Applied Clay Science 242 (2023) 107041

Contents lists available at ScienceDirect

Applied Clay Science

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

Research Paper

Urea intercalated halloysite/sodium alginate composite hydrogels for

slow-release fertilizers
Jiawei Huang 1, Linhong Chen 1, Ming Huang , Mingxian Liu *
Department of Materials Science and Engineering, College of Chemistry and Materials Science, Jinan University, Guangzhou 511443, China

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

Keywords: The application of nanotechnology in the field of agrochemicals release is an effective way to reduce the use of
Halloysite fertilizers and improve their utilization. Here, different ratios of urea were successfully intercalated into hal­
Alginate loysite (Hal) by solid-phase milling method, and the maximum loading of urea was calculated as 14.99 ± 1.33 wt
Urea
%. X-ray powder diffraction (XRD) demonstrated the distance of the Hal (001) plane increased from 0.7 to 1.0
Intercalation
nm by the urea intercalation. Subsequently, urea-Hal‑sodium alginate (SA) hydrogel beads (UHS) were fabri­
Slow release
cated by Ca2+ crosslinking method. SA and Hal content has a significant influence on the morphology and surface
properties of the hydrogel. The optimal ratio of UHS was found as 2 wt% CaCl2, 2 wt% SA, and 2 wt% Hal. UHS
had good water retention and slow release properties, and the water retention rate of UHS was increased by 13%
compared with that of raw soil. The release curve showed that the release time of urea in UHS was 60 times
longer compared to pure urea. Furthermore, using wheat as a plant model, UHS can provide slow-release ni­
trogen nutrients to promote the growth of wheat. In virtue of good swelling and slow-release properties, low cost,
simple preparation process and environmental friendliness, UHS has a promising future in slow-release fertilizers
for modern agriculture technology.

1. Introduction (Timilsena et al., 2015).

As the population continues to grow and living standards improve in
the worldwide, there is an urgent demand for increased crop yields.
However, the continuous decrease in arable land and water resources
largely hindered crop growth (Irfan et al., 2018). Fertilizer application is
an important measure to increase crop yield per unit area, and fertilizer
application is a common method in current food production (Xiang
et al., 2008). Fertilizer, a natural or artificial substance containing
chemical elements that improve the growth and productiveness of
plants, is the most basic and important material input in agricultural
production (Li et al., 2020). China is currently the world's largest con­
sumer of fertilizers, accounting for about one-third of the world's con­
sumption. However, due to the low utilization rate of traditional
fertilizers, excess fertilizers are transferred to the environment through
volatilization, leaching and runoff, resulting in a serious waste of re­
sources and causing a series of environmental problems (Li et al., 2018).
Slow-release fertilizers can effectively improve the utilization of fertil­
izers and reduce the environmental pollution caused by fertilizers
Slow-release fertilizer is a new type of fertilizer that uses physical,
chemical or physicochemical methods to modify fast-acting fertilizers to
achieve a slow release of nutrients and meet the nutrient demand of
crops throughout the growth period (Liu et al., 2019). Nanotechnology
offers the feasibility of exploring nanostructured materials as fertilizer
slow-release carriers (Solanki et al., 2015). With excellent specific sur­
face area and special structure, nanomaterials provide a new choice for
microstructure optimization and macroscopic performance improve­
ment of slow-release fertilizers, and are attracting the attention for
reducing pollution, improving soil fertility and creating a favorable
environment for microorganisms (Rajonee et al., 2017). Nanofertilizer is
a new type of fertilizer developed by using emerging nanotechnology,
pharmaceutical microencapsulation technology and chemical micro­
emulsification technology (Preetha and Balakrishnan, 2017). Nano­
fertilizers can increase nutrients uptake and crop yield by modulating
the effectiveness of fertilizers (Wang et al., 2020); they can also increase
plant defense mechanisms and enhance plant resistance to pests, dis­
eases and abiotic stresses (El-Naggar et al., 2020; Elbasuney et al., 2022;

* Corresponding author.
E-mail address: liumx@jnu.edu.cn (M. Liu).
1
These authors contributed equally to this work and should be considered co-first authors.

