Reactive & Functional Polymers 67 (2007) 769779

REACTIVE
&
FUNCTIONAL
POLYMERS
www.elsevier.com/locate/react

Controlled release NPK compound fertilizer

with the function of water retention
Rui Liang, Mingzhu Liu *, Lan Wu
Department of Chemistry and State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China
Received 18 September 2006; received in revised form 5 December 2006; accepted 6 December 2006
Available online 21 December 2006

Abstract
Controlled release nitrogen, phosphorus and potassium (CRNPK) compound fertilizer with the function of water retention was prepared, which possessed the core/shell structure. Its core was urea formaldehyde (UF) and polyphosphate
potassium (PAK) fertilizer, and the shell was P(acrylic acid-co-acrylamide)/kaolin (P(AA-co-AM)/kaolin) superabsorbent
composite. Analysis results showed that the N, P and K contents were 11.3, 21.1 (shown by P2O5) and 8.6 (shown by
K2O) wt%, respectively. The synthesis conditions of inversion suspension polymerization were studied systematically.
The water absorbency of the product was 91 g/g in tap water. The swelling rate, slow release and water retention properties
of CRNPK were also investigated. Additionally, the eect of temperature on the nutrients release behaviors was studied.
The results showed that the product had high initial swelling rate, and the product not only had a good slow release property but also excellent water retention ability, which could eectively improve the utilization of fertilizer and water resource
at the same time.
2006 Elsevier Ltd. All rights reserved.
Keywords: Controlled release; P(acrylic acid-co-acrylamide)/kaolin superabsorbent; Water absorbency; Core/shell structure

1. Introduction
Fertilizer and water are the important factors
that limit the production of agriculture, so it is very
important to improve the utilization of fertilizer
nutrients and water resources. Slow release fertilizers are made to release their nutrient contents gradually and if possible, to coincide with the nutrient
requirement of a plant. A number of slow release
fertilizers have been developed during the past dec*
Corresponding author. Tel.: +86 931 8912387; fax: +86 931
8912582.
E-mail address: m-zliu@163.com (M. Liu).

ades. There are three types of these fertilizers:

matrix-type formulations constitute the rst major
category of slow or controlled release fertilizers
due to their simple fabrication. The active is dispersed in the matrix and diuses through the matrix
continuum or intergranular openings, that is,
through pores or channels in the carrier phase [1].
Another way of regulating the release of fertilizer
is coated fertilizer, i.e. a fertilizer core is coated by
inert materials. The release of the fertilizer is controlled by diusion through the shell [2]. The third
major category of such fertilizers is accomplished
by means of chemically controlled releasing products, such as urea-formaldehyde [3], polyphosphates

1381-5148/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2006.12.007

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R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

[4]. The release of such kind of slow release fertilizer

is controlled by the degradation rate, which in turn
is aected by various factors, such as molecular
weight of the polymer, and pH, temperature, ions
and microorganisms in soil, etc.
Superabsorbents are three-dimensionally crosslinked hydrophilic polymers capable of swelling
and retaining huge volumes of water in the swollen
state. Recently, research on the use of superabsorbents as water management materials for agricultural and horticultural applications has attracted
great attention and test of superabsorbents for agricultural applications has shown encouraging results
as they have been observed to help reduce irrigation
water consumption, lower the death rate of plants,
improve fertilizer retention in soil, and increase
plant growth rate [5]. However, its applications in
this eld have met some problems because most of
these superabsorbents are based on pure poly(sodium acrylate), and then they are too expensive
and not suitable for saline-containing water and
soils [6]. Recently, there have been many reports
on introducing inorganic clays, such as kaolin, bentonite, montmorillonite [7], attapulgite [8], and mica
[9] into pure polymeric superabsorbents in order to
improve swelling property, hydrogel strengths, and
reduce production costs.
On the basis of the above background and our
previous studies on superabsorbent polymers
[10,11] and slow release fertilizer [1215], in this
work, we prepared controlled release NPK compound fertilizer with the function of water retention,
which possessed the core/shell structure. Its core
was UF and PAK fertilizer, and the shell was
P(AA-co-AM)/kaolin superabsorbent composite.
CRNPK not only had slow release property, but
also could absorb water and preserve the soil moisture at the same time. The present report reveals the
synthesis conditions of inversion suspension polymerization, swelling rate, slow release, and water
retention properties of the CRNPK. The eect of
temperature on the nutrients release in distilled
water was also studied.

