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Research Paper

Modelling the release of nitrogen from controlled

release fertiliser: Constant and decay release

Thanh H. Trinh a,b,*, Kuzilati Kushaari a,**, Anis S. Shuib a,

Lukman Ismail a, Babar Azeem a
a
Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak,
Malaysia
b
Faculty of Chemical Engineering, HCMC University of Technology, Ho Chi Minh, Viet Nam

article info
Urea, when applied to crops is vulnerable to losses from volatilisation and leaching.
Article history: Controlled release urea enhances nitrogen use efficiency by plants which not only in-
Received 25 May 2014 creases the crop yields but also contributes towards environmental pollution control in
Received in revised form terms of the alleviation of hazardous gaseous emissions and water eutrophication. This
7 October 2014 study proposes a multi-diffusion model that simulates nitrogen release from coated urea
Accepted 9 December 2014 particles for both the constant and decay release stages of urea. It is developed for
Published online 25 December 2014 multilayer included the coating and water zone, and integrates a Finite-element method
(FEM) with 2D geometry to enhance the accuracy of simulation by introducing urea
Keywords: diffusivity in water domain as a function of its concentration. Results from the simulations
Controlled-release fertiliser agreed with preliminary experimental data to a standard error of estimate (SEE) that
Finite-element method ranged from 0.0159 to 0.0567 in which the model successfully simulated and predicted
FEM nitrogen release from hours to days from smaller to larger particles. A more thorough
Multi-diffusion model investigation was then conducted for which the model not only predicted nitrogen release
Nitrogen release from coated urea but also described the internal release mechanism of urea from the core
to urea-coated interface and into aqueous environment.
© 2014 IAgrE. Published by Elsevier Ltd. All rights reserved.

plant growth. However, many fertilisers are vulnerable to

1. Introduction
Fertilisers play a vital role to supplement the nutrients
required for plant growth (Plimmer, Gammon, & Ragsdale,
2003). However, plants require different quantities of nutri-
ents during different stages of growth. They need smaller
quantities during infancy and larger amounts during the
development of roots, stalk and stem. Fertiliser demands
therefore change periodically over the entire time span of
losses from volatilisation, leaching and fixation, and in-
vestigators have determined that only 30% of the fertilisers
are used by plants while the balance is lost (Al-Zahrani, 1999).
Such losses have adverse environmental impacts due to the
addition of excess nutrients to air and water (Oertli, 1980;
Plimmer et al., 2003). Similarly, excess fertiliser spoils seed-
lings as only a small quantity of fertiliser is needed during
sprout development (Shaviv, 2000; Trenkel, 1997, 2010).

