Polymer Testing 32 (2013) 502–512

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material properties

Preparation and properties of linear low-density

polyethylene-g-poly (acrylic acid)/organo-montmorillonite
superabsorbent hydrogel composites
Maryam Irani, Hanafi Ismail*, Zulkifli Ahmad
School of Materials and Mineral Resources Engineering, USM Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal,
Penang, Malaysia

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

Article history: Novel superabsorbent hydrogel composites were prepared using waste linear low density
Received 20 November 2012 polyethylene (LLDPE), acrylic acid (AA), and modified montmorillonite (OMMT) clay through
Accepted 2 January 2013 emulsion polymerization. The effects of major factors such as acrylic acid, initiator, cross-
linking agent and OMMT contents and the degree of neutralization of acrylic acid on water
Keywords: absorbency were investigated to obtain optimum conditions with a high swelling capacity.
Hydrogel composites
The prepared samples were characterized using FTIR, XRD, SEM, TGA, solid state 13C NMR and
Waste polymers 29
Si NMR. SEM characterization of the samples showed that hydrogel composites have more
Organoclays
Superabsorbent pores and a higher swelling ratio than clay free hydrogels. The swelling behaviour of the
Swelling behaviour hydrogel composite was investigated in various saline solutions. The hydrogel composite
containing 3 wt% OMMT had the highest water absorbency (800 g/g in distilled water).
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction utilized as a coupling agent for polymer composites [6] and

Linear low density polyethylene (LLDPE) is a linear
polyethylene (PE) involving alkyl short-chain branches that
are incorporated through the insertion of a-olefins (1-
butene, 1-octene, etc.) during the polymerization of ethyl-
ene [1]. Due to its excellent mechanical properties, linear
low density polyethylene (LLDPE) has been widely used in
various applications, including plastic films [2]. Non-
biodegradable synthetic polymers such as LLDPE can
cause environmental pollution [3]. There are various al-
ternatives for reducing the problem of their disposal and
for converting them into valuable products, such as poly-
mer modification and functionalization [4,5]. Chemical
modification and functionalization of synthetic polymers
have been useful methods for increasing their range of
applications. For example, modified polymers can be
* Corresponding author. Tel.: þ60 4 5996113; fax: þ60 4 5941011.
E-mail address: hanafi@eng.usm.my (H. Ismail).
as a compatibilizer for polymer blends [7,8].
Hydrogels are defined as hydrophilic three-dimensional
polymer networks with a corresponding absorption ca-
pacity of up to 10 g/g [9]. Hydrogels have wide application in
a variety of fields, such as agriculture [10], tissue engineer-
ing [11,12], drug delivery [13], water purification [14] and
sensors [15,16]. Because hydrogels are weak and fragile, the
incorporation of clay particles can enhance their mechanical
properties. Different types of clays have been utilized for the
preparation of hydrogel composites, such as kaolin [17],
montmorillonite [18], attapulgite [19] and mica [20].
Montmorillonite (MMT) is a layered aluminium silicate
composed of an aluminium octahedral sheet and two silica
tetrahedral sheets [21,22]. Fig. 1 shows the structure of
MMT. Chemical modification of hydrophilic silicates is
required to improve compatibility with a polymer matrix.
Surfactants, such as alkyl ammonium compounds, have
been utilized to form organo clays [23].
In this work, organo-montmorillonite (OMMT) was
chosen for the preparation of the superabsorbent hydrogel