tory, Xian, China) was recrystallized from water.

Kaolin powder was supplied by Linze Colloidal
Co., Gansu, China. The others were all of analytical
grade and available from commercial sources.
2.2. Preparation of CRNPK

2. Experimental

Urea formaldehyde (UF) was made from urea

and 37% formaldehyde aqueous solution as
described previously [16], and polyphosphate potassium (PAK) was made from potassium dihydrogen
phosphate according to the literature [17]. Five
grams of dried UF powder (<90 mesh) and 5 g
PAK powder (<90 mesh) were placed into 50 ml
2 wt% sodium alginate solution. The mixture was
stirred vigorously until uniform and then slowly
added dropwise to a 0.5 M CaCl2 solution with a
pipette, the drops turned to white beads immediately because the sodium alginate in the drop was
crosslinked by Ca2+ at once (the function of sodium
alginate is the entrapment of UF and PAK). The
spherical beads were left in the CaCl2 solution for
30 min to ensure complete gelling and then separated from the solution, rinsed twice with distilled
water, and dried at room temperature overnight.
Five grams of dried beads obtained from above
process was added into a ask equipped with a
mechanical stirrer, a condenser, and a drop funnel.
A certain amount of tetrachloride, polyethylene glycoloctyl phenyl ether (OP), and sorbite anhydride
monostearic acid ester (span-80) were added into
the ask. The temperature was raised to 65 C using
a water bath while the contents were constantly stirred. As this process continued, a certain amount of
mixed solution of partially neutralized (by ammonia) acrylic acid, acrylamide, kaolin, N,N0 -methylenebisacrylamide
(NNMBA)
solution,
and
ammonium persulfate solution was slowly added
dropwise into the ask. The mixture was ltered
to remove the tetrachloride after being stirred for
2 h at 65 C and dried in an oven at 70 C, and then
the white homogenous granular CRNPK with core/
shell structure was obtained, which core was the
NPK compound fertilizer and the shell was P(AAco-AM)/kaolin superabsorbent composite.

2.1. Materials

2.3. Component analysis of CRNPK

Acrylic acid (AA, Beijing Oriental Chemical Factory, Beijing, China), urea, and sodium alginate
(SA) were of industrial grade. Ammonium persulfate (analytical grade, Xian Chemical Reagent Fac-

Content of nitrogen in the CRNPK was determined

by an element analysis instrument (Germany Elemental Vario EL Corp., model 1106). Contents of potassium and phosphate in the CRNPK were determined

R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

by an Inductively Coupled Plasmas (ICP) instrument

(American TJA Corp., model IRISER/S).
2.4. Characterization of the shell material of CRNPK
by FTIR
The shell material of CRNPK, P(AA-co-AM)/
kaolin was characterized by a Fourier-transform
infrared (FTIR) spectrophotometer (American Nicolet corp., model 170-SX).
2.5. Percentage of P(AA-co-AM)/kaolin shell
The percentage of P(AA-co-AM)/kaolin shell
was determined by mass dierence before and after
coating.
2.6. Measurement of water absorbency
One gram of CRNPK was immersed into a certain
amount of tap water and allowed to soak at room
temperature for 90 min. The swollen CRNPK was ltrated through an 80-mesh sieve to remove nonabsorbed water and weighed. Water absorbency
(WA) of per gram dried CRNPK was calculated
using Eq. (1):
WA

