On the Encapsulation of Natural Pesticide Using Polyvinyl
Alcohol/Alginate–Montmorillonite Nanocomposite for
Controlled Release Application
Azam Rashidzadeh,1 Ali Olad,1 Dariush Salari,2 Mir Jalil Hejazi3
1
Department of Applied Chemistry, Polymer Composite Research Laboratory, Faculty of Chemistry,
University of Tabriz, Tabriz, Iran
2
Department of Applied Chemistry, Petroleum Research Laboratory, Faculty of Chemistry,
University of Tabriz, Tabriz, Iran
3
Department of Plant Protection, Faculty of Agriculture, University of Tabriz, Tabriz, Iran
A representative pesticide, NeemAzal was encapsulated
into polyvinyl alcohol/alginate-montmorillonite (PVA/Alg-
MMT) nanocomposite by cross-linking with glutaralde-
hyde. Different formulations of capsule beads containing
NeemAzal were prepared with different concentration of
materials. Evidence of cross-linking of PVA and Alg was
obtained by comparison of the Fourier transform infrared
spectra of the initial substrates and capsule beads. X-ray
diffraction and transmission electron microscopy techni-
ques confirmed the intercalated structure of capsule bead
nanocomposites. In addition the swelling behavior of cap-
sule beads was investigated. Results showed that swel-
ling ratio of capsule beads decreases with introduction of
MMT as well as increase of PVA content in capsule bead
formulations. The release characteristics of NeemAzal
from capsule beads were monitored using UV–visible
spectrophotometer in distilled water. The addition of
sodium MMT to these formulations was found to have a
profound inhibitory effect on the release of NeemAzal.
Furthermore, the release data were fitted to several
empirical equations to estimate the kinetic parameters.
The NeemAzal encapsulated PVA/Alg-MMT nanocompo-
site capsule beads, designed and discussed in this work,
have the potential for controlled release of pesticide.
POLYM. ENG. SCI., 00:000–000, 2013. V
C 2013 Society of Plastics
Engineers
INTRODUCTION
The growing awareness and concern about the impact of
agrochemicals on the environment and also in food promoted
the idea of using natural pesticides instead of synthetic pesti-
cides [1, 2]. In this regard, botanical pesticides have long been
thought as attractive alternatives to synthetic chemical pesticides
owing to their little threat to the environment and human health
[3]. As one of the botanical pesticides, currently, much attention
was paid on the use of neem-based pesticides. Neem (Azadir-
achta indica), a tropical plant, which is used in medicine and
agriculture industrial products contains compounds with pesti-
cide and insect anti feedant applications [4, 5]. Azadirachtin is
one of isolated compounds from neem with wide applications in
herbal medicine, healthcare products and pesticides [6, 7]. But,
Correspondence to: Ali Olad; e-mail: a.olad@yahoo.com
Contract grant sponsor: The financial support of this work by University of
Tabriz is gratefully acknowledged.
DOI 10.1002/pen.23823
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2013 Society of Plastics Engineers
V pesticides [26, 27]. This can be attributed to clays ability to
POLYMER ENGINEERING AND SCIENCE—2013
as neem is a liquid, it cannot be used directly in soil. The most
convenient method to design the liquid pesticide as a solid form
and also reduce toxicity of pesticides is encapsulation method
[8]. Encapsulation is a process in which a thin film of polymeric
material is used to enclose small solid particles, liquid materials
or gases [9]. This method is useful for entrapment of active
agents like drugs [10], proteins [11], and agrochemicals like fer-
tilizers [12], herbicides [13], and pesticides [14] with enabling
the controlled release of them to the medium. In controlled
release method, not only the utilization of agricultural pesticides
is maintained efficient for longer time but also it reduces the
