a polymer matrix after the initial with con-
trolled crosslinking density and distribution, which is crucial for optimizing
processing steps. This method allows for the preparation of hydrogels with controlled the proper-
ties of the hydrogel
crosslinking for specific
density and applications.
distribution, which is crucial for optimizing the properties of the
hydrogel for specific applications.
3.5. Compounding with Cellulose
3.5. Compounding
Cellulose, awith Cellulose
polymeric compound abundantly found in plant cell walls, is the most
plentiful and sustainably
Cellulose, a polymericsourced
compound material on Earth.
abundantly foundIt possesses a rich
in plant cell variety
walls, is theofmost
func-
tional groups,
plentiful exceptional
and sustainably mechanical
sourced materialproperties,
on Earth. It and a high degree
possesses of chemical
a rich variety adapta-
of functional
groups, exceptional
bility, making mechanical
it ideal properties,
for modification and a high
[127,128]. degree ofthe
Furthermore, chemical
capabilityadaptability,
to render
making it ideal for modification [127,128]. Furthermore, the capability
cellulose into fibrous forms at the micro- or nanometer scale has positioned it as an in- to render cellulose
into fibrous promising
creasingly forms at the micro- or
contender fornanometer
the creation scale has positioned
of hydrogels it as
in recent an increasingly
years. Li et al. [129]
promising
reviewed contender for the creation
various modification methods of hydrogels
of cellulose in and
recenttheyears. Li et al.
application of[129] reviewed
stimuli-respon-
various modification
sive hydrogels methods offertilizers.
in slow-release cellulose and the application
Manuel of stimuli-responsive
et al. [37] conducted a review onhydro-hydro-
gels in delving
gels, slow-release fertilizers.
into their Manuel
properties, et al. [37] conducted
classifications, synthesis a review on hydrogels,
mechanisms, delving
and diverse ap-
into their properties, classifications, synthesis mechanisms, and diverse
plications across various industries. In their article, starch and cellulose were highlighted applications across
various industries.
as copolymers, In their article,
showcasing starch and
their integral cellulose
roles in the were highlighted
development and as copolymers,of
functionality
showcasing
hydrogels. their integral roles in the development and functionality of hydrogels.
Cellulose-based
Cellulose-basedcomposites
composites have
have garnered
garnered significant
significant attention
attentionin recent years
in recent duedue
years to
their potential
to their as reinforcing
potential fillersfillers
as reinforcing in biopolymer
in biopolymermatrices derived
matrices from starch
derived [64,130–132]
from starch [64,130–
(Figure 10). Starch
132] (Figure composite
10). Starch cellulose
composite hydrogels
cellulose are both
hydrogels biodegradable
are both biodegradable and renewable
and renew-
polymers, and these hydrogels can slowly release nutrients to
able polymers, and these hydrogels can slowly release nutrients to plants, providing plants, providing a con-a
trolled and sustained supply of essential elements for plant growth. Bora
controlled and sustained supply of essential elements for plant growth. Bora et al. [133] et al. [133] utilized
wastepaper powder aspowder
utilized wastepaper a modifier
as a in a biodegradable
modifier hydrogel hydrogel
in a biodegradable compositecomposite
composedcom- of
starch, itaconic acid, and acrylic acid. The incorporation of an optimal
posed of starch, itaconic acid, and acrylic acid. The incorporation of an optimal quantity quantity of the mod-
ifier increased
of the modifier theincreased
hydrogel’s theswelling
hydrogel’s capacity fromcapacity
swelling 503 g/g fromto 647503g/g.g/gThe
to NPK-laden
647 g/g. The
hydrogel
NPK-laden demonstrated effective sustained-release
hydrogel demonstrated characteristics,
effective sustained-release with 98% of nitrogen,
characteristics, with 98%
81% of phosphorus,
of nitrogen, 81% of and 95% of potassium
phosphorus, and 95% being releasedbeing
of potassium over released
20 days. over 20 days.

Figure10.
Figure 10.Illustrative
Illustrativescheme
schemeofofstructure
structureofofcellulose
cellulosenanocrystals
nanocrystalscompounded
compoundedwith
withstarch-based
starch-based
hydrogel[130].
hydrogel [130].

3.6. Other Hydrogel Systems

Interpenetrating polymer network (IPN) hydrogels based on starch represent a promis-
ing class of materials that combine the biodegradability and biocompatibility of starch
with the mechanical properties and functional versatility of synthetic polymers. These
hydrogels are formed by the simultaneous or sequential polymerization of starch with
one or more synthetic polymers, resulting in a network structure where both components
Molecules 2024, 29, 4835 14 of 26

are interwoven. This interpenetration enhances the overall performance of the hydrogel,
rendering it appropriate for SRFs. Vudjung et al. explored the synthesis of crosslinked
natural rubber and cassava starch hydrogels through the IPN method [134]. This approach
aimed to enhance mechanical strength and compatibility by integrating multiple network
polymers. These hydrogels demonstrated high water swelling capabilities and favorable
biodegradation properties. However, the rigid nature of the final product precluded its
application as a coating on urea bead surfaces. To mitigate this issue, they sought to inno-
vate it by developing a novel coating membrane from pre-vulcanized natural rubber (NR)
and starch (St), employing the IPN method with sulfur and glutaraldehyde as crosslinking
agents [135]. The release mechanism of urea in both aqueous and soil environments was
characterized as non-Fickian diffusion, suggesting transport through a porous matrix. The
efficacy of encapsulated urea beads in corn and basil cultivation was significantly superior
to that of native urea beads.
Apart from cellulose, starch can also form complexes with other polysaccharides to
construct an SRF system. Pimsen et al. [136] focused on the creation of SRFs utilizing a nano-
zeolite (NZ) composite incorporated into chitosan (CS)–sago starch (ST)-based biopolymers.
The biopolymer nanocomposite was synthesized through an ionotropic gelation method,
employing sodium tripolyphosphate as the crosslinking agent. The swelling capacity of
the biopolymer nanocomposite notably increased with higher molecular weights of CS
and increased crosslinking durations. The NZ-CS/ST nanocomposite exhibited a release of
64.00% phosphorus and 41.93% urea by the 14th day. Majeed et al. [137] investigated the
impact of lignin concentration on the release and biodegradability of urea-modified tapioca
starch-based enhanced-efficiency fertilizers. They found that incorporating lignin at levels
of 5%, 10%, 15%, and 20% into the starch matrix decreased nutrient release in moist soil.
Furthermore, an increase in lignin content was associated with enhanced biodegradability.
The integration of inorganic fillers into starch-based hydrogel SRFs represents a signif-
icant advancement in agricultural technology, offering multifaceted benefits that enhance
the overall efficacy and sustainability of fertilizer applications. This integration is particu-
larly crucial in modern agriculture, where the need for efficient, environmentally friendly,
and cost-effective fertilization methods is paramount. These fillers serve as potent rein-
forcing agents, significantly bolstering the hydrogel’s resilience against mechanical stress,
including wear and compression [138]. Furthermore, they enhance the hydrogel’s capacity
to retain water, ensuring a robust performance in various applications. Lu et al. [139]
studied a novel slow-release fertilizer characterized by high water retention, designated as
HS-BCF, which was synthesized by integrating hydrotalcite and starch into biochar-based
compound fertilizers (BCFs). The findings indicate that the addition of hydrotalcite and
starch to BCFs enhanced the soil water retention capacity by 5–10%. Over 30 days, the
cumulative leaching amounts of nitrogen, phosphorus, and potassium from HS-BCF in soil
were, at most, 49.4%, 13.3%, and 87.4% of those from BCFs, respectively. Furthermore, hy-
drotalcite was found to bind with phosphorus in HS-BCF, thereby improving the longevity
of phosphorus in the fertilizer. Wei et al. [140] reported on a novel slow-release and water
retention fertilizer through the free radical copolymerization of potato starch, acrylic acid,
acrylamide, and maleic anhydride-modified β-cyclodextrin. This synthesis process was
enhanced by incorporating acid-treated halloysite nanotubes, which were engineered to
expand their internal cavities for optimal urea pre-loading. The addition of these halloysite
nanotubes improved the fertilizer’s release profile, effectively regulating the cumulative
release rate of urea from the slow-release formulation.
Starch-based hydrogels SRFs have been extensively studied, with numerous research
findings presented in Table 1.
Molecules 2024, 29, 4835 15 of 26

Table 1. Summary of starch-based SRF hydrogels.