M
1
M0

Where M and M0 referred to the weight of the water

swollen and dry CRNPK, respectively.
2.7. Slow release behaviors of CRNPK
To study the eect of temperature on the release
behaviors of N, P and K, 0.5 g dry samples were
added into conical bottles containing 200 ml distilled water, and then, the bottles were put into incubators whose temperatures were set at 5 C, 20 C
and 35 C, respectively. At certain time intervals
(every 24 h), 2 ml solution was sampled for N, P
and K determination, and an additional 2 ml distilled water was injected into the bottles to maintain
a constant amount of solvent. The N content was
estimated by Kjeldahl method [18], and the P and
K content were determined by ICP method.
To study the slow release behaviors of CRNPK
in soil, the following experiments were carried out:
1 g CRNPK was well mixed with 200 g dry soil
(<26 mesh) and kept in a 200 ml plastic beaker
properly covered and incubated for dierent periods
at room temperature. Throughout the experiments,

771

the soil sample was maintained at 30 wt% water

holding capacity by weighing and adding tap water
if necessary, periodically. After 2, 5, 10, 15, 20, 25
and 30 days incubation period, the remaining granular CRNPK in the beakers were picked out and
washed with distilled water, and then dried at room
temperature overnight to estimate the contents of
N, P and K. For seven measurements, seven beakers
were prepared at the same time. The remaining
amount of N, P and K was estimated by element
analysis instrument and ICP, respectively. The
above tests were carried out in triplicate, and the
average value was taken as the result.
2.8. The largest water-holding ratio of the soil with
CRNPK
The sandy soil used in this study was representative of the area of Lanzhou, which lies in the northwest of China and is a dry and semi-desert region.
2 g CRNPK were well mixed with 200 g dry soil
and placed in a 4.5 cm diameter PVC tube. The bottom of the tube was sealed by nylon fabric (with the
aperture of 0.076 mm) and weighed (marked W1).
The soil samples were slowly drenched by tap water
from the top of the tube until water seeped out from
the bottom. After there was no seeping water at the
tube bottom, the tube was weighed again (marked
W2). Control experiment, i.e. soil without CRNPK
was also carried out. The largest water-holding ratio
(W%) of the soil was calculated from Eq. (2).
W%

W 2  W 1  100
W 2  W 1 200

2.9. Water retention of the soil with CRNPK

Two hundred grams of dry sandy soil (below
26 mesh) mixed with 2 g CRNPK was placed in a
cup (A), and the other 200 g sandy soil without
CRNPK was placed in an identical cup (B),
200 ml tap water was added into both cups, then,
the cups were kept under identical conditions at
room temperature for 20 days. The initial masses
of the mixture (W0) in the two cups were measured
after removal of excess water, and their masses were
recorded every 2 days (Wi) to compare the water
retention of CRNPK. Water retention (WR%) was
calculated by the following Eq. (3):
WR%

Wi
W0

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R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

3. Results and discussion

3.1. The characteristics and structure of CRNPK
The characteristics of CRNPK, i.e., composition,
diameters of dry and swollen samples, and percentage of the shell are presented in Table 1. The structure of CRNPK was core/shell, which core was
fertilizer and the shell was P(AA-co-AM)/kaolin
superabsorbent composite. Because the swelling
degree of P(AA-co-AM)/kaolin shell was bigger
than that of the core, the contact between the shell
and the core was interrupted during swelling process, thus an additional space lled with additional
water between the core and the surrounding hydrogel shell was formed (See Fig. 1). Therefore, the
CRNPK was capable of taking up water not only
Table 1
The characteristics of CRNPK
Characteristics

Values

Nitrogen content
P2O5 content
K2O content
Diameter of dry sample
Diameter of swollen sample
Percentage of P(AA-co-AM)/kaolin shell

