PREPARATION AND CHARACTERIZATION OF CONTROLLED-RELEASE

FERTILIZERS BASED ON POLYMER HYDROGELS

*
Tongsai Jamnongkan and Supranee Kaewpirom*
Department of Chemistry and the Center of Excellence for Innovation in Chemistry,
Faculty of Science, Burapha University, Chonburi 20131, Thailand.
E-mail address: kaewpiro@buu.ac.th

:



70-300
30 PVA-, PVA/CS- CS-hydrogel
25, 10 4
PVA-hydrogel
CS-hydrogel

Abstract: In this study, the release behavior of controlled release fertilizer (CRF)
hydrogels has been investigated. The CRF hydrogels were prepared from poly(vinyl
alcohol), poly(vinyl alcohol)/chitosan and chitosan using glutaldehyde as a crosslinker.
The chemical structure of the CRF hydrogels was observed by Fourier transforms
infrared spectrometer (FT-IR). The CRF hydrogels exhibited the equilibrium swelling
ratio (SR) in the range 70-300%. It was found that, the CRF hydrogels increased the
water retention of the soil. After 30 days, soil containing the PVA-, PVA/CS- and CShydrogels showed the water retention capacities of 25, 10 and 4%, respectively. While
the soil without the CRF hydrogel had already given off most of the water. The release
behavior of nutrients from the CRF hydrogels, both in deionized water and in soil, was
investigated. The PVA hydrogel showed the highest percent cumulative release in
deionized water while CS hydrogel showed the highest percent cumulative release in
soil.
Introduction: Controlled release is a method by which biologically active chemicals
are made available to a target species at a specified rate. Polymers are used as matrix
primarily to control the rate of delivery, mobility, and period of effectiveness of the
chemical components. The principal advantage of controlled release formulations is that
less chemicals are used for a given time period, thus lowering the impact on non target
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species and limiting leaching, volatilization, and degradation. The macromolecular

nature of polymers is the key to limiting chemical losses by these processes. One of
many forms of polymers used in controlled release is polymer hydrogel. Polymer
hydrogels can be defined as three-dimensional polymeric networks that can retain a
significant amount of water within their structures, and swell without dissolving in
water. Polymer hydrogels have been used for agricultural as controlled release
fertilizers. The use of controlled release fertilizers causes an increase in their efficiency,
reduces soil toxicity, minimises the potential negative effects associated with
overdosage and reduces the frequency of the application.
In this study, the CRF hydrogels were prepared from poly(vinyl alcohol), chitosan
and the blend of these two polymers, using glutaraldehyde as a crosslinker. Water
absorbency and nutrients release behavior of such the CRF hydrogels in deionized water
and in soil were investigated.
Methodology: The CRF hydrogels were prepared mixing 10%w/v PVA solution with
1%w/v chitosan solution in 2%w/v acetic acid. The mixture was stirred constantly until
uniform and the appropriate amount of fertilizer solution and the crosslinking agent
were added into the mixture under constant stirring. After well mixing, the mixture was
poured into a Petri disk and the gel formed within 30 minutes. The CRF hydrogels
product was dried at 40 oC in a vacuum oven overnight. The various types of controlled
release fertilizer (CRF) hydrogels, amount of PVA, CS, glutaraldehyde and crosslink
solution are shown in Table 1. The synthesized hydrogels were characterized by FT-IR
and SEM. Water retention and water absorbency characteristics of the CRF hydrogels
were studied using the equation 1 and 2, respectively. In addition, the release behaviors
of nutrients from the CRF hydrogels, both in deionized water and in soil, were
investigated.
Table 1 Composition of CRF hydrogels.

CRF
hydrogels

CS solution
(mL)

PVA
PVA/CS
CS

5.00
10.00

PVA
solution
(mL)
10.00
5.00
-

Fertilizer
solution(a)
(mL)
2.50
2.50
2.50

GA(b)
(mL)
0.25
0.50

Crosslink
solution(c)
(mL)
2.80
1.40
-

(a)

Fertilizer solution was prepared by dissolving 2.0010 g of ammonium nitrate,

3.3015 g of ammonium diphosphate and 2.5275 g of potassium nitrate to make a 100.00
mL aqueous solution.
(b)
1.20 %(w/v) of glutaraldehyde.
(c)
Crosslink solution composes of 50 %w/v methanol (the quencher), 10 %w/v
acetic acid (the pH controller), 1.20 %w/v of glutaraldehyde and 10 %w/v sulfuric acid
(the catalyst), making up a 3:2:1:1 weight ratio solution.