https://doi.org/10.1016/j.clay.2023.107041
Received 23 March 2023; Received in revised form 12 May 2023; Accepted 14 June 2023
Available online 22 June 2023
0169-1317/© 2023 Elsevier B.V. All rights reserved.
J. Huang et al.
Verma et al., 2022).
Current research on nanofertilizers focuses on the direct delivery of
nanoparticles after synthesis, encapsulation of desired plant nutrients
into nanomaterials, and application of nanocoatings made from nano­
particles to plant nutrients (Guo et al., 2018; Roshanravan et al., 2014;
Zhang et al., 2020). Micronutrients in nano form improve their
bioavailability to plants, thus improving plant growth and nutrient
quality (Chhipa, 2017). Faced with numerous nanoparticle options, in
order to reduce the cost of fertilizers and their environmental impact,
researchers have focused on natural materials such as natural poly­
saccharides and clays that are non-toxic, readily available, and relatively
inexpensive, such as sodium alginate (SA). SA is a natural poly­
saccharide macromolecule derived from algae with good biocompati­
bility and degradability, and has been widely studied and applied in
food, medicine, and fertilizers (Chalitangkoon et al., 2020; Sar­
avanakumar et al., 2020). SA can be used to prepare porous membranes,
hydrogel bead, or microspheres by cross-linking with Ca2+ ions, but the
resulting hydrogels are poorly swelled in water. So, if the pure SA
hydrogel was used as fertilizer carrier, the low water absorbance limited
the release ratio. When clay-based nanomaterials are added into SA, the
water swelling properties of hydrogels can be well enhanced since the
clays have good hydrophilicity.
Halloysite (Hal) are naturally occurring aluminosilicate clay min­
erals with a high aspect ratio and hollow tubular structure with the
chemical composition Al2Si2O5(OH)4⋅nH2O. The crystal structure of
hydrated Hal possess 10 Å interlayer space due to the presence of water
molecules between Hal layers, while the dehydrated Hal exhibited 7 Å
interlayer space due to the loss of water between Hal layers (Santagata
and Johnston, 2022). Hal is a kaolin-like structure consisting of an
overlapping layer of Si-centered tetrahedra and a layer of Al-centered
octahedra (Lisuzzo et al., 2022). The inner wall of Hal is an alumi­
num‑oxygen octahedral layer with an inner surface group composed of
positively charged aluminoxane (Al-OH) groups, and the outer wall is a
silicon‑oxygen tetrahedral layer with an outer surface composed of
negatively charged silicon‑oxygen (Si–O) groups (Ferrante et al., 2023;
Yuan et al., 2015). Due to the unique tubular structure and the presence
of hydroxyl groups, it can be modified by the reaction of different sub­
stances with the hydroxyl groups on the Hal surface(Ferrante et al.,
2023). Hal is often used as drug carriers, tissue repairing, food pack­
aging, composite functional materials, cosmetic raw materials and other
fields (Cao et al., 2020; Deshmukh et al., 2023; Feng et al., 2022; Saleh
et al., 2021; Santos et al., 2019).
Therefore, the composite hydrogel beads prepared by Hal and SA are
good fertilizer carriers (Zhang et al., 2020). Urea is an amide nitrogen
fertilizer, and the -NH2 groups in urea form a hydrogen bond with the
-OH group on the inner surface of Hal. The urea-Hal complex is then
added to the SA hydrogel to avoid the burst release of the active
ingredient, thus achieving a slow release of fertilizer (Fan et al., 2013;
Horváth et al., 2011; Wei et al., 2019).
In this work, urea-Hal-SA hydrogel beads (UHS) were prepared by
dropping urea intercalated Hal/SA into calcium chloride solution via the
ionic cross-linking (Khunova et al., 2013). The structure and
morphology of urea intercalated Hal were characterized. The swelling
properties and release properties of the UHS were also investigated.
