b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6

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Research Paper

Parametric evaluation using mechanistic model for

release rate of phosphate ions from chitosan-
coated phosphorus fertiliser pellets

N.N.R. Ahmad a, W.J.N. Fernando b, M.H. Uzir a,*

a
School of Chemical Engineering, Universiti Sains Malaysia, Nibong Tebal, 14300 Pulau Pinang, Malaysia
b
Faculty of Engineering, University of Peradeniya, Peradeniya, Sri Lanka

article info
Evaluation of nutrient release from a controlled-release fertiliser (CRF) using mechanistic
Article history: model is important in order to increase the understanding towards the mechanism that
Received 29 January 2013 might involve in a release process. In this study, a mechanistic model was used to evaluate
Received in revised form the parameters that govern the phosphate release rate through chitosan-coated phos-
18 September 2014 phorus fertiliser. The model considers the phenomena of boundary layer formation on the
Accepted 24 September 2014 external surface of the coat and the coating thickness changes due to erosion. Static release
Published online experiments were conducted in order to study the effect of the number of coatings and pH
conditions to the release rate of phosphate ions. The respective parameters of the phos-
Keywords: phate release such as diffusion coefficient were evaluated using the model in both cases.
Diffusion The diffusivity of the phosphate was found to increase as the number of coatings and pH
Modelling values of the medium decreased. Regeneration of the released data for the phosphate ions
Coated fertiliser using the model indicated a very satisfactory fit with the experimental data.
Phosphate © 2014 IAgrE. Published by Elsevier Ltd. All rights reserved.
Release rate
Chitosan

coating material. Various coating materials have been used to

1. Introduction
The application of controlled-release fertilisers (CRF) in agri-
cultural sector is one of the methods that can be used to
enhance the nutrient consumption efficiency as well as min-
imising the environmental problems due to leaching of un-
controlled nutrient released (Al-Zahrani, 2000). Among these
CRF types, coated fertilisers are more commonly used in
practice (Shaviv, 2000). The nutrients release rate is controlled
by encapsulating the fertiliser granules or pellets into a type of
coat different types of fertilisers, but the current trend shows
that polymer coated fertilisers are the most popular types of
CRF and having great advantages over conventional types of
coatings (Du, Tang, Zhou, Wang, & Shaviv, 2008). However, the
use of conventional polymer coating usually deals with the
high cost of material and accumulation of undesired synthetic
residues in soil (Golman, 2011; Trenkel, 2010). Recently, a
number of studies have been focused on the use of biode-
gradable polymers as the promising coating materials for
fertilisers (Chen, Xie, Zhuang, Chen, & Jing, 2008; Han, Chen, &