0142-9418/$ – see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymertesting.2013.01.001
 M. Irani et al. / Polymer Testing 32 (2013) 502–512
Fig. 1. Schematic illustration of MMT structure.
composites. LLDPE-g-PAA and LLDP-g-PAA/OMMT were
prepared, and their swelling behaviour was compared. The
aim was to identify the potential application of waste
polymers, such as LLDPE, through graft polymerization, and
to reduce the cost of preparing hydrogels by using waste
polymer and clay.
2. Experimental section
2.1. Materials
N,N’-methylene bis acrylamide (MBA, chemically pure)
and sorbitan monostearate (Span 60) were from Aldrich.
Benzoyl peroxide (BP), sodium hydroxide and toluene were
purchased from Merck. Acrylic acid (AA, from Fluka) was
used without purification. Waste LLDPE was obtained from
Juara One Resources Sdn Bhd, Bukit Mertajam, Penang,
Malaysia. Organoclay (OMMT) was supplied by Nanocor,
Inc. Nanomer 1.30 T was used as a surface-modified mont-
morillonite, with 15–30 wt% of octadecylamine. The orga-
noclay was in powder form, with an 18–23 micron particle
size.
2.2. Instrumental analysis
FTIR spectra of prepared samples were taken from KBr
pellets using a Perkin-Elmer Spectrum one apparatus. FTIR
spectra of the samples were obtained in a range between
4000 cm1 and 550 cm1.
The solid state CP/MAS NMR experiments were carried
out using a Bruker 400 MHz ultrashield spectrometer,
operating at 100.577 MHz for 13C and 79.460 MHz for 29Si.
Thermogravimetric analysis (TGA) of the prepared
samples was carried out using a Perkin- Elmer Pyris 6 TGA
503
analyser from 50 to 700  C at a heating rate of 10  C/min,
with a nitrogen flow of 10 ml/min.
Micrographs of the prepared samples were collected
using a field emission scanning electron microscope
(FESEM, ZEISS Supra-35VP). Before the SEM observation,
the samples were coated with a thin layer of platinum.
The wide angle X-ray diffraction (WAXD) measurements
of the prepared samples were obtained using a Panalytical
X’Pert PRO - MRD PW3040 with a Cu anode, running at
40 kV and 30 mA; scanning from 3 to 40 at 3 /min.
A Brookfield viscometer (Brookfield DV- IIþ Viscometer,
spindle R4) was used to measure viscosity as a scale of gel
strength [17]. 3.0 g of the prepared sample was added to
a 600 ml beaker containing of 400 ml distilled water. The
viscosity was measured after 1 hour.
2.3. Preparation of linear low-density polyethylene-g-poly
(acrylic acid), (LLDPE-g-PAA), superabsorbent hydrogel
Preparation of LLDPE-g-PAA consisted of two steps. In
the first step, one gram of waste LLDPE was dissolved in
toluene (20 ml) at 90  C in a four necked reaction flask,
equipped with a thermometer, and a mechanical stirrer,
under nitrogen flow to remove the oxygen from the system.
Then, the temperature was lowered to 60  C, and an
appropriate amount of Span 60 (0.3 g) (used as an emul-
sifier) was added to the solution. After 10 minutes, an
appropriate amount of benzoyl peroxide (BP) (0.03-0.05 g)
(used as an initiator), which was dissolved in 10 ml toluene,
was added to the solution. In the second step, an exact
amount of acrylic acid (AA) (5-13 g) was partially neutral-
ized with sodium hydroxide solution (3 M) with cooling
(ice bath) under stirring for 5 min. Then, the acrylic acid
solution was added to the reaction flask. After 10 minutes,
an appropriate amount of crosslinking agent (MBA) (0.004-
0.010 g) dissolved in 10 ml of distilled water was added to
the solution. After the solution reached the gel point, the
temperature was increased to 70  C for 3 hours. Then, the
samples were washed with ethanol, cut into small pieces
and dried at 80  C for 12 hours. This was followed by
milling and screening.
Acrylic acid homopolymers and unreacted monomers
were extracted from the product by soxhlet extraction,
using an ethanol-water mixture (80:20) over 24 hours [24].
2.4. Preparation of linear low-density polyethylene-g-poly
(acrylic acid)/organo-montmorillonite (LLDPE-g-PAA/OMMT)
superabsorbent hydrogel composite
The preparation of the LLDPE-g-PAA/OMMT super-
absorbent hydrogel was similar to that of the LLDPE-g-PAA
material; except that, in the second step, an appropriate
amount of OMMT (0.30-1.10 g) was added to the acrylic
acid solution under stirring, for 10 minutes.
2.5. Property investigation
2.5.1. Measurements of equilibrium water absorption
A certain amount of sample (0.1  0.01 g) with particle
sizes between 60 and 100 mesh (150-250 mm) was
immersed in 50 ml of saline solution (0.9 wt%) or 400 ml of
504 M. Irani et al. / Polymer Testing 32 (2013) 502–512

distilled water. The samples were then allowed to absorb Table 1

water at room temperature for 24 hours. Then, after the Effect of different parameters on the water absorbencies of LLDPE-g-PAA
superabsorbent hydrogel.
swollen samples were separated from any excess water by
filtering via a 100-mesh screen, they were weighed. The Sample AA/LLDPE Neutralization Initiator MBA (wt%) Qeq
absorbency (QH2O) of the samples was calculated using the ratio degree of AA (%) (wt%)