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%WR

Wt W
100
Wo W

(1)

Where W, Wo and Wt refer to the weight of

sandy soil mixed dry hydrogels, sandy soil and
hydrogels when added water and weighed
every day of each cup, respectively.

% SR

W s Wd
100
Wd

(2)

Where Ws and Wd refer to the weight of

swollen
and
dry
hydrogels,
respectively.

Results, Discussion and Conclusion: The FT-IR spectra of PVA-, CS- and PVA/CShydrogels are shown in Fig. 1. An observed vibration peak at 1214 cm-1, which refers to
COC groups (Fig. 1a), indicates a possible formation of acetal bridges by the
reactions between hydroxyl groups of PVA and aldehyde groups of glutaraldehyde. A
characteristic peak of chitosan hydrogel is found at 1651 cm1 (Fig. 1b). This
corresponds to the formation of imine bond (C=N) via Schiffs base structure by the
reactions between amino groups of chitosan and aldehyde groups of glutaraldehyde.
The FT-IR spectrum of the PVA/CS hydrogel film (Fig 1c) shows the characteristic
peaks of both chitosan hydrogel and PVA hydrogel. Those include the peak around
1651 cm-1, relating to the imine bond (C=N), and a peak around 1214 cm-1, relating to
COC groups.

Fig. 1. The FT-IR spectra of (a) PVA-, (b) CS- and (c) PVA/CS-hydrogels.
Water retention behavior of soil containing the CRF hydrogels and soil without the
CRF hydrogels are shown in Fig. 2. It was found that the CRF hydrogels increase water
retention of the soil. After 30 days, the water retention capacities of the soil containing
PVA-, PVA/CS- and CS-hydrogels are 25, 10 and 4%, respectively. While the soil
without the CRF hydrogels had already given off most of the water. Hence, all the CRF
hydrogels show high water retention capacity in soil, and with their use, water can be
saved and managed.

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Fig. 2. Water retention of soil with (a)

PVA-, (b) PVA/CS-, (c) CS- hydrogels
and (d) soil without hydrogel.

Fig. 3. Swelling ratio of (a) PVA

hydrogel, (b) PVA/CS hydrogel and (c)
CS hydrogel.

The effect of chemical structure of the hydrogels on their water absorbency is shown
in Fig. 3. It was found that, at equilibrium, the PVA hydrogel shows the highest water
absorbency (~300%) among the three hydrogels. PVA/CS- and CS-hydrogels show
equilibrium water absorbency around 225 and 70%, respectively. Hydrophilic groups
are responsible for such high water absorbency. Since PVA is more hydrophilic than
CS, thus, the higher the PVA content within the CRF hydrogels, the higher the water
absorbency is. This is one of the most important properties of the CRF hydrogels, used
in agriculture, for they can absorb more water during raining or irrigating.
The morphologies of fractured surface of polymer hydrogels are shown in Fig. 4.
The polymer hydrogels were dried at 40 oC in a vacuum oven overnight before the SEM
morphological investigation. It was found that PVA hydrogel exhibited rough texture,
due to its porous structure, while CS hydrogel had dense architecture. In addition, the
porous seemed to decrease with decreasing PVA content. Therefore, the pore structures
have influence to the swelling ratio of hydrogels.