* Corresponding author. Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh,
Perak, Malaysia. Tel.: þ60 1 07700361.
** Corresponding author. Tel.: þ60 1 94107181.
E-mail addresses: onalone2000@gmail.com, ththanh@hcmut.edu.vn (T.H. Trinh), kuzilati_kushaari@petronas.com.my (K. Kushaari).
http://dx.doi.org/10.1016/j.biosystemseng.2014.12.004
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 3 0 ( 2 0 1 5 ) 3 4 e4 2
Fig. 1 e a) Agrium® coated urea used in release experiment; b) SEM of Agrium® coated urea (magnified 180£).
The development of controlled-release fertilisers (CRF) is a
green technology that not only reduces fertiliser loss caused
by volatilisation and leaching but also alters the kinetics of
nutrient release, which, in turn, provides nutrients to plants at
a pace that is more compatible with their metabolic needs.
Urea is chosen for many CRF applications because of its high
nitrogen content, low-cost and economical availability (Kent,
2007). It is believed that the initial world class study of the
application of CRF was done by Ortil in 1962 (Shaviv, Raban, &
Zaidel, 2003b). CRFs are generally divided into three groups:
reservoir, chemically controlled release, and matrix type (Al-
Zahrani, 1999). In reservoir formulations, the fertiliser core is
encapsulated within an inert carrier and these are regarded as
coated fertilisers where nutrient release is controlled by the
diffusion through the coating. Sulphur-coated urea (SCU) and
polyethylene-coated urea are examples of this type of
formulation. Chemically controlled release fertilisers are
synthetically produced organic nitrogen, low solubility com-
pounds that include condensation products from urea and
acetaldehyde such as urea-formaldehyde. Matrix (or mono-
lithic) CRFs hold active ingredients that are dispersed within
the matrix where they are initially dissolved and then diffused
across the matrix continuum to the external surface (Al-
Zahrani, 1999).
Nutrient release from coated CRFs is generally controlled
by diffusion through the coated layer (Plimmer et al., 2003;
Shaviv et al., 2003b) and numerous recent studies have
focused on predicting nutrient release behaviour. The
simplest approach is regression modelling reported and used
by Kochba, Gambash, and Avnimelech (1990), Gandeza, Shoji,
and Yamada (1991), Medina, Sartain, and Obreza (2009),
Wilson, Rosen, and Moncrief (2009) and Zheng, Liang, Ye, and
He (2009). Kochba et al. (1990) used a semi-empirical model
where the release of CRF was considered a first-order process.
However, they ignored effects from geometry and size, and
also failed to account for the lag period. Gandeza et al. (1991)
developed a semi-empirical model to study the effect of soil
temperature on nutrient release from CNR-polyolefin-coated
urea using a quadric equation: CNR ¼ a þ b(CT) þ c(CT)2.
Wang, Alva, Li, and Zhang (2011) also studied the effect of
temperature on the release rate by using a regression model
that reduced experimental time from days to hours. However,
each of these models only related to a specific coating
material.
35
A second approach was proposed in 1980 by Jarrell and
Boersma (1980) who developed a mathematical model of
urea release from sulphur coated urea (SCU) particle. Glasser,
Stajer, Vidensky, Svandova, and Knor (1987) employed a one-
dimensional coordinate diffusion system to predict the
release of nutrient from polymer-coated granules in which a
nonlinear release was produced by assuming that the diffu-
sion coefficient (D) was time dependent. Lu and Lee (1992)
applied Fick's law as a spherical coordinate for the release of
nitrogen from latex coated urea (LCU). Shavit, Shaviv, Shalit,
and Zaslavsky (1997) proposed a new type of CRF using a
mixture of soluble fertiliser with a thickener as the coating
material. He used the simple model introduced by Lee (1985) to
compare experimental data where ai (equal to 0.5) was
considered the Fick release factor. Zhang, Nyborg, and
Izaurralde (1997) introduced a soil retardation factor (Sb) as a
diffusion resistance parameter to simulate the release of ni-
trogen from polymer coated urea (PCU) with which he evalu-
ated the effect of the coating layer on the release rate. Al-
Zahrani (1999) modelled the unsteady state of the polymeric
membrane particle by assuming a well-mixed condition
within the spherical particle. Later, Ni, Liu, Lü, Xie, & Wang
(2011) compared experimental results with this model. In
most of the cited modelling studies, the reigning hypothesis
was that the release of nutrients from coated fertiliser was
controlled by a single solute diffusion mechanism.
Based on Raban's experiments, Shaviv et al. (2003b) posited
that the release profile from a single polymer coated granule
had a sigmoidal shape consisting of three stages: an initial
stage during which no release is observed (lag period); a stage
of constant or steady state release; and finally, a stage of
gradual decay of release. Shaviv, Raban, and Zaidel (2003a)
also developed a statistical model for a population of gran-
ules. Lu et al., 2007 proposed a mathematical model for urea
release from a scoop of PCU taking into account the popula-
tion effect. His model was based on the mass balance equation
of a pseudo-steady state according to Fick's law. He neglected
the first stage of the release process and used a “trial and
error” method to estimate the diffusion coefficient. Ito,
Golman, and Shinohara (2003) used a 'random walk' method
to estimate the effective diffusivity (De) of coating material for
different starch fractions.
The finite-element method (FEM) has been applied since
2003 to study the release of CRF (Shavit, Reiss, & Shaviv, 2003).
36 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2
Fig. 2 e (a) Dissolution model of a spherical urea particle in water environment; (b) Geometry and mesh generation of a urea
dissolution model for coated urea in Comsol.
However, the geometry used in his model was not a particle
type specific. Trinh, KuShaari, Basit, Azeem, and Shuib (2014)
used 2D geometry and the FEM model to simulate urea release
from coated particle but this model only served the second
stage of release. Therefore, the objective of this study aims to
extend our prior study (Trinh, KuShaari, et al. 2014) to the
decay release rate stage. By applying the multi-diffusion
mechanism in this model, a sigmoidal release profile was
obtained and validated by a release test with Agrium® coated
urea. The model was also compared with experimental data
from literature to confirm its reliability and robustness and
further showed the advantages of FEM in the study of urea
release behaviour by a thorough investigation of the release
mechanism within the coated particle.
2. Experiments for model verification
2.1. Material
We used Agrium® coated urea to study its release profile. All
the urea particles under investigation were weighed on an
individual basis and coating thickness range from 59 to 72 mm
as determined by TM3030 scanning electron microscope (SEM,
Hitachi) as shown in Fig. 1.
2.2. Nitrogen release experiment
The release test was performed in a beaker containing 250 ml
distilled water at 27  C. For each interval of 2e5 days, urea
concentration was measured with a U-2010 spectrometer
(Hitachi) at a wavelength of 210 nm. We constructed the ni-
trogen release profile from these results. More explicit
experimental details are found elsewhere (Trinh, Dao,
KuShaari, Ismail, & Shuib, 2014).
3. Model development
Figure 2a illustrates the dissolution model of a spherical urea
particle surrounded by water defined as the fluid zone. Urea
particles comprise two parts: the urea core and the coating
layer. This model assumed that the coating layer was satu-
rated with water at the time (t0) of initial release. Water within
the core begins dissolving the solid urea where urea concen-
tration is maintained at a saturated level as long as solid urea
exists in the core. Nitrogen, in the form of urea, begins its
release through the coating layer by diffusion with a constant
rate. Hence, it is called “constant release” stage. When solid
urea in the core is totally dissolved, urea concentration de-
creases, and a “decay release” stage begins and then continues
to the end of the process.
Based on mass transport equation for porous medium, the
transient stage of urea diffusion through the coating is rep-
resented by Eq. (1) (Lu et al., 2007).

