Surface Engineering

ISSN: 0267-0844 (Print) 1743-2944 (Online) Journal homepage: http://www.tandfonline.com/loi/ysue20

Effect of pre-coat solution temperature on

fluidized bed urea coatings
M. Y. Naz, S. A. Sulaiman, B. Ariwahjoedi & K. Z. K. Shaari
To cite this article: M. Y. Naz, S. A. Sulaiman, B. Ariwahjoedi & K. Z. K. Shaari (2015) Effect
of pre-coat solution temperature on fluidized bed urea coatings, Surface Engineering, 31:7,
486-491, DOI: 10.1179/1743294414Y.0000000381
To link to this article: http://dx.doi.org/10.1179/1743294414Y.0000000381

Published online: 25 Sep 2014.

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Date: 18 August 2016, At: 22:46

Effect of pre-coat solution temperature on

fluidized bed urea coatings
M. Y. Naz*1, S. A. Sulaiman2, B. Ariwahjoedi1 and K. Z. K. Shaari3
In this study, coating properties of the native cassava starch were improved by reacting it with
urea and di-sodium tetraborate. The FTIR spectroscopy was used to study the possible reaction
mechanism of the coating formulation. The prepared starch dispersions were used to coat
3?45 mm urea granules in a swirling fluidised bed reactor. An in-house built fluidised bed with an
intermittent top spraying facility was used to coat the urea beds fluidised above their minimum
level of fluidisation. The pre-coat solution temperature was varied from 50 to 80uC and the
corresponding coated urea samples were further characterised for their surface morphology,
coating hardness and nitrogen release time. The SEM images revealed that the surface of the
coated urea was harder, denser and smoother as compared to the uncoated urea. Significant
improvements in mechanical parameters of coated urea were seen with an increase in solution
temperature and mass of the di-sodium tetraborate. The overall nutrients release time of the
coated urea in water was increased from 63?33 to 209 s. The surface hardness and coating
thickness of coated urea was also increased with an increase in pre-coat solution temperature
and di-sodium tetraborate mass in the coating composition.
Keywords: Carbohydrate polymers, Di-sodium tetraborate, Coated urea, Scanning electron microscopy

Introduction
Urea is a widely used nitrogenous fertiliser in agriculture
sector. Normally, the urea particles contain a high
percentage (46%) of nutrients essential for the plant
growth. Global urea market has shown stable growth
during last decade, even in 20082009 recession years.
Today it is one of the most popular and accessible
nitrogen fertilisers, which is mainly used in agriculture,
but also has other end-uses, such as urea-formaldehyde
resins and melamine, livestock feed, etc. These nonfertiliser applications accounted for 15% of global urea
demand in 2013 and this figure is expected to grow in
near future.1 In next few years, the global urea consumption will be driven by Asia Pacific region, North America
and Latin America. But still, the majority of urea will be
consumed by countries, where it is produced, and only a
small amount of the product is expected to be delivered to
the global market.
Urea is always preferred over other available nitrogenous fertiliser due to high nitrogen content, low cost,
low fire or explosions hazards, low storage risks, wide
applications, soil friendly and acidification, immediate
nitrogen supply, etc. However, it also owns some
1

Department of Fundamental and Applied Sciences, Universiti Teknologi

PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
Department of Mechanical Engineering, Universiti Teknologi
PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
3
Department of Chemical Engineering, Universiti Teknologi PETRONAS,
Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
2

*Corresponding author, email yasin603@yahoo.com

486

2015 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 11 July 2014; accepted 15 September 2014
DOI 10.1179/1743294414Y.0000000381

disastrous features which should be tracked and

controlled. It is highly soluble in water and hygroscopic
water, therefore, requires better packaging quality. If
urea contains impurities more than 2%, it cannot be
used as a fertiliser, since the impurities are toxic to
certain crops, particularly citrus. It is less stable,
decomposes even at room temperatures that results in
serious loss. As a result of the chemical reaction that
takes place when urea is applied to the soil, special care
must be taken to ensure that the nitrogen is not lost
when the ammonium evaporates. This can make urea
impractical for gardeners dealing with large plots of
land. In past studies, it has been approximated that 20 to
70% of the used urea escapes to the environment via
leaching, nitrification and volatilization which not only
harms the surrounding environment but also decreases
the overall urea performance.2