Starch/Additives Fertilizer Modification Performance References

In water: hydrogel wax coated
urea (BHWCU) <60% within
Cassava 24 h, in 7 days, 89.1%, 68.6%,
CSt-g-PAA networks and
starch–PAA/natural Urea and 41.5% in BHWCU/2:8, [141]
linear NR/PVA blends
rubber/PVA BHWCU/6:4, and BHWCU/9:1
formulations. In soil: hydrogel
wax coated urea <68% in 20 days
Crosslinking of cassava starch Uncoated urea released 100%
Cassava starch-g-
Urea and acrylonitrile using MBA after 28 days in soil, coated urea [15]
poly(acrylonitrile)
applied as a coating 70% in 108 days
Corn starch–Poly Diammonium Crosslinking of starch, AA, 60% N release during 30 days
[142]
(AA-co-AM) phosphate and AM using MBA in soil
High-amylose maize starch
High-amylose maize graft copolymerization with
The release percentages of KNO3
starch-g-poly(sodium disodium maleate, using
Potassium and KH2 PO4 were between 92 [143]
acid maleate-disodium KMnO4 -NaHSO3 redox
and 67% and 89 and 61% in 320 h
maleate) system, and covalently
crosslinked with MBA
Urea released from hydrogels
DMSt1, DMSt2, and DMSt3 after
Poly (N, Crosslinking of starch, N,
14,000 min was found as 80.2%,
N-dimethylacrylamide Urea N-dimethylacrylamide, and [144]
45.5%, and 67.7% in well water
–maleic acid)–starch maleic acid using MBA
and 81.5%, 46.6%, and 68.9%
in tap water
Sodium alginate and
Sodium alginate– carboxymethyl starch sodium
carboxymethyl starch were compounded, and
Urea In soil: >25 days [145]
sodium– polydopamine (PDA) film was
polydopamine formed on its surface by
self-polymerization
Corn starch–castor oil Starch–castor oil
Nitrogen-controlled release
superabsorbent– Urea SAP–polyurethane-coated urea [146]
period of 60–150 days in water
polyurethane in smooth rotating drum
In water: 61.6% within 10 h and
Starch Starch carbamate and sodium almost completely release >16 h.
carbamate–sodium Urea alginate through cationic ion In soil: 58.5% of urea released [147]
alginate–SRF crosslinking within 25 days and exceeded
50 days for complete release
Stearic acid as inner coating In water: 50.3% within 15 h,
Starch phosphate layer and starch phosphate nearly complete release over
carbamate–PVA– Urea carbamate–PVA film 25 h. In soil: 46.6% was released [148]
stearic acid crosslinked with citric acid as within 20 d, extending to
external layer approximately 30 d
Crosslinking of starch and 63.71% N release during
Chitosan–starch Urea [149]
chitosan using glutaraldehyde seven days in soil

4. Release Mechanisms and Kinetics

4.1. Release Mechanisms
The release of nutrients from SRF hydrogels is a complex, multi-stage process involving
various mechanisms. A comprehensive understanding of these mechanisms is essential
for optimizing the design and application of hydrogels in agriculture. Nutrient release
typically follows three distinct phases, the lag phase, the constant release phase, and the
decay period, each contributing uniquely to the overall release dynamics [150]. During
Molecules 2024, 29, 4835 16 of 26

the lag phase, the hydrogel absorbs water from the surrounding environment, initiating
the swelling process. This initial stage is characterized by minimal nutrient release, as the
hydrogel primarily undergoes hydration and expansion. Following this is the constant
release stage, during which the hydrogel reaches an equilibrium state, and nutrients are
steadily released. This stage is driven by the diffusion of nutrients through the polymer
matrix and the continued hydration and expansion of polymer chains. The decay phase
occurs when the release rate of nutrients begins to decline, typically due to the depletion of
available nutrients within the hydrogel or changes in environmental conditions.
Release mechanisms involve multiple processes, including diffusion through the
polymer and the hydration, expansion, and dissolution of polymer chains [151–153]. Dif-
fusion through the polymer matrix is critical, enabling nutrients to diffuse from higher to
lower concentration regions. This process is influenced by the polymer network, nutrient
molecule size, and the crosslinking degree. The hydration and expansion of polymer chains
also play an essential role. As the hydrogel absorbs water, the polymer swells, creating
additional space within the polymer matrix, which facilitates nutrient movement and
release into the environment. The degree of swelling depends on factors like polymer
hydrophilicity, crosslinking, and environmental conditions such as ionic strength and pH.
Polymers with higher hydrophilicity and lower crosslinking density tend to exhibit greater
swelling, enhancing nutrient release.
Various kinetic models have been developed to understand how swelling impacts
nutrient release [154,155]. Swelling behavior occurs in two stages: an initial rapid swelling
phase, followed by a gradual and slower swelling phase. In the initial phase, water rapidly
penetrates the hydrogel’s porous matrix, driven by the polymer’s hydrophilic nature. In the
gradual swelling phase, water penetrates the pores induced by the relaxation of polymer
chains. This process is slower and more protracted, reflecting the gradual uptake of water
and the continued expansion of the polymer matrix. Polymers with higher hydrophilicity
and lower crosslinking tend to exhibit more rapid swelling, while higher crosslinking
density and lower hydrophilicity result in slower, more gradual swelling.
Environmental factors, such as temperature, pH, and ionic strength, significantly
affect swelling and, consequently, nutrient release. For instance, higher temperatures
enhance the diffusion of water into the hydrogel matrix, speeding up swelling and nutrient
delivery. Changes in pH can affect the ionization of functional groups, altering the swelling
behavior of the hydrogel. Ionic strength can affect osmotic pressure, which drives water
absorption [156,157]. Dudu et al. [144] synthesized a novel superabsorbent based on
N,N-dimethylacrylamide, maleic acid (MA), and starch (St), designated as DMSt1 , and
evaluated its performance as a controlled-release fertilizer in lettuce cultivation. They
subjected DMSt1 to surface modifications using HCl and NaOH, resulting in negatively
and positively charged variants, DMSt2 and DMSt3 , respectively. The latter exhibited
the highest maximum swelling rate of 37.38% in deionized water. The acid and base
treatments altered the anionic and cationic properties of DMSt1 , leading to distinct swelling
behaviors at varying pH levels. The hydrogels derived from DMSt1 , DMSt2 , and DMSt3
demonstrated remarkable water uptake capacities, with equilibrium swelling values of
7163.7% at pH 10, 15708% at pH 10, and 27838% at pH 8, respectively. de Lima et al. [158]
developed a hydrogel through the copolymerization of cassava gum and polyacrylamide.
The hydrogel exhibited the maximum swelling at pH 7, absorbing approximately 270 times
its initial mass. At pHs 4 and 2, the swelling capacity decreased to 150 and 250 times,
respectively. This reduction in swelling at lower pH values is attributed to the protonation
of carboxylate anions, which diminishes repulsive forces and impedes swelling. In more
alkaline environments, the swelling percentage also decreased, reaching 100 at pH 10. This
phenomenon is explained by the “charge shielding effect”, which weakens electrostatic
interactions, as excess Na+ ions hinder the formation of simple COO bonds, a consequence
of the hydrolysis process. Al Rohily et al. [159] investigated the swelling properties of
fertilizer materials derived from phosphorylated alginate grafted with polyacrylamide
(PAM). They found that the degree of crosslinking and the presence of pendant ionic
Molecules 2024, 29, 4835 17 of 26

groups within the polymer matrix significantly influence the swelling behavior. In these
hydrogels, ionic charges play a key role, as the repulsion between adjacent fixed charges
causes network expansion and subsequent swelling. Shang et al. [154] used the Korsmeyer–
Peppas and pseudo-second-order kinetic models to analyze the swelling characteristics of
temperature-responsive hydrogels, concluding that water transport is primarily governed
by Fickian diffusion and polymer chain relaxation.
Overall, the release of nutrients from SRF hydrogels involves a combination of dif-
fusion, swelling and deswelling, chemical degradation, mechanical stress, ion exchange,
and temperature effects. These mechanisms work synergistically to provide a controlled
and sustained release of nutrients to plants, enhancing nutrient use efficiency and promot-
ing plant growth. A clear understanding of these mechanisms and their interaction with
environmental factors is essential for designing effective hydrogel-based fertilizers.

4.2. Kinetic Models

The development of release kinetic models for fertilizers plays a critical role in agri-
cultural science, particularly optimizing nutrient delivery to plants. These models are
essential for understanding and predicting the behavior of fertilizers under various envi-
ronmental conditions, aiding in maximizing crop yields while minimizing environmental
impact. Quantitative analysis is vital for developing these models because nutrient release
is dynamic—fertilizers do not release nutrients at a constant rate. Instead, the release
rate can vary significantly depending on factors such as temperature, moisture, and soil
biological activity. Quantitative analysis allows for the measurement of these variables over
time, providing data that can be used to construct mathematical models that accurately
predict nutrient release patterns. For instance, the type of fertilizer, whether a conven-
tional, slow-release, or controlled-release formulation, significantly impacts the release
kinetics. Given the variability in nutrient release mechanisms among various types of SRFs
and the intricate interplay of factors such as composition, soil moisture, and temperature,
the release mechanisms of SRFs cannot be simply characterized. Typically, four primary
mathematical models are employed to elucidate these mechanisms: the zero-order, first-
order, Korsmeyer–Peppas, and Higuchi kinetic models can be represented by the following
equations (Equations (1)–(4), respectively):

Zero-order model: Mt /M∞ = k0 t (1)

First-order model: Mt /M∞ = 1 − e(−k1 t) (2)