11.3%
21.1%
8.6%
2.02.5 mm
1315 mm
30.9%

in form of swollen P(AA-co-AM/kaolin) gel, but

also in form of additional free water between the
core and the surrounding hydrogel shell, which
could enhance the water absorbency obviously [19].
3.2. FTIR analysis of P(AA-co-AM)/kaolin (the
shell material)
The infrared spectra of kaolin powder, P(AA-coAM) and P(AA-co-AM)/kaolin are shown in
Fig. 2AC, respectively. The observed peaks are at
3427 cm1, corresponding to NH stretching of
acrylamide unit, 2926 cm1, corresponding to the
CH stretching of acrylate unit, 1716 cm1, corresponding to the stretching of C@O in acrylate unit,
1662 cm1, corresponding to the carbonyl moiety of
the acrylamide unit, 1167 cm1, corresponding to
the COO stretching of acrylate unit, 1038 cm1
(1094 cm1) corresponding to the SiO stretching
of kaolin.
The infrared analysis result of P(AA-co-AM)/
kaolin in Fig. 2C shows that all the characteristic
groups, i.e., COOH (or COONa), CONH2,
CH, and SiO, exist in the product. In addition,
by comparing Fig. 2A and C, the absorption peaks
at 3624 and 915 cm1, contributed to OH group on
kaolin powder (see Fig. 2A), disappeared after the

Fig. 1. The photographs and schematic graphs of dry CRNPK (A) and swollen CRNPK (B).

R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

773

Water absorbency (g/g)

70

60

50

Fig. 2. The FTIR spectra of kaolin (A), P(AA-co-AM) (B),

P(AA-co-AM)/kaolin (C).

10

20

30

40

AM (wt%)
Fig. 3. The eect of AM content on the water absorbency.

reaction (see Fig. 2C). Therefore, it is suggested that

graft copolymerization between OH groups on
kaolin and monomers took place during the reaction [20].
3.3. Inuence of the parameters on water absorbency
For the swollen CRNPK, the water absorbency
consists of two parts: the water absorbed by
P(AA-co-AM)/kaolin and the water between the
core and the surrounding hydrogel shell (see
Fig. 1). Therefore, any factor that could aect the
two kinds of water would aect the water absorbency of CRNPK. According to Flory [21], the
water absorbency of superabsorbent polymer
depends on the amount of the hydrophilic groups,
crosslinking density, polymer network behavior,
and elasticity of the polymer networks, type of solvent and ionic strength of the external solution, etc.
To improve the swelling capacity of the product,
various reaction parameters are employed. The
details of the inuences of the reaction parameters
on water absorbency in tap water, such as the content of AM, kaolin, crosslinker, initiator, neutralization degree of AA are given below.
3.3.1. Eect of AM content on the water absorbency
Hydrophilic group plays an extremely important
part in water absorbency. In the P(AA-co-AM)/
kaolin polymeric system, the ratio of dierent
hydrophilic groups can be adjusted by changing
the proportion of AA to AM. The eect of AM content on water absorbency of CRNPK is shown in
Fig. 3. As can be seen from Fig. 3, there exists a
maximum when the AM content is 25 wt%. The
increase of water absorbency when AM content is