* Corresponding author. Tel.: þ60 4599 6464; fax: þ60 4594 1013.
E-mail address: chhekarl@usm.my (M.H. Uzir).
http://dx.doi.org/10.1016/j.biosystemseng.2014.09.015
1537-5110/© 2014 IAgrE. Published by Elsevier Ltd. All rights reserved.
 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6
Nomenclature
R rate of phosphate release, g min1
Z thickness of the pellet, m
A area of the nutrient mass transfer, m2
Cav average nutrient concentration released at time t,
g m3
kc mass transfer coefficient for external surface of
the coat, m min1
C2 nutrient concentration at the outer surface of the
chitosan coat at a time t, g m3
Ca nutrient concentration outside the pellet at a
distance ∞ from the inner boundary of the
chitosan coat, g m3
C1 nutrient concentration within the pellet, g m3
C2(x,t) concentration of nutrient outside the pellet at a
distance x from the inner boundary of the coat at a
time t, g m3
Hu, 2009; Ni, Liu, Lu, Xie, & Wang, 2011; Ni et al., 2010; Wu,
2008).
Chitosan is one of the biodegradable polymers, which is
available in abundant in nature. This natural polysaccharide
has been widely used in biomedical, pharmaceutical and
agricultural fields due to its biocompatibility, non-toxicity and
biodegradability (Aranaz et al., 2009; Sionkowska, 2011). The
application of chitosan can be found in the form of gels,
membranes, coatings and beads (Krajewska, 2005). However,
chitosan-based materials are hydrophilic in nature and make
it less stable to be used in its pure form. Cross-linking reaction
is one of the modification methods, which can be used to
improve its stability, including the water vapour barrier
properties (Rinaudo, 2006; Tsai & Wang, 2008). Several studies
have been reported on the chitosan-coated fertilisers, which
mainly focused on encapsulating urea and nitro-
genephosphorusepotassium (NPK) compound fertilisers
(Chen, Lu, Zhang, Wu, & Deng, 2005; Teixeira et al., 1990; Wu &
Liu, 2008; Xia, Zhang, Zhao, & Wang, 2009). Nevertheless, none
of them reported on the applicability of coating phosphorus
fertiliser using the chitosan film.
The application of mathematical model in the controlled-
release fertiliser systems is very important in order to opti-
mize the design of CRF and later to produce fertilisers that can
meet the nutrients requirement by plants (Shaviv, 2000;
Zheng, Liang, Ye, & He, 2009). Mechanistic model is a type of
model derived based on a real physical phenomenon, which
takes place during a release process (Siepmann & Siepmann,
2008). Unfortunately, the evaluation of nutrient release ki-
netics from the chitosan-coated fertilisers using mechanistic
model equations is yet to be extensively explored. Some of the
previous studies only assessed the parameters of nutrient
release using the empirical model, which does not provide a
better insight on the actual mechanisms (Wu & Liu, 2008). For
the case of chitosan membrane system, capillary pore model
and free volume model have been used to investigate the so-
lute diffusional properties across the membrane (Krajewska,
2001a, 2001b). There have been several mechanistic models
79
Cm nutrient concentration within the membrane,
g m3
x distance from the membrane surface, m
Co original concentration of nutrient within the
pellet, g m3
D diffusion coefficient of nutrient within the
membrane or coating layer, m2 min1
Df diffusion coefficient of nutrient within the bulk,
m2 min1
l coating thickness at time t, m
r K(D/Df)0.5
K solute partition coefficient
lo initial thickness of the chitosan coat, m
m dissolution rate constant of the coating film,
m min1
t time, min
reported on the controlled-release systems, however, most of
them have not taken into account the effect of boundary layer
formation occurred on the surface of the external coat (Du,
Zhou, Shaviv, & Wang, 2004; Ko, Cho, & Rhee, 1996; Koizumi,
Ritthidej, & Phaechamud, 2001; Langer & Peppas, 1983;
Shaviv, Raban, & Zaidel, 2003). In fact, in the real application
of controlled-release of nutrients into a static release medium,
the presence of such a boundary layer could impart additional
resistance for the solute fluxes and can affect the transport
parameters across the membrane layer (Dworecki, Slezak,
Ornal-Wasik, & Wasik, 2005).
The purpose of this study is to investigate the phosphate
ions release rate from the chitosan-coated phosphorus fertil-
isers based on the variation of pH conditions and number of
coatings. The parameters of release kinetics were evaluated
using a carefully derived mechanistic model. The model was
developed by considering the formation of boundary layer on
the external surface of the coat. It also considered the effect of
coating thickness to the release rate. Coated fertilisers could
be custom-designed if the factors affecting the release of nu-
trients could be parameterized so that the release rate could
be estimated, prior to manufacturing of such coatings.
2. Materials and method
2.1. Materials
Calcium dihydrogen phosphate was purchased from Acros
Organics (Geed, Belgium) and of analytical grade. Calcium
oxide powder was supplied by Hamburg Chemical GmbH
(Germany). Chitosan (degree of deacetylation > 85%, molar
