Process Safety and Environmental Protection 121 (2019) 133–142

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Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Encapsulation of urea with alkyd resin-starch membranes for

controlled N2 release: Synthesis, characterization, morphology and
optimum N2 release
Chigozie Francolins Uzoh a,∗ , Okechukwu Domnic Onukwuli a , Ikenna Henry Ozofor b ,
Raphael Stone Odera a
a
Chemical Engineering Department, Faculty of Engineering, Nnamdi Azikiwe University, Awka, Nigeria
b
Chemical Engineering Department, Michigan Technological University, Michigan, USA

a r t i c l e i n f o a b s t r a c t

Article history: Nitrogen released into soils from uncoated urea granules is lost continuously due to volatilization, leach-
Received 19 August 2018 ing, denitrification, nitrous emission, water eutrophication and surface run-off. Reducing the release rate
Received in revised form 19 October 2018 can increase its efficiency of use and reduce nitrogen pollution. In this research, granular urea fertilizer
Accepted 22 October 2018
was encapsulated with alkyd resin-starch bio-composites as materials of biodegradable and regenera-
Available online 25 October 2018
tive resources to obtain controlled release coated urea (CRCU). Different bio-composites were synthesized
from each of castor seed oil and rubber seed oil based alkyd resin (modified with sorbitol, maleic and
Keywords:
phthalic anhydride) and cassava starch. Effects of sorbitol, maleic anhydride and pthalic anhydride on the
Controlled release
Encapsulation
release kinetics of the CRCU were evaluated. Optimum nitrogen release characteristic of the CRCU was
Response surface methodology evaluated as a function of coating thickness, release time and pH. Structural and morphology elucida-
Biodegradable tion of the raw urea and encapsulated ureas were established using FTIR and SEM instrumental analysis,
Release kinetics respectively. Nutrient release kinetic of the different coated urea was determined using Kjeldahl method.
Process optimization FTIR result confirmed the esterification reaction and hydrogen bonding integrity of the alkyd resins and
starch. The SEM images of the raw urea appears rough and have fine openings while that of CRCUs pos-
sess a seemingly decrease in membrane porosity and ordered uniform layer. 31.66 and 48.61% cumulative
nitrogen release were obtained with coating thickness of 6.4(mm), time of 24 days, pH of 8 and 2.2(mm),
time of 24 days, pH of 8 for RSO-St-S and CSO-St-S encapsulated urea, respectively. The encapsulated
ureas perfectly satisfy the requirements of European Standard EN 13,266 for CRFs. It can be concluded
that the synthesized CRCU efficiently retard nitrogen release.
© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Environmental issues have risen to the forefront in matters
pertaining to materials and their applications. Surface coating
materials are no exception. Surface coating is a general descrip-
tion for any material that can be applied as a continuous film to a
surface; so it can be claimed that coatings are present everywhere
in our daily lives (Uzoh, 2017). Changes in consumer preferences
and VOC regulation have mandated that industry reduce the VOC in
coating. In some cases this has necessitated a switch from solvent-
based to water-based technology (Arendt et al., 2015). Waterborne
alkyd technology has been very successful, therefore, investigating
∗ Corresponding author.
E-mail address: cf.uzoh@unizik.edu.ng (C.F. Uzoh).
the viability and feasibility of waterborne alkyd resin as green and
sustainable coating material for control release urea (CRU) is more
acute than ever. Since alkyds are hydrophobic, the alkyd polymer
must be designed and modified to exist in the polar, aqueous envi-
ronment. An ideal CRU is coated with a natural or semi natural
environmentally friendly macromolecular materials that retards
fertilizer release to such a low pace that a single application to the
soil can meet the nutrient requirements of the specific crop.
Uncoated urea, when applied to crops is vulnerable to losses
from volatilization, nitrous emission, leaching, denitrificatication
and water eutrophication. Urea is the most widely used fertilizer
globally because of its high nitrogen content (46%), low cost, and
ease of application (Zheng et al., 2009). Therefore, the development
of CRCU has been a subject of interest for decades (Rindt et al., 1968;
Irfana et al., 2018). Film-coated urea is used to increase urea utiliza-
tion efficiency. Common urea fertilizer is vulnerable to loss through