Korsmeyer–Peppas model: Mt /M∞ = ktn (3)
Higuchi model: Mt /M∞ = kH t1/2 (4)
Specifically, the parameter Mt /M∞ denotes the percentage of fertilizer released from
the hydrogel at a specific time t. The constants k0 , k1 , kH , and k represent the release
constants for the zero-order, first-order, Higuchi, and Korsmeyer–Peppas models, respec-
tively. The release mechanisms are classified according to the diffusion index (n) as fol-
lows: (1) Fickian diffusion mechanism: n < 0.43; (2) non-Fickian diffusion mechanism:
0.43 < n < 0.85; and (3) Case-II transport mechanism: n > 0.85 [129].
Indeed, the slow-release model of the SRF hydrogel exhibits variation across different
stages. Shaghaleh et al. [160] developed an aminated cellulose nanofiber (A-CNF) fertilizer
hydrogel by encapsulating ammonium nitrate (AN) within the A-CNF matrix. During the
initial phase, the hydrogel demonstrated rapid AN release within the first 72 h, conforming
to a first-order kinetic model (k1 = 0.068–0.0575). This phase involved the swelling of A-
CNF when exposed to buffer or soil media, where pH levels influenced AN diffusion. In the
subsequent phase, spanning 144 to 504 h, the hydrogel followed a zero-order kinetic mecha-
nism, demonstrating a controlled release with a lower AN release rate (k0 = 0.0023–0.0027).
The final release phase, occurring between 720 and 1540 h, involved the degradation of the
hydrogel’s polymeric network, particularly in soil conditions. This degradation resulted
Molecules 2024, 29, 4835 18 of 26

in the breakdown of A-CNFs and the formation of oligomeric fragments, enlarging the
pore structure and enhancing AN release, which was previously restricted within the dense
hydrogel matrix. This stage followed the Higuchi model, with an increased release rate
(kH = 0.0281–0.0268). Notably, soil properties significantly moderated the AN release rates
across all stages and pH levels, compared to buffer media, leading to a more consistent and
stable AN release profile.
Water permeation and the subsequent chain relaxation in hydrogels are pivotal in
determining swelling dynamics and nutrient release kinetics. Tanan et al. [141] developed
biodegradable semi-IPN hydrogels composed of cassava starch (CSt)-g-PAA, natural rubber
(NR), and PVA. Urea release in both aqueous and soil environments conformed to the
Korsmeyer–Peppas model. When NR content was ≤50%, the behavior was non-Fickian,
with both water diffusion and polymer chain relaxation governing the swelling process.
When NR content exceeded 50%, diffusion was pseudo-Fickian (n < 0.5), indicating that
hydrophobicity rather than chain relaxation primarily controlled water penetration, leading
to a lower equilibrium swelling ratio (Seq ). These findings show that Seq and n values can
be adjusted by altering the NR/PVA ratio to meet specific application needs. Chamorro
et al. [161] prepared cassava starch hydrogels in an aqueous environment. Upon swelling,
the polymer matrix undergoes macromolecular relaxation, transitioning to a rubbery state
that typically allows for solute diffusion into the surrounding aqueous phase. However, if
the rate of water penetration is significantly lower than the polymer chain relaxation rate,
the diffusion is characterized as “less Fickian” with an “n” value less than 0.5, although
it remains within the Fickian classification. The release kinetics of potassium followed
a less Fickian diffusion pattern, suggesting that its release is predominantly governed
by the water intake rate, which promotes swift diffusion through the hydrogel’s rubbery
matrix. Nitrogen release, on the other hand, was influenced by the hydrogel’s high fluidity,
which facilitated water permeation into the biopolymer network. The release kinetic
models mentioned above are the most widely used in the study of hydrogel SRFs, but
due to the complexity of the fertilizer release process, other kinetic models have been
studied and applied, such as the Peppas–Sahlin, Hixson–Crowell, and Ritger–Peppas
models [150,158,162,163].
In conclusion, release kinetic models are indispensable tools in agricultural science.
They provide a quantitative framework for understanding and predicting fertilizer behav-
ior, which is crucial for optimizing nutrient delivery to plants and ensuring sustainable
agricultural practices. By combining quantitative analysis with mathematical and geomet-
rical models, researchers can develop more effective and environmentally friendly fertilizer
formulations, ultimately leading to healthier plants and higher crop yields

5. Conclusions and Future Directions

In the pursuit of sustainable agricultural practices, the development of controlled-
release fertilizers (CRFs) and smart fertilizers has garnered significant attention. These
innovative fertilizers are designed to optimize nutrient delivery to crops in a manner
that closely aligns with their growth requirements, thereby enhancing plant health and
productivity while minimizing environmental impacts. The use of eco-friendly starch
hydrogels in the formulation of these fertilizers not only aids in slow-release mechanisms
but also contributes to improved water retention in soil, a critical factor in arid and semi-
arid regions where water scarcity is a pressing issue. Starch hydrogels, derived from
renewable plant sources, offer a biodegradable and environmentally friendly alternative
to traditional synthetic polymers used in fertilizer encapsulation. These hydrogels can
be engineered to have varying degrees of permeability, allowing for precise control over
the release of nutrients into soil. The incorporation of starch hydrogels into fertilizer
formulations can significantly reduce the initial burst effect commonly associated with
conventional fertilizers, where a large amount of nutrients is released quickly, often leading
to nutrient leaching and runoff.
 newable plant sources, offer a biodegradable and environmentally friendly alternative to
traditional synthetic polymers used in fertilizer encapsulation. These hydrogels can be
engineered to have varying degrees of permeability, allowing for precise control over the
release of nutrients into soil. The incorporation of starch hydrogels into fertilizer formu-
Molecules 2024, 29, 4835 lations can significantly reduce the initial burst effect commonly associated with conven- 19 of 26
tional fertilizers, where a large amount of nutrients is released quickly, often leading to
nutrient leaching and runoff.
Figure
Figure1111provides
providesaaschematic
schematicdepiction
depictionofofplant
plantgrowth
growthin inrelation
relationto
tothe
therelease
releaseof of
fertilizer,
fertilizer,highlighting
highlightingthethediscrepancy
discrepancybetween
betweenthetheconventional
conventionalratesratesof
offertilizer
fertilizerrelease
release
and
andthethenutrient
nutrientrequirements
requirementsof ofplants
plants[164,165].
[164,165].Corn,
Corn,for forinstance,
instance,undergoes
undergoesdistinct
distinct
growth
growth phases, sowing, seedling, tasseling, and grain filling, each withvarying
phases, sowing, seedling, tasseling, and grain filling, each with varyingnutrient
nutrient
demands.
demands. Traditional
Traditional fertilizers
fertilizers like
like urea,
urea, due
due to
to their
their high
high solubility,
solubility,release
releasenutrients
nutrients
rapidly,
rapidly, often at times when the plant requires them the least. This mismatchcan
often at times when the plant requires them the least. This mismatch canlead
leadto to
inefficiencies
inefficienciesininnutrient
nutrientutilization
utilizationandandpotential
potentialenvironmental
environmentalharm. harm.

Figure11.
Figure 11.Schematic
Schematicrepresentation
representationof ofplant
plantgrowth
growthvs.
vs.released
releasedfertilizer
fertilizerfor
fordifferent
differentfertilizers:
fertilizers:A:
A:
rawfertilizer;
raw fertilizer;B:B:slow-release
slow-releasefertilizer;
fertilizer;C:
C:controlled
controlledororsmart
smartfertilizer
fertilizer[9].
[9].

Smartfertilizers,
Smart fertilizers,on onthe
theother
otherhand,
hand,arearedesigned
designedto torelease
releasenutrients
nutrientsininaacontrolled
controlled
mannerthat
manner thatmimics
mimicsthe thenatural
naturaluptake
uptakepatterns
patternsof ofplants.
plants.By Byadjusting
adjustingthethecomposition
composition
andstructure
and structureofofstarch
starch hydrogels,
hydrogels, researchers
researchers cancan modulate
modulate the the release
release kinetics
kinetics of nutri-
of nutrients,
ents, ensuring
ensuring that
that they arethey are available
available to the
to the plant plant
when when This
needed. needed. This approach
approach not only
not only enhances
crop yieldscrop
enhances but also
yieldsreduces thereduces
but also overall amount of fertilizer
the overall amount required, making
of fertilizer agriculture
required, making
more sustainable
agriculture and cost-effective.
more sustainable The potential
and cost-effective. Theof smart fertilizers
potential extends beyond
of smart fertilizers extends
traditional soil-based agriculture to soilless cultures, including hydroponics and aeroponics.
In these systems, precise control over nutrient delivery is crucial for maintaining optimal
plant growth conditions. Starch hydrogels can be adapted for use in nutrient reservoirs,
providing a steady and controlled release of nutrients directly to plant roots. This appli-
cation can lead to more efficient nutrient use and reduced waste, further supporting the
sustainability of soilless cultivation methods.
Despite promising developments in the field of smart fertilizers, several challenges
remain. The development of truly responsive fertilizers that can adapt to changing envi-
ronmental conditions and plant needs is still in its infancy. Future research should focus on
integrating advanced sensing technologies with fertilizer formulations to create fertilizers
that can dynamically adjust their release rates based on real-time data on soil conditions,
weather patterns, and plant health. Moreover, the commercialization of these advanced
fertilizers requires a careful consideration of cost-effectiveness and scalability. While the
benefits of using starch hydrogels and other eco-friendly materials are clear, their adoption
will depend on their economic viability compared to traditional fertilizers.
The development of slow-releasing fertilizers with water retention capabilities using
eco-friendly starch hydrogels represents a significant step forward in sustainable agriculture.
By aligning nutrient release with plant growth needs and enhancing soil moisture retention,
these fertilizers can contribute to more efficient and environmentally friendly farming
practices. As research continues to advance, the potential for these smart fertilizers to
revolutionize agriculture and support global food security becomes increasingly evident.
Molecules 2024, 29, 4835 20 of 26

