Desalination 146 (2002) 319–323

Physical and chemical characteristics of polymer coatings

in CRF formulation

Maria Tomaszewska*, Anna Jarosiewicz, Krzysztof Karakulski

Technical University of Szczecin, Institute of Chemical and Environment Engineering, Pułaskiego 10, 70-322 Szczecin,
Poland
Tel. +48 (91) 449-47-30; Fax +48 (91) 433-03-52; email: mariatom@mailbox.ps.pl

Received 1 February 2002; accepted 3 April 2002

Abstract

Investigations on the preparation of controlled-release fertilizer coated with polymers, have been described.
The polymer materials used were polysulfone (PSF), cellulose acetate (CA) and polyacrylonitrile (PAN). The
polymer coatings were formed on the granular NPK fertilizer by the phase inversion technique. The
measurements of thickness and porosity of prepared coating and microphotographic observation of the coating
were performed. The thickness of fertilizer coatings, measured by the micrometer screw was in the range from
0.21–1.14 mm — depredating on the polymer type. It was found, that a higher concentration of polymer in film
forming solution causes a decrease of the porosity of the obtained coating. The microphotographs of the coatings
obtained for this study demonstrate that the prepared coatings in all cases were asymmetric with thin skin layer
formed on the top of the coating. The polymer coatings were characterised using Fourier transform infrared
spectroscopy (FT-IR). The coatings, formed on the fertilizer, were compared with coatings prepared from the
same polymer but without the contact with fertilizer. It was observed that the spectra of pure polymer showed the
peaks with lower intensity.

Keywords: Polymers; Polymer coated fertilizer; Controlled release

*Corresponding author

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7–12, 2002.

0011-9164/02/$– See front matter © 2002 Elsevier Science B.V. All rights reserved
320 M. Tomaszewska et al. / Desalination 146 (2002) 319–323
1. Introduction
Controlled-release fertilizers (CRF) are
made to release their nutrient contents gradually
and to coincide with the nutrient requirement of
a plant [1]. These fertilizers can be physically
prepared from the granules of the soluble
fertilizers by coating them with the materials,
which reduce their dissolution rate. The use of
controlled-release fertilizers causes an increase
in their efficiency, reduces soil toxicity, mini-
mises the potential negative effects associated
with overdosage, reduces the frequency of the
application [2–4]. Moreover, these materials
may improve soil for cultivation with regard to
better soil aeration and friability and soil erosion
prevention.
The coating materials used should be inex-
pensive and exhibit a good coating property. In
addition, they should undergo testing for degra-
dation in soil which might form any toxic sub-
stance that could affect the crop [5]. The type of
coating is responsible for the mechanism of
release of macroelements from encapsulated
fertilizer.
2. Experimental
The commercial granular NPK 6-20-30 ferti-
lizer, produced by Chemical Plant “Police” S.A.
was used in the laboratory tests to prepare the
coating of fertilizer. The polymer materials
applied were polysulfone (PSF), cellulose acetate
(CA) and polyacrylonitrile (PAN). The coating
solutions were prepared by the dissolution of
the solid polymer in adequate solvent. Table 1
shows the compositions of coating forming
solutions.
The NPK fertilizer was successively added
to adequate polymer solution, and was covered
by a thin layer of the solution. Subsequently,
granules were dropped into water, where the
gelation process takes place. The coated granules
were removed from the precipitation bath and
then dried to a constant mass. The multiple
coatings were prepared by immersion of the
Table 1
Composition of coating forming solutions
Polymer, Solvent, Modifying Precipitation
wt.% wt.% agent bath
Cellulose Acetone 74–77 Formamide Water
acetate
16–18
Polyacrylo- N,N-dimethyl- — Water
nitrile formamide
16–18 82–84
Polysulfone N,N-dimethyl- — Water
10–20 formamide
80–90
single coated fertilizer into adequate polymer
solution, then into water and drying.
The measurements of thickness, porosity of
prepared coating and microphotographic observ-
ation of the coating were performed. The coating
porosity was evaluated by a comparison of the
weight of dry and wet coating. The weight
differences estimated the amount of water,
which was contained in the coating pores. The
microphotographic study of the coating was
also carried out to study their morphology. The
microphotographs were taken with a SEM
(scanning electron microscopy Jeol JSM-6100).
The chemical characteristics of polymer coatings
were performed using Fourier transform infrared
spectroscopy (FT-IR). The FT-IR spectra of the
samples were recorded on the spectrophoto-
meter (JASCO FT-IR 430). Scanning was
carried out between 4000 and 500 cm–1 wave-
length with using diffuse reflection equipment.
3. Results
It was found what type of polymer and
concentration of the polymer in film forming
solution affects the physical properties of
prepared coatings [7]. The results showed that
in the case of single coatings from cellulose
acetate the porosity was in the range of 88.5 to
65.5%. The porosity of single coatings from
 M. Tomaszewska et al. / Desalination 146 (2002) 319–323
PAN ranged from 60.4 (for 16% of polymer in
film forming solution) to 53.1 (for 18% of PAN
in film forming solution) whereas, from PSF it
was 53 and 19.4% for 12.5 and 18% of polymer
in solution, respectively [7]. The thickness of
fertilizer coatings, measured by micrometer
screw, ranged from 0.21 to 1.14 mm. The
obtain-ed results demonstrate that the thickness,
similar to porosity, is dependent on the type of
polymer and on the polymer concentration in
casting solutions. It was observed that in the
case of coatings prepared from PAN and CA
their thickness was much smaller in comparison
with that prepared from PSF. The thicknesses
of single coatings prepared from 18% polymer
solution were: for polysulfone 1.1 mm, for
cellulose acetate 0.32 mm and for polyacrylo-
nitrile 0.27 mm. Moreover, in the case of PAN
and PSF the coating prepared from solution
with a higher polymer concentration in the cast-
ing solution exhibited a large thickness,
whereas for CA the thickness even insig-
nificantly decreases with increase of polymer
concentration.
Fig. 1 presents the SEM images of cross-
section of single coatings. The performed
microphotographic observations showed that
the prepared coatings in all cases were asym-
metrical with thin skin layer on the top of
coating. The skin layer is more compact and
dense. It acts as a barrier, thereby reduces the
intragranular diffusion of water from soil, the
Fig. 1. SEM of cross-section of single coatings: a) PAN 17; b) PSF 18; c) CA 18.
321
dissolution of ingredients and transfer outside
the encapsulated granule. The spongy layer,
comprising the main part of the coating, has the
structure of macroporous honeycomb with large
pores (PSF), or in case of PAN this layer forms
the cylindrical elongated macropores.
It was found that the physical and chemical
properties of polymer coatings vary in the
presence of the fertilizer. The fertilizer during
the formation of the membrane slightly dis-
solves and diffuses into the forming coating.
The salt addition causes faster polymer precipi-
tation during the immersion step, hence a more
open structure of the coating is formed [8]. Part
of the mineral components of coating was
leached during the forming.
It was observed that the coating prepared
without the contact with fertilizer (prepared on
glass pearls) exhibits different physical proper-
ties in comparison to the coating prepared from
the same polymer solution, but prepared on the
granule fertilizer. The thickness of coating pre-
pared from 18% polysulfone solution on glass
pearls was 10 times smaller. Their porosity
decreases to 15% in comparison to the case
when the coating was removed from the granule
of fertilizer (19.4%).
The decrease of porosity was found too in
the case of PAN and CA coatings formed on
glass pearls.
The influence of fertilizer amounts in film
forming solution on the coating properties was
322 M. Tomaszewska et al. / Desalination 146 (2002) 319–323