https://doi.org/10.1016/j.psep.2018.10.015
0957-5820/© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
134 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Nomenclature
ANOVA Analysis of variance
CSO-St-S Castor seed oil alkyd resin-starch biopolymer mod-
ified with sorbitol (D-glucitol)
CCRD Central composite rotatable design
CRCU Controlled release coated urea
DF Degree of freedom
F-value Test statistics of F distribution
FFA Free fatty acid
MA Maleic anhydride
p-value Smallest level of significance that would lead to the
rejection of the null hypothesis in test statistics
PA Phthalic anhydride
RSM Response surface methodology
RSO-St-S Rubber seed oil alkyd resin-starch biopolymer
modified with sorbitol (D-glucitol)
X Coded independent system variables
Y Dependent variables, predicted response
␤ Constant coefficient of mathematical model
⑀ Random error of mathematical model
nitrous emission, leaching, de-nitrification and water eutrophica-
tion which are commonly caused by application of urea without
any coating. The nutrient demand of the plant can be met more
closely by designing an appropriate controlled release system to
increase efficiency and reduce the risk of overdosing the plant. CRU
also decrease cost for agriculture by reducing the amount of fertil-
izer needed and the labor and fuel cost associated with the repeated
application of fertilizer. In general, the release mechanism begins
with a wetting process where water penetrates in fertilizer through
the coating. The dissolution process comes, quickly dissolves the
soluble fertilizer core when water reaches the inner wall of the
coat, and then increases the internal pressure of the solution. The
third process is the release of nutrient from the core to the outer
space. Fig. 1 illustrates the entire release process of fertilizer
Alkyd resins are widely used in paint industry and although they
have a long history about 70–100 years, today the developments
in alkyds are still welcomed and innovations are still needed. The
major hindrances to industrial alkyd resin production are their rel-
ative high solvent content and economic viability. Therefore, much
current research interest is geared towards the development of new
approach that will guarantee the decrease in solvent borne alkyd
resin and the production cost (Gooch, 2002). Alkyds emulsions are
synthetic resins derived from ester-based polymers that are modi-
fied with vegetable oil or fatty acids. It is a binder with good wood
penetration, which is important in exterior paints. Due to its good
bond integrity with −OH group, alkyd emulsions are expected to
Fig. 1. A demonstration of an entire nutrient release process.
be one of the good alternatives for the base of the next genera-
tion waterborne coatings. Research on application of waterborne
alkyd membrane in CRCU is therefore both relevant and important
(Gooch, 2002). Rubber seed oil (RSO) and Castor seed oil (CSO) are
among the most abundant vegetable oil grown in tropical countries.
They are inedible, therefore, cannot interfere in the food chain. d-
glucitol, is a type of polyol with six hydroxyl groups. d-glucitol is
a cheap biodegradable and renewable resource, the production is
very huge especially for d-glucitol aqueous solution. It is consid-
ered as a potential raw material for the manufacture of alkyd resin
since it has similar properties to polyvinyl alcohol. It is expected,
therefore, that a better controlled capability on release of nutri-
ents with characteristic of being cheaper, more biodegradable and
friendlier to the environment will be obtained from urea encapsu-
lated with RSO/CSO-d-Glucitol modified waterborne alkyd. These
advantages are in line with the future development directions of
controlled release fertilizers.
Sulfur and organic polymer have been used as control release
coating materials (Azeem et al., 2014). A 24-hour dissolution test
in water was done to evaluate coating effectiveness. The authors
found that the oil-only coating was absolutely ineffective to with-
stand water permeability. The sulfur-only coating was mildly
effective, whereas a combination of both gave effective controlled
release results. However, they have limitation of high cost, pro-
cess complexity, inconsistence result and environmental issues
(Azeem et al., 2014). Synthetic polymers such as polyethylene,
polystyrene, polyacrylamide, and polysulfone offered promising
results with respect to controlled released characteristics, batch
to batch uniformity and water retention properties when used as
coating materials to produce CRF. However, these materials could
not be used to produce CRF on industrial use due to augmented
cost, non-biodegradability and high solvent content. Azeem et al.
(2016) used waterborne polymer modified with polyvinyl alco-
hol to synthesize a cheap and biodegradable coating for controlled
release urea (CRU). Due to profound hydrophilic nature and poor
mechanical properties of starch, the coated film could not produce
promising results. In another account, Yang et al. (2012) studied
the swelling and diffusion model of a hydrophilic film coating on
controlled-released urea particle using latex. They concluded that
the film coating through latex dewatering is a promising environ-
mental benign process. However, the inconsistency in the release
rate is responsible for complication that led to fertilizer release not
being synchronized with the plant demand. Consequently, plants
are starved of nutrients or unable to use the fertilizer released. From
the foregoing, a paradigm shift has been observed on the frontiers
to use cost effective and environmentally friendly material to pro-
duce CRF. For a material to be used as feed stock for controlled
release coated urea (CRCU), these criteria must be met; it must meet
all ecologically relevant standards; it must conventionally be sus-
tainable, cost effective and environmental friendly; it must achieve
 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Fig. 2. Granular urea fertilizer.
the desired release property effectively. The production of CRCU
should begin with original industrial grade urea granules rather
than melting, transforming, dissolving or polymerization to fabri-
cate controlled release matrices with other materials (see Fig. 2)
Coating material should be selected with a view to its (i) affinity
with urea; (ii) its ability to permeate water and urea solution; (iii)
its capability to impede immediate urea escape from the coating
surface; (iv) its ability to release urea in a manner that meets a
crop’s metabolic requirements over a specified period of time; and
(v) its biodegradability, sustainability, environmental friendly and
cheap (Azeem et al., 2014).
Apparently, no such material(s) exist which possess these ideal
traits. Bio-composite based on RSO/CSO-d-glucitol resin/starch can
be conceived and modified to significantly achieve these prop-
erties. The use of RSO/CSO-d-glucitol resin/starch bio-composite
as coating material for granular fertilizer is not seen in literature.
Moreover, effects of impact factor on the nitrogen release kinetic of
different types of controlled release fertilizer (CRF) have not been
adequately investigated. In fact, some methods have been adopted
