Materials Science & Engineering C 90 (2018) 333–340

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Materials Science & Engineering C

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

Slow-release NPK fertilizer encapsulated by carboxymethyl cellulose-based T

nanocomposite with the function of water retention in soil
⁎
Ali Olada, , Hamid Zebhia, Dariush Salaria, Abdolreza Mirmohsenia, Adel Reyhani Tabarb
a
Polymer Composite Research Laboratory, Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
b
Department of Soil Science, Faculty of Agriculture, University of Tabriz, Tabriz, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, new slow release fertilizer encapsulated by superabsorbent nanocomposite was prepared by in-situ
Slow release fertilizer formulation graft polymerization of sulfonated-carboxymethyl cellulose (SCMC) with acrylic acid (AA) in the presence of
Hydrogel nanocomposite polyvinylpyrrolidone (PVP), silica nanoparticles and nitrogen (N), phosphorous (P), and potassium (K) (NPK)
Swelling kinetic fertilizer compound. The prepared materials were characterized by FT-IR, XRD and scanning electron micro-
Water retention
scopy (SEM) techniques. The incorporation of NPK fertilizer into hydrogel nanocomposite network was verified
Superabsorbent
by results of these analyses. Also, the swelling behavior in various pH and saline solutions as well as water
retention capability of the prepared hydrogel nanocomposite was evaluated. The fertilizer release behavior of
the NPK loaded hydrogel nanocomposite was in good agreement with the standard of Committee of European
Normalization (CEN), indicating its excellent slow release property. These good characteristics revealed that the
hydrogel nanocomposite fertilizer formulation can be practically used in agricultural and horticultural appli-
cations.

1. Introduction SHs can be advantageous in the reduction of irrigation of water con-

Water and fertilizer are two main operative factors which put lim-
itations on agricultural production [1,2]. Excessive application of
agrochemicals to increase food production not only causes large eco-
nomic and resource losses, but also causes serious environmental pol-
lution [3]. Nowadays, water deficiency is one of the global problems.
Considering these issues, effort to find controlled release fertilizer for-
mulations (CRFs) or slow–release fertilizer formulations (SRFs) with
high selectivity and effectiveness is one of the scientist's serious chal-
lenges [4–7]. Compared with conventional fertilizers, these formula-
tions (CRFs or SRFs) prevent the loss of chemicals during irrigation and
mitigate their degradation by microbial decomposition, photolysis and
hydrolysis. At the same time, considering the water deficiency problem,
development of efficient water reservoir systems such as super-
absorbent hydrogels is necessary [8,9].
Superabsorbent hydrogels (SHs) are cross-linked polymers that can
absorb large amount of water and saline solutions due to the presence
of hydrophilic functional groups in their unique three-dimensional
network structure [10]. SHs due to their good water retention and
thereafter slow release of water from swollen SH have found extensive
applications in various industries such as agriculture and horticulture
[11–15]. In these industries, especially in desert regions, utilization of
sumption and improving the fertility of the soil [16,17]. Therefore, the
soluble NPK fertilizer encapsulated by hydrogel would be an ideal slow
release SH formulation. Carboxymethyl cellulose (CMC) based SH hy-
drogels synthesized by graft polymerization with acrylic acid (AA)
monomers has been widely used in agriculture [18–22]. However, the
high production cost and low mechanical strength of SH hydrogels
(especially in natural-based hydrogels) limited their use in agriculture.
Recently, to overcome these limitations, addition of low cost inorganic
compounds such as clays and silicates has attracted great attention
[23–26]. Silica (SiO2) particles have been widely used in ceramic
technology, electronic devices, and polymer material industries in-
cluding thixotropic agent, thermal insulators, and composite fillers.
Some studies have been shown that the usage of silica nanoparticles in
hydrogel composition significantly influences its physical, mechanical,
and also swelling characteristics. Addition of silica nanoparticles will
increase the swelling capacity of the hydrogel nanocomposite due to
their hydrophilic hydroxyl groups. Moreover, hydroxyl groups of the
silica can interact with the functional groups of hydrogel components
which results in the formation of additional physical cross-linking
points within the hydrogel network. These additional cross-linking
points will improve the mechanical strength of the nanocomposite
[27–29]. Also, using water soluble linear nonionic polymers (such as