Funding: This research was funded by National Natural Science Foundation of China (No. 22178124),
High-level Talent Research Start-up Project Funding of Henan Academy of Sciences (No. 232018005,
231818017), Joint Fund of Henan Province Science and Technology R&D Program (No. 225200810010,
230618025), Key Scientific and Technological Project of Henan Province (No. 232102230101), and
Fundamental Research Fund of Henan Academy of Sciences (No. 230618025).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Association, I.F. Fertilizer Outlook 2019–2023. In Proceedings of the 87th IFA Annual Conference, Montreal, QC, Canada, 11–13
June 2019.
2. Naz, M.Y.; Sulaiman, S.A. Slow release coating remedy for nitrogen loss from conventional urea: A review. J. Control. Release 2016,
225, 109–120. [CrossRef] [PubMed]
3. Govindasamy, P.; Muthusamy, S.K.; Bagavathiannan, M.; Mowrer, J.; Jagannadham, P.T.; Maity, A.; Halli, H.M.; Sujayananad,
G.K.; Vadivel, R.; Das, T.K.; et al. Nitrogen use efficiency—A key to enhance crop productivity under a changing climate. Front.
Plant Sci. 2023, 14, 1121073. [CrossRef] [PubMed]
4. Gil-Ortiz, R.; Naranjo, M.A.; Ruiz-Navarro, A.; Atares, S.; Garcia, C.; Zotarelli, L.; San Bautista, A.; Vicente, O. Enhanced
Agronomic Efficiency Using a New Controlled-Released, Polymeric-Coated Nitrogen Fertilizer in Rice. Plants 2020, 9, 1183.
[CrossRef]
5. Messiga, A.J.; Dyck, K.; Ronda, K.; van Baar, K.; Haak, D.; Yu, S.; Dorais, M. Nutrients Leaching in Response to Long-Term
Fertigation and Broadcast Nitrogen in Blueberry Production. Plants 2020, 9, 1530. [CrossRef]
6. Li, S.; Chen, G. Contemporary strategies for enhancing nitrogen retention and mitigating nitrous oxide emission in agricultural
soils: Present and future. Environ. Dev. Sustain. 2019, 22, 2703–2741. [CrossRef]
7. Li, T.; Gao, B.; Tong, Z.; Yang, Y.; Li, Y. Chitosan and graphene oxide nanocomposites as coatings for controlled-release fertilizer.
Water Air Soil Pollut. 2019, 230, 1–9. [CrossRef]
8. Wei, X.; Bao, X.; Yu, L.; Liu, H.; Lu, K.; Chen, L.; Bai, L.; Zhou, X.; Li, Z.; Li, W. Correlation Between Gel Strength of Starch-Based
Hydrogel and Slow Release Behavior of Its Embedded Urea. J. Polym. Environ. 2020, 28, 863–870. [CrossRef]
9. Duan, Q.; Jiang, S.; Chen, F.; Li, Z.; Ma, L.; Song, Y.; Yu, X.; Chen, Y.; Liu, H.; Yu, L. Fabrication, evaluation methodologies and
models of slow-release fertilizers: A review. Ind. Crops Prod. 2023, 192, 116075. [CrossRef]
10. Fu, J.; Wang, C.; Chen, X.; Huang, Z.; Chen, D. Classification research and types of slow controlled release fertilizers (SRFs)
used—A review. Commun. Soil Sci. Plant Anal. 2018, 49, 2219–2230. [CrossRef]
11. Kassem, I.; Ablouh, E.-H.; El Bouchtaoui, F.-Z.; Jaouahar, M.; El Achaby, M. Polymer coated slow/controlled release granular
fertilizers: Fundamentals and research trends. Prog. Mater. Sci. 2024, 144, 101269. [CrossRef]
12. Beig, B.; Niazi, M.B.K.; Jahan, Z.; Hussain, A.; Zia, M.H.; Mehran, M.T. Coating materials for slow release of nitrogen from urea
fertilizer: A review. J. Plant Nutr. 2020, 43, 1510–1533. [CrossRef]
13. El Assimi, T.; Blažic, R.; Vidović, E.; Raihane, M.; El Meziane, A.; Baouab, M.H.V.; Khouloud, M.; Beniazza, R.; Kricheldorf, H.;
Lahcini, M. Polylactide/cellulose acetate biocomposites as potential coating membranes for controlled and slow nutrients release
from water-soluble fertilizers. Prog. Org. Coat. 2021, 156, 106255. [CrossRef]
14. Li, H.; Wang, N.; Zhang, L.; Wei, Y.; Zhang, L.; Ma, Y.; Ruso, J.M.; Liu, Z. Engineering and slow-release properties of lignin-based
double-layer coated fertilizer. Polym. Adv. Technol. 2023, 34, 2029–2043. [CrossRef]
15. Jyothi, A.N.; Pillai, S.S.; Aravind, M.; Salim, S.A.; Kuzhivilayil, S.J. Cassava starch-graft-poly (acrylonitrile)-coated urea fertilizer
with sustained release and water retention properties. Adv. Polym. Technol. 2018, 37, 2687–2694. [CrossRef]
16. Meng, W.; Zhang, X.; Zhang, Y.; Zhang, X.; Zhu, W.; Huang, H.; Han, X.; Liu, Y.; Xu, C. Poly (vinyl alcohol)/sodium alginate
polymer membranes as eco-friendly and biodegradable coatings for slow release fertilizers. J. Sci. Food Agric. 2023, 103, 3592–3601.
[CrossRef]
17. Andry, H.; Yamamoto, T.; Irie, T.; Moritani, S.; Inoue, M.; Fujiyama, H. Water retention, hydraulic conductivity of hydrophilic
polymers in sandy soil as affected by temperature and water quality. J. Hydrol. 2009, 373, 177–183. [CrossRef]
18. Burke, D.R.; Akay, G.; Bilsborrow, P.E. Development of novel polymeric materials for agroprocess intensification. J. Appl. Polym.
Sci. 2010, 118, 3292–3299. [CrossRef]
19. Snyder, C.S.; Bruulsema, T.W.; Jensen, T.L.; Fixen, P.E. Review of greenhouse gas emissions from crop production systems and
fertilizer management effects. Agric. Ecosyst. Environ. 2009, 133, 247–266. [CrossRef]
20. Channab, B.-E.; El Idrissi, A.; Zahouily, M.; Essamlali, Y.; White, J.C. Starch-based controlled release fertilizers: A review. Int. J.
Biol. Macromol. 2023, 238, 124075. [CrossRef]
21. Matmin, J.; Ibrahim, S.I.; Mohd Hatta, M.H.; Ricky Marzuki, R.; Jumbri, K.; Nik Malek, N.A.N. Starch-Derived Superabsorbent
Polymer in Remediation of Solid Waste Sludge Based on Water–Polymer Interaction. Polymers 2023, 15, 1471. [CrossRef]
Molecules 2024, 29, 4835 21 of 26