mass is 100e1000 kDa) was purchased from Chito-Chem,
Malaysia. Sodium carbonate, glacial acetic acid, and citric
acid were purchased from Fisher Scientific (Malaysia).
Aqueous solutions of different pH values were prepared using
citric acid and sodium carbonate.
80 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6
2.2. Preparation and characterisation of chitosan-coated
phosphorus fertiliser pellets
2.2.1. Preparation of the coated fertiliser pellets
The powder of calcium dihydrogen phosphate (as a source of
phosphate ions) and calcium oxide (as filler) were mixed ac-
cording to the weight ratio of 14.31:8.00 in order to prepare the
powdered fertiliser mixture. Preparation of the pellet required
about 1.9 g of the mixture in order to fill up a stainless steel
cylindrical mould with a diameter of 2 cm. The mixture in the
mould was compressed with a pressure of 500 psi using a
hand-held hydraulic press. The formed pellets with the
thickness of approximately 4 mm were left to dry in an oven
(Carbolite, Parsons Lane) at 100  C for 3 h.
In order to prepare the coating solution, about 4% w/v of
chitosan powder was dissolved in 50 mL of 4% acetic acid
solution. The solution was continuously stirred for 30 min at
room temperature. Citric acid (0.80% /w chitosan solution)
was then added as an agent to cross-link the chitosan solu-
tion. The mixture was left for 2 h with constant stirring. In the
case of 4% acetic acid solution (pH 2.4), the added citric acid
would be slightly dissociated, however preliminary estima-
tion based on dissociation constant indicated that citric acid
dissociation is only minimal. The purpose of chitosan cross-
linking is to improve its water barrier properties and in-
crease its stability for the application in the acidic medium.
The mechanism of cross-linking action is illustrated in Fig. 1.
The fertiliser pellets were coated by dipping them into the
cross-linked chitosan solution in order to form a single layer
Fig. 1 e Formation of amide linkage via cross-linking
reaction between the amino groups of chitosan and
carboxylic groups of citric acid.
coating. The coated pellets were then left to dry under the
continuous flow of air. After 15 min, it was observed that the
coat was completely dried without any visible surface mois-
ture on the surface of the pellet. Double and triple-coated
layers were obtained by dipping the pellets in the coating so-
lution for two and three times respectively with a gap of
15 min of air drying. The second and third coatings were
carried out without disturbing the previously formed layer of
coat. The dried pellets obtained were kept in a closed
container in order to avoid moisture and water contamina-
tions in between the dipping, such that there would be no
modification of the original coatings. The coated pellets were
left to dry in the oven at 40  C for 12 h.
2.2.2. Measurement of the initial coating thickness
Before undergoing the release rate experiment, the initial
thickness of the single, double and triple-coated films were
measured using a micrometer screw gauge (Mitutoyo, Japan).
The measurements were conducted on the dry coating films
after they were peeled off from the upper surface of the pel-
lets. For each coating, the measurements were taken 10 times
at different locations and the average thickness was calcu-
lated. The same procedure was carried out for double and
triple-coated films.
2.2.3. Fourier Transform Infrared (FTIR) spectra analysis
The non-cross-linked and cross-linked chitosan coating films
were characterised using an FTIR spectrophotometer
(IRPrestige-21, Shimadzu). The samples were pelletised with
KBr powder and analysed under the scanning range from 400
to 4000 cm1.
2.2.4. Coating film morphology
The changes of surface morphology for the double-coated film
before and after the nutrient release rate tests under different
pH values were observed using a scanning electron micro-
scopy (SEM) (Zeiss, BP 35). Platinum was used to coat the films
using an ion-sputtering device before carrying out any
observation.
2.3. Release rate study
The phosphate release rate through the chitosan-coated
phosphorus fertiliser pellets were studied based on the vari-
ation of number of coatings and pH conditions of aqueous
solution. All the coated pellets (single, double and triple
layers) as well as the one without coating were immersed in
different cylinders containing 70 ml of pH 5.7 aqueous solu-
tions and left for 10 days. Measurement of phosphate release
from the uncoated pellet was used as a control experiment.
The samples were taken for day 1, 3, 5, 8 and 10. For each
sampling, about 20 ml of sample was withdrawn and added
with another 20 mL of fresh aqueous solution with pH 5.7. In
order to study the effect of pH conditions, the same procedure
was repeated for double-coated pellet with the pH values of
5.7, 7.1 and 8.5. Each sample was analysed for phosphate ions
concentration using a phosphate low range meter (Hanna
Instruments, HI 93713) with appropriate dilutions. The phos-
phate concentrations in the sample were measured based on
the application of ascorbic acid method.
 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6 81