⁎
Corresponding author.
E-mail address: a.oladgz@tabrizu.ac.ir (A. Olad).

https://doi.org/10.1016/j.msec.2018.04.083
Received 3 July 2017; Received in revised form 6 April 2018; Accepted 27 April 2018
Available online 30 April 2018
0928-4931/ © 2018 Elsevier B.V. All rights reserved.
A. Olad et al.
polyvinylpyrrolidone (PVP)) being compatible with CMC, creates a
highly porous hydrogels and increases their water absorption capacity
[30].
On the basis of described background and to obtain such controlled
release formulation, we attempted to prepare a novel SRF formulation
based on SCMC-g-poly(AA)/PVP/Silica (Hyd/PVP/Silica) in this work.
Also, the effect of silica nanoparticles on the water retention and slow
release property of the prepared SH nanocomposite formulation was
studied. Furthermore, repeatable swelling of prepared SH nano-
composite at various pH values and salt solutions were investigated.
2. Experimental
2.1. Materials
Acrylic acid (AA), N,N′-methylene bisacrylamide (MBA), ammo-
nium persulfate (APS), sodium hydroxide, chlorosulfonic acid, urea,
potassium dihydrogen phosphate, ammonium dihydrogen phosphate,
polyvinylpyrrolidone (PVP, Mw 25,000−30,000), and dimethylforma-
mide (DMF) were purchased from Merck company. Carboxymethyl
cellulose sodium salt (NaCMC) (> 99.5%) (viscosity of
1000–1500 mPas for a 4% aqueous solution at 25°) was purchased from
Fluka BioChemika. Ethanol (96%) was purchased from Mojallali re-
agent chemicals Co. (Iran, Tabriz). Rice husk (RH) was provided from a
supplier in Rasht, Iran. All other reactants were of analytical grade and
all solutions were prepared with distilled water.
2.2. Preparation of silica nanoparticles
Silica nanoparticles were prepared according to our reported pro-
cedure [31]. Briefly, rice husk was washed with distilled water to re-
move its soil and dust. Then, it was acid-washed two times. In the first
step, rice husk was acid-leached by reflux boiling in HCl aqueous so-
lution (3% V/V) with the ratio of 50 g/L under stirring in a round-
bottomed flask at 100° for 2 h. The obtained mixture was filtered and
then rice husk was washed with distilled water for several times.
Thereafter, the filtered rice husk was dried in an oven at 100° for 24 h.
In the second step, the rice husk was acid-leached by reflux boiling in
H2SO4 aqueous solution (10% V/V). In continue filtration and drying
processes were performed similar to the previous step. Finally, the dried
rice husk sample was calcined in a furnace at 900° for 5 h, yielding
white-colored ash which contained 90–97% silica.
2.3. Preparation of Hyd/PVP/silica nanocomposite
Sulfonation of CMC was performed according to the method of
Gamzazade et al. [32]. One gram of SCMC was mixed adequately with
30 mL distilled water in a three necked glass round-bottomed flask
equipped with a mechanical stirrer, a reflux condenser, and a nitrogen
purge line. The prepared mixture was stirred continuously at 40° for
10 min to obtain a homogeneous solution. Then, 1 g PVP and 0.05 g
silica nanoparticles were added to the prepared solution while stirring.
A few minutes later, 7.2mL of 65% neutralized AA and 0.018 g cross-
linker agent (MBA) were added to the mixture. After purging with ni-
trogen to remove the dissolved oxygen, 0.05 g APS was added to the
mixture as initiator agent. Thereafter, temperature of the reaction
mixture was raised up to 60° and kept at this condition for 4 h to
complete the polymerization process. The gel like product was cut into
small pieces, and then it was immersed in ethanol for 24 h to remove
unreacted species. Afterwards, the dehydrated hydrogel sample was
dried in an oven at 70° for 24 h. For comparison, a neat hydrogel sample
without addition of PVP and silica nanoparticles was also synthesized
similar to the above described method.
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Materials Science & Engineering C 90 (2018) 333–340
2.4. Preparation of Hyd/PVP/silica/NPK formulation
To prepare SRF formulation based on Hyd/PVP/Silica/NPK by in-
situ polymerization method, a pre-determined amount of urea (10 g),
ammonium dihydrogen phosphate (5 g), and potassium dihydrogen