Slow release urea

The nitrogen use efficiency can be enhanced by number
of possible ways including nitrification inhabitations,
urease inhabitation, controlled release of nitrogen, etc.
From last few decades, the technology of coating the
urea granules for controlled release of nitrogen has
gained the attention of the scientific community.
However, the maximum benefit from the coated urea
is only possible when the nutrients release sufficiently
prolongs and synchronises with the nutrients uptake by
the plants. The release rate normally depends upon the
nature and physical properties of the coating materials.
Up until now, different materials have been tested for

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Natural carbohydrate polymer coatings for green urea

1 Reaction scheme for starch-urea-borate complex formation

coating the urea granules.35 Among them, neem

(Azadirachta indica L.), resins, sulphur and synthetic
and natural polymers are more common and have
extensively been used as coating materials. The neem
and sulphur coated fertilisers cannot meet the goals
mainly because of high cost and inconsistent results.6 On
the other hand, the most effective polymers used so for
in coating the urea are non-degradable, expensive and
unfriendly to the environment.5 Therefore, it is imperative to find the cheap and biodegradable coating
alternatives such as natural biopolymers, zinc sulphate,
ammonium chloride, copper sulphate, phosphogypsum,
potassium chloride, etc.4,5 The synthetic or natural
polymers that contain enzymatically or hydrolytically
the labile groups or bonds are called biodegradable
polymers. The synthetic polymers have some obvious
advantages over the natural polymers including batch to
batch uniformity, predictable physio-chemical properties and tailor-made character.7 However, these polymers are quite expensive and remind us to focus on
inherently biodegradable natural counterparts.8

Starch based coatings

In this scenario, the natural carbohydrate polymers
might be the most appealing choice to meet the
standards set by most of the urea coating processes.8,9
In particular, starch is also an attractive choice on behalf
of its low cost and natural abundance. However, the use
of native starches for urea encapsulation is limited due
to their softness, hydrophilicity, low moisture resistance,
poor processability, high brittleness, etc. It necessitates
the further modifications of the native starches by
reacting them with chemical thickeners and crosslinkers.10 The physico-chemical and coating properties
of the pure starches can be improved after reacting them
with urea and di-sodium tetraborate. Under specific
reaction conditions, these additives can cause extensive
chemical makeup of the used starches.2,11,12 The possible
reaction mechanism of starch with urea and di-sodium
tetraborate has been explained in Fig. 1.
In the present case, the cassava starch was reacted
with urea and di-sodium tetraborate to obtain the
desired coating formulation. The FTIR spectroscopy
was used to study the possible reaction mechanism of
the coating material formation. The developed coating

material was used to coat the urea granules in an inhouse built fluidized bed reactor. The coating solution
was warmed up to a preferred temperature range (50
80uC) for better control over its physical properties and
to spray onto fluidized urea by using an axisymmetric
full cone nozzle operated by 5 bar hydraulic pressure.
The outer surface morphology of coated and uncoated
samples was analysed through scanning electron microscopy (SEM). The coating thickness, total release time
and surface hardness were used to study the nitrogen
release efficiency of the coated urea.