22. Azeem, B.; Elboughdiri, N.; KuShaari, K.; Jamoussi, B.; Ghernaout, D.; Ghareba, S.; Raza, S.; Gasmi, A. Valorization of almond
shells’ lignocellulosic microparticles for controlled release urea production: Interactive effect of process parameters on longevity
and kinetics of nutrient release. J. Coat. Technol. Res. 2021, 19, 643–660. [CrossRef]
23. Azeem, B.; KuShaari, K.; Man, Z.B.; Basit, A.; Thanh, T.H. Review on materials & methods to produce controlled release coated
urea fertilizer. J. Control. Release 2014, 181, 11–21. [CrossRef] [PubMed]
24. Chen, J.; Fan, X.; Zhang, L.; Chen, X.; Sun, S.; Sun, R.C. Research Progress in Lignin-Based Slow/Controlled Release Fertilizer.
ChemSusChem 2020, 13, 4356–4366. [CrossRef] [PubMed]
25. Chen, J.; Lu, S.; Zhang, Z.; Zhao, X.; Li, X.; Ning, P.; Liu, M. Environmentally friendly fertilizers: A review of materials used and
their effects on the environment. Sci. Total Environ. 2018, 613–614, 829–839. [CrossRef] [PubMed]
26. Fertahi, S.; Ilsouk, M.; Zeroual, Y.; Oukarroum, A.; Barakat, A. Recent trends in organic coating based on biopolymers and
biomass for controlled and slow release fertilizers. J. Control. Release 2021, 330, 341–361. [CrossRef]
27. Irfan, S.A.; Razali, R.; KuShaari, K.; Mansor, N.; Azeem, B.; Ford Versypt, A.N. A review of mathematical modeling and simulation
of controlled-release fertilizers. J. Control. Release 2018, 271, 45–54. [CrossRef]
28. Jennett, T.S.; Zheng, Y. Component characterization and predictive modeling for green roof substrates optimized to adsorb P and
improve runoff quality: A review. Environ. Pollut. 2018, 237, 988–999. [CrossRef]
29. Lawrencia, D.; Wong, S.K.; Low, D.Y.S.; Goh, B.H.; Goh, J.K.; Ruktanonchai, U.R.; Soottitantawat, A.; Lee, L.H.; Tang, S.Y.
Controlled release fertilizers: A review on coating materials and mechanism of release. Plants 2021, 10, 238. [CrossRef]
30. Vejan, P.; Khadiran, T.; Abdullah, R.; Ahmad, N. Controlled release fertilizer: A review on developments, applications and
potential in agriculture. J. Control. Release 2021, 339, 321–334. [CrossRef]
31. Wesołowska, M.; Rymarczyk, J.; Góra, R.; Baranowski, P.; Sławiński, C.; Klimczyk, M.; Supryn, G.; Schimmelpfennig, L. New
slow-release fertilizers—Economic, legal and practical aspects: A Review. Int. Agrophys. 2021, 35, 11–24. [CrossRef]
32. Yuan, S.; Cheng, L.; Tan, Z. Characteristics and preparation of oil-coated fertilizers: A review. J. Control. Release 2022, 345, 675–684.
[CrossRef] [PubMed]
33. Madduma-Bandarage, U.S.K.; Madihally, S.V. Synthetic hydrogels: Synthesis, novel trends, and applications. J. Appl. Polym. Sci.
2021, 138, 50376. [CrossRef]
34. Liu, Y.; Zhu, Y.; Mu, B.; Wang, Y.; Quan, Z.; Wang, A. Synthesis, characterization, and swelling behaviors of sodium carboxymethyl
cellulose-g-poly(acrylic acid)/semi-coke superabsorbent. Polym. Bull. 2022, 79, 935–953. [CrossRef]
35. Yang, Y.; Liang, Z.; Zhang, R.; Zhou, S.; Yang, H.; Chen, Y.; Zhang, J.; Yin, H.; Yu, D. Research Advances in Superabsorbent
Polymers. Polymers 2024, 16, 501. [CrossRef] [PubMed]
36. Ma, X.; Wen, G. Development history and synthesis of super-absorbent polymers: A review. J. Polym. Res. 2020, 27, 136. [CrossRef]
37. Manuel, M.; Jennifer, A. A review on starch and cellulose-enhanced superabsorbent hydrogel. J. Chem. Rev. 2023, 5, 183–203.
[CrossRef]
38. Salimi, M.; Channab, B.-E.; El Idrissi, A.; Zahouily, M.; Motamedi, E. A comprehensive review on starch: Structure, modification,
and applications in slow/controlled-release fertilizers in agriculture. Carbohydr. Polym. 2023, 322, 121326. [CrossRef]
39. Qamruzzaman, M.; Ahmed, F.; Mondal, M.I.H. An Overview on Starch-Based Sustainable Hydrogels: Potential Applications and
Aspects. J. Polym. Environ. 2022, 30, 19–50. [CrossRef]
40. Meng, R.; Wu, Z.; Xie, H.-Q.; Xu, G.-X.; Cheng, J.-S.; Zhang, B. Preparation, characterization, and encapsulation capability of the
hydrogel cross-linked by esterified tapioca starch. Int. J. Biol. Macromol. 2020, 155, 1–5. [CrossRef]
41. Haq, F.; Yu, H.; Wang, L.; Teng, L.; Haroon, M.; Khan, R.U.; Mehmood, S.; Bilal Ul, A.; Ullah, R.S.; Khan, A.; et al. Advances in
chemical modifications of starches and their applications. Carbohydr. Res. 2019, 476, 12–35. [CrossRef]
42. Masina, N.; Choonara, Y.E.; Kumar, P.; du Toit, L.C.; Govender, M.; Indermun, S.; Pillay, V. A review of the chemical modification
techniques of starch. Carbohydr. Polym. 2017, 157, 1226–1236. [CrossRef] [PubMed]
43. Dragan, E.S.; Apopei, D.F. Synthesis and swelling behavior of pH-sensitive semi-interpenetrating polymer network composite
hydrogels based on native and modified potatoes starch as potential sorbent for cationic dyes. Chem. Eng. J. 2011, 178, 252–263.
[CrossRef]
44. Kiatkamjornwong, S.; Mongkolsawat, K.; Sonsuk, M. Synthesis and property characterization of cassava starch grafted poly
[acrylamide-co-(maleic acid)] superabsorbent via γ-irradiation. Polymer 2002, 43, 3915–3924. [CrossRef]
45. Czarnecka, E.; Nowaczyk, J. Semi-Natural Superabsorbents Based on Starch-g-poly(acrylic acid): Modification, Synthesis and
Application. Polymers 2020, 12, 1794. [CrossRef] [PubMed]
46. Czarnecka, E.; Nowaczyk, J. Synthesis and Characterization Superabsorbent Polymers Made of Starch, Acrylic Acid, Acrylamide,
Poly(Vinyl Alcohol), 2-Hydroxyethyl Methacrylate, 2-Acrylamido-2-methylpropane Sulfonic Acid. Int. J. Mol. Sci. 2021, 22, 4325.
[CrossRef]
47. Noordergraaf, I.-W.; Witono, J.R.; Heeres, H.J. Grafting Starch with Acrylic Acid and Fenton’s Initiator: The Selectivity Challenge.
Polymers 2024, 16, 255. [CrossRef]
48. Aniagor, C.O.; Afifi, M.A.; Hashem, A. Rapid and efficient uptake of aqueous lead pollutant using starch-based superabsorbent
hydrogel. Polym. Bull. 2022, 79, 6373–6388. [CrossRef]
49. Supare, K.; Mahanwar, P.A. Starch-derived superabsorbent polymers in agriculture applications: An overview. Polym. Bull. 2022,
79, 5795–5824. [CrossRef]
Molecules 2024, 29, 4835 22 of 26

50. Khan, M.A.; Bhattacharia, S.K.; Kader, M.A.; Bahari, K. Preparation and characterization of ultra violet (UV) radiation cured
bio-degradable films of sago starch/PVA blend. Carbohydr. Polym. 2006, 63, 500–506. [CrossRef]
51. Parvathy, P.C.; Jyothi, A.N. Synthesis, characterization and swelling behaviour of superabsorbent polymers from cassava
starch-graft-poly(acrylamide). Starch Starke 2012, 64, 207–218. [CrossRef]
52. Amiri, F.; Kabiri, K.; Bouhendi, H.; Abdollahi, H.; Najafi, V.; Karami, Z. High gel-strength hybrid hydrogels based on modified
starch through surface cross-linking technique. Polym. Bull. 2019, 76, 4047–4068. [CrossRef]
53. Ma, D.; Zhu, B.; Cao, B.; Wang, J.; Zhang, J. The Microstructure and Swelling Properties of Poly Acrylic Acid-Acrylamide Grafted
Starch Hydrogels. J. Macromol. Sci. Part B 2016, 55, 1124–1133. [CrossRef]
54. Zamani-Babgohari, F.; Irannejad, A.; Kalantari Pour, M.; Khayati, G.R. Synthesis of carboxymethyl starch co (polyacrylamide/
polyacrylic acid) hydrogel for removing methylene blue dye from aqueous solution. Int. J. Biol. Macromol. 2024, 269, 132053.
[CrossRef] [PubMed]
55. Bazoubandi, B.; Soares, J.B.P. Amylopectin-graft-polyacrylamide for the flocculation and dewatering of oil sands tailings. Miner.
Eng. 2020, 148, 106196. [CrossRef]
56. Mahmoodi-Babolan, N.; Nematollahzadeh, A.; Heydari, A.; Merikhy, A. Bioinspired catecholamine/starch composites as
superadsorbent for the environmental remediation. Int. J. Biol. Macromol. 2019, 125, 690–699. [CrossRef]
57. Zhang, Q.; Wang, Z.; Zhang, C.; Aluko, R.E.; Yuan, J.; Ju, X.; He, R. Structural and functional characterization of rice starch-based
superabsorbent polymer materials. Int. J. Biol. Macromol. 2020, 153, 1291–1298. [CrossRef]
58. Siyamak, S.; Laycock, B.; Luckman, P. Synthesis of starch graft-copolymers via reactive extrusion and their ammonium sorption
properties. Chem. Eng. J. 2020, 398, 124291. [CrossRef]
59. Zou, W.; Yu, L.; Liu, X.; Chen, L.; Zhang, X.; Qiao, D.; Zhang, R. Effects of amylose/amylopectin ratio on starch-based
superabsorbent polymers. Carbohydr. Polym. 2012, 87, 1583–1588. [CrossRef]
60. Bao, X.; Yu, L.; Simon, G.P.; Shen, S.; Xie, F.; Liu, H.; Chen, L.; Zhong, L. Rheokinetics of graft copolymerization of acrylamide
in concentrated starch and rheological behaviors and microstructures of reaction products. Carbohydr. Polym. 2018, 192, 1–9.
[CrossRef]
61. Bao, X.; Yu, L.; Shen, S.; Simon, G.P.; Liu, H.; Chen, L. How rheological behaviors of concentrated starch affect graft copolymeriza-
tion of acrylamide and resultant hydrogel. Carbohydr. Polym. 2019, 219, 395–404. [CrossRef]
62. Sethi, S.; Saruchi; Medha; Thakur, S.; Kaith, B.S.; Sharma, N.; Ansar, S.; Pandey, S.; Kuma, V. Biopolymer starch-gelatin embedded
with silver nanoparticle–based hydrogel composites for antibacterial application. Biomass Convers. Biorefinery 2022, 12, 5363–5384.
[CrossRef]
63. Motamedi, E.; Motesharezedeh, B.; Shirinfekr, A.; Samar, S.M. Synthesis and swelling behavior of environmentally friendly
starch-based superabsorbent hydrogels reinforced with natural char nano/micro particles. J. Environ. Chem. Eng. 2020, 8, 103583.
[CrossRef]
64. Olad, A.; Doustdar, F.; Gharekhani, H. Fabrication and characterization of a starch-based superabsorbent hydrogel composite
reinforced with cellulose nanocrystals from potato peel waste. Colloids Surf. A 2020, 601, 124962. [CrossRef]
65. Li, A.; Zhang, J.; Wang, A. Utilization of starch and clay for the preparation of superabsorbent composite. Bioresour. Technol. 2007,
98, 327–332. [CrossRef]
66. Mahmoud, G.A.; Abdel-Aal, S.E.; Badway, N.A.; Abo Farha, S.A.; Alshafei, E.A. Radiation synthesis and characterization of
starch-based hydrogels for removal of acid dye. Starch Stärke 2014, 66, 400–408. [CrossRef]
67. Relleve, L.S.; Aranilla, C.T.; Barba, B.J.D.; Gallardo, A.K.R.; Cruz, V.R.C.; Ledesma, C.R.M.; Nagasawa, N.; Abad, L.V. Radiation-
synthesized polysaccharides/polyacrylate super water absorbents and their biodegradabilities. Radiat. Phys. Chem. 2020, 170,
108618. [CrossRef]
68. Yoshii, F.; Zhao, L.; Wach, R.A.; Nagasawa, N.; Mitomo, H.; Kume, T. Hydrogels of polysaccharide derivatives crosslinked with
irradiation at paste-like condition. Nucl. Instrum. Methods Phys. Res. Sect. B 2003, 208, 320–324. [CrossRef]
69. Zhai, M.; Yoshii, F.; Kume, T.; Hashim, K. Syntheses of PVA/starch grafted hydrogels by irradiation. Carbohydr. Polym. 2002, 50,
295–303. [CrossRef]
70. Saif, M.J.; Naveed, M.; Asif, H.M.; Akhtar, R. Irradiation applications for polymer nano-composites: A state-of-the-art review.
J. Ind. Eng. Chem. 2018, 60, 218–236. [CrossRef]
71. Goganian, A.M.; Hamishehkar, H.; Arsalani, N.; Khiabani, H.K. Microwave-Promoted Synthesis of Smart Superporous Hydrogel
for the Development of Gastroretentive Drug Delivery System. Adv. Polym. Technol. 2015, 34, 21490. [CrossRef]
72. Naikwadi, A.T.; Sharma, B.K.; Bhatt, K.D.; Mahanwar, P.A. Gamma Radiation Processed Polymeric Materials for High Performance
Applications: A Review. Front. Chem. 2022, 10, 837111. [CrossRef] [PubMed]
73. Abd El-Rehim, H.; Hegazy, E.-S.A.; Diaa, D. Radiation synthesis of eco-friendly water reducing sulfonated starch/acrylic acid
hydrogel designed for cement industry. Radiat. Phys. Chem. 2013, 85, 139–146. [CrossRef]
74. Sapuła, P.; Bialik-Was,
˛ K.; Malarz, K. Are Natural Compounds a Promising Alternative to Synthetic Cross-Linking Agents in the
Preparation of Hydrogels? Pharmaceutics 2023, 15, 253. [CrossRef]
75. Braşoveanu, M.; Nemţanu, M.R.; Duţă, D. Electron-beam processed corn starch: Evaluation of physicochemical and structural
properties and technical-economic aspects of the processing. Braz. J. Chem. Eng. 2013, 30, 847–856. [CrossRef]
76. Bashir, K.; Aggarwal, M. Physicochemical, structural and functional properties of native and irradiated starch: A review. J. Food
Sci. Technol. 2019, 56, 513–523. [CrossRef]
Molecules 2024, 29, 4835 23 of 26