phosphate (5 g) was dissolved in a solution of SCMC under constant
stirring. Next steps for the synthesis of SRF formulation were performed
in compliance with the described procedure in Section 2.3.
2.5. Characterization methods
The FTIR spectra of Hyd/PVP/Silica, NPK and Hyd/PVP/Silica/NPK
were recorded by a Bruker Tensor 27 FTIR at the wavenumber range of
400–4000 cm−1 using samples prepare as KBr pellets. Wide angle X-ray
diffraction patterns of Hyd/PVP/Silica, NPK and Hyd/PVP/Silica/NPK
were also measured using a Siemens D500 X-ray diffractometer
(Siemens AG, Karlsruhe, Germany) with Cu Kα radiation in 2Ɵ range of
2° to 70°. The surface morphologies of Hyd/PVP/Silica and Hyd/PVP/
Silica/NPK formulation were studied using MIRA3 FEG-SEM (Tescan,
Czech) scanning electron microscope.
2.6. pH-sensitivity and pulsatile behavior
To investigate on-off switching behavior as well as reversible
swelling (pH = 8) and deswelling (pH = 2) property of the prepared
hydrogels, diluted 0.1 M aqueous solutions of NaOH and HCl were used.
First, 0.05 g dried hydrogel sample was transferred into a tea bag and
then, it was immersed in distilled water at room temperature. The
swollen hydrogel samples were removed from the distilled at certain
time intervals and were weighted after removing the surface water by a
filter paper. Each experiment was performed in 4 times. The equili-
brium swelling ratio (Seq (g/g)) was calculated using the following
equation:
Ws − Wd
Seq (g / g ) =
Wd (1)
where Seq (g/g) is equilibrium swelling ratio, Ws (g) is the weight of the
swollen hydrogel sample, and Wd (g) is the weight of the dry hydrogel
sample.
2.7. Saline sensitivity and pulsatile behavior
To investigate on-off switching behavior of prepared samples, 1 g of
dried hydrogel sample was immersed in distilled water and 0.1 M
aqueous solution of NaCl, periodically. The equilibrium swelling ca-
pacity was calculated similar to the previously mentioned method.
2.8. Water retention behavior of soil with and without SRF formulation
To investigate water retention of soil containing synthesized SRF
formulation, a plastic cup containing well-mixed dry sample of SRF
formulation and 100 g of dry loamy sand soil (below 20 mesh) was
prepared. Thereafter, 50 mL distilled water was poured into the plastic
cup and weighed (W0). As comparison, another 100 g of dry loamy sand
soil without SRF formulation was placed in an identical plastic cup and
after addition of 50 mL distilled water weighed (W). The plastic cups
were kept at room temperature and weighed every day (Wt) over a
period of 30 days. Finally, the water retention percent (WR%) of soil
was determined by following equation:
Wt − W
WR% = × 100
W0 − W (2)
2.9. Slow release behavior of synthesized SRF formulation
To study release of NPK fertilizer from synthesized SRF formulation,
A. Olad et al.
0.05 g of SRF formulation was placed in a dialysis bag and immersed in
100 mL distilled water. At certain time intervals, 10 mL solution was
sampled for NPK fertilizer determination, and 10 mL an additional of
distilled water was added into the beaker to maintain a constant volume
of solvent. The amount of fertilizer released from SRF formulation was
determined using digital conductivity meter from the calibration curve.
The fertilizer concentration was calculated according to a standard
curve, and accumulative release was obtained by the following formula:
n−1
VE ∑1 Ci + V0 Cn
E= × 100
m0 (3)
where E is the accumulative release (%) of NPK fertilizer, and VE and V0
are the sampling volume and the initial volume of release medium in
mL, respectively. Ci and Cn are the fertilizer concentrations (mg/mL), i
and n are the sampling times, and m0 is the mass of fertilizer in the SRF
formulation (mg).
For release experiments of SRF formulation in soil, a dry sample of
synthesized SRF formulation was well-mixed with 100 g of dry loamy
sand soil (below 20 mesh). Then the soil mixture slowly poured into a
200 mL glass column which equipped with ceramic membrane and
valve. Next, 70 mL distilled water was added into soil containing
column until it reached the soil-water saturation point. The moisture