for this purpose, but only on one factor at a time approach. There is
no reported literature on the interaction of the impact factors gov-
erning the nutrient release rate of CRF. In this research, therefore,
an attempt was made to design a novel, environmental friendlier,
low cost and sustainable waterborne RSO/CSO based alkyd resin
modified with d-glucitol and starch for urea fertilizer coating. An
experimental process design that established the optimum condi-
tion for maximum desired responses was formulated in terms of
the nutrient release impact factors.
2. Materials and methods
2.1. Materials and pre-treatment
Granular fertilizer was obtained from Eke Awka market in Awka
south local government Area of Anambra state. Sieve analysis was
carried out on the fertilizer granules to obtain a uniform range
of granules. Granules of 2–2.8 mm were used for all experimental
runs. The granules were properly sealed to avoid leaching on expo-
®
sure to the atmosphere. Acetic acid was procured from JHD . On the
other hand, refined starch was gotten from Burgoyne Burbidges and
Co (India). The castor seed oil was bought locally from Eke market
in Awka, Awka South Local Government. The refined rubber seed
135
oil was purchased from the Rubber Research Institute of Nigeria,
Iyanomon, Benin city. The analytical grade maleic anhydride, d-
glucitol, Calcium oxide, Sodium bisulphate (NaHSO4 ), xylene and
trimethylolpropane was procured and used without further purifi-
cation. The raw material and the product were characterized
with Scanning Microscopy Electron (SEM), UV–vis spectrometer
and infrared spectroscopy (FTIR) for structural elucidation. Gas
Chromatography- Mass Spectrometry was to evaluate the fatty acid
present in the oils.
2.2. Synthesis of alkyd resin from RSO and CSO using d-glucitol
100 g of RSO and CSO each was charged into a reactor with 2% of
sulphuric acid in the presence of 2% pumice for the dehydration pro-
cess. It was heated to about 260–298 ◦ C at constant reaction time
of 20 min. in an inert atmosphere of nitrogen. The water generated
from the reaction was collected through a dean-stark apparatus.
Alkyds were prepared with dehydrated CSO and RSO separately
from phthalic anhydride, d-glucitol and maleic anhydride, using
lithium hydroxide as catalyst. The reactions was carried out in a four
necked round bottom flask titled with a motorized stirrer, a dean-
stark trap titled with water-cooled condenser and nitrogen in let
tube at a temperature of about 220–260 ◦ C. Xylene was employed
as an azeotropic solvent. During alcoholysis, the triglycerides of
the oil blends were converted to monoglycerides by reaction with
d-glucitol, catalysed by lithium hydroxide at 180–200 ◦ C. Maleic
anhydride, d-glucitol and xylene were added in other to com-
plete the polymerization process. The process was repeated with
phthalic anhydride. The concentrations of the alkyd solutions were
determined. The progress of reaction was monitored by measuring
the evolved water of reaction and periodically checking the acid
number by titration in accordance to ASTM D 1980-87. The dry
schedule was determined according to ASTM D 1640. The plausible
reaction scheme is shown in Scheme 1.
2.3. Encapsulation of granular urea with RSO or CSO alkyd resin-
starch bio-composite
Preparations of RSO or CSO Alkyd Resin- Starch Bio-composite
were done using two round bottom flasks. 10 g each of the RSO and
CSO based alkyd resin was dissolved in 100 ml of deionized water
separately at 90 ◦ C followed by the addition of aqueous solution
136 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Scheme 1. Plausible reaction scheme for sorbitan monoester.
Fig. 3. IR spectra of (a) RSO, (b) starch, and (c) blend films (St-RSO) cross-linked
with acetic acid content.
of 10 g of starch dissolved in100 ml of deionized water. The tem-
perature was maintained at 90 ◦ C and stirred for 90 min to achieve
homogeneity. The mixture was allowed to cool to room tempera-
ture and an aqueous solution of acetic acid was added and agitated
for another 90 min. 25 g of starch was weighed and added to the
mixture to enhance its handling ability. The resultant biopolymers
were properly covered; kept at room temperature and were subse-
quently used for the coating of the urea granules. The encapsulated
urea was prepared by forming balls of the biopolymer using the
hands and fingers, after which urea granule was encapsulated into
each balls such that, the urea forms the core and the biopolymer, the
sheath. This was done for five different coating thicknesses and then
put into the oven to dry. Sieve analysis was used to get a constant
diameter for five different coating thicknesses. An FLP 1.5 Rotary
Fluidized Bed Coater
(RFBC) can be used for large scale production of the capsule
once the optimum coating thickness is established via experimental
process design.
2.4. Determination of coating thickness nitrogen release of the
encapsulated granules
Vanier calipers were used to obtain the external diameter of the
encapsulated urea. Upon subtraction of the average diameter of the
urea granules, the thickness of the coat is thus obtained. Varying
coating thicknesses were obtained. The dissolution of the coated
urea in distilled water was studied by determining the amount of
nitrogen released after 30 days. As described by (Azeem et al., 2016),
two grams of each sample was submerged in 200 ml of distilled
water in a properly sealed beaker. The time taken for the entire
nitrogen released from the different coating thickness per time by
using the Kjeldahl method of distillation was recorded.
2.5. Experimental process design and optimization of the nitrogen
release process
The study considered response surface methodology (RSM)
based on a 24 full factorial central composite rotatable design
 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Fig. 4. Urea encapsulated with RSO and CSO based alkyd resin-starch bio-composite modified with MA only, MA and sorbitol, respectively.
(CCRD) to optimize the nutrient release process in view of its
economical way of obtaining optimal response with least num-
ber of experiments. RSM provide adequate and reliable metric by
developing a mathematical model with a robust approximation for
obtained data. A CCRD of four independent variables at five levels
will aid the experimental design by generating thirty experiments
with eight replicate run for each design. The studied process param-
eter include: reaction time, reaction temperature, coating thickness
and pH. An optimization problem was then formulated such that
this response should fall within a given range for a better prod-
uct quality and productivity. To study all standard effects of these
process variables on the responses analytically often requires fit-
ting appropriate predictive model usually obtained from regression
analysis to the resulting data from which detailed statistical analy-
sis and optimization exercise are based. Preliminary investigation
conducted by the author using steepest ascent method shows that
curvature effects are possible. In view of curvature a reduced order
quadratic model (ROQM) can be generalized for the various inves-
tigations as expressed in Eq. (1).