77. Sánchez-Moreno, V.E.; Sandoval-Pauker, C.; Aldas, M.; Ciobotă, V.; Luna, M.; Vargas Jentzsch, P.; Muñoz Bisesti, F. Synthesis
of inulin hydrogels by electron beam irradiation: Physical, vibrational spectroscopic and thermal characterization and arsenic
removal as a possible application. J. Polym. Res. 2020, 27, 184. [CrossRef]
78. More, A.P.; Chapekar, S. Irradiation assisted synthesis of hydrogel: A Review. Polym. Bull. 2024, 81, 5839–5908. [CrossRef]
79. Moghaddam, R.H.; Dadfarnia, S.; Shabani, A.M.H.; Moghaddam, Z.H.; Tavakol, M. Electron beam irradiation synthesis of porous
and non-porous pectin based hydrogels for a tetracycline drug delivery system. Mater. Sci. Eng. C 2019, 102, 391–404. [CrossRef]
80. Abd El-Mohdy, H.L.; Hegazy, E.A.; El-Nesr, E.M.; El-Wahab, M.A. Synthesis, characterization and properties of radiation-induced
Starch/(EG-co-MAA) hydrogels. Arab. J. Chem. 2016, 9, S1627–S1635. [CrossRef]
81. Bhuyan, M.M.; Chandra Dafader, N.; Hara, K.; Okabe, H.; Hidaka, Y.; Rahman, M.M.; Mizanur Rahman Khan, M.; Rahman, N.
Synthesis of Potato Starch-Acrylic-Acid Hydrogels by Gamma Radiation and Their Application in Dye Adsorption. Int. J. Polym.
Sci. 2016, 2016, 9867859. [CrossRef]
82. Chen, F.; Miao, C.; Duan, Q.; Jiang, S.; Liu, H.; Ma, L.; Li, Z.; Bao, X.; Lan, B.; Chen, L.; et al. Developing slow release fertilizer
through in-situ radiation-synthesis of urea-embedded starch-based hydrogels. Ind. Crops Prod. 2023, 191, 115971. [CrossRef]
83. Fekete, T.; Borsa, J.; Takács, E.; Wojnárovits, L. Synthesis of carboxymethylcellulose/starch superabsorbent hydrogels by gamma-
irradiation. Chem. Cent. J. 2017, 11, 46. [CrossRef] [PubMed]
84. Finkenstadt, V.L.; Willett, J.L. Reactive Extrusion of Starch-Polyacrylamide Graft Copolymers: Effects of Monomer/Starch Ratio
and Moisture Content. Macromol. Chem. Phys. 2005, 206, 1648–1652. [CrossRef]
85. Willett, J.L.; Finkenstadt, V.L. Initiator effects in reactive extrusion of starch-polyacrylamide graft copolymers. J. Appl. Polym. Sci.
2006, 99, 52–58. [CrossRef]
86. Willett, J.L.; Finkenstadt, V.L. Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers Using Various Starches. J. Polym.
Environ. 2006, 14, 125–129. [CrossRef]
87. Willett, J.L.; Finkenstadt, V.L. Comparison of Cationic and Unmodified Starches in Reactive Extrusion of Starch–Polyacrylamide
Graft Copolymers. J. Appl. Polym. Sci. 2009, 17, 248–253. [CrossRef]
88. Willett, J.L.; Finkenstadt, V.L. Starch-poly (acrylamide-co-2-acrylamido-2-methylpropanesulfonic acid) graft copolymers prepared
by reactive extrusion. J. Appl. Polym. Sci. 2015, 132, 42405. [CrossRef]
89. Li, T.-T.; Feng, L.-F.; Gu, X.-P.; Zhang, C.-L.; Wang, P.; Hu, G.-H. Intensification of Polymerization Processes by Reactive Extrusion.
Ind. Eng. Chem. Res. 2021, 60, 2791–2806. [CrossRef]
90. Liu, H.; Xie, F.; Yu, L.; Chen, L.; Li, L. Thermal processing of starch-based polymers. Prog. Polym. Sci. 2009, 34, 1348–1368.
[CrossRef]
91. McGauran, T.; Harris, M.; Dunne, N.; Smyth, B.M.; Cunningham, E. Development and optimisation of extruded bio-based
polymers from poultry feathers. Eur. Polym. J. 2021, 158, 110678. [CrossRef]
92. Moad, G. Chemical modification of starch by reactive extrusion. Prog. Polym. Sci. 2011, 36, 218–237. [CrossRef]
93. Xie, F.; Yu, L.; Liu, H.; Chen, L. Starch Modification Using Reactive Extrusion. Starch Starke 2006, 58, 131–139. [CrossRef]
94. Xu, E.; Campanella, O.H.; Ye, X.; Jin, Z.; Liu, D.; BeMiller, J.N. Advances in conversion of natural biopolymers: A reactive
extrusion (REX)–enzyme-combined strategy for starch/protein-based food processing. Trends Food Sci. Technol. 2020, 99, 167–180.
[CrossRef]
95. Siyamak, S.; Laycock, B.; Luckman, P. Synthesis of starch graft-copolymers via reactive extrusion: Process development and
structural analysis. Carbohydr. Polym. 2020, 227, 115066. [CrossRef]
96. Zhuang, Y.; Saadatkhah, N.; Morgani, M.S.; Xu, T.; Martin, C.; Patience, G.S.; Ajji, A. Experimental methods in chemical
engineering: Reactive extrusion. Can. J. Chem. Eng. 2023, 101, 59–77. [CrossRef]
97. Jiang, T.; Chen, F.; Duan, Q.; Bao, X.; Jiang, S.; Liu, H.; Chen, L.; Yu, L. Designing and application of reactive extrusion with twice
initiations for graft copolymerization of acrylamide on starch. Eur. Polym. J. 2022, 165, 111008. [CrossRef]
98. McKenna, G.B. Deformation and flow of matter: Interrogating the physics of materials using rheological methods. J. Rheol. 2012,
56, 113–158. [CrossRef]
99. Serrero, A.; Trombotto, S.; Cassagnau, P.; Bayon, Y.; Gravagna, P.; Montanari, S.; David, L. Polysaccharide Gels Based on Chitosan
and Modified Starch: Structural Characterization and Linear Viscoelastic Behavior. Biomacromolecules 2010, 11, 1534–1543.
[CrossRef]
100. Stojkov, G.; Niyazov, Z.; Picchioni, F.; Bose, R.K. Relationship between Structure and Rheology of Hydrogels for Various
Applications. Gels 2021, 7, 255. [CrossRef]
101. Narita, T.; Mayumi, K.; Ducouret, G.; Hébraud, P. Viscoelastic properties of poly (vinyl alcohol) hydrogels having permanent
and transient cross-links studied by microrheology, classical rheometry, and dynamic light scattering. Macromolecules 2013, 46,
4174–4183. [CrossRef]
102. Kavanagh, G.M.; Ross-Murphy, S.B. Rheological characterisation of polymer gels. Prog. Polym. Sci. 1998, 23, 533–562. [CrossRef]
103. Wetton, R.E.; Marsh, R.D.L.; Van-de-Velde, J.G. Theory and application of dynamic mechanical thermal analysis. Thermochim.
Acta 1991, 175, 1–11. [CrossRef]
104. Sha, H.; Zhang, X.; Harrison, I.R. A dynamic mechanical thermal analysis (DMTA) study of polyethylenes. Thermochim. Acta 1991,
192, 233–242. [CrossRef]
105. Badia, J.-D.; Santonja-Blasco, L.; Martínez-Felipe, A.; Ribes-Greus, A. Dynamic Mechanical Thermal Analysis of Polymer Blends.
In Characterization of Polymer Blends; Wiley: Hoboken, NJ, USA, 2014; pp. 365–392.
Molecules 2024, 29, 4835 24 of 26