following formula: 1. Effect of AA to LLDPE weight ratio

A 5:1 80 0.35 0.08 420
B 7:1 80 0.35 0.08 570
Q H2O ¼ ðm2  m1 Þ=m1 (1)
C 9:1 80 0.35 0.08 600
where m2 and m1 are the weights of swelling gel and the D 11:1 80 0.35 0.08 580
E 13:1 80 0.35 0.08 500
dried gel, respectively. 2. Effect of neutralization degree of AA
A 9:1 50 0.35 0.08 480
2.5.2. Swelling kinetics B 9:1 60 0.35 0.08 550
The swelling kinetics of superabsorbent hydrogel in C 9:1 70 0.35 0.08 570
D 9:1 80 0.35 0.08 600
distilled water was measured according to the following
E 9:1 90 0.35 0.08 500
procedure. A series of weighed dried samples (0.05 g) were 3. Effect of initiator content
immersed in excess distilled water. The swollen hydrogels A 9:1 80 0.30 0.08 430
were separated with a mesh screen and weighed at set B 9:1 80 0.35 0.08 600
intervals (every 15 min). This procedure was repeated until C 9:1 80 0.40 0.08 550
D 9:1 80 0.45 0.08 490
the weight of the swollen samples remained constant. The E 9:1 80 0.50 0.08 450
water absorbency at any given moment was calculated 4. Effect of crosslinker content
according to Eq. (1). A 9:1 80 0.35 0.00 150
B 9:1 80 0.35 0.04 460
C 9:1 80 0.35 0.06 530
2.5.3. Swelling in salt solutions
D 9:1 80 0.35 0.08 600
Water absorbance capacity of the superabsorbent E 9:1 80 0.35 0.10 490
hydrogel composite was evaluated in various saline solu-
Qeq: equilibrium water absorbency, (g/g).
tions (FeCl3, CaCl2, and NaCl) with different concentrations
using the method in Section 2.5.1.