below 25 wt% could be attributed to the synergistic

eect of CONH2 group and COO group. On the
other hand, COO group has better hydrophilic
ability than CONH2, so water absorbency would
decrease with the further increase of AM content.
Additionally, AM is a nonionic monomer, and it
almost does not ionize in solution, so the ions in
solution have little inuence on it. Thus AM could
improve the salt-resistance ability of CRNPK,
which is extremely important for CRNPK due to
the existence of many kinds of ions in soil.
3.3.2. Eect of kaolin content on the water
absorbency
There are three kinds of way for kaolin particle in
the P(AA-co-AM)/kaolin [7]: the rst way, kaolin
particle serves as a crosslinking point chemically
bonded with the polymer, in this way, the network
structure and water absorbency would change with
the change of kaolin content; the second way, kaolin
particle acts as terminal point chemically bonded
with the polymer, in this way, the network structure
and water absorbency hardly changes with the
change of kaolin content; the third way, kaolin particle serves as a ller physically lled in the network
of polymer, in this way, the network structure
hardly change with the change of kaolin content,
however, water absorbency would decrease because
the content of hydrophilic groups is lower at a
higher kaolin content, and then the osmotic pressure dierence decreases.
The eect of kaolin content on water absorbency
is shown in Fig. 4. When the kaolin content is below
10 wt%, kaolin mainly exists in the rst way mentioned above in the P(AA-co-AM)/kaolin, i.e.,

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R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

80

Water absorbency (g/g)

Water absorbency (g/g)

80

70

60

70

60

50

10

20

0.08

30

kaolin (wt%)

exists as crosslinking points, which could improve

the network structure of the polymer composite,
as a result enhance the water absorbency; with the
increase of kaolin content (1020 wt%), the
increased kaolin mainly exists in the second way,
i.e., exists as terminal points, which would not aect
the water absorbency, so no considerable change in
water absorbency is observed; when the kaolin content is above 20 wt%, the additional amount of kaolin probably exists in the third way, i.e., acts as a
non-reactive ller, which contribute to the decrease
of water absorbency of the polymer. Moreover, the
shrinkage of the P(AA-co-AM)/kaolin would
decrease the space between the hydrogel shell and
the fertilizer core, therefore, decrease the water
absorbency of CRNPK further. A similar phenomenon has been reported by others [22].
3.3.3. Eect of crosslinker content on the water
absorbency
Crosslinking density is an important swelling
control element. Relatively small changes in crosslinking density can have a major inuence on water
absorbency. The eect of crosslinker content on
water absorbency is shown in Fig. 5. It can be seen
that the water absorbency reaches a maximum at
the crosslinker content of 0.1 wt%. When the crosslinker content is below 0.1 wt%, the decrease of
water absorbency could be attributed to two reasons: rst, an increase of soluble part in the
P(AA-co-AM)/kaolin polymer, which decrease the
water absorbency of the polymer; second, the
decrease of the hydrogel strength, which make the
hydrogel shell soft and could not retain the water
between the surrounding hydrogel shell and the fer-

0.16

Fig. 5. The eect of crosslinker content on the water absorbency.

tilizer core, consequently, the water absorbency

decreases obviously. On the other hand, when the
crosslinker content is beyond 0.1 wt%, the decrease
of water absorbency could be owed to the increase
of the crosslinking density, which in turn decreases
the space left for water to enter the polymer. Additionally and importantly, the decrease of swelling
degree of P(AA-co-AM)/kaolin would make the
space between the hydrogel shell and the core
decrease, which also contribute to the decrease of
water absorbency of CRNPK.
3.3.4. Eect of neutralization degree of AA on the
water absorbency
The eect of neutralization degree of AA on the
water absorbency is shown in Fig. 6. It is clear that
the water absorbency increases from 30% to 70%

80

Water absorbency (g/g)

Fig. 4. The eect of kaolin content on the water absorbency.

0.12

Crosslinker (wt%)

60

40
40

60

80

Neutralization degree of AA (%)

Fig. 6. The eect of neutralization degree of AA on the water
absorbency.