2.4. Theoretical modelling of the phosphate release
The mathematical model was developed based on the
following assumptions; (1) the nutrient released process took
place on the upper surface of the pellet and in a one-
dimensional coordinate system, (2) the nutrient released
was diffusion dependent, (3) the thickness of the pellet un-
dergoing nutrient release was fixed at a constant value and
time independent during the release process and (4) the
thickness of the coating layer was uniform. The rate of
nutrient release, R from the fertiliser pellet at a given time, t
could be expressed as;
dCav
R ¼ ZA
dt
where Z is the thickness of the pellet, A is the area of the
nutrient mass transfer, and Cav is the average nutrient con-
centration released at time, t. The nutrient was assumed to
diffuse from the core of the pellet to the outer surface through
the coating layer. The expression for the nutrient transfer rate
from the upper surface of the pellet to the surrounding me-
dium could be described using Eq. (2);
R ¼ kc AðC2  Ca Þ
nutrient from the coat's boundary is dependent on the thick-
ness of the coat.
The model uses the following initial and boundary condi-
tions, first proposed by Hoogervorst et al. (1978);
ðaÞ C1 ðx; t ¼ 0Þ ¼ Co for  ∞ < x < 0
ðbÞ Cðx; t ¼ 0Þ ¼ Cm ðxÞ ¼ KC0 f  x=l þ 1Þ for 0 < x < l (5)
ðcÞ C2 ðx; t ¼ 0Þ ¼ 0 for l < x < ∞
where C1 (x, t ¼ 0) is the initial solute concentrations within
the pellet, Cm is the solute concentration within the mem-
brane and C2 (x, t ¼ 0) is the initial solute concentration in the
bulk fluid and x is referred to the transport region. It was
assumed that for conditions (a) and (c), the thickness of the
pellet (Z) is significantly thicker than the thickness of the
(1)
chitosan coat (l). Thus, the ratio of both thicknesses could be
taken as Z/l / ∞. Meanwhile, condition (a) assumes that the
nutrient distribution is uniform across the pellet at the
beginning of the nutrient release process.
For the condition near the wall of the membrane where
(x ¼ l), the concentration C2 (l, t) in Eq. (4) could therefore be
expressed as Eq. (7) using the correlation given by Eq. (6).
  1    
ierfc y ¼ pffiffiffiffi$exp  y2  y$erfc y (6)
(2) p

