REACTIVE

&
FUNCTIONAL
Reactive & Functional Polymers 67 (2007) 769–779
POLYMERS
[Link]/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 reten-
tion 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 effect 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 prop-
erty but also excellent water retention ability, which could effectively improve the utilization of fertilizer and water resource
at the same time.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Controlled release; P(acrylic acid-co-acrylamide)/kaolin superabsorbent; Water absorbency; Core/shell structure

1. Introduction ades. There are three types of these fertilizers:

matrix-type formulations constitute the first major
Fertilizer and water are the important factors category of slow or controlled release fertilizers
that limit the production of agriculture, so it is very due to their simple fabrication. The active is dis-
important to improve the utilization of fertilizer persed in the matrix and diffuses through the matrix
nutrients and water resources. Slow release fertiliz- continuum or intergranular openings, that is,
ers are made to release their nutrient contents grad- through pores or channels in the carrier phase [1].
ually and if possible, to coincide with the nutrient Another way of regulating the release of fertilizer
requirement of a plant. A number of slow release is coated fertilizer, i.e. a fertilizer core is coated by
fertilizers have been developed during the past dec- inert materials. The release of the fertilizer is con-
trolled by diffusion through the shell [2]. The third
*
Corresponding author. Tel.: +86 931 8912387; fax: +86 931
major category of such fertilizers is accomplished
8912582. by means of chemically controlled releasing prod-
E-mail address: m-zliu@[Link] (M. Liu). ucts, such as urea-formaldehyde [3], polyphosphates

1381-5148/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2006.12.007
770 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779

[4]. The release of such kind of slow release fertilizer tory, Xi’an, China) was recrystallized from water.
is controlled by the degradation rate, which in turn Kaolin powder was supplied by Linze Colloidal
is affected by various factors, such as molecular Co., Gansu, China. The others were all of analytical
weight of the polymer, and pH, temperature, ions grade and available from commercial sources.
and microorganisms in soil, etc.
Superabsorbents are three-dimensionally cross- 2.2. Preparation of CRNPK
linked hydrophilic polymers capable of swelling
and retaining huge volumes of water in the swollen Urea formaldehyde (UF) was made from urea
state. Recently, research on the use of superabsor- and 37% formaldehyde aqueous solution as
bents as water management materials for agricul- described previously [16], and polyphosphate potas-
tural and horticultural applications has attracted sium (PAK) was made from potassium dihydrogen
great attention and test of superabsorbents for agri- phosphate according to the literature [17]. Five
cultural applications has shown encouraging results grams of dried UF powder (<90 mesh) and 5 g
as they have been observed to help reduce irrigation PAK powder (<90 mesh) were placed into 50 ml
water consumption, lower the death rate of plants, 2 wt% sodium alginate solution. The mixture was
improve fertilizer retention in soil, and increase stirred vigorously until uniform and then slowly
plant growth rate [5]. However, its applications in added dropwise to a 0.5 M CaCl2 solution with a
this field have met some problems because most of pipette, the drops turned to white beads immedi-
these superabsorbents are based on pure poly(so- ately because the sodium alginate in the drop was
dium acrylate), and then they are too expensive crosslinked by Ca2+ at once (the function of sodium
and not suitable for saline-containing water and alginate is the entrapment of UF and PAK). The
soils [6]. Recently, there have been many reports spherical beads were left in the CaCl2 solution for
on introducing inorganic clays, such as kaolin, ben- 30 min to ensure complete gelling and then sepa-
tonite, montmorillonite [7], attapulgite [8], and mica rated from the solution, rinsed twice with distilled
[9] into pure polymeric superabsorbents in order to water, and dried at room temperature overnight.
improve swelling property, hydrogel strengths, and Five grams of dried beads obtained from above
reduce production costs. process was added into a flask equipped with a
On the basis of the above background and our mechanical stirrer, a condenser, and a drop funnel.
previous studies on superabsorbent polymers A certain amount of tetrachloride, polyethylene gly-
[10,11] and slow release fertilizer [12–15], in this coloctyl phenyl ether (OP), and sorbite anhydride
work, we prepared controlled release NPK com- monostearic acid ester (span-80) were added into
pound fertilizer with the function of water retention, the flask. The temperature was raised to 65 °C using
which possessed the core/shell structure. Its core a water bath while the contents were constantly stir-
was UF and PAK fertilizer, and the shell was red. As this process continued, a certain amount of
P(AA-co-AM)/kaolin superabsorbent composite. mixed solution of partially neutralized (by ammo-
CRNPK not only had slow release property, but nia) acrylic acid, acrylamide, kaolin, N,N0 -methyl-
also could absorb water and preserve the soil mois- enebisacrylamide (NNMBA) solution, and
ture at the same time. The present report reveals the ammonium persulfate solution was slowly added
synthesis conditions of inversion suspension poly- dropwise into the flask. The mixture was filtered
merization, swelling rate, slow release, and water to remove the tetrachloride after being stirred for
retention properties of the CRNPK. The effect of 2 h at 65 °C and dried in an oven at 70 °C, and then
temperature on the nutrients release in distilled the white homogenous granular CRNPK with core/
water was also studied. shell structure was obtained, which core was the
NPK compound fertilizer and the shell was P(AA-
2. Experimental co-AM)/kaolin superabsorbent composite.