Wheat was used as a plant model to study the effect of UHS on crop
growth. The results showed that the nano-fertilizer based on urea
intercalated clay has good swelling and slow-release properties, which
showed promising applications in the modern agriculture field.
2. Experimental section
2.1. Main reagents and instruments
Halloysite (Hal) was obtained from Guangzhou Runwo Materials
Technology Co. Ltd., China. The elemental composition of Hal by X-ray
fluorescence (XRF) was determined as follows (wt.-%): SiO2, 46.65;
2
Applied Clay Science 242 (2023) 107041
Al2O3, 41.14; SO3, 5.51; K2O, 1.17; CaO, 1.77; MgO, 1.13; Fe2O3, 1.131;
Na2O, 0.37; TiO2, 0.11. Sodium alginate (SA) (viscosity range of
1.05–1.15 Pa⋅s) was obtained from Tianjin Yongda Chemical Reagent
Co. Ltd., China. Urea was provided by Tianjin Damao Chemical Reagent
Factory, China. Wheat seeds were acquired from Sunong Seed Industry
Co., Ltd. (Jiangsu, China). Anhydrous calcium chloride was purchased
from Sinopharm Group Chemical Reagent Co. Sulfuric acid was acquired
from Guangzhou Chemical Reagent Factory, China. Deionized water was
used in all the experiments.
2.2. Preparation of Urea- Hal
Urea and Hal were ground in different mass ratios (1:1, 1:2, 1:3)
using the solid phase grinding method, and after 15 min of grinding, the
free urea was washed off with ethanol. The products were then dried in
an oven at 60 ◦ C to obtain the different ratios of the ground products,
which are respectively marked as UH11, UH21, and UH31.
2.3. Preparation of UHS hydrogel beads
Urea, Hal and UH (UH11, UH21, UH31) were dispersed in deionized
water, 2 wt% SA was added and stirred for 1 h. The mixture of Hal and
SA was slowly added dropwise to CaCl2 solution using a syringe with a
diameter of 0.8 mm. After standing for 30 min, the beads were filtered,
washed 3 times with pure water and lyophilized to obtain Urea-SA (US),
Hal-SA (HS), UH11-SA (USH11), UH21-SA (USH21) and UH31-SA
(USH31) hydrogel beads.
2.4. Characterization of UH and UHS hydrogel beads
After preparation of a 0.05 wt% UH dispersion, the particle size
distribution was tested and recorded using a Zeta potential particle size
analyzer. UHS hydrogel beads were lyophilized, and the surface of the
lyophilized sample was sprayed with a layer of gold. The surface and
cross-sectional morphology was observed using the Zeiss Sigma 500
scanning electron microscope (SEM) machine. Aqueous dispersions of
0.05 wt% Hal and UH were dropped onto a copper grid supported by a
carbon film and the morphology was observed using transmission
electron microscopy (TEM) at an accelerated voltage of 100 kV. Infrared
spectra of urea, Hal, UH and UHS in the range of 4000 to 400 cm− 1 were
measured using Fourier Transform Infrared spectroscopy (FTIR). Urea,
Hal, UH and UHS were measured using an X-ray diffractometer (XRD).
The diffractograms were acquired on a MiniFlex-600 diffractometer
(MiniFlex-600, Rigaku Corporation, Japan) in the range 5–70◦ , and the
scanning speed was 10◦ /min under accelerating voltage of 40 kV with
current of 40 mA. The stability of urea, HNTs, UH, and UHS was tested
with a thermogravimetric (TG) analyzer (Mettler Toledo, Co. Ltd.,
Switzerland) under nitrogen atmosphere from 30 ◦ C to 800 ◦ C at a rate
of 10 ◦ C/min.
2.5. Swellability of UHS hydrogel beads
0.1 g of UHS (1, 1.5, 2 wt% CaCl2 concentration, SA content, Hal
content) was placed in a 200 mesh nylon bag in a container containing
500 mL of deionized water. At regular intervals, the nylon bag was
removed from the water, and the excess water was wiped from the
surface with filter paper and weighed. The swelling ratio of Q (g/g) was
calculated using the formula of
Mt − M0
Q (g/g) =
M0
where, the initial mass of the dried hydrogel beads is M0 (g); the
dissolved mass of the UHS at time t is Mt (g).
J. Huang et al. Applied Clay Science 242 (2023) 107041