pollution of the environment. Moreover, it was proved that con-
trolled release technology is effective for improving the effi-
ciency of agricultural pesticides [15].
In this context, the use of natural polymers, due to their eco-
friendly nature, cost effectiveness, free availability, and their
biodegradability nature, seems to be the best choice in agro-
chemical release [16, 17]. Alginate (Alg), a naturally occurring
water-soluble linear polysaccharide, is made up of 1–4 linear
copolymers of b-D-manuronic (M) and a-L-guluronic (G) acids
[18]. It is widely used in agricultural applications for controlled
release of pesticides, due to its hydrophilicity and biocompatibil-
ity and the fact that it can be produced relatively economically
[19]. Encapsulation of neem (Azadirachta indica) was success-
fully carried out using Alg as a controlled release polymer [8].
In another work, controlled release neem capsule of Alg was
coated with natural rubber to retard the release of pesticide [20].
On the other side, it was stated that the synthesis of polymeric
beads of alginate with other polymers can improve leaching of
pesticide during the preparation of beads [21]. Polyvinyl alcohol
(PVA) has also been used as a polymer matrix for the encapsu-
lation of reactive agents due to its biodegradability and of par-
ticularly low toxicity [22, 23]. In the previous studies, it was
proved that in Alg/PVA capsules prepared for controlled release
of neem (Azadirachta indica), the release of neem pesticide
increases with the increase in PVA content [24]. But on the
other hand the strengths of polymeric capsules can increase by
addition of PVA to Alg.
Moreover, it was proved that the release of pesticides from
bead formulations can be controlled by adding modifying agents
such as clay minerals [25]. Various types of clay minerals have
been used to slow down the release of pesticides in polymer
based controlled release formulations. Because of large specific
surface area and considerable ion-exchange capacity, clay min-
erals have been examined as controlled release formulations of
 TABLE 1. Formulation concentration and characteristics of bead samples.
Formulation CB1 CB2 CB3
PVA (mL) 0 2.5 5 7.5
Alg (mL) 10 7.5 5 2.5
NeemAzal (mL) 2.5 2.5 2.5
Alg/Na-MMT(mL) 0 0 0 0
Bead diameter (mm) 2.2 2.34 2.63
Encapsulation Efficiency (%) 78.3 77.4.3 76.5
adsorb pesticides and desorb them at a slow rate. Moreover,
clay minerals can also help in supplying nutrients toward plants.
Therefore these materials are more favorable to be used in con-
trolled release formulations. As one of mineral clays, montmo-
rillonite (MMT) is a layered silicate with crystal structure
consists of stacked layers made of two silica tetrahedrons fused
to an edge-shared octahedral sheet of alumina. The layer thick-
ness is approximately 1 nm and the lateral dimensions may vary
from 300Å to several microns, giving an aspect ratio (length/
thickness) greater than 1000 [28]. MMT clay, due to its high
specific surface area, ion-exchange capacity, good intercalation
property, chemical and mechanical stabilities, environmentally
friendly, relatively low cost and also its abundance in nature is
undoubtedly one of the best choices for controlled release for-
mulations [29].
The aim of this work is to evaluate the possibility of using
PVA/alg-MMT nanocomposite capsules for encapsulation of
neem and to study the release characteristic of neem from glu-
taraldehyde (GA) cross-linked capsules prepared under various
conditions.
EXPERIMENTAL
Materials
Poly vinyl alcohol (Mw 5 72000), GA as a cross-linking agent
and methanol were purchased from Merck and were used without
further purification. Sodium montmorillonite KSF (specific sur-
face area 5 20–40 m2/g, cation exchange capacity 5 30 meq/100
g) and sodium alginate (viscosity of 5.0–40.0 cps for a 1% solu-
tion at 25 C) were obtained from Sigma-Aldrich (USA). NeemA-