Fig. 4. SEM of fractured surface of (a) PVA-, (b) PVA/CS- and (c) CS-hydrogels.
Nutrients (N, P, K) release behavior of the CRF hydrogels in the deionized water, at
room temperature, is shown in Fig. 5A. It was found that all the hydrogels showed high
initial nitrogen release rate then the rate became slower. In addition, PVA hydrogel
shows higher cumulative release than PVA/CS hydrogel which shows higher
cumulative release than CS hydrogel. This is because PVA is more hydrophilic than CS,
so that it can adsorb more water within its structure. The water, then, dissolves nitrogen
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compounds in the CRF hydrogels. Consequently, the nitrogen releases. Unlike nitrogen,
the phosphorus release rate of the CRF hydrogels in deionized water was high at the
initial and then became constant. The PVA hydrogel shows the highest percent
cumulative release of phosphorus, both initial and at equilibrium, due to its high
hydrophilicity. Theoretically, phosphorus is released after hydrolyzing cleavage of P
OP bonds. In this study, phosphorus (in form of dihydrogen ammonium phosphate) in
the CRF hydrogels releases after the hydrogels adsorb water, leading hydrolysis process
taking place. Therefore, phosphorus diffuses out of the CRF hydrogels with the higher
swelling ratio more easily and faster than from the CRF hydrogels with the lower
swelling ratio. Like phosphorus, it was found that the potassium release rate is fast at
the beginning due to the high concentration difference between the inside structure of
the CRF hydrogels and the outer solution. Then, the potassium release rate decreases as
the concentration difference decreases. Besides, it was found that PVA-hydrogel shows
the highest percent cumulative release of potassium, both initial and at equilibrium. The
hydrophilicity of the PVA hydrogel is responsible for making potassium nitrate
solution, since it can adsorb water within its structure. The water, then, dissolves
potassium nitrate making concentration difference between the inside structure of the
hydrogel and the outer solution. Consequently, potassium releases from the hydrogel. It
can be concluded from the above results that the chemical structure of the CRF
hydrogel is one of the factors affecting the release behavior of nitrogen, phosphorus and
potassium nutrients from the CRF hydrogels. In the other words, the release behavior of
nutrients is controlled by varying the chemical structure of the CRF hydrogels.
In soil, nutrients release behavior of the CRF hydrogels, at the room temperature, is
exhibited in Fig. 5B. It can be seen from the figure that all the CRF hydrogels showed
high initial release rate and the rate become slower after 1-6 days. In contrast with the
release behavior in water, CS- and PVA-hydrogel display the highest and the lowest
percent cumulative release, respectively, regardless of time. This is due to the fact that
chitosan has reactive amino and hydroxyl groups, which provide the possibility to
degradation. Moreover, for all the synthesized CRF hydrogels, the swelling ratio in soil
solution is less than that in deionized water. Thus the diffusion of soluble fertilizers
from the CRF hydrogels into soil is more difficult. Therefore, the release of nutrients
from the CRF hydrogels in soil is slower than that in deionized water.
In this study, it can be concluded that the CRF hydrogels were prepared from PVA,
PVA/CS and CS using glutaraldehyde as a crosslinker. All the synthesized CRF
hydrogels exhibited high initial swelling rates. PVA hydrogel showed the highest
equilibrium water absorbency (~300%) among the three hydrogels while PVA/CS- and
CS-hydrogels showed equilibrium water absorbency around 225 and 70%, respectively.
This is one of the most important properties of the CRF hydrogels, used in agriculture,
for they can absorb more water during raining or irrigating. The water retention of soil
containing the CRF hydrogels was also examined. It was found that the CRF hydrogels
increased the water retention of the soil. On the 30 th day, the water retentions of soil
with PVA-, PVA/CS- and CS-hydrogels were 25, 10 and 4%, respectively. While the
soil without CRF hydrogels had already given off most of the water. The release
behavior of nutrients from the CRF hydrogels, both in deionized water and in soil, was
also investigated. In deionized water, the PVA hydrogel showed highest percent
cumulative release among the three prepared hydrogels. The nutrients release behavior
also relates to degree of swelling of the CRF hydrogels. The higher the swelling ratio,
the more the release amount is. However, the nutrients release behavior of the CRF
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hydrogels in soil is different from that in deionized water. It was found that CShydrogel exhibited the highest the percent cumulative release of nutrients among the
three prepared hydrogels. This is because chitosan is an excellent biodegradable
material and is easily degraded by microorganisms and ions existing in soil.

(A)

(B)

Fig. 5. Release behavior of nutrients in (A) deionized water and (B) soil from (a)
PVA-, (b) PVA/CS- and (c) CS-hydrogels.
References:
1. N.V. Majeti, R. Kuma, React. Funt. Polym., 2000, 46, 127.
2. W. Lan and L. Mingzhu, Carbohyd. Polym., 2008, 72, 240-247.
Keywords: chitosan, controlled release fertilizer, polymer hydrogel, swelling ratio,
water retention.
Acknowledgements
Financial support from the Center of Excellence for Innovation in Chemistry
(PERCH-CIC), Commission on Higher Education, Ministry of Education is gratefully
acknowledged. Acknowledgements also go to Department of Chemistry, Faculty of
Science, Burapha University. The authors also thank Dr. Siridech Boonsang for his
priceless advisory.

35th Congress on Science and Technology of Thailand