2 
v Cðr; tÞ 2 vCðr; tÞ vCðr; tÞ
De þ ¼ε (1)
vr2 r vr vt
Since the urea particle is motionless, it is assumed that
urea flux from the coating interface to the liquid environment
is controlled by the diffusion of urea in liquid. Hence, diffusion
is calculated on the basis of mass transport equation of urea in
water as follows:
v2 Cðr; tÞ 2Durea vCðr; tÞ vCðr; tÞ
Durea þ ¼ (2)
vr2 r vr vt
Within the water zone, urea diffusivity in liquid, Durea,
varies according to urea concentration displacement as
described by Eq. (3) (Cussler, 2009).
 
Durea ðr; tÞ ¼ 1:380  0:0782Cðr; tÞ þ 0:00464Cðr; tÞ2 105 cm2 s1
(3)
Finite element method (FEM) and 2D geometry was
employed for our urea release model. Comsol Multiphysics
4.3a (FNL license) was used to investigate urea release
behaviour. This model is specifically developed for single
coated particle and because this particle is spherical, the
model's geometry was based on one quarter of a sphere. Ge-
ometry and meshing steps were done for single urea particle
(Fig. 2b) where the fluid zone diameter, i.e. the distance from
the centre of the urea particle centre to the water boundary
(R1), was set at twenty-two times of the core radius (R0) (Trinh,
Shaari, Shuib, & Ismail, 2013). A mesh convergence analysis
 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2 37