content in the column was maintained approximately constant (30 wt
%) by adding distilled water throughout the period of experiment.
Similar to the above mentioned method, 10 mL of the solution was
collected and its fertilizer content was determined by digital con-
ductivity meter at certain time intervals.
3. Results and discussion
3.1. FT-IR spectra analysis
Fig. 1 shows the FTIR spectra of synthesized Hyd/PVP/Silica, Hyd/
PVP/Silica/NPK, and pure NPK fertilizer. As shown in NPK fertilizer
spectrum, two peaks appeared at 3338 and 3452 cm−1 are related to
stretching vibration of OeH and NeH groups in NPK fertilizer com-
position. Furthermore, the peaks appeared at 2804 cm−1, 1460 cm−1,
1153 cm−1, and 1090 cm−1 indicate the OeH stretching vibration, the
P]O stretching vibration, the P–OH stretching vibration, and the
HO–P–OH bending vibration, respectively. Moreover, the absorption
peak which corresponds to PO4 vibration was found at 557 cm−1. The
stretching vibrations of OeN]P and eONO2 bonds in ammonium di-
hydrogen phosphate appeared as low intensity absorption bands be-
tween 729 cm−1 and 788 cm−1. Also, the C]O absorption band of urea
was appeared at 1620 and 1670 cm−1as a two sharp peak [26]. As
shown in Hyd/PVP/Silica spectrum, low intensity absorption peaks
appeared at 1263 cm−1 and 813 cm−1 are related to the asymmetric
stretching vibration of S]O group, and its symmetric stretching vi-
bration appeared at 1010 cm−1. Also, the peak at 1140 cm−1 is due to
the symmetric stretching vibration of CeOeS [33–35]. These peaks
revealed that OH groups of CMC are partially sulfonated. Absorption
bands appeared at 580 and 685 cm−1 are corresponded to symmetric
and asymmetric stretching vibration of SieOeSi bonds, respectively.
These characteristic absorption peaks of silica confirming that silica
nanoparticles have been incorporated into hydrogel network, success-
fully. Also, significant characteristic peaks at 1670 and 1710 cm−1 are
assigned to the carbonyl groups of AA. Furthermore, the broad band at
3200–3500 cm−1 is due to stretching vibration of OH bonds in the
carboxylic acid functional groups in the hydrogel which confirms the
grafting reaction of SCMC chains with AA. In addition to the above
mentioned peaks, the absorption band at 1220 cm−1 relating to CeN
bonds, confirms the presence of PVP in hydrogel network [36]. Ac-
cording to the FTIR spectra of Hyd/PVP/Silica/NPK and Hyd/PVP/Si-
lica, the appearance of NPK characteristic peaks in FTIR spectra of Hyd/
PVP/Silica/NPK confirms the successful encapsulation of NPK fertilizer
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Materials Science & Engineering C 90 (2018) 333–340
compound within the superabsorbent nanocomposite network.
3.2. XRD pattern analysis
To study the structure and crystallinity of the prepared samples,
XRD patterns Hyd/PVP/silica and Hyd/PVP/silica/NPK formulation
were recorded. As shown in Fig. 2 for Hyd/PVP/silica, a typical broad
peak appeared at 2Ɵ = 22.5°, verifies the presence of silica nano-
particles in the Hyd/PVP/silica composition [31]. The characteristic
peaks of pure urea contain a set of peaks at 2Ɵ = 23°, 25°, 29°, 32°, 36°,
and 37° [31,37]. Also, the characteristic peaks of pure ammonium di-
hydrogen phosphate and potassium dihydrogen phosphate appeared at
2Ɵ = 17.5°, 23°, 29°, 34°, 38.5°, 45°, 51.5°, 58.5°, 60.5°, 62°, 69° and
2Ɵ = 17.5°, 24°, 31°, 34°, 46°, 47°, and 49°, respectively [31,38,39]. In
the case of Hyd/PVP/silica/NPK XRD pattern, appearance of NPK
characteristic peaks confirms the incorporation of the NPK fertilizer
compound into the hydrogel nanocomposite network.
3.3. Surface morphology analysis
The surface structure and morphologies of Hyd/PVP/silica and
Hyd/PVP/silica/NPK formulation were investigated using scanning
electron microscope (SEM) technique. As can be obviously seen in
Fig. 3a, Hyd/PVP/silica has highly porous morphology which is related
to incorporation of silica nanoparticles and its physical crosslinking
effect. This interconnected porous network increases the contact surface
area of hydrogel nanocomposite which leads to easier and faster dif-