Materials and methods

The food grade cassava starch with degree of substitution 0?80 was modified with di-sodium tetraborate
(Na2B4O7.10H2O) and urea. The starch was commercially available, whereas, the modifiers were supplied by
R & M Chemicals. The urea for coating purposes was
obtained from the local fertilizer plant. The food grade
starch was dried at 110uC for removal of all moisture
contents or until no further weight transformations over
time. Herein, desired volume of deionised water was
taken in a steeliron mixed container and heated upto
80uC. The heating was carried out through a fully
automated DIPO induction cooker (TCK35-E). Once
the desired temperature was attained, the measured
quantity of starch was added into the system. For

2 Pictorial view of in-house built uidised bed reactor

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Natural carbohydrate polymer coatings for green urea

3 FTIR spectra of native and modied starch solutions

complete gelatinisation, the starch suspension was

further reacted and stirred for 30 min. After 30 min of
heating, the measured quantities of urea and borate were
added into the starch suspension. The formed adhesive
solution was set to react further for 1 h at a constant
temperature of 80uC and 4005 rev min21 stirring.
Figure 2 portrays an in-house built simple fluidised
bed reactor used to coat 3?45 mm urea granules. An air
blower was used to fluidise 200 g urea batch above its
minimum level of fluidisation. The prepared coating
solution was sprayed onto the fluidised urea granules.
An axi-symmetric full cone spray nozzle was used to
spray the solution at 50, 60, 70 and 80uC heating
temperature and 5 bar load pressure. The nozzle orifice
and maximum free passage diameters were 1?19 and
0?64 mm respectively. The summary of the fluidized bed
coater design parameters is given in Table 1. The spray
pulse on-off duty cycle was controlled by a PROVAL
pneumatic double actuated solenoid valve and a
programmable digital time relay (SIGMA, PTC-15).
The coating solution was sprayed for 100 ms after every
10 s. The surface morphology of the coated and
uncoated urea was analysed through SEM images, the
coating hardness was examined by using an Erweka
TBH-325-TD tablet tester and nutrients release time was
measured through a dissolution rate test.

Results and discussion

The heating temperature at which the starch granules
in dispersion go through a conversion from their
Table 1 Summary of the uidized bed design parameters
Parameter

Value
1330 kg/m3
200 g
0.003533 m3
0.4367
3.4 cmH2O
4 m/s
8.2 m/s
30.8 m/s
417 m3/h
856 m3/h
3215 m3/h
1.417 kW

Urea density
Mass of urea batch
Volume of packed bed
Bed void fraction
Pressure drop
Minimum fluidizing velocity
Complete fluidizing velocity
Terminal velocity
Flow rate for minimum fluidization
Flow rate for complete fluidization
Terminal flow rate
Power of air blower

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crystalline state to a gel state is known as gelatinization

temperature. It is an important parameter while
characterising the non-Newtonian polymers under
certain described conditions. It helps in identifying
the type of the contents and heterogeneity among the
granules. The individual starch granules have a certain
gelatinisation temperature range. Each granule goes
through gelatinisation at a specific temperature within
such heating range.13 It has been observed that the
starch adhesives prepared at 80uC own extra appealing
results as compared to other commercially available
starch based coating materials.13,14 The same response
temperature range (7580uC) was used in this research
for development of starch based coating solution for
nitrogen release retardant coatings.
It has also been revealed in past research that the
gelatinisation temperature range depends on difference
of level of crystallites heterogeneity within the starch
granules.15 Herein, initially 5% aqueous dispersion of
the tapioca starch (in the absence of urea and borate)
was heated to gelatinise at 80uC for 30 min. The solution
was continuously agitated at 400 rev min21 by using an
overhead stirrer. This gelatinisation range of the tapioca
starch showed a high level of heterogeneity among its
crystallites and consequently the varying tightness in
granule compactness.16
The reaction mechanism of the modified starch was
studies by using FTIR spectroscopy. The obtained
spectra of the native and modified starches have been
given in Fig. 3. A new peak was identified in the FTIR
spectrum of the modified starch at 1555 cm3. This peak
was most probably due to the presence of the secondary
amide. This secondary amide was generated from
polymerisation of starch and urea in the presence of
di-sodium tetraborate as catalyst. The presence of the
secondary amide confirms that the reaction was following the mechanism proposed in Fig. 1.
The surface morphology of the coated fertilisers varies
greatly depending on the choice of the coating material
and the used coating mechanism.17 In the present case,
the urea was coated by using a swirling fluidised bed
coater with top spraying facility. In this process, the
coating solution is atomized into fine droplets by using
an appropriate nozzle. The resulting droplets can be
successful or unsuccessful in reaching and attaching

Naz et al.