2.1. Materials 2.3. Component analysis of CRNPK

Acrylic acid (AA, Beijing Oriental Chemical Fac- Content of nitrogen in the CRNPK was determined
tory, Beijing, China), urea, and sodium alginate by an element analysis instrument (Germany Elemen-
(SA) were of industrial grade. Ammonium persul- tal Vario EL Corp., model 1106). Contents of potas-
fate (analytical grade, Xi’an Chemical Reagent Fac- sium and phosphate in the CRNPK were determined
 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779 771

by an Inductively Coupled Plasmas (ICP) instrument the soil sample was maintained at 30 wt% water
(American TJA Corp., model IRISER/S). holding capacity by weighing and adding tap water
if necessary, periodically. After 2, 5, 10, 15, 20, 25
2.4. Characterization of the shell material of CRNPK and 30 days incubation period, the remaining gran-
by FTIR ular CRNPK in the beakers were picked out and
washed with distilled water, and then dried at room
The shell material of CRNPK, P(AA-co-AM)/ temperature overnight to estimate the contents of
kaolin was characterized by a Fourier-transform N, P and K. For seven measurements, seven beakers
infrared (FTIR) spectrophotometer (American Nic- were prepared at the same time. The remaining
olet corp., model 170-SX). amount of N, P and K was estimated by element
analysis instrument and ICP, respectively. The
2.5. Percentage of P(AA-co-AM)/kaolin shell above tests were carried out in triplicate, and the
average value was taken as the result.
The percentage of P(AA-co-AM)/kaolin shell
was determined by mass difference before and after 2.8. The largest water-holding ratio of the soil with
coating. CRNPK
2.6. Measurement of water absorbency The sandy soil used in this study was representa-
tive of the area of Lanzhou, which lies in the north-
One gram of CRNPK was immersed into a certain west of China and is a dry and semi-desert region.
amount of tap water and allowed to soak at room 2 g CRNPK were well mixed with 200 g dry soil
temperature for 90 min. The swollen CRNPK was fil- and placed in a 4.5 cm diameter PVC tube. The bot-
trated through an 80-mesh sieve to remove non- tom of the tube was sealed by nylon fabric (with the
absorbed water and weighed. Water absorbency aperture of 0.076 mm) and weighed (marked W1).
(WA) of per gram dried CRNPK was calculated The soil samples were slowly drenched by tap water
using Eq. (1): from the top of the tube until water seeped out from
M the bottom. After there was no seeping water at the
WA ¼ 1 ð1Þ
M0 tube bottom, the tube was weighed again (marked
W2). Control experiment, i.e. soil without CRNPK
Where M and M0 referred to the weight of the water
was also carried out. The largest water-holding ratio
swollen and dry CRNPK, respectively.
(W%) of the soil was calculated from Eq. (2).
2.7. Slow release behaviors of CRNPK ðW 2  W 1 Þ  100
W% ¼ ð2Þ
W 2  W 1 þ 200
To study the effect of temperature on the release
behaviors of N, P and K, 0.5 g dry samples were
2.9. Water retention of the soil with CRNPK
added into conical bottles containing 200 ml dis-
tilled water, and then, the bottles were put into incu-
Two hundred grams of dry sandy soil (below
bators whose temperatures were set at 5 °C, 20 °C
26 mesh) mixed with 2 g CRNPK was placed in a
and 35 °C, respectively. At certain time intervals
cup (A), and the other 200 g sandy soil without
(every 24 h), 2 ml solution was sampled for N, P
CRNPK was placed in an identical cup (B),
and K determination, and an additional 2 ml dis-
200 ml tap water was added into both cups, then,
tilled water was injected into the bottles to maintain
the cups were kept under identical conditions at
a constant amount of solvent. The N content was
room temperature for 20 days. The initial masses
estimated by Kjeldahl method [18], and the P and
of the mixture (W0) in the two cups were measured
K content were determined by ICP method.
after removal of excess water, and their masses were
To study the slow release behaviors of CRNPK
recorded every 2 days (Wi) to compare the water
in soil, the following experiments were carried out:
retention of CRNPK. Water retention (WR%) was
1 g CRNPK was well mixed with 200 g dry soil
calculated by the following Eq. (3):
(<26 mesh) and kept in a 200 ml plastic beaker
properly covered and incubated for different periods Wi
WR% ¼ ð3Þ
at room temperature. Throughout the experiments, W0
772 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779