k 
k

k hydrophilic in nature. The mechanical properties of starch were
Yn = ˇ0 + ˇi Xi + ˇij Xi Xj + ıij Xi Xj + ε
i=1 i< j=2 i=1 j=1
Yn is the measured system response(nitrogen release) for n-
investigations (n = 1 and 2) corresponding to RSO and CSO alkyd
resin encapsulated urea nitrogen release processes, respectively.
The first term by the right side of the equation ˇ0 is the intercept,
137
the second terms characterizes the main linear effects of individ-
ual process variables, the third term incorporates the interaction
effects between the variables, while the fourth term represents
the main quadratic effects and ε is the random error of experi-
mentation. Xi and Xj represents the matrix of the uncoded process
variables. Eq. (1) serves as the global (or generalized) predictive
equation from which specific solution may be derived. The deter-
mination of the unknown coefficients of ˇ0 , ˇi , ˇij and ıij for nth
investigation is accomplished via regression analysis implemented
on the statistical analysis software Design-Expert Version 10 trial
from the stat-Ease Inc. using the experimental data obtained for ‘n’.
3. Results and discussion
3.1. Chemical formation of starch-alkyd resin bio-composite
ROH from d-glucitol and glycerol on reaction with RCOOH from
the oils and polybasic acid gave an ester (RCOOR) and water. RCOOR
was mixed with the starch to form a bio-composite. Starch is
(1) improved when it is blended with RSO and CSO based alkyd resin.
Nevertheless, according to Izhar et al, 2014 (Izhar et al., 2014), since
both starch and OH are polar substances with hydroxyl group in
their chemical structure, the blend of starch and d-glucitol exhibits
poor water retention properties. Therefore, acetic acid is introduced
as a crosslinker which facilitates the formation of intermolecu-
lar and intramolecular hydrogen bonds between hydroxyl groups
138 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142

Fig. 5. SEM micrograph uncoated urea.