4 500 times magnied SEM images of uncoated urea and

coated with starch suspensions at 80uC solution
tempearture: a uncoated urea; b coated with 50/00/00
composition; c coated with 50/15/2?5 composition

themselves to the granules surface. The coating solution

that does not attach itself to a granule is spray dried and
may be elutriated out of the bed if it is light, and remains
in the bed if it is sufficiently heavier for drag forces.
These fines in the bed can join other spray dried fines to
form fines agglomeration. They can also be captured by
larger particles causing snow ball growth.

Natural carbohydrate polymer coatings for green urea

In spray coating process, the period of spray injection

is of special importance. When an atomised solution
successfully collides with granules, it wets their surface.
Depending on the conditions inside the bed, wetted
particles may collide and form liquid bridges between
them or they can be dried resulting in a layered growth.
If there is an excessive wetting, many granules will join
to form bridges among them. Therefore, joining together
to form large wet clumps will lead to defluidisation of
the granules bed and this phenomenon is known as wet
quenching.18 In case of moderately wetted granules, a
number of solid particles will remain joined together
when their liquid bridges are dried. The continuing
existence of these solid bridges will depend on their
strength. If the solution binding forces are strong
enough and the solid bridges join together many
granules, then these granules would remain joined and
the bed will eventually collapses. In this case, the
fluidising gas cannot fluidise these large granules. This
phenomenon is also known as dry quenching. At the
same time, if the binding forces are strong enough but
the solid bridges join together very few granules, then
the fluidisation process will continue and the resulting
product will have only few granules joined together to
form agglomerates. On the other hand, if the binding
forces are relatively weak, the dried solid bridges will
break leaving some coating on the surface of the
granules. This will eventually lead to a coated product.19
In this study, the wet and dry quenching was avoided
by spraying the solution for 100 ms with stoppage time
of 10 s.
In general, the coating material represents 315% of the
total weight of the finished product. Therefore, it may
change significantly the morphology of the targeted
surface. The coating percentage depends upon the
physic-chemical properties of the coating material and
the process temperature. The SEM photographs of
coated and uncoated urea granules with magnification
of 5006 are given in Fig. 4. The coating morphology and
corresponding changes in urea surface properties were
analysed from these grabbed photographs. Figure 4a
reveals that the outer surface of the uncoated urea
granules was less dense with a higher degree of roughness.
The porosity level on the surface of the granules was
found quite high in the absence of a coating layer.
Figure 4b and c represent the SEM photographs of
surface of the granules coated with two different solution
compositions at heating temperature of 80uC. These
photographs reveal that the surface of the coated urea
was denser and smoother as compared to the uncoated
ones. The coated surfaces were also found uniform, hard
and compact. Significant improvements in these mechanical parameters were seen with an increase in solution
temperature and mass of the di-sodium tetraborat in the
composition. At 80uC temperature, the granules coated
with 50/15/2?5 composition were having smooth surfaces
with a crystalline texture than that coated with 50/00/00
composition. The later one was giving dense forest like
growth on the surface of the treated urea as shown in
Fig. 4b.
It has been experienced that the development of bonds
in carbohydrate polymers are generally hydrophilic.20,21
Therefore, the efficiency of the surface coverings for
controlling the nutrients discharge was checked by
dissolution rate test. 10 g of each coated and uncoated