3. Results and discussion in form of swollen P(AA-co-AM/kaolin) gel, but

also in form of additional free water between the
3.1. The characteristics and structure of CRNPK core and the surrounding hydrogel shell, which
could enhance the water absorbency obviously [19].
The characteristics of CRNPK, i.e., composition,
diameters of dry and swollen samples, and percent- 3.2. FTIR analysis of P(AA-co-AM)/kaolin (the
age of the shell are presented in Table 1. The struc- shell material)
ture of CRNPK was core/shell, which core was
fertilizer and the shell was P(AA-co-AM)/kaolin The infrared spectra of kaolin powder, P(AA-co-
superabsorbent composite. Because the swelling AM) and P(AA-co-AM)/kaolin are shown in
degree of P(AA-co-AM)/kaolin shell was bigger Fig. 2A–C, respectively. The observed peaks are at
than that of the core, the contact between the shell 3427 cm1, corresponding to N–H stretching of
and the core was interrupted during swelling pro- acrylamide unit, 2926 cm1, corresponding to the
cess, thus an additional space filled with additional C–H stretching of acrylate unit, 1716 cm1, corre-
water between the core and the surrounding hydro- sponding to the stretching of C@O in acrylate unit,
gel shell was formed (See Fig. 1). Therefore, the 1662 cm1, corresponding to the carbonyl moiety of
CRNPK was capable of taking up water not only the acrylamide unit, 1167 cm1, corresponding to
the –CO–O– stretching of acrylate unit, 1038 cm1
(1094 cm1) corresponding to the Si–O stretching
Table 1
The characteristics of CRNPK of kaolin.
The infrared analysis result of P(AA-co-AM)/
Characteristics Values
kaolin in Fig. 2C shows that all the characteristic
Nitrogen content 11.3%
groups, i.e., –COOH (or –COONa), –CONH2,
P2O5 content 21.1%
K2O content 8.6% –CH, and Si–O, exist in the product. In addition,
Diameter of dry sample 2.0–2.5 mm by comparing Fig. 2A and C, the absorption peaks
Diameter of swollen sample 13–15 mm at 3624 and 915 cm1, contributed to –OH group on
Percentage of P(AA-co-AM)/kaolin shell 30.9% 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) 769–779 773

70

Water absorbency (g/g)

60

50

10 20 30 40
Fig. 2. The FTIR spectra of kaolin (A), P(AA-co-AM) (B),
P(AA-co-AM)/kaolin (C). AM (wt%)

Fig. 3. The effect of AM content on the water absorbency.