where kc is the mass transfer coefficient for external surface of " pffiffiffiffiffiffi pffiffiffiffiffiffi ∞  n  #
2r Dt 1 4r2 Dt X 1r nl
the coat, C2 is the nutrient concentration at the outer surface C2 ðl; tÞ ¼ Co $pffiffiffiffi þ 2 $ $ierfc pffiffiffiffiffiffi
ðr þ 1Þl p ðr  1Þl n¼1 1 þ r 2 Dt
of the chitosan coat at time, t and Ca is the nutrient concen-
tration outside the pellet at a distance ∞ from the inner (7)
boundary of the chitosan coat. Combination of Eqs. (1) and (2) It can be proven that for all values of r > 0, the term
resulted in Eq. (3); pffiffiffiffiffiffi
ð1  r=1 þ rÞn $ierfcðnl=2 DtÞ converges rapidly with n. Thus,
Eq. (7) could be simplified into:
dCav
Z ¼ kc ðC2  Ca Þ (3) "
dt pffiffiffiffiffiffi pffiffiffiffiffiffi    #
2r Dt 1 4r2 Dt 1  r l
During the nutrient release process, the chitosan coat was C2 ðl; tÞ ¼ Co $pffiffiffiffi þ $ierfc pffiffiffiffiffiffi (8)
ðr þ 1Þl p ðr2  1Þl 1 þ r 2 Dt
assumed to behave as a membrane. As the time of release
For a distance far away from the surface of the pellet, it was
getting longer, a boundary layer slowly formed on the surface
assumed that the concentration of phosphate ions is negli-
of the coated pellet. The formation of the layer has a signifi-
gible (i.e. Ca / 0 when x / ∞). Then, substitution of Eq. (8) into
cance role in governing the nutrients transport rate through
Eq. (3) resulted in the following equation;
the coat (Dworecki et al., 2005). The presence of additional
" pffiffiffiffiffiffi pffiffiffiffiffiffi    #
resistance due to this boundary layer causes the release pro- dCav 2r Dt 1 4r2 Dt 1  r l
cess to be a rate-limiting diffusion (Pedley & Fischbarg, 1980; Z ¼ kc Co $pffiffiffiffi þ 2 $ierfc pffiffiffiffiffiffi (9)
dt ðr þ 1Þl p ðr  1Þl 1 þ r 2 Dt
Pohl, Saparov, & Antonenko, 1998). According to
Re-arrangement of Eq. (9) into a more convenient form
Hoogervorst, de Goede, Versluijs, and Smit (1978), the math-
leads into;
ematical descriptions of the solute concentration profile in the
aqueous medium with significant effect of the liquid bound- pffiffiffiffiffiffi "  #
dCav Dt 2r 1 4r2 l
ary layer formation can be expressed using Eq. (4) below; Z ¼ kc Co $pffiffiffiffi  $ierfc pffiffiffiffiffiffi (10)
dt l ðr þ 1Þ p ð1 þ rÞ2 2 Dt
" pffiffiffiffiffiffi ! pffiffiffiffiffiffi ∞  n
2r Dt x1 4r2 Dt X 1r Eq. (10) is only valid for the nutrient release process for the
C2 ðx;tÞ ¼ Co $ierfc pffiffiffiffiffiffiffi þ 2 $
ðr þ 1Þl 2 Df t ðr  1Þl n¼1 1 þ r coated pellets with a constant coating thickness. However, for
!# (4)
nl xl the nutrient release in an acidic medium, the chitosan coating
$ierfc pffiffiffiffiffiffi þ pffiffiffiffiffiffiffi
2 Dt 2 Df t film could be exposed to erosion and later dissolved in the
aqueous solution (El-Sherbiny, Abdel-Bary, & Harding, 2006;
where C2 (x,t) is the concentration of nutrient outside the Wu, Su, & Ma, 2006). Thus, the coat thickness, l could also be
pellet at a distance x from the inner boundary of the coat at assumed to decrease with time as expressed by the following
time, t, Co is the original concentration of nutrient within the equation;
pellet, D is the diffusion coefficient of nutrient within the
l ¼ lo expð  mtÞ (11)
membrane or coating layer, Df is the diffusion coefficient of
nutrient within the bulk, l is the coating thickness at time, t, r where lo is the initial thickness of the chitosan coat and m is
is represented by K(D/Df)0.5 and K is the solute partition coef- the dissolution rate constant of the coating layer. Incorpora-
ficient. It can be seen from Eq. (4) that the concentration of tion of Eq. (11) into Eq. (10) resulted into Eq. (12);
82 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6