was performed in order to estimate the accuracy of the

Table 1 e Agrium® coating parameters used in the model.
simulation. The BDF method, which used backward differen-
tial formulas, was applied to solve Eqs. (1)e(3) with 10118 de- Parameter
grees of freedom. The model had 20096 elements with an Radius, mm 1.5
average mesh quality of 0.9664 after conducting mesh Coating thickness, mm 64
convergence analysis. The error between iterations ranged Lag time t0, day 3.0
Effective diffusivity (Deff), m2 s1 1.6  1014
from 1019 to 1016 during the calculation. Initial values and
boundary conditions were specified for the model depending
on each stage of the release. Related equations used in this solid urea core was completely dissolved at which time (t1) the
model were as follows: entire urea core is liquefied and saturated with urea.
Total urea mass of a single coated urea particle was
mcore ðt1 Þ ¼ Murea Vcore Csat (10)
calculated as:
Eq. (10) defines the end (stop) condition for the constant
mtotal urea ¼ Vcore durea (4)
release stage in compliance with the model. After the constant
where, release stage finished, the process then changed to “decay
release” stage.
mtotal urea is total urea mass of the coated urea particle, g,
Vcore is volume of urea core, m3, 3.2. “Decay release” stage
durea is urea density, g/m3.
Decay release begins when the solid urea core is completely
The amount of urea released at any time t is defined as the dissolved. Urea concentration within the core continually
integral of diffusion flux at the outer shell of urea particle decreases due to the release of urea to the water zone. At this
(r ¼ R0 þl). point, the boundary and initial conditions were derived from
the results of the constant release stage. Boundary condition
Zt
for decay release stage was:
mreleased ðtÞ ¼ Murea Adiff Jurea ðr; tÞdt (5)
t¼0 Durea VCDR ðR1 ; tÞ ¼ 0 ðt  t1 Þ (11)
Urea mass within urea core is: and the initial condition was
Zt
CDR ðr; t1 Þ ¼ CCR ðr; t1 Þ ð0  r  R1 Þ (12)
mcore ðtÞ ¼ mtotal urea  Murea Acore Jurea ðR0 ; tÞdt (6)
t¼0 where

where
CDR(r, t1) is the initial urea concentration of decay release
2 1 stage, mol m3,
Jurea is urea diffusive flux, mol m s
CCR(r, t1) is urea concentration at the end of constant
Adiff is urea particle surface, m2
release stage, mol m3.
Acore is urea core surface, m2.

3.1. “Constant release” stage The urea concentration profile is determined by CDR ðr; tÞ
within the particle. Urea concentration at the urea core at any
As mentioned above, we assumed that water penetration had time t was calculated by Eq. (13):
finished before urea release occurred; an interval called the
mcore ðtÞ
lag time (t0). The lag time was not a subject in this study and CDR ðR0 ; tÞ ¼ ðt  t1 Þ (13)
Vcore
was obtained from other related experiments. From time t0
therefore, if the urea solution at the surface of the urea core is As mentioned by Shaviv (2005), a good quality CRF releases
saturated and the concentration at the outer layer of the fluid more than 90% of its urea after the stated time. Additionally,
field is zero, then the boundary conditions are as follows the release rate slows considerably when mrelease(t) reaches
(Trinh, KuShaari, et al. 2014): mtotal urea. However, as this increases calculation time and re-
sources and is unnecessary, we composed the end condition
CCR ðR0 ; tÞ ¼ Csaturated ðt0  t  t1 Þ (7) for this stage as.