of OH and starch to improve the integrity of the bio composite

blends. The chemical structure of RSO resin-Starch (RSO-St) and
CSO resin-Starch (CSO-St) blends were further be explained by
the FTIR analysis as shown in Fig. 3. The FTIR spectra of starch
and the alkyd were studied and compared with the spectra of the
encapsulated urea. Fig. 3 shows the presence of OH stretching
vibration (3426 cm−1 ), the intramolecular hydrogel (1646 cm−1 )
and CH2 OH stretching vibration (1260 cm−1 ) as well as C O C
ring vibration (928 cm−1 ,858 cm−1 ) in the granular starch. For the
RSO-St, a broad band at 3400-3100 cm−1 due to O H stretching
vibration and another band at 2936 cm−1 assigned as C H stretch- Fig. 6. (a) SEM micrograph of CSO-St MA coated urea (b) SEM micrograph of CSO-St
MA-sorbitol (D-glucitol) coated urea.
ing vibration were observed. The absorption peaks of 922 cm−1
represent C C stretching. The 1200-1100 cm−1 region contains a
number of modes, which have been shown to be sensitive to the
degree of crystallinity in RSO-St. Similar results were obtained for
CSO-St. The peak at 1147 cm−1 is crystallinity-dependent; this is
in accordance with the work of Jayasekara, 2004 (Jayasekara et al.,
2004). The FTIR spectra shows the following three sets of changes
in the film: (a) the peak at 3300-3400 cm−1 of absorption bands
weakened; (b) the crystallinity-dependent 1147 cm−1 peak of ester
weakened; and (c) the absorption peak of 922 cm−1 of RSO resin
disappeared and the peak of 854 cm−1 shifted.
The weakness, disappearance, and shift of the characteristic
absorption bands may result from the interaction of different −OH
groups in the starch and the alkyd molecular chains. So it may be
deduced from these results that the starch was linked with alkyd
by chemical binding introduced by acetic acid. This kind of link-
age has great effect on the improvement of compatibility. Fig. 4
(a–d) show the encapsulated urea. Maleic anhydride (MA) only, MA
and sorbitol (D-glucitol) were used to significantly evaluate release
behavior of the capsule. As observed from Fig. 4a the dark brown
color the capsule is due high oxidation associated with CSO during
dehydration process and subsequent reaction with glycerol.

3.2. Microscopic characteristic of the encapsulated urea

The encapsulated ureas were characterized using SEM to com-

pare their morphologies to the original urea obtained. Morphology
refers to the study of form and structure of a material-in this case,
the encapsulated urea. The encapsulated urea constitutes RSO-St
maleic anhydride coated urea modified with and without sorbitol.
Images were taken from the samples to present the micro struc-
ture. As earlier stated, it should be noted that the coated urea is
hydrophilic in nature owing to the structure of its constituent mate-
rials. The image of uncoated urea is shown in Fig. 5 while that
of coated urea are shown in Figs. 6 and 7 (a and b, respectively).
The optical image for the uncoated urea is seen to appear rough
and have fine openings where water can penetrate so as to dis-
Fig. 7. (a) SEM micrograph of RSO-St MA coated urea (b) SEM micrograph of RSO-St
MA-sorbitol (D-glucitol) coated urea.
solve the urea granule. An asymmetric structure and porosity are
clearly observed at the magnification of x1000. However, a seem-
ingly decrease in membrane porosity and emergency of symmetric
and asymmetric structure are noticed Figs. 6 and 7. This is as a
result of encapsulation with the bio-composite. The slower the pen-
etration time the longer it will take for the urea to dissolve and
 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142 139

Fig. 8. Normal probability plots of residuals obtained from (a) RSO-St-S and (b) CSO-St-S data analysis.

subsequently escape to the outer surface of the sample. This char- Table 1
ANOVA for the Response Surface Reduced Order Quadratic Model (RSROQM) in
acteristic is desirable for increasing the encapsulation efficiency
terms of only the significant process variables.
of the released material, which in this study is urea. The elemen-
tary nanolayers of the bio-composite can be seen in the image of F-Value P-Value
Source
Fig. 6a. Using SEM, it is difficult to determine the actual interlayer RSO-St-S CSO-St-S RSO-St-S CSO-St-S
spacing of the bio-composite with and without sorbitol. In order
Model 12.05 11.78 <0.0001 <0.0001
to determine the d-spacing, high-resolution transmission electron A-Coating Thickness 36.47 41.01 <0.0001 <0.0001
microscopy would be needed. From Figs. 6b and 7 b, it can be con- B-Temperature 12.09 20.04 <0.0024 <0.0001
cluded the membrane can withstand the hydrostatic pressure of C -Time 16.07 16.71 <0.0006 <0.0019
the dissolved nitrogen for long due to the tiny pore diameter. D- pH 0.079 0.093 <0.07809 <0.0875
AD 2.21 4.32 0.1525 0.0956
BC 12.77 11.02 0.0019 0.0029
CD 13.10 10.58 0.0017 0.0043
3.3. Experimental process Design/Factor screening A2 5.50 5.23 0.0294 0.0239
D2 11.43 9.94 0.0030 0.0029