fusion of water molecules into hydrogel network and induces a larger
enhancement in its water absorption capacity. In the case of Hyd/PVP/
silica/NPK formulation (Fig. 3b), the crystals of NPK ingredients such as
urea, ammonium dihydrogen phosphate, and potassium dihydrogen
phosphate are distributed on the surface and also within the pores of
the hydrogel nanocomposite. It should be noted that, the interlinked
pores of Hyd/PVP/silica/NPK formulation can delay dissolution of
loaded fertilizer into swelling medium and results in the slow release
behavior of formulation.
3.4. Swelling studies
The water absorption capacity of hydrogels is significantly influ-
enced by swelling medium salinity and pH value. Generally, the water
absorption capacity of hydrogels in saline solutions is decreased com-
pared to the values in distilled water. This phenomenon is often at-
tributed to a screen effect of the additional cations which causes non-
efficient anion-anion repulsive electrostatic forces. As shown in Fig. 4,
prepared hydrogel samples are swelled in distilled water and deswelled
in saline solution of NaCl. Moreover, the absorption-desorption beha-
vior of them is quite repeatable. This sudden swelling-deswelling (on-
off swelling) behavior at distilled water and saline solution demon-
strated that prepared hydrogels are salt-sensitive and smart hydrogels.
Also, the pH-dependent swelling reversibility of the prepared hydrogels
was investigated in different solutions with pH = 2 and 8. As shown in
Fig. 5, at pH = 8, the hydrogel samples swell due to anion-anion
electrostatic repulsion while at pH = 2, they shrink immediately due to
the protonation of carboxylate groups. These on-off and pulsatile be-
haviors of prepared samples in different pH values demonstrate that the
hydrogels are pH-sensitive and fall into the smart hydrogels category.
3.5. Water retention behavior of Hyd/PVP/silica/NPK in soil
Fig. 6 shows the water retention behavior of Hyd/NPK, Hyd/PVP/
NPK, and Hyd/PVP/silica/NPK formulations in loamy sand soil. Ex-
perimental results show that the addition of prepared formulations into
loamy sand soil composition increases the water retention of the soil for
a longer period of time whereas unmodified soil completely vaporized
the absorbed water after 14 days. In addition, it can be seen that Hyd/
A. Olad et al.
Fig. 1. The FTIR spectra of NPK, Hyd/PVP/silica, and Hyd/PVP/silica/NPK.
PVP/NPK modified soil and also Hyd/PVP/silica/NPK modified one
have better water retention behavior in comparison with neat hydrogel
(Hyd/NPK) modified soil. This finding demonstrates that PVP and silica
nanoparticles which are incorporated in hydrogel network of formula-
tion, improve the water retention behavior of formulations. As a result,
the use of Hyd/PVP/silica/NPK formulation in soil can decrease irri-
gation frequencies and enhance the ability of plants to fight against
drought.
3.6. Fertilizer release studies
In order to study the fertilizer release profile of pure NPK, Hyd/
PVP/NPK, and Hyd/PVP/silica/NPK formulations, conductivity
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Materials Science & Engineering C 90 (2018) 333–340
measurements were performed as a function of time in water and soil
and is presented in Fig. 7a and b, respectively. As shown in Fig. 7a,
according to the ease of dissolution of pure NPK fertilizer in water, its
complete release was accomplished within 6 h. In contract, Hyd/NPK,
Hyd/PVP/NPK, and Hyd/PVP/silica/NPK formulations showed a pre-
ferable sustained release behavior which is related to the barrier effect
of polymeric matrix in hydrogel network. The fertilizer content in Hyd/
NPK, Hyd/PVP/NPK, and Hyd/PVP/silica/NPK formulations released
31, 16.9, 11.2%, and 62.1, 44.5, 32.1%, and 89, 75.3, 65.3% within
1 day, 1 week, and 1 month, respectively. Fig. 7b shows the release
patterns of pure NPK, Hyd/NPK, Hyd/PVP/NPK, and Hyd/PVP/silica/
NPK formulations in soil. As can be seen, the cumulative release rate of
pure NPK is high initially, which is related to the ease of dissolution of
A. Olad et al. Materials Science & Engineering C 90 (2018) 333–340