Fig. 1. Schematic diagram of the preparation process of UHS.

2.6. Water retention of UHS hydrogel beads by the formula:

Mt − M
The 100 g of sand and 1 g of UHS sieved through 100 mesh nylon Wt = × 100%
M0 − M
cloth were placed in a beaker with 50 mL of water, and another beaker
with 100 g of sand also sieved was added as a control. The beakers were where, the masses of beaker and soil are M (g) and the initial mass of
weighed and the initial mass M0 was obtained. Each beaker was weighed beaker, USH, soil, and water are M0 (g); the masses weighed at t time
every 1 day for 8 days. The water retention rate of UHS was calculated

Fig. 2. FTIR spectrum (A) and XRD pattern (C) of Hal, UH11 and urea. FTIR spectrum (B) and XRD pattern (D) of SA, HS and UHS11.

3
J. Huang et al.
Fig. 3. Particle size distribution and zeta potential of Hal (A), UH11 (B), UH21 (C), UH31 (D).
intervals are Mt (g).
2.7. Loading capacity and slow release of UHS hydrogel beads
Hal and urea in different mass proportions were ground sufficiently
and washed with ethanol to remove the free urea, and the sample was
dried and weighed for the mass of M1, and the urea loading (LE(%))
could be calculated by the formula:
M1 − M2
LE(%) = × 100%
M1
where, the mass of the dried sample is M1, the mass of Hal is M2.
The 0.1 g of lyophilized UHS hydrogel beads were placed in a dialysis
bag, 5 mL of pure water was added and placed in a beaker containing
100 mL of pure water. To determine the urea content in water by color
development with p-dimethylbenzaldehyde, 2 g of p-dimethylamino­
benzaldehyde (PDAB) was dissolved in 48 mL of anhydrous ethanol and
2 mL of sulfuric acid was added to obtain a PDAB solution. The standard
curve was first obtained by measuring the absorbance of different con­
centrations of ureasolution and PDAB. Then 5 mL of the solution was
taken in a beaker at intervals (adding 5 mL of water to make up) and 1
mL of PDAB was added. Absorbance was measured at 432 nm and the
absorbance of the sample was compared with the standard curve to
obtain the amount of urea released at each time interval(Shen et al.,
2020). The release curve is fitted with the Boltzmann equation, calcu­
lated using the formula:
(a − b)
y = b+
1 + e dt
t− t0
4
Applied Clay Science 242 (2023) 107041
where, t represents the release time, y is the amount of urea released at
the corresponding t time, t0 is the initial release time, and dt is the first
order derivative of t.
2.8. Pharmacodynamics of UHS hydrogel beads
Filter paper was placed in the Petri dishes followed by 0.1 g US and
USH hydrogel beads, respectively, and blank filter paper was used as a
control group. The wheat seeds were cleaned and transferred to the Petri
dishes. Ten wheat seeds were placed in each group, and then 6 mL of
deionized water was added and incubated for 7 days. After 7 days, the
germination rate, root length and shoot length of different groups were
counted.
3. Results and discussion
3.1. Characterization results of UHS hydrogel beads
To load urea into Hal, an intercalation method was employed by a
solid-phase grinding method (Fig. 1). This was a quick, effective, and
economic way, which can be carried out at any labs. To investigate the
interactions between urea and Hal, a series of characterizations were
conducted. The IR spectra of urea, Hal, UH, and UHS were compared in
Fig. 2A and B. The absorption bands at 3696 and 3622 cm− 1 can be
attributed to the stretching vibrations of the external and internal O–H
groups of the Hal (Madejová, 2003). The new absorption peaks at 3504
and 3390 cm− 1 for UH were due to N–H groups in urea (Frost and
Kristof, 1997). The absorption peaks at 1676, 1615, 1590 and 1460
cm− 1 were attributed to the C– – O double bond of urea and the
J. Huang et al.
Fig. 4. TEM image of Hal and UH11 (A). The interaction model of urea and Hal (B).
absorption band of NH2. When urea was inserted into Hal, these ab­
sorption peaks were shifted to 1666, 1623, 1589, and 1474 cm− 1,
indicating the interfacial interactions between urea and Hal. The
carboxyl absorption peak of SA was shifted from 1407 to 1425 cm− 1,
indicating a successful cross-linking of SA and Ca2+ ions. In addition,
hydrogen bonding interactions between the carbonyl group (from urea)
and the hydroxyl group (from Hal, SA) occur (Letaief et al., 2006).
XRD was then performed to investigate the interlayer space change
(Fig. 2C). The diffraction peaks at 23o were attributed to the charac­
teristic peaks of urea, and the diffraction peaks of Hal appeared at 12o,
20o, and 25o, corresponding to the (001), (020,110), and (002) planes,
respectively (Brindley et al., 1946). After the intercalation of urea into
Hal, the distance of the Hal (001) plane increased from 0.7 to 1.0 nm,
along with the presence of the characteristic peak of urea, which in­
dicates that urea was successfully intercalated into Hal. The hydrogel
beads of Hal, UH and SA were made by ionic cross-linking method, and
5
Applied Clay Science 242 (2023) 107041
the products after lyophilization were tested by XRD (Fig. 2D). Pure SA
is amorphous structure, so they do not exhibit characteristic peaks in
XRD, while characteristic peaks of Hal are present in both HS and UHS
(Brindley et al., 1946).
The particle size distribution and zeta potential of the products after
solid-phase grinding with different ratios of Hal and urea were tested
(Fig. 3). The average particle size of Hal used in this work was 205.5 nm,
and after solid phase grinding, the average particle sizes of UH11, UH21
and UH31 were 212.5, 262.8 and 289.9 nm, respectively. The zeta po­
tentials of Hal, UH11, UH21 and UH31 were − 21.4, − 19.9, − 20.3 and
− 19.4 mV, respectively, and the potentials of products after solid-phase
grinding were slightly increased. This may be due to the electrostatic
interactions between urea and Hal, where the positive charge of the
amino group in urea was partially neutralized, thus changing the dis­
persibility of the material and leading to a change in the measured
average particle size. The UH composites maintained a good negative
J. Huang et al. Applied Clay Science 242 (2023) 107041

Fig. 5. TGA (A) and DTG (B) of the Hal, Urea, UH11 and UHS11.

Fig. 6. SEM images of the surface (A) and cross-section (B) of the UHS11 hydrogel bead.