The process characterization (or factor screening) aided with RSO-St-S Std. Dev. 9.85 R-Squared 0.8443
Mean 54.03 Adj R-Squared 0.7742
the ANOVA function of the statistical software Design-Expert Ver-
C.V. % 18.23 Pred R-Squared 0.5779
sion 10 trial from the stat-Ease Inc. was carried out to evaluate the PRESS 5259.73 Adeq Precision 14.649
process variables which provide the most important effects in tune
CSO-St-S Std. Dev. 5.74 R-Squared 0.8220
with the research objectives. In view of the standard statistical cri-
Mean 75.13 Adj R-Squared 0.7870
teria for adequacy a reduced order quadratic model of the general C.V. % 6.14 Pred R-Squared 0.5805
form given in Eq. (1) was considered appropriate for predicting the PRESS 1987.70 Adeq Precision 17.252
overall process characteristics. The ANOVA results for the nitrogen DF: Model = 9, Residual = 20, Total = 29.
release derived from the predictive model shows that the main lin-
ear effects due to individual control factors; coating thickness (x1 ),
temperature (x2 ) and time (x3 ) coded A, B and C, respectively, are
significant variables indicated with the observed p-values < 0.05 in
the numerical analyses. This is equally true with the linear inter- N2 = 70.28 − 17.90A + 0.33B + 6.05C + −4.99BC − 4.46CD
action effects between time and pH (CD), temperature and time +3.44A2 + 2.67D2 (3)
(BC) for both RSO-St and CSO-St modified with sorbitol (RSO-St-S
and CSO-St-S, respectively). The quadratic effects of coating thick- Where N1 and N2 are the predicted values of the dependent vari-
ness and pH denoted by A2 and D2 , respectively are significant in the ables (i.e nitrogen released) for the two (2) investigated samples.
nitrogen release kinetics of urea encapsulated with RSO-St-S and Coefficients A, B, C and D are main linear effects of the inde-
CSO-St-S. pendent process variables; coating thickness, temperature, time
The data obtained for specific investigation were refitted with and pH, respectively in coded units. BC and CD represent the lin-
a modified model obtained by excluding the non-significant vari- ear interaction effects between temperature/time and time/pH,
ables from the general predictive equation and the results of respectively. A2 and D2 are the quadratic effects of the respective
statistical analyses obtained for the sequence of experimentations process variables. The P̈redicted R-Squaredöf 0.5779 and 0.5805 are
are summarized in the Table 1. The coefficients of determination in reasonable agreement with the respective Ädjusted R-Squaredöf
R–squared (R2 ) values of 0.8443 and 0.8220 obtained for the RSO- 0.7742 and 0.7870; i.e. the difference is less than 0.2. The Model
St-S and CSO-St-S nitrogen release kinetic, respectively, show that F-values of 12.05 and 11.78 further indicate that the models are
more than 80% of the overall system variability can be explained by significant. There is only a 0.01% probability that the M̈odel F-
the empirical models of Eqs. (2)–(3). Eqs. (2)–(3) are specific cases Valuesẗhis large could occur due to noise. P Values of less than 0.05
of the general predictive equation derived for individual investi- indicate model terms are significant. Ädequacy Precisionm̈easures
gations from the multivariate regression analyses implemented on the signal to noise ratio(SN). A ratio greater than 4 is desirable. SN
the Design expert in terms of only the significant factors. ratio of 14.649 and 17.252 indicate adequate signal. This model can
be used to navigate the design
The diagnostics analyses completed via normal probability plots
N1 = 45.57 − 12.14A + 6.99B + 8.13C + 8.80BC − 8.91CD
of residuals for the two distinct investigations are presented in
+4.31A2 + 6.24D2 (2) Fig. 8. A visual inspection of the graphs is sufficient to say that the
140 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Fig. 9. 3D plots for impact factor (pH and coating thickness) interaction on (a) RSO-St-S and (b) CSO-St-S encapsulated urea for nitrogen release.
residuals follow a normal distribution. A picture of points which
interlock a straight line with some moderate scatter is expected
with normal data.
3.4. Analysis of the Nitrogen release characteristic of RSO-St-S
and CSO-St-S as a Function of Release Factors
Factor screening analysis of nutrient release characteristics of
the encapsulated urea shows that coating thickness, temperature,
time and pH are all important factors which provide the most
important effects in tune with the research objectives. It is very
interesting to note that the interaction effect of RSO-St-S and CSO-
St-S are significantly similar in the entire two orthogonal axes. The