zal-T/S containing 1 wt% Azadirachtin A, purchased from
Trifolio-M GmbH (Germany) was selected as natural pesticide to
study the slow release characteristic of prepared nanocomposite
capsules. Other agents used in this work were all analytical grade
and all solutions were prepared with distilled water.
Preparation of Polyvinyl Alcohol/Alginate-Montmorillonite
Capsule Beads
The capsules used in this work were prepared from mixture
of Alg, PVA and MMT. The formulation for preparing the cap-
sules is given in Table 1. Sodium alginate solution (3%, w/v) in
distilled water was prepared under constant stirring. Alg-MMT
nanocomposite was prepared through solution method. The
proper amount of MMT (10% w/w, with respect to Alg) was
dispersed in distilled water for 24 h and then was further treated
by ultrasonication (Bandelin D-12207, Germany). The MMT
suspension was added drop wise into Alg solution while agita-
tion for 6 h. Also, PVA solution (10% w/v) in distilled water
2 POLYMER ENGINEERING AND SCIENCE—2013
CB4 CBN1 CBN2 CBN3 CBN4
0 2.5 5 7.5
0 0 0 0
2.5 2.5 2.5 2.5 2.5
10 7.5 5 2.5
2.97 1.98 2.23 2.46 2.82
76.8 82.8 82.2 81.6 81.8
was prepared in a heating mantle at 70 C under constant stir-
ring. After complete cooling, NeemAzal pesticide (2000 ppm)
was added and mixed thoroughly with Alg, Alg-MMT nanocom-
posite, PVA or a mixture of them using a magnetic stirrer. Then
polymer solution containing NeemAzal pesticide was added
drop wise into cross-linking solution containing methanol, 2%
(w/v) GA as a cross-linking agent and 1% (w/v) of 1 N HCl as
a catalyst with constant stirring. The beads formed in methanol
were kept for overnight. Then the beads were washed with dis-
tilled water and then dried.
Capsule Beads Characterization
Bead Size Measurement. To estimate the bead diameters, five
samples of the completely dried beads from the different formu-
lations were selected, and their sizes were measured using a
micrometer screw gauge (Mitutoyo, Japan) with an accuracy of
60.01 mm (Table 1).
Fourier Transforms Infrared Spectroscopy. A Fourier trans-
forms infrared (FT-IR) spectrometer, Bruker Tensor 27 (Ger-
many), was used to detect any chemical interactions between
materials. The beads were ground and mixed thoroughly with
potassium bromide and pellets were formed under a hydraulic
pressure of 600 kg/cm. The FT-IR spectra of the pellets were
then recorded in the wave number range of 400–4000 cm21.
X-Ray Diffraction Spectroscopy. XRD is a versatile and non-
destructive technique which is used for identification of the
crystalline phases present in solid materials and analyzing the
structural properties. The X-ray diffraction (XRD) patterns of
pristine MMT, Alg-MMT nanocomposite and PVA/Alg-MMT
nanocomposite were obtained using Siemens D500 diffract
meter with Cu ka radiation (k 5 1.5418Å) at room temperature,
operating at a voltage of 35 kV for a scan range of 2h 5 2–70 .
Transmission Electron Microscopy. The structure of PVA/Alg-
MMT nanocomposite and dispersion of MMT nanoclays was
visually observed using transmission electron microscopy
(TEM). The electron microscope (LEO 960, Germany) was
operated at 100 kV. The solution prepared for bead samples was
put on a formvar-coated copper grid and dried to make a film,
which was then analyzed using TEM.
Swelling Study of Capsule Beads
Swelling study of the beads was carried out by investigation
of the percentage of water uptake by the beads at a definite
time intervals. The dried preweighed bead samples were incu-
bated in distilled water at room temperature. Then the swollen
DOI 10.1002/pen
bead samples were removed from the solution at regular time
intervals and the weight of the swollen bead samples was deter-
mined. Experiment was carried out in triplicate and the average
value was calculated. The swelling ratio [S.R. (g/g)] was calcu-
lated by using Eq. 1