mrelease ðt2 Þ
CCR ðR1 ; tÞ ¼ 0 ðt0  t  t1 Þ (8) percent release ¼  100% ¼ 95% (14)
mtotal urea
and the initial condition is:
3.3. Model verification and comparison with other
CCR ðr; t0 Þ ¼ 0 ðR0  r  R1 Þ (9)
literature
The amount of urea released (mrelease) and the urea mass
within the core (mcore) were calculated using Eqs. (5) and (6). In Prior to validation process, a mesh convergence analysis was
these simulations, urea release time depended on the amount performed to estimate the accuracy of simulation. Percent
of urea (size and shape) and the coating material's properties released of nitrogen at transition time between constant
(thickness, diffusivity, porosity). This stage ended when the release and decay release stage was used to determine the
38 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2

by experimentation. For ease of understanding, this section is

Table 2 e Geometry and effective diffusivity parameter
divided into three subsections. In the first subsection, the re-
used in simulation trials for model verification.
sults are presented for the model validation using experi-
Name R0 l Deff  1014 Reference
mental data in which nitrogen release was investigated using
(mm) (mm) (m2s1)
Agrium® coated urea. To confirm the reliability and robust-
CAP150R1 0.8925 0.0711 70.0 Lu et al., 2007 ness of this model, different studies of coated urea release
CAP300R1 0.8925 0.2489
(taken from the literature) were also modelled as depicted in
MPO 1 1.2 0.0375 1.2
the second subsection. In the third subsection, results are
MPO 2 1.2 0.0917 Shaviv et al. (2003b)
presented for model projections of the internal mechanism of
MPO 3 1.2 0.1833
nitrogen release from the coated particle.
Latex 7.06 0.353 39.5 Lu and Lee (1992)

estimation accuracy of simulation, and chosed an appropriate
mesh size. Secondly, model verification was conducted with
our experimental data from the release test of Agrium® coated
urea. The model was set up for a single granule based on
specific parameters as shown in Table 1.
Standard error of the estimate (SEE), was used to determine
the accuracy between simulation and experiment.
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P 2
y  yest
SEE ¼
n
where
y is the experimental data
yest is the simulation results
n is number of given data
Thirdly, in order to further validate the model reliability
and robustness, a comparison was conducted with other
experimental data obtained from literature. Simulation trials
were done for three types of coating material (included small
and large particles) of Cellulose Acetate Propionate (CAP);
Modified Polyolefin (MPO); and Latex Film in which release
time ranged from hours to days. Geometry and effective
diffusivity parameters used in these trials are summarised in
Table 2.
4.1. Model verification through the release of nitrogen
from Agrium® coated urea
Mesh convergence analysis was performed to estimate the
accuracy of simulation as in Table 3. Percent released
converged to the second decimal place for mesh size factors
from 0.7 to 1.1 which is sufficient to the accuracy that can be
obtained from experiments. Error between mesh size factor of
0.7 and 1.0 was 0.00125%, hence the factor of 1.0 was chosen
(15) for the model.
The simulation result is plotted in Fig. 3 and corresponded
well with our experimental data. The standard error of esti-
mate (SEE) was 0.0300, which is acceptable for the prediction
of nitrogen release. The minor discrepancy between the
experimental and simulation results may be attributed to
differences in particle shape, the particles population effect,
and asymmetry of coating thickness. Predicted data is also
presented as a straight line in the release curve from the
beginning of the release and shows a decrease in release rate
during the second stage. Both predicted and experimental
data presented similar sigmoidal release trends in agreement
with the cited literature (Ito et al., 2003; Lu et al., 2007; Lu &
Lee, 1992; Shaviv et al., 2003b).
4.2. Comparison with experimental data from other
studies

Simulation trials were done for three types of coating material

4. Results and discussion
(included small and large particles) of Cellulose Acetate Pro-
pionate (CAP), Modified Polyolefin (MPO), and Latex Film in
There are two approaches to study of object behaviour,
which release time ranged from hours to days. Experimental
experimental or modelling. While an experiment represents
real behaviour, it takes time and increases the cost. Simula-
tion therefore plays an important role. Moreover, the model
presented above has advantages that are not easily obtained

Table 3 e Different mesh size factor, number of elements

and percent released.
Mesh size factor Number of Percent
elements released, %
0.7 34,132 48.00538
0.8 27,928 48.00596
0.9 23,172 48.00545
1.0 20,096 48.00663
1.1 17,394 48.00917
1.2 15,442 48.00404
1.3 13,768 47.75444

The shade signifies the chosen mesh size factor.