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5 Nitrogen release time of uncoated and coated urea as function of pre-coat solution temperature

urea was taken in a beaker and 100 mL of deionised

water was added into the system. At room temperature,
the water-urea mixture was agitated by using an
overhead stirrer at constant speed of 300 rev min21
and time for compete dissolution of the individual
samples was noted. Figure 5 depicts the influence of the
pre-coat solution temperature on coating thickness and
nitrogen release time. Very fast discharge of the
nutritional values from the uncoated urea and coated
with unmodified starch solution (50/00/00) was noticed
when compared with samples coated with modified
starch. Time needed for complete release from uncoated
urea granules was about 63?332 s. It was also seen
that the nitrogen release time considerably increases
with an increase in pre-coat solution temperature from
50 to 80uC. The highest release time of 209 s was
achieved with 50/15/2?5 composition and heating temperature of 80uC. Similar kind of outcomes were
predicted in the studies conducted by Choi and
Meisen22,23 on the sulphur coated urea samples.

Shi et al.24 also coated the urea granules with plastic

starch compounds and showed that the nitrogen
discharge duration of such coatings was greater when
compared with coatings of other materials.
The nitrogen release from the urea coated with
biodegradable materials is directly affected by the
thickness and quality of the coatings.25 The dissolution
of urea into the soil solution follows microbial and
hydrolytic degradation of the protective coating layer
and the presence of micro-pores and imperfections.
Figures 4 and 5 reveal that the coating thickness and
quality increases with an increase in heating temperature. The best coating quality and thickness was
achieved at heating temperature of 80uC with 50/15/2?5
compositions. These parameters directly affect the
release rate of the coated urea. Figure 5 also shows that
the release rate increases with an increase in coating
thickness which depends upon the heating temperature.
In these studies, the maximised release time and coating
thickness were attained at heating temperature of 80uC.

6 Coating thickness and surface hardness as function of pre-coat solution temperature

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In addition to thickness and release time, the encapsulated urea should also demonstrate sufficient surface
hardness to withstand against the normal handling and
storage without surface fractures.26 The mechanical
strength of the coated urea can be studied through
surface hardness test. In the present case, Erweka TBH325-TD tablet hardness tester was used to serve this
purpose. The mechanical strength of coated and uncoated
urea was measured by squeezing tightly onto the
individual granules and monitoring the surface fractures.
For each statistic, 10 urea granules with roughly the same
shape and size were arbitrarily selected and their
mechanical strength was measured by observing the
corresponding applied pressures. The generated data is
plotted in Fig. 6. From these outcomes, it was concluded
that the surface hardness highly stands on the solution
composition and pre-coat solution temperature. The
hardness tests reveal that the surface hardness of
uncoated urea and coated with unmodified starch
solution (50/00/00) was very low than that coated with
modified starch (50/15/2?5). Furthermore, the surface
hardness was considerably improved with an increase in
solution temperature. It might be due to the fact that urea
coated with modified starch and optimized temperature
of 80uC was having denser coats with reduced porosity
level.27

Conclusion
In this detailed note, the cassava starch was successfully
modified with urea and di-sodium tetraborate for slow
release urea coating applications. After depiction of the
adhesive physical properties; a fluidized bed top spraying
technique was used to coat 200 g urea batches at solution
temperature ranging from 50 to 80uC. The SEM photographs revealed that the surface of the urea coated at
higher heating temperatures was denser and smoother
when compared with the uncoated urea. The surface of the
urea granules coated with 50/15/2?5 composition at 80uC
heating temperature was found uniform, hard, compact
and water resistant. It was concluded that the coating
thickness, surface hardness and nitrogen release time
increase with an increase in di-sodium tetraborate mass
in solution and pre-coat solution heating temperature.

Natural carbohydrate polymer coatings for green urea

Acknowledgements
This research work is partially funded by the Long Term
Research Grant Scheme (LRGS) of the Ministry of
Higher Education Malaysia no. 15-8200-137-4-3.

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