pffiffiffiffiffiffi "
dCav Dt 2r 1 4r2
Z ¼ kc Co $pffiffiffiffi 
dt ðlo expð  mtÞÞ ðr þ 1Þ p ð1 þ rÞ2
 # (12)
ðlo expð  mtÞÞ
$ierfc pffiffiffiffiffiffi
2 Dt

The diffusion model provided by Eq. (12) can be used to

describe the nutrient released process from the coated pellets,
undergoing film thickness changes with respect to time.

3. Results and discussion

3.1. Initial thickness of the coating film

Table 1 shows the results of the measurement of the initial

thickness of the coating film. Obviously, the average thickness
of the coating film increases with an increase of the number of
coatings. The thicknesses of the double and triple-coated
films are approximately 1.5 and 2 times higher compared to
the single layer of coating film respectively. However, the
increment of the thickness is not directly proportional to the
number of coatings. During the addition of the subsequent
coating, the first layer of polymer coat could be slightly dis-
solved into the second layer, which possibly explains such a
condition. Such an observation is also supported by similar
findings reported by Tomaszewska and Jarosiewicz (2002).
3.2. FTIR analysis
The FTIR spectra of non-cross-linked and cross-linked chito-
san samples are shown in Fig. 2. For the non-cross-linked
chitosan sample, the presence of peak at the frequency
around 3444.87 corresponds to the presence of eOH stretch in
chitosan. A peak observed at 1643.35 cm1 represents the
amide (I) band in chitosan (Salam, Venditti, Pawlak, & El-
Tahlawy, 2011; Yin, Luo, Chen, & Khutoryanskiy, 2006). The
CeO stretch vibration in chitosan was indicated by the peak at
1068.56 cm1. It was also observed that the cross-linked chi-
tosan sample exhibited the analogous FTIR spectrum
compared to the non-cross-linked chitosan. However, the
cross-linked chitosan spectrum indicates a characteristic
peak which was found at the frequency of 1712.79 cm1. This
peak could be attributed to the stretching of carbonyl groups
in the secondary amide linkage of cross-linked chitosan,
whose appearance has been previously observed at about
1716 cm1 (Salam et al., 2011). The presence of this peak cor-
responds to the cross-linking reaction that might occur be-
tween the amine groups from the chitosan and carboxylic
groups from the acid (citric acid) (Fig. 1).
Table 1 e Initial thickness of different coating films, lo.
Coating film Average thickness (mm)
Single 63
Double 96
Triple 128
Fig. 2 e FTIR spectra for (a) non-cross-linked and (b) cross-
linked chitosan with citric acid solution.
3.3. Morphology of the coating film
The SEM images of double coating films before and after 10
days of release tests were closely compared. It can be seen
from Fig. 3(A) that the initial coating film has a compact sur-
face without any pores and cracks. The figure also shows that
the chitosan film has a dense structure, which could be due to
the cross-linking reaction between the citric acid and chito-
san, as revealed by the FTIR analysis in Section 3.2. After 10
days of immersion in the aqueous solution of different pH
values, the coating surface structure has changed accordingly.
Coating film immersed in pH 5.7 (Fig. 3(B)) showed a spongy
structure with pores clearly present on its surface. The hy-
drolysis of amide bond in acidic condition is one of the
possible reactions, which can take place on the chitosan layer
(Mujika, Formoso, Mercero, & Lopez, 2006) and therefore, leads
to the erosion of chitosan as observed in Fig. 3(B). The pore
structures were not observed from the images of chitosan
films after the release tests at pH 7.1 and 8.5 (Fig. 3C and D).
This explains that the chitosan films are more stable under
the neutral and basic conditions with no erosion detected,
which observation was also reported by Wu et al. (2006).
3.4. Phosphates release rate
The trend of phosphate ions released under different number
of coatings could be observed from Fig. 4. It can be apparently
seen that the triple-coated pellets show the lowest phosphate
ions concentration in the aqueous solution, followed by the
double and single coated pellets. An increase in the number of
coatings corresponds to the increase in the thickness as
shown previously in Table 1. Thus, the thicker the coating
layer will result in a lower phosphate release rate. This is due
to the fact that a longer resistance path will be formed that
hinders the nutrient to diffuse out from the centre of the
pellet.
 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6 83

Fig. 3 e SEM images of the double coating film before (A) and after 10 days of release test under pH 5.7 (B), 7.1 (C) and 8.5 (D).