reaction (see Fig. 2C). Therefore, it is suggested that
graft copolymerization between –OH groups on below 25 wt% could be attributed to the synergistic
kaolin and monomers took place during the reac- effect of –CONH2 group and –COO group. On the
tion [20]. other hand, –COO group has better hydrophilic
ability than –CONH2, so water absorbency would
3.3. Influence of the parameters on water absorbency decrease with the further increase of AM content.
Additionally, AM is a nonionic monomer, and it
For the swollen CRNPK, the water absorbency almost does not ionize in solution, so the ions in
consists of two parts: the water absorbed by solution have little influence on it. Thus AM could
P(AA-co-AM)/kaolin and the water between the improve the salt-resistance ability of CRNPK,
core and the surrounding hydrogel shell (see which is extremely important for CRNPK due to
Fig. 1). Therefore, any factor that could affect the the existence of many kinds of ions in soil.
two kinds of water would affect the water absor-
bency of CRNPK. According to Flory [21], the 3.3.2. Effect of kaolin content on the water
water absorbency of superabsorbent polymer absorbency
depends on the amount of the hydrophilic groups, There are three kinds of way for kaolin particle in
crosslinking density, polymer network behavior, the P(AA-co-AM)/kaolin [7]: the first way, kaolin
and elasticity of the polymer networks, type of sol- particle serves as a crosslinking point chemically
vent and ionic strength of the external solution, etc. bonded with the polymer, in this way, the network
To improve the swelling capacity of the product, structure and water absorbency would change with
various reaction parameters are employed. The the change of kaolin content; the second way, kaolin
details of the influences of the reaction parameters particle acts as terminal point chemically bonded
on water absorbency in tap water, such as the con- with the polymer, in this way, the network structure
tent of AM, kaolin, crosslinker, initiator, neutraliza- and water absorbency hardly changes with the
tion degree of AA are given below. change of kaolin content; the third way, kaolin par-
ticle serves as a filler physically filled in the network
3.3.1. Effect of AM content on the water absorbency of polymer, in this way, the network structure
Hydrophilic group plays an extremely important hardly change with the change of kaolin content,
part in water absorbency. In the P(AA-co-AM)/ however, water absorbency would decrease because
kaolin polymeric system, the ratio of different the content of hydrophilic groups is lower at a
hydrophilic groups can be adjusted by changing higher kaolin content, and then the osmotic pres-
the proportion of AA to AM. The effect of AM con- sure difference decreases.
tent on water absorbency of CRNPK is shown in The effect of kaolin content on water absorbency
Fig. 3. As can be seen from Fig. 3, there exists a is shown in Fig. 4. When the kaolin content is below
maximum when the AM content is 25 wt%. The 10 wt%, kaolin mainly exists in the first way men-
increase of water absorbency when AM content is tioned above in the P(AA-co-AM)/kaolin, i.e.,
774 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779

80
80

Water absorbency (g/g)

Water absorbency (g/g)

70 70

60

60
50

0.08 0.12 0.16

10 20 30
Crosslinker (wt%)
kaolin (wt%)
Fig. 5. The effect of crosslinker content on the water absorbency.
Fig. 4. The effect of kaolin content on the water absorbency.

exists as crosslinking points, which could improve tilizer core, consequently, the water absorbency
the network structure of the polymer composite, decreases obviously. On the other hand, when the
as a result enhance the water absorbency; with the crosslinker content is beyond 0.1 wt%, the decrease
increase of kaolin content (10–20 wt%), the of water absorbency could be owed to the increase
increased kaolin mainly exists in the second way, of the crosslinking density, which in turn decreases
i.e., exists as terminal points, which would not affect the space left for water to enter the polymer. Addi-
the water absorbency, so no considerable change in tionally and importantly, the decrease of swelling
water absorbency is observed; when the kaolin con- degree of P(AA-co-AM)/kaolin would make the
tent is above 20 wt%, the additional amount of kao- space between the hydrogel shell and the core
lin probably exists in the third way, i.e., acts as a decrease, which also contribute to the decrease of
non-reactive filler, which contribute to the decrease water absorbency of CRNPK.
of water absorbency of the polymer. Moreover, the
shrinkage of the P(AA-co-AM)/kaolin would 3.3.4. Effect of neutralization degree of AA on the
decrease the space between the hydrogel shell and water absorbency
the fertilizer core, therefore, decrease the water The effect of neutralization degree of AA on the
absorbency of CRNPK further. A similar phenom- water absorbency is shown in Fig. 6. It is clear that
enon has been reported by others [22]. the water absorbency increases from 30% to 70%