106. Ramli, R.A. Slow release fertilizer hydrogels: A review. Polym. Chem. 2019, 10, 6073–6090. [CrossRef]
107. Kalita, A.; Elayarajan, M.; Janaki, P.; Suganya, S.; Sankari, A.; Parameswari, E. Organo-monomers coated slow-release fertilizers:
Current understanding and future prospects. Int. J. Biol. Macromol. 2024, 274, 133320. [CrossRef]
108. Wang, X.; Yang, Y.; Zhong, S.; Meng, Q.; Li, Y.; Wang, J.; Gao, Y.; Cui, X. Advances in controlled-release fertilizer encapsulated by
organic-inorganic composite membranes. Particuology 2024, 84, 236–248. [CrossRef]
109. Ahmed Khan, T.; Zakaria, M.E.T.; Kim, H.J.; Ghazali, S.; Jamari, S.S. Carbonaceous microsphere-based superabsorbent polymer as
filler for coating of NPK fertilizer: Fabrication, properties, swelling, and nitrogen release characteristics. J. Appl. Polym. Sci. 2020,
137, 48396. [CrossRef]
110. Chen, L.; Xie, Z.; Zhuang, X.; Chen, X.; Jing, X. Controlled release of urea encapsulated by starch-g-poly(l-lactide). Carbohydr.
Polym. 2008, 72, 342–348. [CrossRef]
111. Zafar, N.; Niazi, M.B.K.; Sher, F.; Khalid, U.; Jahan, Z.; Shah, G.A.; Zia, M. Starch and polyvinyl alcohol encapsulated biodegradable
nanocomposites for environment friendly slow release of urea fertilizer. Chem. Eng. J. Adv. 2021, 7, 100123. [CrossRef]
112. Boetje, L.; Lan, X.; Silvianti, F.; van Dijken, J.; Polhuis, M.; Loos, K. A more efficient synthesis and properties of saturated and
unsaturated starch esters. Carbohydr. Polym. 2022, 292, 119649. [CrossRef]
113. Salimi, M.; Motamedi, E.; Safari, M.; Motesharezadeh, B. Synthesis of urea slow-release fertilizer using a novel starch-g-poly
(styrene-co-butylacrylate) nanocomposite latex and its impact on a model crop production in greenhouse. J. Cleaner Prod. 2021,
322, 129082. [CrossRef]
114. Qiao, D.; Liu, H.; Yu, L.; Bao, X.; Simon, G.P.; Petinakis, E.; Chen, L. Preparation and characterization of slow-release fertilizer
encapsulated by starch-based superabsorbent polymer. Carbohydr. Polym. 2016, 147, 146–154. [CrossRef] [PubMed]
115. Lü, S.; Gao, C.; Wang, X.; Xu, X.; Bai, X.; Gao, N.; Feng, C.; Wei, Y.; Wu, L.; Liu, M. Synthesis of a starch derivative and its
application in fertilizer for slow nutrient release and water-holding. RSC Adv. 2014, 4, 51208–51214. [CrossRef]
116. Sarkar, A.; Biswas, D.R.; Datta, S.C.; Dwivedi, B.S.; Bhattacharyya, R.; Kumar, R.; Bandyopadhyay, K.K.; Saha, M.; Chawla, G.;
Saha, J.K.; et al. Preparation of novel biodegradable starch/poly(vinyl alcohol)/bentonite grafted polymeric films for fertilizer
encapsulation. Carbohydr. Polym. 2021, 259, 117679. [CrossRef]
117. León, O.; Soto, D.; González, J.; Piña, C.; Muñoz-Bonilla, A.; Fernandez-García, M. Environmentally Friendly Fertilizers Based on
Starch Superabsorbents. Materials 2019, 12, 3493. [CrossRef]
118. Perez, J.J.; Francois, N.J. Chitosan-starch beads prepared by ionotropic gelation as potential matrices for controlled release of
fertilizers. Carbohydr. Polym. 2016, 148, 134–142. [CrossRef]
119. Ramírez-Hernández, A.; Aparicio-Saguilán, A.; Mata-Mata, J.L.; González-García, G.; Hernández-Mendoza, H.; Gutiérrez-Fuentes,
A.; Báez-García, E. Chemical modification of banana starch by the in situ polymerization of ϵ-caprolactone in one step. Starch
Starke 2017, 69, 1600197. [CrossRef]
120. Yao, Y.; Shen, Y.; Hu, C.; Wu, H. Superabsorbent fabric: In situ polymerisation of macroporous starch–sodium alginate–
polyacrylate hydrogel on fibre surface. Cellulose 2023, 30, 7113–7128. [CrossRef]
121. Salimi, M.; Motamedi, E.; Motesharezedeh, B.; Hosseini, H.M.; Alikhani, H.A. Starch-g-poly(acrylic acid-co-acrylamide) compos-
ites reinforced with natural char nanoparticles toward environmentally benign slow-release urea fertilizers. J. Environ. Chem. Eng.
2020, 8, 103765. [CrossRef]
122. Bolt, R.R.; Leitch, J.A.; Jones, A.C.; Nicholson, W.I.; Browne, D.L. Continuous flow mechanochemistry: Reactive extrusion as an
enabling technology in organic synthesis. Chem. Soc. Rev. 2022, 51, 4243–4260. [CrossRef]
123. Dong, Q.; Xian, B.; Hong, L.; Xing, L.; Ling, C.; Long, Y.; Xiao, Z.; Pei, C. Preparation of cassava starch-based superabsorbent
polymer using a twin-roll mixer as reactor. Chin. J. Polym. Sci. 2014, 32, 1348–1356. [CrossRef]
124. Qiao, D.; Ma, H.; Yu, L.; Liu, H.; Zou, W.; Chen, L.; Chen, P. Synthesis and characteristics of graft copolymerization of starch-G-
PAM using A twin-roll mixer as reactor for cornstarch with different amylose/amylopectin ratios. Int. Polym. Proc. 2014, 29,
252–259. [CrossRef]
125. Qiao, D.; Tu, W.; Wang, Z.; Yu, L.; Zhang, B.; Bao, X.; Jiang, F.; Lin, Q. Influence of crosslinker amount on the microstructure and
properties of starch-based superabsorbent polymers by one-step preparation at high starch concentration. Int. J. Biol. Macromol.
2019, 129, 679–685. [CrossRef] [PubMed]
126. Xiao, X.; Yu, L.; Xie, F.; Bao, X.; Liu, H.; Ji, Z.; Chen, L. One-step method to prepare starch-based superabsorbent polymer for slow
release of fertilizer. Chem. Eng. J. 2017, 309, 607–616. [CrossRef]
127. Bhaladhare, S.; Das, D. Cellulose: A fascinating biopolymer for hydrogel synthesis. J. Mater. Chem. B 2022, 10, 1923–1945.
[CrossRef]
128. Tan, X.; Lv, Q.; Dong, G.; Zhang, Z.; Chai, D.-f.; Zhao, M.; Zhang, W.; Li, J. Insight into the preparation and improved properties
of cellulose citrate ester hydrogel slow-release fertilizer. Ind. Crops Prod. 2024, 222, 119517. [CrossRef]
129. Li, Z.; Zhang, M. Progress in the preparation of stimulus-responsive cellulose hydrogels and their application in slow-release
fertilizers. Polymers 2023, 15, 3643. [CrossRef]
130. González, K.; Guaresti, O.; Palomares, T.; Alonso-Varona, A.; Eceiza, A.; Gabilondo, N. The role of cellulose nanocrystals in
biocompatible starch-based clicked nanocomposite hydrogels. Int. J. Biol. Macromol. 2020, 143, 265–272. [CrossRef]
131. Moharrami, P.; Motamedi, E. Application of cellulose nanocrystals prepared from agricultural wastes for synthesis of starch-based
hydrogel nanocomposites: Efficient and selective nanoadsorbent for removal of cationic dyes from water. Bioresour. Technol. 2020,
313, 123661. [CrossRef]
Molecules 2024, 29, 4835 25 of 26