The effect of the degree of neutralization of acrylic acid

3. Results and discussion
3.1. Determination of optimum reaction conditions
Reaction conditions for the prepared superabsorbent
hydrogels and hydrogel composites (LLDPE-g-PAA and
LLDPE-g-PAA/OMMT) were optimized. The effect of the
main factors on water absorbency, including the amount of
initiator, crosslinking agent and OMMT, the ratio of mon-
omer to LLDPE and the degree of neutralization of acrylic
acid, were studied. Time, temperature, and emulsifier
content were constant during the reaction.
3.1.1. Effect of the amount of initiator, crosslinking agent, the
ratio of monomer to LLDPE and the degree of neutralization of
acrylic acid, on water absorbency
Table 1 shows the effect of the amount of initiator,
crosslinking agent, the ratio of monomer to LLDPE, and the
degree of neutralization of acrylic acid on water
absorbency.
The water absorbency increased with increasing AA
content. Maximum swelling capacity was obtained when
the sample was synthesized with an AA to LLDPE mass ratio
of 9:1. This could be because the increase in the amount of
AA from a ratio of 5:1 to 9:1 resulted in an increase in the
molecular weight and grafting of the poly acrylic acid
chains [19]. With further increases of AA content, the water
absorbency decreased. This could be due to (a) a preferen-
tial homopolymerization of the acrylic acid over graft
copolymerization or (b) an increased medium viscosity
which hindered the movement of monomer molecules and
free radicals [25].
on hydrogel swelling was identified by varying the degree
of neutralization of acrylic acid from 50 to 90%. Maximum
swelling capacity (of 600 g/g) was obtained when the de-
gree of neutralization of the acrylic acid reached 80%. Water
absorbency increased as the degree of neutralization
increased from 50 to 80%, but decreased with further in-
creases in the degree of neutralization of AA. When acrylic
acid was neutralized with a sodium hydroxide solution, the
negatively charged carboxyl groups attached to the poly-
mer chains produced an electrostatic repulsion; resulting
in an expansion of the network. The electrostatic repulsion
rose as the degree of neutralization increased from 50 to
80%, leading to increased water absorbency. Further in-
creases in the degree of neutralization of AA resulted in
a decreased water absorbency of the prepared super-
absorbent. This behaviour could be due to an increase in
counter ion condensation on the poly-ion [26]. We believe
that, due to the increased amount of counter ions (Naþ)
with increasing degree of neutralization of AA, the con-
densation of counter ions that cover COO ions also
increased, resulting in a decreased formation of hydrogen
bonds between the COO groups and water. This phe-
nomenon causes the water absorbency of the super-
absorbent hydrogel to decrease.
The effect of benzoyl peroxide (BP) (used as an initiator)
on percentage swelling was studied by varying BP content
from 0.3 to 0.5%. The water absorbency increased as the BP
content increased from 0.3 to 0.35%, but decreased with
further increases. The maximum water absorbency (of
600 g/g) was obtained when the amount of initiator was
0.35% which caused the graft polymerization rate to
increase and, consequently, the final water absorbency also
 M. Irani et al. / Polymer Testing 32 (2013) 502–512
increased. When the total amount of initiator was higher
than the optimum value, the water absorbency decreased.
This phenomenon was most likely due to an increase in the
number of radical centres, which increases the crosslink
density. The greater crosslink density prevents the network
expanding to its greatest extent. Furthermore, an increase
in the number of radical centres leads to a decrease in the
chain length and in the molecular weight of the grafted
acrylic acid of the hydrogel. As a result, the water absor-
bency decreases. This may be attributed to the inverse
relationship between the initiator content and the molec-
ular weight [27].
The variation of MBA content of the hydrogel on water
absorbency was studied. The results show that an increase
in the crosslinking agent content from 0.08 to 0.1% leads to
decreased water absorbency. This phenomenon is most
likely due to the fact that, as the amount of crosslinker
increases, more crosslink points are produced during pol-
ymerization and the crosslinking density increases. The
increased crosslinking density leads to a highly crosslinked
and rigid structure, and the polymer network cannot
expand enough to retain such a large amount of water.
Maximum water absorbency is achieved when the amount
of crosslinking agent is 0.08% but, when it is lower than
0.08%, water absorbency decreases due to an increase in
soluble materials [19].
3.1.2. Effect of OMMT content on water absorbency
The influence of OMMT content on the water absor-
bency of the LLDPE-g-PAA/OMMT superabsorbent com-
posite is shown in Table 2. It is obvious that OMMT content
has an important effect. The water absorbency of the
composite in distilled water increased from 600 to 800 g/g,
as 3 wt% of OMMT was introduced. According to the FT-IR
analysis data from this work (see Section 3.2), the –OH
groups of OMMT could participate in the formation of the
composite, which can improve the polymeric network of
the hydrogel and increase the water absorbency. A further
increase in OMMT content to 11 wt% resulted in decreased
water absorbency of 580 g/g. This could be due to the fact
that the interactions between OMMT and acrylic acid
increased gradually with an increasing OMMT content,
resulting in increased formation of physical and chemical
cross-links in the polymeric network. The elasticity of the
polymer chains declined with more cross-links in the pol-
ymeric network. The water absorbency of the composite
declined with decreasing polymer elasticity [18].
Table 2
Effect of OMMT content on the water absorbencies of the superabsorbent
hydrogel composites.a
Sample OMMT percentage (wt%) QH2O (g/g)
LLDPE-g-PAA 0 600
LLDPE-g-PAA/OMMT1 3 800
LLDPE-g-PAA/OMMT2 5 750
LLDPE-g-PAA/OMMT3 7 690
LLDPE-g-PAA/OMMT4 9 630
LLDPE-g-PAA/OMMT5 11 580
a 
Reaction conditions: reaction temperature, 70 C; 80% neutralization
degree of AA; weight ratio of AA/LLDPE in the feed 9:1; weight ratios of
oil-soluble initiator, crosslinker, and emulsifier in the feed of 0.35 wt%,
0.080 wt%, 3.0 wt%.
505
3.2. FTIR spectra analysis
FTIR spectra of LLDPE, LLDPE-g-PAA, OMMT and LLDPE-
g-PAA/OMMT are shown in Fig. 2. The FTIR spectrum of
LLDPE (Fig. 2a) shows two sharp peaks at 2909 and
2843 cm1 that correspond to the CeH symmetric and
asymmetric stretching. Furthermore, CH2 stretching is also
shown at 1463 cm1. After the grafting of acrylic acid
(LLDPE-gPAA), new peaks appeared in the spectrum (see
Fig. 2b). These include a C]O stretching band of AA at
1728 cm1, the symmetric and asymmetric COO stretch-
ing of AA at 1403 and 1579 cm1, a CeO band at 1169 cm1,
as well as a strong and broad peak at 3450 cm1 that cor-
responds to the water molecules. The OMMT spectrum
shows a sharp and medium peak at 3626 cm1 which
corresponds to the hydroxyl groups of OMMT. Furthermore,
the broad band with a maximum at 1035 cm1 was ascri-
bed to the Si–O bond of OMMT. The formation of the
composite was established by the presence of the peaks in
LLDPE-g-PAA/OMMT1 spectrum (see Fig. 2d). The peak at
1015 cm1 proved the existence of OMMT filler in the
composite. The hydroxyl group of OMMT at 3626 cm1
overlapped with the broad peak of the hydrogen bonding in
the region 3460 cm1 to 3626 cm1.
13
3.3. C Nuclear Magnetic Resonance spectroscopy (13C NMR)
13
C solid-state NMR spectroscopy was performed to
confirm the FTIR results. Fig. 3 shows 13C CP MAS spectra of
waste LLDPE (plastic food wrapping) which depicts a sharp
single peak at 32.5 ppm.
The spectrum of LLDPE-g-PAA is shown in Fig. 3. The
broad band at 30-50 ppm is assigned to the CH and CH2 of
PAA which overlapped with CH, CH2 and tertiary carbon of
LLDPE. Carbonyl carbon of AA was detected at 177.63 ppm.
The peak at 62.11 in the LLDPE-g-PAA spectrum is pos-
sibly related to the CeO of dimer PAA. This dimerization of
PAA occurred through condensation of AA monomer under
basic conditions [28]. Fig. 4 shows the dimerization of PAA.
Residual ethanol during soxhlet extraction was trapped
in the sample. Therefore, the peaks at 57.25 and 17.80 ppm
corresponded to the CH2 and CH3 of ethanol respectively.
3.4. Si-NMR
The spectrum of OMMT (Fig. 5) shows an intense Si peak
at about 93.66 ppm, which is attributed to the tetrahedral
(3Si,Al) units of the octahedral sheet [29,30]. This peak
shifted to 92.98 ppm in the LLDPE-g-PAA/OMMT spec-
trum. This phenomenon shows that there should be an
interaction between OMMT particles and the composite
matrix (LLDPE-g-PAA) which led to a shifting of the Si peak,
and that the chemical environment of Si in the OMMT
platelets was changed. These Si-NMR results are consistent
with the FTIR analysis results given above.
3.5. Mechanism of hydrogel formation
Crosslinking graft polymerization of acrylic acid onto
LLDPE was carried out in the presence of an oil-soluble
initiator (benzoyl peroxide) and MBA (used as
506 M. Irani et al. / Polymer Testing 32 (2013) 502–512