two (2) nitrogen release characteristic of RSO-St-S and CSO-St-S
were analyzed collectively based on the various solutions obtained
at possible impact release conditions from the model predictive
Eqs. (2)–(3). The well-known RSM is considered appropriate owing
to its flexibility in navigating the design space. These equations
were solved for the various interaction effects on the nitrogen
release considering at any instance the interactions between two
factors only, assuming the other variables are set at their mean
coded value of zero (0). The analyses and optimization exercises
are completed accordingly using the Design expert 10 trial appli-
cation and the graphical solutions are presented in duplicates (for
easy comparison) as response surface contour diagrams.
The investigation of coating thickness and pH is critical for the
determination of nutrient release rate. The interaction effects on
the process response between pH (D) and coating thickness (A)
in their natural units associated with the two (2) different bio-
composites (a) RSO-St-S and (b) CSO-St-S produced on nitrogen
release characteristic are presented in Fig. 10. As expected for a
typical controlled release process, the nitrogen release RSO-St-S
and CSO-St-S generally decreases readily with increasing coating
thickness, approaching 75% at 5.7 mm even at neutral pH setting of
about 7 indicating sufficient retardation of nitrogen. Such obser-
vations conform to a large extent with the results of literature
(Ding et al., 2016). To understand this phenomenon, it is imper-
ative to understand the mechanism of nutrient release from a
bio-composite or polymer coated film. When a hydrophilic poly-
mer is subjected to dissolution in water, the polymer matrix starts
to swell due to imbibement of water into the coating film (Witono
et al., 2014). Water migrates through dynamic spaces between the
macromolecules of the polymer film and dissolves the core nutri-
ent as soon as it comes in contact with it (Azeem et al., 2014). This
osmotic imbibement of water into the nutrient core is followed by
the development of hydrostatic pressure inside the coating shell. At
a threshold value of the hydrostatic pressure, the swelled network
of the polymer experiences deformation and the active nutrient
starts to release from the micropores developed at the weakest sites
on the coating film (Ko et al., 1996). At this point, coating thickness
plays an important role to control the release rate of the nutri-
ent. Higher coating thickness results higher release time because
it takes longer for the nutrient molecules to diffuse through thick
coating film and reach the outer reservoir (Ito et al., 2003). In addi-
tion the augmented diffusion resistant for higher coating thickness
also increases the release time (Trinh et al., 2014). According to
Ko et al. (1996), a critical value of the coating thickness is neces-
sary for promising release properties. However, coating thickness
less than the critical value may cause the nutrient to immediately
release when subjected to dissolution test in water. This sponta-
neous release is attributed to the presence of holes or microscopic
pores in the coating film.
For the results of effect of coating thickness on release time as
represented in Fig. 9, it can be explained that when water comes
in contact with the coated granule, it takes longer for water to
completely wet thicker coating layer and reach the core nutrient.
Once the core nutrient is dissolved, the swelled macromolecu-
lar hydrogel structure of encapsulated urea coating film bears
the hydrostatic pressure of the dissolved nutrient for longer time
in case of higher coating thickness. Once the dissolved nutrient
reaches the interface, it again takes longer for its escape from
thicker coating layer to the outer reservoir. Hence, thicker coat-
ing films result higher release time and better controlled release
characteristics (Trinh et al., 2014). This principle can only be
attributed to those samples which resulted higher release time.
On the contrary, there are samples which have very low release
time. Interestingly, the synthesized RSO and CSO based alkyd resin
improves the integrity of the microscopic pores in the coating film
as seen in Figs. 5–7
The observed interaction effects on the responses between pH
(D) and time (C) are recorded in Fig. 10. The quadratic effect of pH
is identified with smooth curves on the reference surface contours
even when the single effect of pH is not significant. The process
response is minimized in a similar fashion as the pH is increased
 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142 141