R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

and decreases with further increase in neutralization

degree of AA. When AA is neutralized, the carboxylic acid group turns into carboxylate group. In
water, the negatively charged carboxyl groups set
up an electrostatic repulsion which tends to expand
the network. In a certain range of neutralization
degree, the electrostatic repulsion increases with
the increase of neutralization degree. Furthermore,
the osmotic pressure increases with the increase of
neutralization degree, which also contributed to
the increment of water absorbency. However, further increases in the neutralization degree of AA,
water absorbency decreases due to the increase of
the solubility of the superabsorbent composite.
Moreover, at higher neutralization degree, the
screening eect of the counter ion on the polyanion
chain will lead to a reduction in expansion of the
network, thus result in the decrease of water absorbency of the P(AA-co-AM)/kaolin polymer.
In addition, the bigger the swelling degree of the
polymer is, the larger the space between the hydrogel shell and the fertilizer core is, and then the bigger
the water absorbency of CRNPK is; and vise versa.
3.3.5. Eect of initiator content on the water
absorbency
The dependence of water absorbency on initiator
content was also studied, and the result is presented
in Fig. 7. There is a maximum when the initiator
content is 0.8 wt%. On the one hand, when the initiator content was below 0.8 wt%, the water absorbency of the product was decreased. This may be
due to the decrease of the amount of free radicals
produced by initiator. Thus, the polymer network
could not be formed eciently, and the space

775

between the shell and core is small, which would

result in the decrease of the water absorbency. On
the other hand, at high initiator content (more than
0.8 wt%), large quantities of free radicals produced
by initiator may cause the faster reaction velocity
and the chain transfer to polymers [23], which
would result in the increase of crosslinking density
and aect the water absorbency consequently.
3.4. The swelling rate of CRNPK
The time required to reach maximum swelling
capacity of CNPK was studied and the results are
presented in Fig. 8. One gram of sample was
immersed in an excess amount of tap water and
the water absorbency was measured for every
5 min. The result indicated that the sample had a
high initial swelling rate, and more than 90% of
the maximum swelling capacity of CRNPK is
achieved within 40 min and the equilibrium water
absorbency is reached approximately at 60 min.
Furthermore, the high initial swelling rate is one
of the most important factors for CRNPK which
is used in agriculture, for it could absorb more water
during raining or irrigating.
3.5. Eect of temperature on the releases
of N, P and K
Figs. 911 shows the N, P and K release behaviors of CRNPK in distilled water at temperature
of 5, 20 and 35 C, respectively. It could be seen that
the temperature had considerable eects on the
release behaviors of N, P and K in CRNPK.

100

Water absorbency (g/g)

Water absorbency (g/g)

90

80

70

80

60

40

20

60
0.4

0.8

1.2

Initiator (wt%)
Fig. 7. The eect of initiator content on the water absorbency.

20

40

60

Time (min)
Fig. 8. The swelling rate of CRNPK.

80

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R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

A

Nitrogen released (%)

50
40

30
20

C
10
0

Time (d)
Fig. 9. The eect of temperature on the release of nitrogen: (A)
35 C; (B) 20 C; (C) 5 C.

Phosphorus released (%)

75

60
B

45
C

30

15
2

Time (d)

Potassium released (%)

Fig. 10. The eect of temperature on the release of phosphorus:

(A) 35 C; (B) 20 C; (C) 5 C.
100

A
B

80

60

40

20

Time (d)
Fig. 11. The eect of temperature on the release of potassium:
(A) 35 C; (B) 20 C; (C) 5 C.