zeta potential, indicating that UH also has good water dispersion.
Hal has a hollow tubular structure with a smooth and sharp surface
(Fig. 4A). After solid phase grinding of urea, the product UH has a
tubular structure, but the inner and outer surfaces become rough. The
outer diameter of Hal is slightly increased due to the introduction of urea
in the interlayers of Hal. This indicated that urea was successfully loaded
onto the Hal. The interlayer space of Hal increased from 0.7 to 1.0 nm
due to the mechanochemical intercalation of urea (Fig. 4B).
In order to compare the thermal stability of urea, UH, and UHS, the
thermal decomposition experiment was conducted (Fig. 5). The TGA/
DTG curves of Hal, UH and UHS exhibited a heat absorption peak at
68 ◦ C, which was attributed to the removal of adsorbed water from the
samples. When the temperature was 140 ◦ C, urea started to decompose
and lost weight, while in UH11, weight loss started when the tempera­
ture rose to 160 ◦ C. The weight loss of the material came from the
decomposition of the interlayer urea, indicating that the thermal sta­
bility of urea increased when it was intercalated into the Hal. The TGA/
DTG curve of Hal presented a heat absorption peak at 490 ◦ C due to the
dehydroxylation of Al2Si2O5(OH)4 (Lvov et al., 2008). The UH obtained
by mechanochemical intercalation of urea into the interlayer of Hal
showed a heat absorption peak at 210 ◦ C, which was attributed to the
mass loss due to volatilization/decomposition of urea in the interlayer of
Hal, and the heat absorption peak at 490 ◦ C was attributed to the
dehydroxylation reaction of Hal (Verma et al., 2020). In the UHS curve,
the peak of heat absorption in the temperature range of 220-370 ◦ C was
mainly due to the carbonation of carboxyl groups in SA and the degra­
dation of urea, and the peak of heat absorption occurring at 490 ◦ C was
attributed to the dehydroxylation of Hal (Khunová et al., 2015; Nicolini
et al., 2009). These results indicated that urea was successfully inter­
calated into the Hal and UH was successfully introduced into the SA

6
J. Huang et al.
Fig. 7. The swelling properties of UHS hydrogel beads with different concentrations of CaCl2 solutions (A), different content of SA (B), and different content of Hal
(C). The water retention curve of UHS11 (D).
hydrogel.
UHS samples have a relatively smooth surface even though Hal is
incorporated (Fig. 6A). The smooth surface and the enriched Hal
reduced the rapid uptake of water by the UHS, which can effectively
slow down the release of urea. The cross-section of hydrogel beads is
porous and the cross-linking of Hal with SA and Ca2+ results in a three-
dimensional porous network in the internal morphology of UHS samples
(Fig. 6B). The structure of the hydrogel beads changed from dense on the
surface to loose on the inside due to the cross-linking of SA and Ca2+
with the three-dimensional porous network. When SA was added
dropwise to CaCl2 solution, the surface was rapidly cross linked with
Ca2+ ions, which inhibited the diffusion of Ca2+ into the interior of the
beads. As a result, the cross-linking density of the inner and outer sur­
faces of the beads was different, resulting in a more dense and smooth
surface and a looser and more porous interior (Wang et al., 2019).
3.2. Swellability and water retention of UHS hydrogel beads
The swelling property is one of the important parameters for eval­
uating the strength and elasticity of hydrogels. The factors affecting the
swelling of UHS were investigated by changing the CaCl2 concentration,
SA content, and Hal content. UHS hydrogel beads are formed by cross-
linking SA and Ca2+, so the concentration of CaCl2 can directly affect
their cross-linking density. When the concentration of CaCl2 solution
was 2 wt%, the swelling of UHS hydrogel beads was the highest, and the
equilibrium swelling rate was 17 g/g. When the concentration of CaCl2
solution was less than 2 wt%, the ionic cross-linking of UHS decreases
and its mechanical strength is deteriorated, which weakened the UHS
swelling property (Fig. 7A).
SA content in UHS also affects the degree of cross-linking. The
swelling rate of UHS was tested by varying the amount of SA in UHS
7
Applied Clay Science 242 (2023) 107041
(Fig. 7B). When the SA content of UHS is 2 wt%, the swelling capacity of
UHS in water reaches the maximum, and when the SA content decreases,
the swelling capacity of UHS also becomes weaker. As the SA content
decreases, the carboxyl group of SA in UHS decreases, resulting in a
weakened cross-linkage, and therefore UHS becomes less capable of
retaining water (Chan et al., 2002). Hal in UHS are not only safe and
environmentally friendly, cheap and easy to obtain, but also improve the
swelling and release properties of UHS, so it is necessary to investigate
the effect of Hal content on the swelling ability of UHS. The maximum
swelling rate was reached when the Hal content was 2 wt% (Fig. 7C).
With the increase of Hal content, the swelling ability of UHS gradually
increased. Due to the presence of hydrophilic hydroxyl groups on the
surface of Hal and itself can be used as a cross-linking point, the addition
of Hal can improve the swelling capacity of UHS (Agnihotri and Singhal,
2019; Pasbakhsh et al., 2013). Therefore, the best swelling property of
UHS was achieved when the concentration of CaCl2 solution was 2 wt%,
SA content was 2 wt%, and Hal content was 2 wt%.
As a slow-release fertilizer, the water retention ability of UHS in the
soil was also important. If UHS has good water retention capacity along
with good swelling capacity, then UHS can absorb irrigation water or
rainwater and then slowly release fertilizer and water to help crops
grow. The water retention capacity of UHS11 was tested (Fig. 7D). The
water retention rate of UHS11 soil at room temperature decreased to
38.5 wt% at day 6, while the water retention rate of the control soil
decreased to 26 wt%, which is a 12.5 wt% increase in the water reten­
tion rate of UHS11 compared to pure soil. The water retention rate of
UHS was three times higher than that of pure soil. This indicates that
UHS reduced the evaporation rate of soil water and increased the water
retention rate of the sandy soil.
J. Huang et al. Applied Clay Science 242 (2023) 107041

Fig. 8. Loading rates of urea in Hal (A). The 24 h release kinetic fitting curve of pure urea (B) and urea in US(C), UHS11(D), USH21(E) and USH31(F).