also examined. Therefore, the adequate amounts

(from 1 to 7 wt.%) of powdered NPK fertilizer
(NH4Cl, KCl and NH4H2PO4) were added to
18% solution of PSF and the pearls were coated
with these solutions. The results showed that a
proportional dependence exists between the
porosity of used coating and the amount of ferti-
lizer which was added to this coating forming
solution (Fig. 2). With the increase of fertilizer
concentration in polymer solution the porosity of
used coating increases to 36.9% in the case of 7 Fig. 2. The influence of fertilizer addition on the porosity
wt.% addition. of coatings prepared from polysulfone on glass pearls.
The polymer coatings were characterised us-
ing Fourier transform infrared spectroscopy
(FTIR). The influence of the fertilizer addition
on the IR spectra of a polymer film was also
observed (Fig. 3). The coatings, formed on the
fertilizer were compared with coatings prepared
from the same polymer but without the contact
with fertilizer.
Fig. 3 presents the comparison of PAN
spectra: for pure polymer removed from glass
pearl (denoted as PAN) and coating created on
the fertilizer (PAN*). As can be seen the spect-
rum for the polyacrylonitrile shows the bands at
~2250 cm–1 (the band corresponds to the C≡N),
at 2900, 1750 and 1450 cm–1 (the band corres- Fig. 3. Fourier transform infrared spectra for the poly-
ponds to the C–H). It can be seen that, the acrylonitrile. PAN*: the coating formed on the fertilizer;
spectra of pure polymer showed lower intensity PAN: pure polymer removed from pearl.
than the spectrum of the fertilizer coatings. This
effect was observed in cases of all used poly-
mers. The reason may be that the spectrum of
the coating is composed of two spectra: one for
the polymer and the other for a trace amount of
fertilizer. A similar effect was observed by
Hanafi et al. Moreover, on analysing the spectra
of fertilizer coatings, the bands for the fertilizer
were observed at about 1350 and 3250 cm–1
(Fig. 4), which refers to the NH4+ groups. Very
weak bands from H2PO4–at the wave number of
about 1200–1150 cm–1 (Fig. 3) were also ob-
served. The presence of the fertilizer within the
membrane can indicate that the transport of
macronutrients takes place through the porous
structure of coating. Fig. 4. FT-IR spectra for the polyacrylonitrile sectors.
 M. Tomaszewska et al. / Desalination 146 (2002) 319–323
4. Conclusions
1. The concentration of the polymer in a
casting solution affects the physical properties
of the coating. The coatings prepared from the
solutions of higher polymer concentrations have
lower porosity.
2. The coating formed from polysulfone
showed the most advantageous properties for
all coatings tested — they were low porous and
more compact.
3. The prepared coatings were asymmetric
with thin skin layer on the top of coating.
4. The fertilizer during formation of the
membrane slightly dissolves and diffuses into
the polymer solution. The salt addition causes
faster polymer precipitation during the coating
formation, hence a more porous coating is
formed.
5. FT-IR analysis showed that the prepared
coatings contain an insignificant amount of
fertilizer. The presence of the fertilizer within
the membrane can indicate that the transport of
macronutrients takes place through the porous
structure of coating.
323
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