Ws 2Wd
S:R: ðg=gÞ 5 (1)
Wd
Where Ws (g) is the weight of the swollen bead, and Wd (g)
is the initial weight of the dry bead.

Evaluation of Encapsulation Efficiency

The encapsulation efficiency was calculated as the ratio
between the initial amount of NeemAzal to be encapsulated and
its content in the final product. NeemAzal content in beads was
obtained by refluxing a known weight of the beads with 100
mL of methanol at 65 C. To ensure complete extraction of Nee-
mAzal from beads, refluxing was continued for 1 h. The absorb-
ance of methanol containing the extracted amount of NeemAzal
was recorded at a wavelength of 214 nm in a UV–visible spec-
trophotometer (Shimadzu UV-1700, Japan) using absolute meth-
anol as a blank by means of a calibration curve. Calibration
curve of NeemAzal was obtained by recording the absorption of
a known concentration of NeemAzal in distilled water at a
wavelength of 214 nm by using UV–visible spectrophotometer
[20]. The absorbance values at 214 nm obtained with the respec-
tive concentrations were recorded and plotted.
NeemAzal Release Study
The release profiles of NeemAzal were determined using
capsule bead samples (10 mg) in distilled water (50 mL) with
mild magnetic stirring. At certain time interval, 5 mL of the
release media was taken and equivalent volume of fresh distilled
water was supplemented to maintain a constant volume of the
system. Then the cumulative release of NeemAzal was meas-
ured with UV–Vis spectrophotometer at 214 nm. All measure-
ments were performed in triplicate and the mean value was used
for further data analysis and plotting.
RESULTS AND DISCUSSION
Preparation of Bead Samples
Capsule beads with different formulations were prepared
using Alg, PVA, Alg-MMT, and NeemAzal pesticide which
were shown in Table 1. The cross-linking of polymers was car-
ried out through reaction between functional groups of GA and
polymers. The beads formed are nearly spherical in shape with
the average diameter ranging from 1.98 to 2.97 mm. The size of
the beads changed with the bead preparation formulation such
as PVA, Alg, and Alg-MMT content. The diameter of beads
increased with an increase in PVA content in all bead samples.
This might be due to lower cross-linking of PVA with GA com-
pared with Alg. Furthermore, the introduction of MMT into
cross-linked Alg/PVA decreased the size of beads.
FT-IR Spectra
FT-IR analysis was applied to examine the possible interac-
tions amongst components of the prepared formulations. The
FIG. 1. The FT-IR spectra of the Pure NeemAzal pesticide, PVA, Alg,
MMT, and bead capsules of PVA/Alg and PVA/Alg-MMT nanocomposite.
[Color figure can be viewed in the online issue, which is available at AQ4
wileyonlinelibrary.com.]
FT-IR spectra of pure NeemAZAl pesticide, Alg, PVA, MMT,
as well as CB2 and CBN2 as two examples of prepared con-
trolled release are shown in Fig. 1.
CB2 [PVA/Alg (25%/75%)] and CBN2 [PVA/Alg-MMT
(25%/75%)] samples because of their formulations consisting of
all the components were chosen FT-IR analysis. Since the FT-
IR and XRD characterization of this sample was recorded, for
comparison this sample was tested for FT-IR analysis.
The FT-IR spectra of pure PVA shows major peaks related
to hydroxyl and acetate groups. The broad peak at 3438 cm21 is
due to intermolecular H-bonded OAH stretching. The peaks at
2940 cm21 and 2913 cm21 are assigned as alkyl CAH stretch-
ing vibration. The absorption peaks at 1716 cm21 and 1650
cm21 correspond to C@O stretching and CAO stretching of ace-
tate group [30]. The characteristic absorption bands of Alg are
seen around 1640 cm21 and 1419 cm21 wave numbers which
are due to carboxylate stretching vibrations. The broad band at
3200–3500 cm 21 is due to the stretching absorption of the
hydroxyl groups of the polysaccharide. The bands between 900
and 1200 cm21 are attributed to the OACAO stretching of ether
groups and ACAO stretching of alcoholic groups [31]. In FT-IR
spectra of MMT clay, the strong absorption peaks at 1029 cm21
(SiAO bond stretching), 522 cm21 (AlAO bond stretching) and
462 cm21 (MgAO bond stretching) are characteristic peaks of
MMT. The absorption at 1633 cm21 was assigned to HAOAH
deformation. Also the bands at 3421 and 3622 cm21 are related
to stretching vibration of structural OAH and NAH groups of
MMT, respectively [32, 33]. Bead sample CBN2 containing
Alg–MMT nanocomposite showed the characteristic bands of
MMT clay (1035 cm21 due to SiAO bond stretching, 557 cm21
related to AlAO bond stretching, and 446 cm21 due to MgAO
bond stretching) with slight shift in places as a result of interac-
tions between polymer matrix and MMT. The changes of the
characteristic spectral peaks of pure materials like Alg, PVA,
and MMT with bead formulations in CB2 and CBN2 reflect the
chemical interactions between them. In the typical spectrum of