The effect of pH conditions to the phosphate release
through chitosan film is illustrated in Fig. 5. The figure shows
that the phosphate ions release increases as the pH values are
decreased. The highest release of phosphate ions at pH 5.7
could be attributed to the decrease of coating thickness due to
the erosion of chitosan under the acidic condition. This is
supported by the formation of pores on the surface of coating
film after the release test at pH 5.7 as shown in Fig. 3(A). Low
release rate of phosphate ions observed at pH 7.1 and 8.5 could
be due to the increase in the hydrophobicity of chitosan under
a weakly basic medium (El-Sherbiny et al., 2006).
3.5. Transport parameters of phosphate release and
model validation
The experimental data of phosphate ions concentration ob-
tained at different number of coatings and pH conditions were
used to calculate the rate of released of the phosphate ions at
different period of times. These data were examined for
applicability of the diffusion model as developed in Section
2.4. The diffusion model in Eq. (12) was used to evaluate the
transport parameters in an acidic condition by taking into
account the decrease of coating thickness due to erosion.
Meanwhile, the experimental data for neutral and basic con-
ditions was evaluated using Eq. (10). The parameters of kcCo, r,

Fig. 4 e The profile of phosphate release under pH 5.7 for

uncoated and coated pellets with different number of Fig. 5 e The profile of phosphate release for double-coated
coatings. pellets under different pH values.
84 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6

Table 2 e Values of parameters evaluated for phosphate ions release at pH 5.7 for pellets with different number of coatings.
Number of coatings Parameters
kcCo (g min1 m2) r m (m min1) D (m2 min1)
Single 3.85  106 0.8286 3.1  105 2.75  108
Double 3.83  106 0.7561 3.0  105 2.53  108
Triple 3.81  106 0.6906 3.0  105 2.11  108

conditions, the degree of swelling for the chitosan film is low

Table 3 e Values of parameters evaluated for phosphate
ions release from double-coated pellets at different pH
conditions.
pH values Parameters
kcCo (g min1 m2) r D (m2 min1)
6
5.7 3.83  10 0.7561 2.53  108
7.1 2.81  106 0.5955 2.00  108
8.5 2.40  106 0.5911 1.82  108
m and D were obtained from the parameter fitting procedure
embedded in Matlab® (The MathWorks, Inc).
The results of transport parameters for the case of different
number of coatings and pH conditions are shown in Tables 2
and 3 respectively. For the effect of different number of
coatings, the diffusion coefficient, D evaluated from the model
was found to be the highest for a single coated pellet. This is in
agreement with the high concentration of phosphate released
observed for a single coated pellet (Fig. 4), which was
described previously in Section 3.4. High value of diffusivity, D
for a single coated pellet could be due to lesser effect of
resistance for the nutrient diffusion across a thinner coating
film. Table 2 also shows that there are no appreciable differ-
ences between the values for coating film dissolution rate
constant, m under pH 5.7 for different number of coatings.
This result agrees with the report by Sumner, Krause, Sabot,
Turner, and McNeil (2001) who observed that the degrada-
tion rate is rather constant and independent on the polymer
film thickness.
The results tabulated in Table 3 apparently show that the
diffusion coefficient, D decreases as the pH values increased.
This could be due to the fact that under neutral and basic
and causes the mobility of solute across the coating film be-
comes slower, which in turn reduce the solute diffusivity (El-
Sherbiny et al., 2006; Miller-Chou & Koenig, 2003). The
decrease of the film thickness with respect to time due to
erosion at pH 5.7 also reduces the resistance for the phosphate
diffusion, which explains why the diffusivity value, D was
high at this particular condition.
Figures 6 and 7 provide a plot of the predicted release rate
against the experimental values of the phosphate release rate
based on the model developed for different number of coat-
ings and pH conditions respectively. Both plots seem to pro-
vide approximate values to that of the experimental data. The
difference between the predicted and the experimental
release rate seems to be statistically acceptable, which proves
that the model is able to predict the release rate of phosphate
ions from the chitosan-coated pellets. This, in turn confirms
the estimation of the diffusivity values obtained from the
experimental data.
4. Conclusion
From the investigation, it can be summarised that the phos-
phate release rate and the resulting diffusion coefficient of the
phosphate ions from phosphorus-based fertiliser pellets to
the surrounding are affected by the number of coatings and
the pH conditions. The diffusion coefficient of phosphate ions
seems to increase as the coating numbers and pH of the me-
dium gradually decreased. The mechanistic model developed
in this work has successfully described the release rate of
phosphate ions and at the same time evaluated the