UH31 were prepared, and hydrogel beads were prepared with SA to

Table 1
compare their release behavior. The urea loading of UH11, UHS21, and
Parameters and correlation coefficients of the Boltzmann equation.
UH31 are 8.05 ± 1.28 wt%, 13.61 ± 1.23 wt%, and 14.99 ± 1.33 wt%,
Sample Urea US USH11 USH21 USH31 respectively (Fig. 8A). The kinetic behavior of urea release in water was
a − 3.8172 × 28.8793 32.70559 12.38128 − 46,121.065 simulated using the Boltzmann equation, and the fitting results showed
1011 that the release of urea in US and USH was in good agreement with the
b 100.0107 100.6191 98.32732 100.19297 99.40352
Boltzmann equation (Table 1). The release curves showed that com­
R2 0.9454 0.9795 0.98589 0.97844 0.97269
mercial urea and US released all urea into the water after 1 h and 10 h,
respectively. The release rate of urea in USH was slowed down compared
3.3. Slow-release properties of UHS hydrogel beads with that in US, indicating that it showed that intercalation of urea into
Hal can effectively slow down the release of urea in water. When all the
UHS hydrogel beads have good swelling and water retention prop­ commercial urea was released, UHS11, UHS21, and UH31 released 65
erties, and because urea is intercalated between the layers of Hal, wt%, 65.3 wt%, and 63 wt%, respectively, and when all the urea in US
whether UHS had the ability to slow release is also a main concern. was released, UHS11, UHS21, and UH31 released 87.5 wt%, 90 wt%,
Three urea-Hal with different intercalation ratios of UHS11, UHS21, and and 91 wt%, respectively. At the 8th and 24th h, the release of