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2013 3


FIG. 2. XRD patterns of MMT clay, Alg-MMT nanocomposite, and PVA/
Alg–MMT nanocomposite bead capsule. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]
formulation CB2 and CBN2, the characteristic peak at 1716 cm21
(C@O stretching of PVA) is shifted to 1738 cm21, due to the for-
mation of hydrogen bonding between the hydroxyl and carbonyl
groups of PVA and the carbonyl groups of GA. Furthermore, the
absorption bands related to carboxylate stretching vibrations of
Alg (1640 cm21 and 1419 cm21) show slight shift in places (to
1662 cm21 and 1412 cm21 for CB2 and 1665 cm21 and 1416
cm21 for CBN2, respectively) due to the interaction between
polymers and cross-linking agent [34]. The broad band between
3400 cm21 and 3500 cm21 in PVA and Alg are linked to the
OAH stretching from hydrogen bands. The reaction of PVA or
Alg with GA results in the reduction the intensity of OAH peaks
in bead samples. Also the narrower OAH stretching peak in bead
samples than that of uncross-linked PVA and Alg is evidence of
cross-linking in bead samples.
The characteristic sharp peaks of pure NeemAzal pesticide
are at 3471 (OAH stretching), 2924 (aromatic and/ or vinylic
CAH), 2856 (aliphatic CAH), 1742 (carbonyl stretching), 1459
cm21 (CH2 asymmetric deformation) and 1097 cm21 (CAO
groups) [34, 35]. These peaks were found with slight shift in
place after the formation of the CB2 and CBN2 beads, thereby
indicating the absence of chemical interactions between NeemA-
zal pesticide and polymers. These results confirm that NeemA-
zal pesticide was successfully encapsulated in bead samples.
XRD Patterns
The spacing between clay platelets is an indicator of disper-
sion of MMT clay nanoparticles which determines the extent of
intercalation/exfoliation of clay platelets within a polymer
matrix which can be observed using XRD analysis. Generally,
regular intense reflection in the range of 3 –9 (2h) indicates
ordered intercalated nanocomposites. Figure 2 shows the XRD
patterns of MMT clay, Alg-MMT nanocomposite, and PVA/
Alg-MMT nanocomposite bead capsule (CBN2). Here, the XRD
patterns display common diffraction peak in 3 –9 (2h), indicat-
ing the possibility of having intercalated and flocculated silicate
4 POLYMER ENGINEERING AND SCIENCE—2013
FIG. 3. TEM image of PVA/Alg-MMT nanocomposite bead capsule.
the layers of clay dispersed in polymer. In Fig. 2, the crystalline
peak of MMT is observed at about 7.35 corresponds to the
periodicity in the direction of (001) of the MMT [36].
In the case of Alg-MMT nanocomposite sample, the (001)
peak is shifted toward a lower angle (2h56.02 ). This results
from intercalation of Alg polymer solution between the clay
layers which lead to increase the d-spacing in the direction of
(001) for MMT from 12.019 Å to 14.667 Å. The position and
the intensity of other peaks have been shifted and evidently
reduced, indicating a certain degree of interaction between
MMT and Alg.
In the case of PVA/Alg-MMT nanocomposite, the character-
istic peak related to clay (2h 5 7.35 ) was shifted to lower
degree (2h 5 5.84 ), which is corresponding to a d-spacing of
15.4 Å. The peak shifting from higher diffraction angle to lower
diffraction angle, and increment in the basal spacing of PVA/
Alg-MMT nanocomposite compared to MMT clearly supported
the intercalation of PVA/Alg into the interlayers of MMT. It
can be concluded that addition of PVA to capsule formulations
increases the basal spacing of MMT clay in comparison with
capsules with Alg only. These results show the intercalated
structure of Alg-MMT and PVA/Alg-MMT nanocomposite in
bead formulations.
TEM Images
The clay dispersion within the polymer matrixes has been
characterized by both XRD and TEM which are the most fre-
quently used methods to study the structure of nanocomposites.
Therefore, further investigation of morphology of the obtained
PVA/Alg-MMT nanocomposite bead samples and verifying
intercalation of MMT, TEM micrograph was taken by dropping
solution prepared for bead sample formulation on TEM copper
grids.
CBN2 sample because of its formulation of PVA/Alg-MMT
(25%/75%) consisting of all the components was chosen for
TEM morphology test. Since the FT-IR and XRD characteriza-
tion of this sample was recorded, for comparison this sample
was tested for TEM. The TEM image of CBN2 formulation is
shown in Fig. 3. In this figure, the dark bands and the light
DOI 10.1002/pen
FIG. 4. Swelling behavior of bead capsules as function of time for formu- FIG. 5. Swelling behavior of bead capsules as function of time for formu-
lations without MMT clay. [Color figure can be viewed in the online issue, lations containing MMT clay. [Color figure can be viewed in the online
which is available at wileyonlinelibrary.com.] issue, which is available at wileyonlinelibrary.com.]