Fig. 6 e Comparison between experimental and predicted Fig. 7 e Comparison between experimental and predicted
phosphate release rate for pellets with different number of phosphate release rate for double-coated pellets under
coatings at pH 5.7 condition. variation of pH values.
 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6
parameters values of kcCo, r, m and D. These parameter values
are important and need to be estimated prior to designing the
fertiliser pellets. Pellets can be designed in such a way that the
thickness of the coat follows the predetermined or customer-
desired rate and therefore leading to a reduced waste as well
as minimizing problems associated with nutrient leaching.
Acknowledgements
The authors wish to acknowledge the financial support
received from the USM Incentive Grant (8022033). USM
Fellowship scheme that funds N.N.R. Ahmad is also greatly
acknowledged.
references
Al-Zahrani, S. M. (2000). Utilization of polyethylene and paraffin
waxes as controlled delivery systems for different fertilizers.
Industrial Engineering and Chemistry Research, 39, 367e371.
Aranaz, I., Mengibar, M., Harris, R., Panos, I., Miralles, B.,
Acosta, N., et al. (2009). Functional characterization of
chitosan. Current Chemical Biology, 3, 203e230.
Chen, Q., Lu, W. J., Zhang, W. Q., Wu, J. H., & Deng, X. (2005).
Nutrient release characteristic of chitosan coated urea and
change of penetrability of its coating layer. Journal of East China
University of Science and Technology, 31(6), 764e767.
Chen, L., Xie, Z., Zhuang, X., Chen, X., & Jing, X. (2008). Controlled
release of urea encapsulated by starch-g-poly(L-lactide).
Carbohydrate Polymers, 72, 342e348.
Du, C., Tang, D., Zhou, J., Wang, H., & Shaviv, A. (2008). Prediction of
nitrate release from polymer coated fertilizers using an artificial
neural network model. Biosystems Engineering, 99, 478e486.
Du, C., Zhou, J., Shaviv, A., & Wang, H. (2004). Mathematical
model for potassium release from polymer-coated fertilizer.
Biosystems Engineering, 88(3), 395e400.
Dworecki, K., Slezak, A., Ornal-Wasik, B., & Wasik, S. (2005).
Evolution of concentration field in a membrane system.
Journal of Biochemical and Biophysical Methods, 62, 153e162.
El-Sherbiny, I. M., Abdel-Bary, E. M., & Harding, D. R. K. (2006).
Swelling characteristics and in vitro drug release study with
pH- and thermally sensitive hydrogels based on modified
chitosan. Journal of Applied Polymer Science, 102, 977e985.
Golman, B. (2011). Kinetics of release from polydisperse core
particles coated with layers of fine soluble particles.
International Journal of Chemical Engineering and Applications, 2(4),
283e287.
Han, X., Chen, S., & Hu, X. (2009). Controlled-release fertilizer
encapsulated by starch/polyvinyl alcohol coating. Desalination,
240, 21e26.
Hoogervorst, C. J. P., de Goede, J., Versluijs, C. W., & Smit, J. A. M.
(1978). Nonstationary diffusion through membranes. 2.
Transient diffusion through a membrane separating two
semiinfinite volumes of unstirred solutions. Journal of Physical
Chemistry, 82(11), 1318e1324.
Ko, B., Cho, Y., & Rhee, H. (1996). Controlled release of urea from
rosin-coated fertilizer particles. Industrial and Engineering
Chemistry Research, 35, 250e257.
Koizumi, T., Ritthidej, G. C., & Phaechamud, T. (2001). Mechanistic
modeling of drug release from chitosan coated tablets. Journal
of Controlled Release, 70, 277e284.
85
Krajewska, B. (2001a). Diffusion of metal ions through gel
chitosan membranes. Reactive & Functional Polymers, 47, 37e47.
Krajewska, B. (2001b). Diffusional properties of chitosan hydrogel
membrane. Journal of Chemical Technology and Biotechnology, 76,
636e642.
Krajewska, B. (2005). Membrane-based processes performed with
use of chitin/chitosan materials. Separation and Purification
Technology, 41, 305e312.
Langer, R., & Peppas, N. (1983). Chemical and physical structure of
polymers as carriers for controlled release of bioactive agents:
a review. Journal of Macromolecular Science, Part C: Polymer
Review, 23(1), 61e126.
Miller-Chou, B. A., & Koenig, J. L. (2003). A review of polymer
dissolution. Progress in Polymer Science, 28, 1223e1270.
Mujika, J. I., Formoso, E., Mercero, J. M., & Lopez, X. (2006).
Reaction mechanism of the acidic hydrolysis of highly
twisted amides: rate acceleration caused by the twist of the
amide bond. The Journal of Physical Chemistry B, 110,
15000e15011.
Ni, B., Liu, M., Lu, S., Xie, L., & Wang, Y. (2011). Environmentally
friendly slow-release nitrogen fertilizer. Journal of Agricultural
and Food Chemistry, 59, 10169e10175.
Ni, B., Liu, M., Lu, S., Xie, L., Zhang, X., & Wang, Y. (2010).
Novel slow-release multielement compound fertilizer with
hydroscopicity and moisture preservation. Industrial and
Engineering Chemistry Research, 49, 4546e4552.
Pedley, T. J., & Fischbarg, J. (1980). Unstirred layer effects on
osmotic water flow across gallbladder epithelium. Journal of
Membrane Biology, 54(2), 89e102.
Pohl, P., Saparov, S. M., & Antonenko, Y. N. (1998). The size of the
unstirred layer as a function of the solute diffusion coefficient.
Biophysical Journal, 75, 1403e1409.
Rinaudo, M. (2006). Chitin and chitosan: properties and
applications. Progress in Polymer Science, 31, 603e632.
Salam, A., Venditti, R. A., Pawlak, J. J., & El-Tahlawy, K. (2011).
Crosslinked hemicellulose citrateechitosan aerogel foams.
Carbohydrate Polymers, 84, 1221e1229.
Shaviv, A. (2000). Advances in controlled release of fertilizer.
Advance in Agronomy, 71, 1e49.
Shaviv, A., Raban, S., & Zaidel, E. (2003). Modeling controlled
nutrient release from polymer coated fertilizers: diffusion
release from single granules. Environmental Science and
Technology, 37, 2251e2256.
Siepmann, J., & Siepmann, F. (2008). Mathematical modeling of
drug delivery. International Journal of Pharmaceutics, 364,
328e343.
Sionkowska, A. (2011). Current research on the blends of natural
and synthetic polymers as new biomaterial: review. Progress in
Polymer Science, 36, 1254e1276.
Sumner, C., Krause, S., Sabot, A., Turner, K., & McNeil, C. J. (2001).
Biosensor based on enzyme-catalysed degradation of thin
polymer films. Biosensors & Bioelectronics, 16, 709e714.
Teixeira, M. A., Paterson, W. J., Dunn, E. J., Li, Q., Hunter, B. K., &
Goosen, M. F. A. (1990). Assessment of chitosan gels for the
controlled release of agrochemicals. Industrial and Engineering
Chemistry Research, 29, 1205e1209.
Tomaszewska, M., & Jarosiewicz, A. (2002). Use of polysulfone in
controlled-release NPK fertilizer formulations. Journal of
Agricultural and Food Chemistry, 50, 4634e4639.
Trenkel, M. E. (2010). Slow- and controlled-release and stabilized
fertilizers. Paris, France: IFA.
Tsai, H. S., & Wang, Y. Z. (2008). Properties of hydrophilic chitosan
network membranes by introducing binary crosslink agents.
Polymer Bulletin, 60, 103e113.
Wu, C. (2008). Controlled release evaluation of bacterial fertilizer
using polymer composites as matrix. Journal of Controlled
Release, 132, 42e48.
86 b i o s y s t e m s e n g i n e e r i n g 1 2 9 ( 2 0 1 5 ) 7 8 e8 6
Wu, L., & Liu, M. (2008). Preparation and properties of chitosan-
coated NPK compound fertilizer with controlled-release and
water-retention. Carbohydrate Polymers, 72, 240e247.
Wu, J., Su, Z. G., & Ma, G. H. (2006). A thermo- and pH-sensitive
hydrogel composed of quaternized chitosan/
glycerophosphate. International Journal of Pharmaceutics, 315,
1e11.
Xia, W., Zhang, W. Q., Zhao, X. F., & Wang, W. Q. (2009). Effects of
environmental actors on nutrient release characteristic of
chitosan coated slow release fertilizers. Acta Ecologica Sinica,
29(8), 4560e4564.
Yin, J., Luo, K., Chen, X., & Khutoryanskiy, V. V. (2006). Miscibility
studies of the blends of chitosan with some cellulose ethers.
Carbohydrate Polymers, 63, 238e244.
Zheng, T., Liang, Y., Ye, S., & He, Z. (2009). Superabsorbent
hydrogels as carriers for the controlled release of urea:
experiments and a mathematical model describing the release
rate. Biosystems Engineering, 102, 44e50.