3.3.3. Effect of crosslinker content on the water

absorbency
Crosslinking density is an important swelling 80
control element. Relatively small changes in cross-
Water absorbency (g/g)

linking density can have a major influence on water

absorbency. The effect of crosslinker content on
water absorbency is shown in Fig. 5. It can be seen
60
that the water absorbency reaches a maximum at
the crosslinker content of 0.1 wt%. When the cross-
linker content is below 0.1 wt%, the decrease of
water absorbency could be attributed to two rea-
sons: first, an increase of soluble part in the 40
P(AA-co-AM)/kaolin polymer, which decrease the
40 60 80
water absorbency of the polymer; second, the
decrease of the hydrogel strength, which make the Neutralization degree of AA (%)
hydrogel shell soft and could not retain the water Fig. 6. The effect of neutralization degree of AA on the water
between the surrounding hydrogel shell and the fer- absorbency.
 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779 775

and decreases with further increase in neutralization between the shell and core is small, which would
degree of AA. When AA is neutralized, the carbox- result in the decrease of the water absorbency. On
ylic acid group turns into carboxylate group. In the other hand, at high initiator content (more than
water, the negatively charged carboxyl groups set 0.8 wt%), large quantities of free radicals produced
up an electrostatic repulsion which tends to expand by initiator may cause the faster reaction velocity
the network. In a certain range of neutralization and the chain transfer to polymers [23], which
degree, the electrostatic repulsion increases with would result in the increase of crosslinking density
the increase of neutralization degree. Furthermore, and affect the water absorbency consequently.
the osmotic pressure increases with the increase of
neutralization degree, which also contributed to 3.4. The swelling rate of CRNPK
the increment of water absorbency. However, fur-
ther increases in the neutralization degree of AA, The time required to reach maximum swelling
water absorbency decreases due to the increase of capacity of CNPK was studied and the results are
the solubility of the superabsorbent composite. presented in Fig. 8. One gram of sample was
Moreover, at higher neutralization degree, the immersed in an excess amount of tap water and
screening effect of the counter ion on the polyanion the water absorbency was measured for every
chain will lead to a reduction in expansion of the 5 min. The result indicated that the sample had a
network, thus result in the decrease of water absor- high initial swelling rate, and more than 90% of
bency of the P(AA-co-AM)/kaolin polymer. the maximum swelling capacity of CRNPK is
In addition, the bigger the swelling degree of the achieved within 40 min and the equilibrium water
polymer is, the larger the space between the hydro- absorbency is reached approximately at 60 min.
gel shell and the fertilizer core is, and then the bigger Furthermore, the high initial swelling rate is one
the water absorbency of CRNPK is; and vise versa. of the most important factors for CRNPK which
is used in agriculture, for it could absorb more water
3.3.5. Effect of initiator content on the water during raining or irrigating.
absorbency
The dependence of water absorbency on initiator
content was also studied, and the result is presented 3.5. Effect of temperature on the releases
in Fig. 7. There is a maximum when the initiator of N, P and K
content is 0.8 wt%. On the one hand, when the ini-
tiator content was below 0.8 wt%, the water absor- Figs. 9–11 shows the N, P and K release behav-
bency of the product was decreased. This may be iors of CRNPK in distilled water at temperature
due to the decrease of the amount of free radicals of 5, 20 and 35 °C, respectively. It could be seen that
produced by initiator. Thus, the polymer network the temperature had considerable effects on the
could not be formed efficiently, and the space release behaviors of N, P and K in CRNPK.

100
90
Water absorbency (g/g)

80
Water absorbency (g/g)

80
60

70 40

20
60

0.4 0.8 1.2 0 20 40 60 80

Initiator (wt%) Time (min)

Fig. 7. The effect of initiator content on the water absorbency. Fig. 8. The swelling rate of CRNPK.
776 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779

A For the release behaviors of N, all the curves are

50 similar except the initial release amount, which is
about 9.1% at 5 °C, 26.5% at 20 °C, and 45.8% at
Nitrogen released (%)

40 35 °C, respectively, after two days; and then, the

release rate of N became very slow at the three differ-
30 B ent of temperatures. The main N fertilizer in
CRNPK is UF, whose soluble nitrogen percentage
20 is different in water with different temperatures.
Under the experiment conditions, the higher the tem-
C
10 perature is, the more the soluble UF is. The soluble
nitrogen percentages of UF were determined by the
0
method described in the US patent 4,596,593, and
0 2 4 6 8 the results showed that soluble nitrogen percentages
Time (d) were 8.2%, 24.9% and 45.6% at the temperature of
5 °C, 20 °C, and 35 °C, respectively. The soluble part
Fig. 9. The effect of temperature on the release of nitrogen: (A)
35 °C; (B) 20 °C; (C) 5 °C. could diffuse through the outer P(AA-co-AM)/kao-
lin hydrogel shell and then release out. Therefore,
the higher the temperature is, the more the initial
75 A release amount is. The insoluble part could only be
released after being degraded into soluble, which
process is very slow under the experiment conditions.
Phosphorus released (%)