For the release behaviors of N, all the curves are

similar except the initial release amount, which is
about 9.1% at 5 C, 26.5% at 20 C, and 45.8% at
35 C, respectively, after two days; and then, the
release rate of N became very slow at the three dierent of temperatures. The main N fertilizer in
CRNPK is UF, whose soluble nitrogen percentage
is dierent in water with dierent temperatures.
Under the experiment conditions, the higher the temperature is, the more the soluble UF is. The soluble
nitrogen percentages of UF were determined by the
method described in the US patent 4,596,593, and
the results showed that soluble nitrogen percentages
were 8.2%, 24.9% and 45.6% at the temperature of
5 C, 20 C, and 35 C, respectively. The soluble part
could diuse through the outer P(AA-co-AM)/kaolin hydrogel shell and then release out. Therefore,
the higher the temperature is, the more the initial
release amount is. The insoluble part could only be
released after being degraded into soluble, which
process is very slow under the experiment conditions.
So the N release rate becomes very slow after two
days whatever the temperature is.
For the release behaviors of P, the higher the
temperature is, the higher the P release rate is. The
P fertilizer in CRNPK comes from PAK, and the
P could only be released after hydrolyzing cleavage
of POP bonds, which in turn is strongly aected
by temperature [24]. On the experiment conditions,
the higher the temperature is, the faster the hydrolysis of PAK is, as a result, the faster the P release rate
is. When the temperature is 5 C, the hydrolyzing
process is very slow, and at 20 C, the hydrolyzing
cleavage of POP is accelerated, but the optimal
temperature for the hydrolysis is between 30 and
35 C. Moreover, the low molecular P could diuse
out the P(AA-co-AM)/kaolin hydrogel shell more
easily at high temperature than low temperature,
which also contributes to the higher release rate at
higher temperatures.
For the release behaviors of K, the dependence of
the release on the temperature is mainly due to the
increased diusion rate as the temperature increases.
In PAK, the K+ is adsorbed onto the polymer chain
through static electronic eect. At the beginning of
the release period, the K release rate is fast due to
the big concentration dierence between the fertilizer core and the outer solution. And then, the K
release rate decreases as the decrease of concentration dierence.
In summary, the N, P and K release behaviors of
CRNPK could be controlled by temperature. The

R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

higher the temperature is, the faster the nutrients

release rates are.
3.6. Slow release behaviors of CRNPK in soil
There are obvious dierences for nutrients release
from CRNPK between in distilled water and in soil
because there exist many kinds of ions and microorganisms in soil, therefore, we measured the nutrients
release behaviors of CRNPK in soil, and the results
are shown in Fig. 12. It could be seen from Fig. 12
that the N, P and K in CRNPK released 7.61%,
9.55% and 20.56% after two days, and 28.60%,
40.64% and 83.47% after thirty days, respectively.
This indicated that the CRNPK had an excellent
slow release property in soil.
The nutrients release mechanism of CRNPK in
soil could be illustrated as followings: Firstly, the
shell material, P(AA-co-AM)/kaolin, would be
slowly swollen by soil solution and transformed into
hydrogel after CRNPK was added into soil, and
then the water layer between the hydrogel and the
fertilizer core could also be formed. Secondly, the
absorbed water would continue to slowly diuse
into the fertilizer core, and dissolve the soluble part
of UF and PAK, and then this part of the soluble
fertilizer nutrients would slowly diuse through
the hydrogel shell and release into the soil. In this
stage, diusion would be the release rate-limiting
step. Finally, under the eect of water, ions and
microorganisms existing in the soil, the insoluble
part of UF and PAK would slowly degrade into soluble part, and then slowly release into the soil. In

100
A

Released (%)

80

60
B

40

C
20

10

20

30

Time (d)
Fig. 12. Release behaviors of potassium (A), phosphorus (B),
and nitrogen (C) in soil.

777

this stage, degradation rate determines the nutrients

release rate. Additionally, due to the existing of
many kinds of ions in soil solution, the swelling
degree of P(AA-co-AM)/kaolin is less in soil than
that in distilled water, then the diusion of soluble
fertilizer in it would be dicult, which also contribute to slow release of nutrients from CRNPK [25].
To gain insights into the release process, the following equation based on Ficks law but applicable
to spherical devices was applied [26,27]:
M t =M 0 Ktn
 0:5
Dt
M t =M 0 6
pr2