Fig. 3 e Release profile of Agrium® coated urea.
 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2 39

Table 4 e Comparison of simulation data with results from cited literature (Lu et al., 2007; Lu & Lee, 1992; Shaviv et al.,
2003b).
Name t0 t1 t2 SEE R0 (mm) l (mm) Deff  1014 (m2s1)
CAP150R1 0h 7.75 h 20 h 0.0567 0.8925 0.0711 70.0
CAP300R1 0h 18.47 h 90 h 0.0377 0.8925 0.2489
MPO 1 0.5 d 15.89 d 40 d 0.0179 1.2 0.038 1.2
MPO 2 4.0 d 38.72 d >60 d 0.0169 1.2 0.092
MPO 3 7.0 d 66.84 d >60d 0.0159 1.2 0.183
Latex 22 d 46.30 d 92 d 0.0393 7.06 0.353 39.5

t0 e lag time, t1 e constant release time, t2 e time when 90% nitrogen has already been released, hr e hour, d e day.

data were obtained from the literature using Engauge Digitizer

4.1. A summary of these results is presented in Table 4.
Cellulose Acetate Propionate (CAP) was the coating mate-
rial with the quickest release time. A particle with a radius of
0.8925 mm provided the longest release time of 160 h. As
shown in Fig. 4, the nitrogen release curve best fits experi-
mental data obtained by Lu et al., 2007, and thus, indicated
that this multi-diffusion model is a reliable predictor of ni-
trogen release from small particles with a release range up to a
few hundred hours.
The second trial was run against Shaviv's experiments
(Shaviv et al., 2003b) where particle radius was 1.2 mm and
similar to CAP's but where the release times extended to more
than sixty days (Fig. 5). Our standard error of estimation (SEE)
ranged from 0.0159 to 0.0179, thus showing the estimations
were even better than those predicted for the CAP release.
Hence, the model proved robust with its estimate of nitrogen
release for coated urea particles with longer release time as
usually found in commercial products. Our model also applied Fig. 5 e Release profile for urea particle coated with
well to the third simulation, with release estimates extended modified polyolefin (MPO). Radius of urea cores were
to 120 days for Latex film coated particles as reported by Lu 1.2 mm for all cases. Coating thicknesses were 0.0375,
and Lee (1992) where the particle was the largest (7.065 mm). 0.0917 and 0.1833 mm for MPO 1, 2, and 3 respectively.
This nitrogen release curve is shown in Fig. 6 where the Experimental data obtained from Shaviv et al. (2003b).
simulated (SEE) result and experiment was acceptable. The
model thus proved reliable and robust for the prediction

Fig. 4 e Release profile for urea particle coated with

Cellulose Acetate Propionate (CAP). Radius of urea cores Fig. 6 e Release profile from urea particle coated with latex
were 0.8925 mm for all cases. Coating thicknesses were film. Radius of urea cores and coating thicknesses was 7.06
0.0711 and 0.2489 mm for CAP150R1 and CAP300R1. and 0.353 mm. Experimental data obtained from Lu and
Experimental data obtained from Lu et al., 2007. Lee (1992).
40 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2

Fig. 7 e Urea mass profile in particle and core: a) constant release; b) decay release stage. There is no release during phase I.
The release occurs and reaches balance during phase II. Release rate keeps constant in phase III. And phase IV is the
decrease in release rate.

nitrogen release from polymer coated urea particle over a
wide range of sizes and release intervals.
4.3. Coated urea release behaviour
Figure 7a depicts the mass profile of urea within the core as
well as a coated particle during the stage of constant release. It
also presents end condition and transition between constant
and decay release rate stages. Of interest here is the delay in
the release profile related to the mass profile within the par-
ticle. In phase I, the urea core quickly dissolved while the urea
mass remained constant, meaning there was no release
observed during this period. This phenomenon can be
explained by the movement and saturation of the urea front