60
So the N release rate becomes very slow after two
B days whatever the temperature is.
45 For the release behaviors of P, the higher the
temperature is, the higher the P release rate is. The
C P fertilizer in CRNPK comes from PAK, and the
30
P could only be released after hydrolyzing cleavage
of P–O–P bonds, which in turn is strongly affected
15 by temperature [24]. On the experiment conditions,
the higher the temperature is, the faster the hydroly-
2 4 6 8 sis of PAK is, as a result, the faster the P release rate
Time (d) is. When the temperature is 5 °C, the hydrolyzing
process is very slow, and at 20 °C, the hydrolyzing
Fig. 10. The effect of temperature on the release of phosphorus:
(A) 35 °C; (B) 20 °C; (C) 5 °C.
cleavage of P–O–P is accelerated, but the optimal
temperature for the hydrolysis is between 30 and
35 °C. Moreover, the low molecular P could diffuse
100 A
B out the P(AA-co-AM)/kaolin hydrogel shell more
easily at high temperature than low temperature,
80 C which also contributes to the higher release rate at
Potassium released (%)

higher temperatures.
60 For the release behaviors of K, the dependence of
the release on the temperature is mainly due to the
increased diffusion rate as the temperature increases.
40
In PAK, the K+ is adsorbed onto the polymer chain
through static electronic effect. At the beginning of
20 the release period, the K release rate is fast due to
the big concentration difference between the fertil-
0 izer core and the outer solution. And then, the K
0 2 4 6 8 release rate decreases as the decrease of concentra-
Time (d) tion difference.
Fig. 11. The effect of temperature on the release of potassium: In summary, the N, P and K release behaviors of
(A) 35 °C; (B) 20 °C; (C) 5 °C. CRNPK could be controlled by temperature. The
 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779 777

higher the temperature is, the faster the nutrients this stage, degradation rate determines the nutrients
release rates are. release rate. Additionally, due to the existing of
many kinds of ions in soil solution, the swelling
3.6. Slow release behaviors of CRNPK in soil degree of P(AA-co-AM)/kaolin is less in soil than
that in distilled water, then the diffusion of soluble
There are obvious differences for nutrients release fertilizer in it would be difficult, which also contrib-
from CRNPK between in distilled water and in soil ute to slow release of nutrients from CRNPK [25].
because there exist many kinds of ions and microor- To gain insights into the release process, the fol-
ganisms in soil, therefore, we measured the nutrients lowing equation based on Fick’s law but applicable
release behaviors of CRNPK in soil, and the results to spherical devices was applied [26,27]:
are shown in Fig. 12. It could be seen from Fig. 12
M t =M 0 ¼ Ktn ð4Þ
that the N, P and K in CRNPK released 7.61%,  0:5
9.55% and 20.56% after two days, and 28.60%, Dt
M t =M 0 ¼ 6 ð5Þ
40.64% and 83.47% after thirty days, respectively. pr2
This indicated that the CRNPK had an excellent
where Mt/M0 is the released fraction at time t; K is
slow release property in soil.
the release factor, n is the release exponent, D is the
The nutrients release mechanism of CRNPK in
diffusion coefficient, and r is the radius of the spher-
soil could be illustrated as followings: Firstly, the
ical bead.
shell material, P(AA-co-AM)/kaolin, would be
The values of K, n, and D for N, P, and K release
slowly swollen by soil solution and transformed into
from CRNPK in soil were calculated, and the
hydrogel after CRNPK was added into soil, and
results are summarized in Table 2.
then the water layer between the hydrogel and the
fertilizer core could also be formed. Secondly, the
absorbed water would continue to slowly diffuse 3.7. The largest water-holding ratio of the soil with
into the fertilizer core, and dissolve the soluble part CRNPK
of UF and PAK, and then this part of the soluble
fertilizer nutrients would slowly diffuse through Besides its slow release property, the other one
the hydrogel shell and release into the soil. In this of the most important characters of the CRNPK
stage, diffusion would be the release rate-limiting is its water retention capacity, or in other words,
step. Finally, under the effect of water, ions and its effective utilization of water in arid and desert
microorganisms existing in the soil, the insoluble regions. It was reported [28] that the use of super-
part of UF and PAK would slowly degrade into sol- absorbent in the agricultural field could increase
uble part, and then slowly release into the soil. In the largest water-holding capacity and water reten-
tion capacity of soil. Therefore, experiments to test
the water-holding capacity and water retention
behaviors of soil with the addition of CRNPK were
100
performed.
A Experimentation showed that the largest water-
80 holding ratio of the soil with the addition of CRNPK
was 40.8 wt%, while that of the soil without CRNPK
Released (%)