4
5

where Mt/M0 is the released fraction at time t; K is

the release factor, n is the release exponent, D is the
diusion coecient, and r is the radius of the spherical bead.
The values of K, n, and D for N, P, and K release
from CRNPK in soil were calculated, and the
results are summarized in Table 2.
3.7. The largest water-holding ratio of the soil with
CRNPK
Besides its slow release property, the other one
of the most important characters of the CRNPK
is its water retention capacity, or in other words,
its eective utilization of water in arid and desert
regions. It was reported [28] that the use of superabsorbent in the agricultural eld could increase
the largest water-holding capacity and water retention capacity of soil. Therefore, experiments to test
the water-holding capacity and water retention
behaviors of soil with the addition of CRNPK were
performed.
Experimentation showed that the largest waterholding ratio of the soil with the addition of CRNPK
was 40.8 wt%, while that of the soil without CRNPK
was 28.2 wt%. This indicated that the addition of
CRNPK to soil could improve the largest waterholding capacity of the soil. Moreover, it was also
observed that the water ow rate thought the soil
was slowed down when the CRNPK was added to
the soil. So the soil with the addition of CRNPK
could hold much more water during the irrigation
period or raining time than the soil without it, and
decrease the water losses through inltration, as a
result save water resource during irrigation. This is
a signicant advantage of CRNPK over normal
slow-release fertilizers.

778

R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769779

Table 2
The K, n, and D for N, P, and K release from CRNPK in soil
Nutrients

Release
factor K

Release
exponent n

Diusion
coecient D (cm2/d)

N
P
K

0.051
0.059
0.164

0.54
0.77
0.52

2.96  104
5.31  104
2.34  103

3.8. Water retention behaviors of soil with CRNPK

Fig. 13 shows the water retention behaviors of
the soil with (A) and without (B) CRNPK. It could
be found that the addition of CRNPK to soil could
obviously increase the water retention and decrease
the water evaporation. The water retention ratio of
soil without CRNPK had only remained 7 wt% on
the 10th day, while that of the soil with CRNPK
was 23.7 wt%. After 20 days, the soil without
CRNPK had already given o all the water, while
the soil with CRNPK still had 14 wt% water retention ratio.
The absorbed water in the P(AA-co-AM)/kaolin
hydrogel and the water between the hydrogel shell
and the fertilizer core could be slowly released with
the decrease of the soil moisture, and then used by
the plants. Simultaneously, nutrition could also be
released slowly with the water. Therefore, the swollen CRNPK is just like a micro-reservoir to retain
and supply moisture and nutrition to crops, and
thus could increase the utilization eciency of water
and fertilizer at the same time.
In addition, we also observed that the soil without CRNPK hardened and cracked after about 12
days at room temperature, whereas the soil with

Water retention (%)

40

CNSW still kept continuous conguration. Furthermore, the introduction of kaolin into P(AA-co-AM)
renders the shell material biodegradable and environment friendly [29], therefore, it was not harmful
to the soil.
The study shows that besides its slow release
property, the CRNPK has good water retention
and moisture preservation capacity, which are the
properties that the normal slow release fertilizers
do not have. It is especially signicant for the arid
and desert areas.
4. Conclusions
Controlled release NPK compound fertilizer with
the function of water retention was prepared, which
possessed the core/shell structure. Its core was UF
and PAK fertilizer, and the shell was P(AA-coAM)/kaolin superabsorbent composite. Experimental results showed that: (1) in CRNPK, the N, P and
K contents were 11.3, 21.1 (shown by P2O5) and 8.6
(shown by K2O) wt%, respectively; (2) the water
absorbency was about 91 g/g in tap water; (3) the
product had a high initial swelling rate; (4) it had
good slow release property in soil and the temperature had an obviously eect on the nutrients release
in distilled water; and (5) CRNPK could greatly
improve the water holding ability and water retention properties of the soil, and improve the availability of fertilizer and water resource to crops,
simultaneously.

30

Acknowledgements
A

20

This work was supported by Special Doctorial

Program Funds of the Ministry of Education of
China (Grant No. 20030730013).

10
B
0

References
0

12

16

20

Time (d)
Fig. 13. Water retention behaviors of soil with 1 wt% CRNPK
(A) and soil without CRNPK (B).

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