Fig. 8 e Urea front movement in coating layer are presented by urea concentration in granule and water environment in 2D
plots from 100 to 15000s during constant release stage. Colour legend represents urea concentration in range of
0e0.2 mol m¡3. The movement of urea front (red) from 100 to 9000s causes a delay in the release. At time 13000s, the release
occurs and is represented by the change in environment's concentration.
 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2 41

Fig. 9 e Urea concentration profile in coating layer during constant release stage: a) phase I (nitrogen movement through
coating layer and there no release), b) phase II (the release occurs and increases its rate), c) phase III (nitrogen releases at
constant rate); and decay release stage: phase IV (d, e, f). Urea concentration inside the core reduces by time (from d to f).
White arrows present urea diffusive flux, which related to nitrogen release rate. It becomes smaller from d to f. Colour
legend represents urea concentration in range of 0e1.1 £ 104 mol m¡3.

within the coating layer before reaching the particle's outer
shell as seen in Fig. 8. From time t ¼ 100e13000s, we observe
the movement of the urea front from the particle's core to its
surface. Figure 9a also shows no release of urea into the water
zone. Many previous researchers did not account for this
phenomenon which is an oversight that may have increased
discrepancies between modelling and experiment results.
During phase II when the urea front reached the interface
between the particle and the environment, urea began to
release to the environment and the rate of release increased
until it reached a constant rate. This transient stage happened
very rapidly compared to the entire release period and is
difficult to observe experimentally.
During phase III, urea release gained a steady state and
maintained a constant rate. Figure 8 shows an increase of
accumulated urea to the water zone that is experimentally
measureable. However, this steady state is not maintained
indefinitely and drops to an uneven pace when the solid urea
core is completely dissolved, at which time the decay release
stage begins.
Fig. 9d, e, f depict Phase IV of urea concentration profile
during the decay release rate at days 24, 38, 57, respectively.
Urea concentration within the core constantly decreased as
urea concentration in the water zone increased. This led to a
decrease in the gradient of urea concentration between the
urea core and the water zone as seen in Fig. 7b. Hence the
diffusion flux (white arrows) decreased from day 24 to 57
during Phase IV as seen in Fig. 9. This change in diffusion flux
is the main reason for the reduction of the nitrogen release
rate.
5. Conclusion
The FEM and 2D geometry model as supported by Comsol
Multiphysics 4.3 was modelled and then validated with an
Agrium® urea release test. The model was able to reliably
simulate the nitrogen release from polymer coated particles
by the investigation of various coated urea types as per cited
literate. This model suitable predicted nitrogen release for
most polymer coated urea particles introduced to the market
which covers a wide range of particles sizes and release pe-
riods. In addition, the model demonstrated nitrogen release
behaviour(s) and mechanism that led to discrepancies be-
tween prior simulations and experimental results. However,
challenges remain for the model's further development with
respect to the effect of urea concentration on effective diffu-
sivity as well as effects from particle shape and population
size, etc. Nonetheless, the present model confidently pre-
dicted the nitrogen release behaviour of coated fertiliser.
42 b i o s y s t e m s e n g i n e e r i n g 1 3 0 ( 2 0 1 5 ) 3 4 e4 2
Acknowledgement
The authors would like to offer their profoundest gratitude to
OneBAJA, Center for Biofuel and Biochemical (CBBR), and
Universiti Teknologi PETRONAS, Malaysia for providing a
congenial work environment and state-of-the-art research
facilities. The research grant extended to us by the Ministry of
Education, Malaysia (MOE) (LRGS Fasa 1/2011) for ongoing
research projects and the technical support from National
Institute of Forensic Medicine, Vietnam is also highly
acknowledged. The writing suggestions shared by Dr. Noridah
Osman, Universiti Teknologi PETRONAS, Malaysia, is highly
appreciated.
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