Fig. 2. The XRD patterns of Hyd/PVP/silica and Hyd/PVP/silica/NPK.

Fig. 4. On-off switching behavior of Hyd, Hyd/PVP, and Hyd/PVP,silica:
swelling in distilled water and deswelling in NaCl (0.1 M).
fertilizer compound. However, the complete fertilizer release of un-
treated NPK is reached within 4 h. In contrast, the Hyd/NPK, Hyd/PVP/
NPK, and Hyd/PVP/silica/NPK formulations fertilizer release on the
first day, 1 week, and 1 month was about 14.6, 16.7, 29%, and 27.6,
34.6, 56.4%, and 54.6, 72.3, 83.6%, respectively. The obtained results
from cumulative release of fertilizer in distilled water and soil de-
monstrate that the sum of fertilizer release for Hyd/PVP/silica/NPK
formulation was lower than 15% on the first day and was not above
75% on the 1 month. This finding indicates that the slow release
character of the Hyd/PVP/silica/NPK formulation prepared in this
work has a good compliance with the standard of slow release fertilizers
of the Committee of European Normalization (CEN) [40]. Mechanisms
of fertilizer release from prepared formulations can be explained as
follows. The NPK fertilizer used in the prepared formulations is com-
posed of urea, potassium dihydrogen phosphate, and ammonium di-
hydrogen phosphate. After addition of the formulation in water, first
the hydrogel swelled and absorbed water dissolves the fertilizer. Ac-
cording to dynamic exchange of the water in hydrogel and release
medium, the dissolved fertilizer is released gradually in water via
polymeric shell. Fertilizer release rate is primarily significant due to the
Fig. 5. On-off switching behavior of Hyd, Hyd/PVP, and Hyd/PVP, silica:
difference of the soluble material between inside and outside of the
swelling in pH = 8 and deswelling in pH = 2.