regions stand for the silicate layers of MMT and the polymers, formulations. Therefore, penetration of the water molecules
respectively. TEM image of CBN2 as one of the PVA/Alg- through the Alg/PVA capsule beads is more difficult compared
MMT nanocomposites demonstrated that the clay platelets were to that for the pure Alg beads [24]. As can be seen from Fig. 5,
almost intercalated with few stack layers. It was confirmed that the lowest amount of swelling ratio was observed for the bead
the gap between MMT layers were expanded and these layers sample containing 75 wt% PVA and 25 wt% Alg-MMT due to
were dispersed in the PVA/Alg matrix rather uniformly. There- the less amount of Alg presents in this bead sample. These
fore, TEM image in combination with XRD analysis results results suggest that with increase the PVA and Alg/Na-MMT
clearly supported the statement that well intercalated nanocom- contents, swelling ratio of bead samples decreases.
posite with silicate layers spacing was achieved in PVA/Alg-
MMT nanocomposite.
Pesticide Release
The encapsulation efficiency was calculated as the ratio
Swelling Studies between the initial amount of NeemAzal to be encapsulated and
its content in the final product. From the calibration curve, the
To study the swelling behavior of bead samples, the dried
concentration of NeemAzal in bead samples was obtained by
preweighed bead samples were immersed in distilled water and
knowing the absorbance value. As shown in Table 1, the encap-
the weight of the swollen samples was determined at regular
sulation efficiency for all bead samples is greater than 76%
time intervals. The swelling behavior of bead capsules as func-
which is indicative of good encapsulation capacity of samples
tion of time for formulations without MMT clay and also, for
formulations containing MMT clay was shown in Figs. 4 and 5,
respectively. The observed trends in the swelling kinetics are
very similar for all bead samples. Initially, the rate of water
uptake sharply increases, and then followed by a slower rate
until the equilibrium is reached. As can be seen from Fig. 6, the
water absorbency for bead samples containing clay was always
lower than that of samples without clay. The pure alginate cap-
sules showed a maximum equilibrium swelling ratio of 340 dur-
ing 8 h which decreased to 313 with the incorporation of MMT
in the capsule formulation. This phenomenon might be related
to the generation of cross-linking points due to role of MMT
clay as the physical cross-linking agent which restricted move-
ment of alginate in the beads. Furthermore, upon introducing
PVA to the bead formulations and with increasing the PVA con-
tent in the formulations, the swelling ratio decreases gradually.
Alginate is a natural water-soluble polymer with large amount
of hydroxyl and carboxyl groups that impart hydrophilicity to
the polymer. In contrast, PVA is a linear polymer with a small
hydrated volume compared with alginate, and thus PVA endows
a more compact network of macromolecular chains to the bead FIG. 6. Comparison of swelling ratio of bead capsules in distilled water.