8
J. Huang et al.
Fig. 9. Appearance (A), germination rate (B), root length statistics (C), and shoot length statistics, (D) of wheat seeds cultured in water, US, and UHS for 0, 3, 5, and
7 days.
commercial urea, US, UHS11, UHS21, and UH31 were 100 wt%, 97 wt
%, 82 wt%, 86 wt%, 87 wt% and 100 wt%, 100 wt%, 96 wt%, 98 wt%
97 wt%, respectively. The total release time of UHS11, UHS21, and
UH31 urea was 60 h, 36 h, and 36 h, respectively. Compared with
commercial urea, UHS increased the sustained release time of urea by
36–60 times, up to 60 h (Fig. 8B). This indicates that UHS has good slow-
release properties and provides a new idea to reduce the environmental
pollution of fertilizers.
3.4. Effect of UHS hydrogel on wheat growth
As one of the three major cereals, wheat is suitable for growing in
deeper tillage soils, which facilitates water storage and fertilization and
promotes root development (Rao et al., 2018). The previous study sug­
gested that Hal had very low toxicity toward wheat growth, so it was a
safe material used as fertilizer carrier of urea (Chen et al., 2021). UHS
has good swelling capacity and water retention ability, which can pro­
vide moist conditions for wheat soil. At the same time, as a slow-release
fertilizer, its efficacy capacity is of utmost importance. USH11 samples
were used to assess the efficacy of USH with a urea loading of 8.05 ±
1.28 wt%, using US with the same urea content as a comparison and
blank filter paper as a control. At day 3, the root and stem lengths of
wheat in the US and UHS groups were not as high as those in the control
group. However, by day 5 and 7, wheat growth in both US and UHS
groups was better than that of the control group, with the UHS group
showing the best growth. The root and stem lengths of wheat in the UHS
9
Applied Clay Science 242 (2023) 107041
group did not differ much from the US group at day 5. At day 7, the root
length of wheat in the UHS group was 4.04 cm which was 1.15 times
longer than that of the control group, and the stem length was 6.25 cm
which was 20% higher than that of the control group. Moreover, the root
length and stem length were also longer than those of the US group
(without Hal) (Fig. 9A-D). UHS has good slow-release and water reten­
tion properties, and after absorbing water and swelling, it continuously
provides nutrients to wheat, and UHS can promote the growth of wheat,
thus increasing the yield of wheat.
4. Conclusions
Different ratios of urea were successfully intercalated into Hal by
solid-phase milling to obtain the product UH, which was able to achieve
a loading of 14.99 ± 1.33 wt%. The optimal formulation of UHS was
determined by adjusting the Ca2+ concentration, SA content, and Hal
content to obtain UHS hydrogel beads with better swelling properties
using the ionic cross-linking method. The obtained UHS had good water
retention and slow release, and the experimental results concluded that
the water retention of UHS was increased by 13% compared with pure
soil. Moreover, the release time of urea in UHS was 60 times longer than
that of commercial urea. Meanwhile, using wheat as a plant model, UHS
can provide slow-release nutrients to promote wheat growth. With good
swelling and slow-release properties, as well as low cost, simple prep­
aration process and environmental friendliness, UHS has a broad pros­
pect in slow-release fertilizers.
J. Huang et al.
CRediT authorship contribution statement
Jiawei Huang: Methodology, Validation, Formal analysis, Investi­
gation, Data curation, Writing – original draft, Writing – review &
editing, Visualization. Linhong Chen: Methodology, Validation, Formal
analysis, Investigation, Data curation, Writing – original draft, Visuali­
zation. Ming Huang: Validation, Investigation, Writing – review &
editing. Mingxian Liu: Conceptualization, Methodology, Writing – re­
view & editing, Resources, Supervision, Project administration, Funding
acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (52073121), Fundamental Research Funds for the
Central Universities (21622406), and Project Team of Foshan National
Hi-tech Industrial Development Zone Industrialization Entrepreneurial
Teams Program (2220197000129).
References
Agnihotri, S., Singhal, R., 2019. Effect of sodium alginate content in acrylic acid/sodium
humate/sodium alginate superabsorbent hydrogel on removal capacity of MB and
CV dye by adsorption. J. Polym. Environ. 27, 372–385.
Brindley, G., et al., 1946. The clay minerals halloysite and meta-halloysite. Nature 157,
225–226.
Cao, X., et al., 2020. Halloysite nanotubes@ polydopamine reinforced polyacrylamide-
gelatin hydrogels with NIR light triggered shape memory and self-healing capability.
Compos. Sci. Technol. 191, 108071.
Chalitangkoon, J., et al., 2020. Silver loaded hydroxyethylacryl chitosan/sodium
alginate hydrogel films for controlled drug release wound dressings. Int. J. Biol.
Macromol. 159, 194–203.
Chan, L., et al., 2002. Cross-linking mechanisms of calcium and zinc in production of
alginate microspheres. Int. J. Pharm. 242, 255–258.
Chen, L., et al., 2021. Phytotoxicity of halloysite nanotubes using wheat as a model: seed
germination and growth. Environ. Sci. Nano 8, 3015–3027.
Chhipa, H., 2017. Nanofertilizers and nanopesticides for agriculture. Environ. Chem.
Lett. 15, 15–22.
Deshmukh, R.K., et al., 2023. Halloysite nanotubes for food packaging application: a
review. Appl. Clay Sci. 234, 106856.
Elbasuney, S., et al., 2022. Ferric oxide colloid: towards green nano-fertilizer for tomato
plant with enhanced vegetative growth and immune response against fusarium wilt
disease. J. Inorg. Organomet. Polym. Mater. 32, 4270–4283.
El-Naggar, M.E., et al., 2020. Soil application of nano silica on maize yield and its
insecticidal activity against some stored insects after the post-harvest. Nanomaterials
10, 739.
Fan, L., et al., 2013. In situ generation of sodium alginate/hydroxyapatite/halloysite