Fig. 10. 3D plots for impact factor (pH and time) interaction on (a) RSO-St-S and (b) CSO-St-S encapsulated urea for nitrogen release.

Fig. 11. 3D plots for impact factor (time and temperature) interaction on (a) RSO-St-S and (b) CSO-St-S encapsulated urea for nitrogen release.

from a low value of 5 to mean values between 7 and 9. pH of 5 to 9
covers most soil pH worldwide. The pH analysis shows a slightly
complicated behavior with regions of optimal nitrogen release
appearing in certain localized space. Specifically, from Fig. 10 (a
and b), release rates of nitrogen showed the similar trend under
different pH treatments; the release rates were slightly high at low
and high pH treatments but did not show obvious differences in
each incubation period (?? > threshold-0.05 in Table 1).Thus, after
20 days of incubation (from Fig. 10 a and b), the cumulative curves
of nitrogen release rates looked like shape of a “u” letter pulled
wide with the treatments of pH range from 5 to 9, and the lower
release rates appeared in that of pH 6–7 treatments (Fig. 10). It
indicates that the better-controlling effect of the coated urea can
be displayed at soil of weak acid or neutral pH. Transition to the
optimum nitrogen release may be achieved with pH of 7 obtained
from the optimization solution.
Figs. 11 display the response for the interactive factors; time (C)
vs temperature (B). An interesting observation is recorded where
the two samples responses show intrinsic similarities in the two
orthogonal axes. One noticeable unusual result is the apparent lin-
ear (one-directional) response observed in the system response
with respect to C and B axes. This does not reflect, explicitly, a
typical behavior of constant and decay release characteristic of con-
trolled release fertilizer. This observation may be due to interaction
effect of other nutrient release factors and varying temperatures at
which the crops are found.. However, it is noticeable that higher
temperatures resulted in higher release rate throughout the incu-
bation time. The release degree of nitrogen from RSO-St-S and
CSO-St-S encapsulated urea were not more than 10% within 6days
incubation time and 62% after 30 days, even at higher tempera-
ture (see Fig. 11). A fertilizer is commonly referred to as a slow or
controlled-release fertilizer (SRF or CRF) if the following require-
ments are fulfilled; no more than 15% of nutrients are released
within 24 h, no more than 75% of nutrients are released within 28
days, and at least 75% of nutrients are released by the stated release
time (European Standard EN 13,266, 2001). Therefore, it can be
142 C.F. Uzoh et al. / Process Safety and Environmental Protection 121 (2019) 133–142
Table 2
Optimum values of process parameters for maximum responses.
Optimum values
Process Parameters RSO-St-S
Nitrogen Release (%) 31.66
Coating Thickness (mm) (A) 6.40
Temperature (Celsius) (B) 25
Time (days)(C) 24
pH 8 8
Desirability 1 1
concluded that RSO-St-S and CSO-St-S encapsulated urea are CRFs.
The consistent linear behavior (in which increasing the input value
leads to a corresponding increase in output with respect to C and B
axes) implies that no definite optimal solution could be obtained for
the two variables. If such optimal condition exists for the present
case, then it definitely lies in a range outside the sampled space. The
selection of a useful optimal condition for the two variables would
thus be guided strictly by a balance of compromise between their
effects on system response and economic implication. Therefore,
knowledge of plant metabolic requirement is a prerequisite in the
design of CRFs.
3.5. Optimization process
As anticipated for nutrient release kinetics of a typical CRF, the
need for optimization arise where the CRF provide some obvi-
ous advantages like; reduced material cost, robust release profile
etcetera are desired. Of particular interest is the nitrogen release
rate which is a critical issue highlighted in the research objectives.
We may recall that a major objective is to contrive a route to obtain
an encapsulated urea with a robust release profile and a reduced
material cost for industrial application. Other avenues for process
optimization are through increased nutrient release time, reduced
temperature and a neutral pH which in effect minimize the overall
cost of fertilizer application and use simultaneously. Optimization
problem may be compounded when the processes pose a multi-
ple desired targets which may be a combination of two or more
of above stated conditions. This is actually the case with nitrogen
use efficiency (NUE) and many other real systems for that mat-
ter. A standard approach to this problem is to formulate a global
optimization criterion through which the necessary trade-off may
be effected so as to achieve what may be considered as the best
combination to the desired result.
The optimization exercise for the two (2) identical nitrogen
release profile (RSO-St-S and CSO-St-S encapsulated urea) was
conducted separately utilizing the flexibility of the Design Expert
optimization tool function. Eqs. (2)–(3) were solved for the best
solutions such that the responses (Yn ) are minimized within the
design space. No unique solutions were possible. A usual approach
which involves selecting the best solution based on economic
considerations is adopted and the chosen optimal solutions were
presented in Table 2. Experiment was then performed using the
optimal result of the numerical optimization executed by Design
expert and the results were in reasonable agreement (33 and 47%
cumulative nitrogen release for RSO-St-S and CSO-St-S encapsu-
lated urea, respectively). Given that the various optimum nitrogen
release times and temperatures were not considerably far sepa-
rated from each other, the selection of desired optimum solution
of Table 2 was mainly influenced by the availability and cost of
encapsulating material.
4. Conclusion
A biodegradable RSO and CSO based alkyd resin modified with
maleic anhydride and d-glucitol each and blended with starch was
CSO-St-S
used to encapsulate a granular urea.. FTIR result confirmed the
48.61
esterification reaction and hydrogen bonding integrity of the alkyd
2.20
25 resins and starch. SEM on the other hand, confirmed the poros-
24 ity of the coats hence validating it ability to absorb water. 31.66
and 48.61% cumulative nitrogen release were obtained with coat-
ing thickness of 6.4(mm), time of 24 days, pH of 8 and 2.2(mm),
time of 24 days, pH of 8 for RSO-St-S and CSO-St-S encapsulated
urea, respectively.
Acknowledgement
The authors would like to pay their most profound gratitude to
the Tertiary Education Trust Fund (TETFUND), Nigeria, for the hefty
research grants extended for the accomplishment of this research
activity. The provision of state of the art research facilities provided
by the Nnamdi Azikiwe University, Awka is also highly appreciated.
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