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2013 5


FIG. 7. Release profile of NeemAzal from formulations without MMT
clay. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
for entrapment of liquid NeemAzal pesticide. From Table 1, it
was evident that introduction of MMT in formulations results in
increasing the encapsulation efficiency. This can be attributed to
the large surface area and ion-exchange capacity of MMT which
adsorb NeemAzal pesticide.
Release of NeemAzal from bead samples was examined by
suspending a known amount of the beads into distilled water.
The amount of NeemAzal released into the medium as a func-
tion of the time was monitored by the characteristic band of
NeemAzal at 214 nm. Figure 7 compares the release of NeemA-
zal versus time for all formulations without MMT clay. As can
be seen from Fig. 7, a low concentration of pesticide was slowly
released to the release medium as a function of time. The
release pattern for Alg only bead (CB1 formulation) is different
from others. Initial release is very fast and reached complete
release in 24 h. In contrast, the release pattern from the Alg/
PVA formulations was similar for all formulations. In all cases,
the initial release was fast, but it slowed in continue and com-
plete release was not measurable at the end of the experiment.
This slow release effect can be ascribed to a physical entrap-
ment effect of the pesticide within the Alg/PVA. When PVA
content was increased in Alg/PVA formulations, decrease in the
NeemAzal pesticide release was also observed. This phenom-
enon can be attributed to decrease in swelling ratio with increas-
ing the PVA content in the formulations which retards the
penetration of water molecules into the matrix and therefore dif-
fusion of NeemAzal pesticide becomes difficult.
Comparison of release patterns of formulations containing
MMT clay (Fig. 8) compared with the one without MMT clay
(Fig. 7) indicated a significant decrease in the quantity of Nee-
mAzal pesticide released in water. This may be related to the
larger specific surface area of MMT clay and also considerable
ion-exchange capacity of clay which slows done the release of
pesticide [25–27]. Same finding was reported by Gerstl et al. for
controlled release of alachlor and atrazine pesticides from Alg/
MMT beads [37]. They attributed this finding to both interaction
of the pesticides with the MMT clay and increased tortuosity
resulting from a disruption of the pore network in the presence
6 POLYMER ENGINEERING AND SCIENCE—2013
FIG. 8. Release profile of NeemAzal from formulations containing MMT
clay. [Color figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
of the clay. The slower release rate of pesticides means the lon-
ger the duration of pesticide application. The lowest rate of
release was obtained with formulation of CBN4 with 75:25 wt%
of PVA/Alg-MMT (10 wt% clay). The observations show that
the cumulative release of NeemAzal pesticide from the beads
occur in a very controlled manner, which is an important neces-
sity in controlled release formulations to protect the environ-
ment and health.
As stated before this formulation has the lowest swelling
ratio as well. Therefore to reduce the pesticide release, it is
needed to further reduce the swelling ratio. This can be achieved
with increasing the MMT content from 10 wt% (which has been
done in this work) to higher wt% of MMT. In this case, but the
issue of the agglomeration of MMT at higher loadings may
restrict the percent of MMT. To find the optimum amount of
MMT, further works should be done in future works.
Taking into the account of bead diameters it is clear that
there is an inverse relationship between diameter of beads and
the rate of release of NeemAzal pesticide. The similar observa-
tion has been reported for alachlor release from alginate beads
[37]. The pesticide releases faster from the small radius beads,
whereas its release is slower from the larger sized beads.
To understand the pesticide release mechanisms, several
mathematical models have been used. The criterion for selecting
the most appropriate model is based on the goodness of fitting
the obtained results. Hence the release data have been analyzed
with the following mathematical models.
The kinetic release data of NeemAzal in water were analyzed
applying the more generalized form, valid for the first 60% of
the fractional release, proposed by Korsmeyer and Peppas [38].
Mt
5kKP tn (2)
M1
Where (Mt/M1) is the released fraction at time t, kKP is a
constant incorporating characteristic of the macromolecular net-
work system and the active ingredient (here NeemAzal pesti-
cide), n is the diffusional exponent which is indicative of the
transport mechanism. The value of n  0.5 means that the pesti-
cide release mechanism approaches to a Fickian diffusion
DOI 10.1002/pen
 TABLE 2. Kinetic parameters of various models for release data of NeemAzal.

Formulations

Kinetic models Parameter CB1 CB2 CB3 CB4 CBN1 CBN2 CBN3 CBN4

Korsmeyer-Peppas R2 0.974 0.966 0.986 0.988 0.958 0.972 0.971 0.985

n 0.236 0.471 0.824 0.735 0.531 0.710 0.932 0.745
kKP 3 102 44.6 33.37 17.8 18.2 31.8 84.1 12.3 14.4
Higuchi R2 0.985 0.933 0.938 0.916 0.988 0.856 0.891 0.945
kH 3 102 21.15 18.84 38.08 35.47 34.12 33.66 36.22 32.86
Zero-order R2 0.893 0.963 0.985 0.989 0.875 0.966 0.982 0.972
k0 3 102 7.3 13.16 12.03 11.36 11.64 11.63 10.92 8.49
First-order R2 0.939 0.954 0.995 0.993 0.933 0.973 0.98 0.992
k1 3 102 14.34 24.55 19.48 17.9 19.81 17.24 15.98 12.95