nanotubes nanocomposite hydrogel beads as drug-controlled release matrices.
J. Mater. Chem. B 1, 6261–6270.
Feng, Y., et al., 2022. Systematic studies on blood coagulation mechanisms of halloysite
nanotubes-coated PET dressing as superior topical hemostatic agent. Chem. Eng. J.
428, 132049.
Ferrante, F., et al., 2023. A computational and experimental investigation of halloysite
silicic surface modifications after alkaline treatment. Appl. Clay Sci. 232, 106813.
Frost, R.L., Kristof, J., 1997. Intercalation of halloysite: a Raman spectroscopic study.
Clay Clay Miner. 45, 551–563.
10
Applied Clay Science 242 (2023) 107041
Guo, H., et al., 2018. Nano-enabled fertilizers to control the release and use efficiency of
nutrients. Curr. Opin. Environ. Sci. Health 6, 77–83.
Horváth, E., et al., 2011. Study of urea intercalation into halloysite by thermoanalytical
and spectroscopic techniques. J. Therm. Anal. Calorim. 105, 53–59.
Irfan, S.A., et al., 2018. A review of mathematical modeling and simulation of controlled-
release fertilizers. J. Control. Release 271, 45–54.
Khunova, V., et al., 2013. The effect of halloysite modification combined with in situ
matrix modifications on the structure and properties of polypropylene/halloysite
nanocomposites. Express Polym Lett. 7, 471–479.
Khunová, V., et al., 2015. The effect of urea and urea-modified halloysite on performance
of PCL. J. Therm. Anal. Calorim. 120, 1283–1291.
Letaief, S., et al., 2006. Reactivity of ionic liquids with kaolinite: Melt intersalation of
ethyl pyridinium chloride in an urea-kaolinite pre-intercalate. J. Colloid Interface
Sci. 302, 254–258.
Li, W., et al., 2018. Comprehensive environmental impacts of fertilizer application vary
among different crops: Implications for the adjustment of agricultural structure
aimed to reduce fertilizer use. Agric. Water Manag. 210, 1–10.
Li, H., et al., 2020. Input of Cd from agriculture phosphate fertilizer application in China
during 2006–2016. Sci. Total Environ. 698, 134149.
Lisuzzo, L., et al., 2022. Pickering emulsions stabilized by halloysite nanotubes: from
general aspects to technological applications. Adv. Mater. Interfaces 9, 2102346.
Liu, J., et al., 2019. Bio-based elastic polyurethane for controlled-release urea fertilizer:
Fabrication, properties, swelling and nitrogen release characteristics. J. Clean. Prod.
209, 528–537.
Lvov, Y.M., et al., 2008. Halloysite clay nanotubes for controlled release of protective
agents. ACS Nano 2, 814–820.
Madejová, J., 2003. FTIR techniques in clay mineral studies. Vib. Spectrosc. 31, 1–10.
Nicolini, K.P., et al., 2009. Dehydrated halloysite intercalated mechanochemically with
urea: thermal behavior and structural aspects. J. Colloid Interface Sci. 338, 474–479.
Pasbakhsh, P., et al., 2013. Characterisation of properties of various halloysites relevant
to their use as nanotubes and microfibre fillers. Appl. Clay Sci. 74, 47–57.
Preetha, P.S., Balakrishnan, N., 2017. A review of nano fertilizers and their use and
functions in soil. Int. J. Curr. Microbiol. App. Sci. 6, 3117–3133.
Rajonee, A.A., et al., 2017. Preparation, characterization and evaluation of efficacy of
phosphorus and potassium incorporated nano fertilizer. Adv. Nanopart. 6, 62.
Rao, K.M., et al., 2018. Polysaccharide based hydrogels reinforced with halloysite
nanotubes via polyelectrolyte complexation. Mater. Lett. 213, 231–235.
Roshanravan, B., et al., 2014. Preparation of encapsulated urea-kaolinite controlled
release fertiliser and their effect on rice productivity. Chem. Speciation Bioavail. 26,
249–256.
Saleh, M., et al., 2021. Halloysite nanotube vehicles for drug delivery through a model
blood–brain barrier. Clay Clay Miner. 69, 603–611.
Santagata, M., Johnston, C.T., 2022. A study of nanoconfined water in halloysite. Appl.
Clay Sci. 221, 106467.
Santos, A.C., et al., 2019. Evolution of hair treatment and care: prospects of nanotube-
based formulations. Nanomaterials 9, 903.
Saravanakumar, K., et al., 2020. Physical and bioactivities of biopolymeric films
incorporated with cellulose, sodium alginate and copper oxide nanoparticles for food
packaging application. Int. J. Biol. Macromol. 153, 207–214.
Shen, Y., et al., 2020. Synthesis and characterization of double-network hydrogels based
on sodium alginate and halloysite for slow release fertilizers. Int. J. Biol. Macromol.
164, 557–565.
Solanki, P., et al., 2015. Nano-fertilizers and their smart delivery system. Nanotechnol.
Food Agric. 81–101.
Timilsena, Y.P., et al., 2015. Enhanced efficiency fertilisers: a review of formulation and
nutrient release patterns. J. Sci. Food Agric. 95, 1131–1142.
Verma, A., et al., 2020. Graphite modified sodium alginate hydrogel composite for
efficient removal of malachite green dye. Int. J. Biol. Macromol. 148, 1130–1139.
Verma, K.K., et al., 2022. Recent trends in nano-fertilizers for sustainable agriculture
under climate change for global food security. Nanomaterials 12, 173.
Wang, L., et al., 2019. Stretchable hydrophobic modified alginate double-network
nanocomposite hydrogels for sustained release of water-insoluble pesticides.
J. Clean. Prod. 226, 122–132.
Wang, C., et al., 2020. Chitosan-modified halloysite nanotubes as a controlled-release
nanocarrier for nitrogen delivery. Appl. Clay Sci. 198, 105802.
Wei, H., et al., 2019. Preparation and characterization of slow-release and water-
retention fertilizer based on starch and halloysite. Int. J. Biol. Macromol. 133,
1210–1218.
Xiang, Y., et al., 2008. Recent advances on the technologies to increase fertilizer use
efficiency. Agric. Sci. China 7, 469–479.
Yuan, P., et al., 2015. Properties and applications of halloysite nanotubes: recent
research advances and future prospects. Appl. Clay Sci. 112, 75–93.
Zhang, S., et al., 2020. Self-assembly of hydrophobic and self-healing bionanocomposite-
coated controlled-release fertilizers. ACS Appl. Mater. Interfaces 12, 27598–27606.