60 was 28.2 wt%. This indicated that the addition of

CRNPK to soil could improve the largest water-
B holding capacity of the soil. Moreover, it was also
40
observed that the water flow rate thought the soil
C was slowed down when the CRNPK was added to
20 the soil. So the soil with the addition of CRNPK
could hold much more water during the irrigation
0 period or raining time than the soil without it, and
0 10 20 30
decrease the water losses through infiltration, as a
Time (d) result save water resource during irrigation. This is
Fig. 12. Release behaviors of potassium (A), phosphorus (B), a significant advantage of CRNPK over normal
and nitrogen (C) in soil. slow-release fertilizers.
778 R. Liang et al. / Reactive & Functional Polymers 67 (2007) 769–779

Table 2
The K, n, and D for N, P, and K release from CRNPK in soil
Nutrients Release Release Diffusion
factor K exponent n coefficient D (cm2/d)
N 0.051 0.54 2.96  104
P 0.059 0.77 5.31  104
K 0.164 0.52 2.34  103

3.8. Water retention behaviors of soil with CRNPK CNSW still kept continuous configuration. Further-
more, the introduction of kaolin into P(AA-co-AM)
Fig. 13 shows the water retention behaviors of renders the shell material biodegradable and envi-
the soil with (A) and without (B) CRNPK. It could ronment friendly [29], therefore, it was not harmful
be found that the addition of CRNPK to soil could to the soil.
obviously increase the water retention and decrease The study shows that besides its slow release
the water evaporation. The water retention ratio of property, the CRNPK has good water retention
soil without CRNPK had only remained 7 wt% on and moisture preservation capacity, which are the
the 10th day, while that of the soil with CRNPK properties that the normal slow release fertilizers
was 23.7 wt%. After 20 days, the soil without do not have. It is especially significant for the arid
CRNPK had already given off all the water, while and desert areas.
the soil with CRNPK still had 14 wt% water reten-
tion ratio.
4. Conclusions
The absorbed water in the P(AA-co-AM)/kaolin
hydrogel and the water between the hydrogel shell
Controlled release NPK compound fertilizer with
and the fertilizer core could be slowly released with
the function of water retention was prepared, which
the decrease of the soil moisture, and then used by
possessed the core/shell structure. Its core was UF
the plants. Simultaneously, nutrition could also be
and PAK fertilizer, and the shell was P(AA-co-
released slowly with the water. Therefore, the swol-
AM)/kaolin superabsorbent composite. Experimen-
len CRNPK is just like a micro-reservoir to retain
tal results showed that: (1) in CRNPK, the N, P and
and supply moisture and nutrition to crops, and
K contents were 11.3, 21.1 (shown by P2O5) and 8.6
thus could increase the utilization efficiency of water
(shown by K2O) wt%, respectively; (2) the water
and fertilizer at the same time.
absorbency was about 91 g/g in tap water; (3) the
In addition, we also observed that the soil with-
product had a high initial swelling rate; (4) it had
out CRNPK hardened and cracked after about 12
good slow release property in soil and the tempera-
days at room temperature, whereas the soil with
ture had an obviously effect on the nutrients release
in distilled water; and (5) CRNPK could greatly
improve the water holding ability and water reten-
40 tion properties of the soil, and improve the avail-
ability of fertilizer and water resource to crops,
simultaneously.
Water retention (%)

30

Acknowledgements
20 A
This work was supported by Special Doctorial
Program Funds of the Ministry of Education of
10 China (Grant No. 20030730013).
B
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