controlled release, whereas an n value of n 5 1.0 indicates that
the pesticide release mechanism approaches to Case II transport
(zero order) and the n value between 0.5 and 1.0 shows that
pesticide release mechanism is anomalous (non-Fickian) diffu-
sion or a mixed diffusion and chain relaxation mechanisms [39].
For comparison purposes, the same percentage was applied
to all models described below.
The Higuchi model [40] describes the release of pesticide as
a square root of time.
Mt
5kH t1=2
M1
where Mt is the amount of pesticide released when the release
time equals t and 1, M1 is the total amount of pesticide
released and, KH is the Higuchi dissolution constant. This model
shows good correlation in the release profiles whose predomi-
nant mechanism is simple Fickian diffusion.
The zero-order kinetic model is expressed by the following
equation [41]:
Mt
5k0 t
M1
where Mt/M1 is the fractional pesticide release, t is the release
time (min), and k0 is the zero order release constant. The release
profiles that present a better fit to this model generally agree
with those that show a Case II transport mechanism in the Kors-
meyer–Peppas model.
The first-order equation can be expressed as [42]:
Mt
5 12e2k1 t
M1
where k1 is the first-order release constant. This model shows
good correlations in the release profiles whose predominant
mechanism is simple diffusion anomalous behavior.
The parameters obtained in all the release tests by applying
all the mathematical models are compiled in Table 2. The good-
ness of fit was evaluated using the R2 values. As it is evident
from Table 2, in the case of CB1 and CBN1, the pesticide
release data showed the best fit to the Higuchi model whose
predominant mechanism is simple Fickian diffusion. Taking into
account the value of n (lower than 0.5 for CB1 and close to 0.5
for CBN1) from Korsmeyer-Peppas model, it can be concluded
that in these formulations the NeemAzal pesticide release fol-
lows the Fickian diffusion type transport which supports the
higuchi model. For CB2 formulation, the good fitness was found
with Korsmeyer-Peppas model. Referring to R2 values, first-
order kinetic model showed the best fit with release data for
other formulations, except with CBN3. In first-order kinetic
model, predominant mechanism is simple diffusion anomalous
behavior. These results match well with the value of the expo-
nent n between 0.5 and 1.0, calculated with the Korsmeyer–Pep-
pas model, obtained for the anomalous (non-Fickian) transport.
Non-Fickian or anomalous diffusion occurs when the diffusion
(3)
and relaxation rates are comparable. Therefore in these formula-
tions, pesticide release depends on two simultaneously rate proc-
esses, water migration into the beads and diffusion through
continuously swelling bead samples [43]. CBN3 formulation
presented an acceptable fitting to the zero-order kinetic model.
In this case, n value was determined to be 0.932 which is close
to 1 and Case II transport mechanism in the Korsmeyer–Peppas
model. This indicated that the release mechanism approaches to
Case II transport mechanism which reflects the influence of
polymer relaxation on the pesticide molecules movement within
the matrix.
(4)
CONCLUSION
NeemAzal encapsulated PVA/NaAlg-MMT nanocomposite
bead capsules were prepared using GA as cross-linking agent.
The results of FT-IR analysis confirmed that NeemAzal pesti-
cide was successfully encapsulated in bead samples. TEM image
with combination of XRD technique demonstrated the interca-
lated structure of nanocomposite in bead samples. Results indi-
cated that PVA/Alg–MMT nanocomposite showed a large
(5)
encapsulation capacity for liquid NeemAzal pesticide. Con-
trolled release profiles were obtained for all capsule bead formu-
lations. Increasing the PVA content is favorable to the slow
release. Moreover, owing to the synergistic effect of MMT clay,
nanocomposite capsule beads showed slower release rate of pes-
ticide. Therefore, the PVA/NaAlg-MMT nanocomposite having
controlled release property is especially suitable for encapsula-
tion of liquid pesticides like NeemAzal.
NOMENCLATURE
GA Glutaraldehyde
MMT Montmorillonite

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2013 7

PVA Polyvinyl alcohol
TEM Transmission electron microscopy
XRD X-ray diffraction
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DOI 10.1002/pen