132. Bahadoran Baghbadorani, N.; Behzad, T.; Karimi Darvanjooghi, M.H.; Etesami, N. Modelling of water absorption kinetics
and biocompatibility study of synthesized cellulose nanofiber-assisted starch-graft-poly(acrylic acid) hydrogel nanocomposites.
Cellulose 2020, 27, 9927–9945. [CrossRef]
133. Bora, A.; Sarmah, D.; Karak, N. Cellulosic wastepaper modified starch/itaconic acid/acrylic acid-based biodegradable hydrogel
as a sustain release of NPK fertilizer vehicle for agricultural applications. Int. J. Biol. Macromol. 2023, 253, 126555. [CrossRef]
[PubMed]
134. Vudjung, C.; Saengsuwan, S. Synthesis and properties of biodegradable hydrogels based on cross-linked natural rubber and
cassava starch. J. Elastomers Plast. 2017, 49, 574–594. [CrossRef]
135. Vudjung, C.; Saengsuwan, S. Biodegradable IPN hydrogels based on pre-vulcanized natural rubber and cassava starch as coating
membrane for environment-friendly slow-release urea fertilizer. J. Polym. Environ. 2018, 26, 3967–3980. [CrossRef]
136. Pimsen, R.; Porrawatkul, P.; Nuengmatcha, P.; Ramasoot, S.; Chanthai, S. Efficiency enhancement of slow release of fertilizer
using nanozeolite–chitosan/sago starch-based biopolymer composite. J. Coat. Technol. Res. 2021, 18, 1321–1332. [CrossRef]
137. Majeed, Z.; Ramli, N.K.; Binti Mansor, N.; Man, Z. Lignin loading effect on biodegradability and nitrogen release properties of
urea modified tapioca starch in wet soil. Key Eng. Mater. 2014, 594, 798–802. [CrossRef]
138. Abdul Khalil, H.P.S.; Chong, E.W.N.; Owolabi, F.A.T.; Asniza, M.; Tye, Y.Y.; Rizal, S.; Nurul Fazita, M.R.; Mohamad Haafiz, M.K.;
Nurmiati, Z.; Paridah, M.T. Enhancement of basic properties of polysaccharide-based composites with organic and inorganic
fillers: A review. J. Appl. Polym. Sci. 2019, 136, 47251. [CrossRef]
139. Lu, J.; Li, Y.; Cai, Y.; Jiang, P.; Yu, B. Co-incorporation of hydrotalcite and starch into biochar-based fertilizers for the synthesis of
slow-release fertilizers with improved water retention. Biochar 2023, 5, 44. [CrossRef]
140. Wei, H.; Wang, H.; Chu, H.; Li, J. Preparation and characterization of slow-release and water-retention fertilizer based on starch
and halloysite. Int. J. Biol. Macromol. 2019, 133, 1210–1218. [CrossRef]
141. Tanan, W.; Panichpakdee, J.; Suwanakood, P.; Saengsuwan, S. Biodegradable hydrogels of cassava 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. 2021, 101, 237–252. [CrossRef]
142. Jin, S.; Wang, Y.; He, J.; Yang, Y.; Yu, X.; Yue, G. Preparation and properties of a degradable interpenetrating polymer networks
based on starch with water retention, amelioration of soil, and slow release of nitrogen and phosphorus fertilizer. J. Appl. Polym.
Sci. 2013, 128, 407–415. [CrossRef]
143. León, O.; Soto, D.; Muñoz-Bonilla, A.; Fernández-García, M. Amylose Modified Starches as Superabsorbent Systems for Release
of Potassium Fertilizers. J. Polym. Environ. 2022, 30, 2314–2328. [CrossRef]
144. Dudu, T.E.; Alpaslan, D.; Aktas, N. Synthesis of controlled release hydrogels from dimethylacrylamide/maleic acid/starch and
its application in lettuce cultivation. J. Polym. Res. 2022, 29, 524. [CrossRef]
145. Li, Y.; Ma, Y.; Chang, F.; Zhu, H.; Tian, C.; Jia, F.; Ke, Y.; Dai, J. Slow-Release Urea Fertilizer with Water Retention and
Photosensitivity Properties Based on Sodium Alginate/Carboxymethyl Starch Sodium/Polydopamine. Processes 2024, 12, 842.
[CrossRef]
146. Zhao, C.; Tian, H.; Zhang, Q.; Liu, Z.; Zhang, M.; Wang, J. Preparation of urea-containing starch-castor oil superabsorbent
polyurethane coated urea and investigation of controlled nitrogen release. Carbohydr. Polym. 2021, 253, 117240. [CrossRef]
[PubMed]
147. Lv, Q.; Xiao, T.; Dong, G.; Tan, X.; Zhang, Z.; Zhao, M.; Zhu, M.; Li, J.; Zhang, W. Preparation and characterization of starch
carbamate modified natural sodium alginate composite hydrogel blend formulation and its application for slow-release fertilizer.
Int. J. Biol. Macromol. 2024, 278, 134713. [CrossRef]
148. Mu, Z.; Zhang, W.; Chai, D.-f.; Lv, Q.; Tan, X.; Yuan, R.; Dong, G. Preparation and characterization of slow-release urea fertilizer
encapsulated by a blend of starch derivative and polyvinyl alcohol with desirable biodegradability and availability. Int. J. Biol.
Macromol. 2024, 271, 132693. [CrossRef]
149. Ee Huey, C.; Zaireen Nisa Yahya, W.; Mansor, N. Allicin incorporation as urease inhibitor in a chitosan/starch based biopolymer
for fertilizer application. Mater. Today Proc. 2019, 16, 2187–2196. [CrossRef]
150. Lakshani, N.; Wijerathne, H.S.; Sandaruwan, C.; Kottegoda, N.; Karunarathne, V. Release Kinetic Models and Release Mechanisms
of Controlled-Release and Slow-Release Fertilizers. ACS Agric. Sci. Technol. 2023, 3, 939–956. [CrossRef]
151. Priya, E.; Sarkar, S.; Maji, P.K. A review on slow-release fertilizer: Nutrient release mechanism and agricultural sustainability.
J. Environ. Chem. Eng. 2024, 12, 113211. [CrossRef]
152. Firmanda, A.; Fahma, F.; Syamsu, K.; Mahardika, M.; Suryanegara, L.; Munif, A.; Gozan, M.; Wood, K.; Hidayat, R.; Yulia, D.
Biopolymer-based slow/controlled-release fertilizer (SRF/CRF): Nutrient release mechanism and agricultural sustainability.
J. Environ. Chem. Eng. 2024, 12, 112177. [CrossRef]
153. Lin, C.-C.; Metters, A.T. Hydrogels in controlled release formulations: Network design and mathematical modeling. Adv. Drug
Deliv. Rev. 2006, 58, 1379–1408. [CrossRef] [PubMed]
154. Shang, H.; Yang, X.; Liu, H. Temperature-responsive hydrogel prepared from carboxymethyl cellulose-stabilized
N-vinylcaprolactam with potential for fertilizer delivery. Carbohydr. Polym. 2023, 313, 120875. [CrossRef] [PubMed]
155. Dai, H.; Zhang, Y.; Ma, L.; Zhang, H.; Huang, H. Synthesis and response of pineapple peel carboxymethyl cellulose-g-poly
(acrylic acid-co-acrylamide)/graphene oxide hydrogels. Carbohydr. Polym. 2019, 215, 366–376. [CrossRef] [PubMed]
Molecules 2024, 29, 4835 26 of 26

156. Damiri, F.; Salave, S.; Vitore, J.; Bachra, Y.; Jadhav, R.; Kommineni, N.; Karouach, F.; Paiva-Santos, A.C.; Varma, R.S.; Berrada, M.
Properties and valuable applications of superabsorbent polymers: A comprehensive review. Polym. Bull. 2024, 81, 6671–6701.
[CrossRef]
157. Zhang, W.; Wang, P.; Liu, S.; Chen, J.; Chen, R.; He, X.; Ma, G.; Lei, Z. Factors affecting the properties of superabsorbent polymer
hydrogels and methods to improve their performance: A review. J. Mater. Sci. 2021, 56, 16223–16242. [CrossRef]
158. de Lima, I.S.; Sousa, H.R.; Silva, A.S.; de Oliveira, L.H.; Muniz, E.C.; Osajima, J.A.; Silva-Filho, E.C. Superabsorbent hydrogel
from cassava gum (Manihot esculenta) to release water and macronutrients. Ind. Crops Prod. 2024, 219, 119045. [CrossRef]
159. Al Rohily, K.; El-Hamshary, H.; Ghoneim, A.; Modaihsh, A. Controlled Release of Phosphorus from Superabsorbent Phosphate-
Bound Alginate-Graft-Polyacrylamide: Resistance to Soil Cations and Release Mechanism. ACS Omega 2020, 5, 32919–32929.
[CrossRef]
160. Shaghaleh, H.; Alhaj Hamoud, Y.; Xu, X.; Wang, S.; Liu, H. A pH-responsive/sustained release nitrogen fertilizer hydrogel based
on aminated cellulose nanofiber/cationic copolymer for application in irrigated neutral soils. J. Cleaner Prod. 2022, 368, 133098.
[CrossRef]
161. Chamorro, A.F.; Palencia, M.; Arrieta, Á.A. Development of High-Efficiency Fertilizer by Hydrogels Obtained from Cassava
Starch and Citric Acid for Slow Release of Ammonium and Potassium. Gels 2024, 10, 434. [CrossRef]
162. Sempeho, S.I.; Kim, H.T.; Mubofu, E.; Hilonga, A. Meticulous Overview on the Controlled Release Fertilizers. Adv. Chem. 2014,
2014, 363071. [CrossRef]
163. Vo, P.T.; Nguyen, H.T.; Trinh, H.T.; Nguyen, V.M.; Le, A.-T.; Tran, H.Q.; Nguyen, T.T.T. The nitrogen slow-release fertilizer based
on urea incorporating chitosan and poly(vinyl alcohol) blend. Environ. Technol. Innov. 2021, 22, 101528. [CrossRef]
164. Pogorzelski, D.; Filho, J.F.L.; Matias, P.C.; Santos, W.O.; Vergütz, L.; Melo, L.C.A. Biochar as composite of phosphate fertilizer:
Characterization and agronomic effectiveness. Sci. Total Environ. 2020, 743, 140604. [CrossRef] [PubMed]
165. Jiang, S.; Duan, Q.; Ma, L.; Song, Y.; Xie, H.; Liu, H.; Chen, L.; Yu, L. Preparation and characterization of slow-release fertilizer
through coating acrylate epoxidized soybean oil. Environ. Technol. Innov. 2024, 34, 103626. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.