Fig. 3. SEM images of Hyd/PVP/silica (a) and Hyd/PVP/silica/NPK (b).

337
A. Olad et al. Materials Science & Engineering C 90 (2018) 333–340

system and fertilizer, n is the diffusional exponent which is indicative of

the transport mechanism. The value of n ≤ 0.5 means that the fertilizer
release mechanism approaches to a Fickian diffusion controlled release,
whereas an n value of n = 1.0 indicates that the fertilizer release me-
chanism approaches to Case II transport (zero order) and the n value
between 0.5 and 1.0 shows that fertilizer release mechanism is anom-
alous (non Fickian) diffusion [42,43].
Fig. 7c and d shows the plots of release fractions of fertilizer for
Korsmeyer-Peppas model in water and soil, respectively. Table 1 pre-
sented the obtained parameters for Hyd/NPK, Hyd/PVP/NPK, and
Hyd/PVP/silica/NPK formulations. As can be seen from Table 1, the n
value is obtained lower than 0.5 for all formulations release of fertilizer
in water and soil. This finding is the indicative of Fickian diffusion
controlled release.
The prepared formulation in this work exhibits several advantages
in compared with other formulations already described in the literature
[16,44]. One-step preparation process of fertilizer loaded formulations
by in-situ polymerization technique does not require extra steps of
Fig. 6. Water retention behavior of the loamy sand soil with Hyd, Hyd/PVP, coating procedure in which fertilizer granules are coated with hydro-
Hyd/PVP/silica, and without fertilizer formulation. gels. Moreover, the use of silica nanoparticles not only increases the
water absorption capacity and providing slow release property, but also
it can significantly reduce the final production cost of the prepared
hydrogel. But after a while, because of the decrease of this difference,
formulation. In comparison with earlier prepared formulations
the rate of release slows down.
[17,45,46], the Hyd/PVP/silica/NPK formulation developed in this
Also, the kinetic of release data of fertilizer from prepared for-
research showed excellent pH and salt sensitivity as well as good water
mulations were analyzed by using the more generalized form proposed
retention behavior in loamy sand soil. Finally, it can be concluded that
by Korsmeyer and Peppas [41].
using of this formulation not only can increase quality and quantity of
Mt agricultural products but also can improve fertility and water con-
= KKP t n servation of soil.
M∞ (4)

where (Mt/M∞) is the released fraction of fertilizer at time t, kKP is a

constant incorporating characteristic of the macromolecular network

Fig. 7. Fertilizer release behaviors of pure NPK, Hyd/NPK, Hyd/PVP/NPK, Hyd/PVP/silica/NPK formulations in distilled water (a), and in soil (b), and plots of

338
A. Olad et al.
Table 1
The parameters of diffusion Korsmeyer-Peppas model for NPK release from formulations in distilled water and in soil.
Formulation
Kinetic model Equation Parameter Hyd/NPK
Water
Korsmeyer-Peppas R2 0.9931
Mt
= kKP t n n 0.3024
M∞
KKP × 102 2.71
4. Conclusion
Accordingly, we synthesized a novel SRF hydrogel nanocomposite
by in-situ graft polymerization of acrylate-based monomers onto SCMC
backbone in the presence of PVP, silica nanoparticles, and NPK ferti-
lizer. FTIR and XRD results confirmed that grafting of SCMS chains with
AA monomers has been performed successfully. Also, the prepared
formulations showed a good pH and salt sensitivity as well as excellent
water retention behavior in loamy sand soil. Study on the fertilizer
release of formulations demonstrated a slow release behavior.
Moreover, the fertilizer release kinetic studies revealed that the devel-
oped SRF formulations follow a fickian diffusion mechanism. These
observations suggest that prepared Hyd/PVP/silica/NPK formulation
can improve the utilization of fertilizer and water conservation in
agricultural and horticultural applications.
Compliance with ethical standards
Funding: This study was funded by Department of Applied
Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran.
Conflict of interest: The authors declare that they have no conflict of
interest.
Acknowledgements
The financial support of this work by the University of Tabriz is
gratefully acknowledged.
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Materials Science & Engineering C 90 (2018) 333–340
Hyd/PVP/NPK Hyd/PVP/silica/NPK
Soil Water Soil Water Soil
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