Fig. 2. FTIR spectra of (a) LLDPE, (b) LLDPE-g-PAA, (c) OMMT, and (d) LLDPE-g-PAA/OMMT1.

crosslinking agent). A proposed LLDPE-g-PAA/MMT for- hydrogen abstraction on the LLDPE backbone chain can
mation mechanism is shown in Fig. 6. Benzoyl peroxide occur on the tertiary carbon atoms of the LLDPE chains to
used as an oil-soluble initiator can be decomposed under produce tertiary carbon radicals (as shown in Fig. 6). These
heating to form benzoate radicals. One possible type of active centres on the backbone chains can initiate the

13
Fig. 3. C solid-state NMR spectrum of (a) LLDPE and (b) LLDPE-g-PAA.
 M. Irani et al. / Polymer Testing 32 (2013) 502–512
Fig. 4. Dimerization of PAA
grafting of AA. Because MBA (used as a crosslinking agent)
is present in the reaction, a crosslinked structure is formed.
MBA is a bifunctional crosslinking agent; therefore, after
the initiator is added to the solution, a macroradical is
formed that contains four reactive sites. These active sites
can link with the radicals on the acrylic acid, and LLDPE. It
should be mentioned that in Fig. 6 only two active sites on
MBA are shown. OMMT particles were dispersed amongst
the polymeric network. In addition, the FTIR results show
that there are interactions between the OH groups of
OMMT and the functional groups (COOH and -COO) of
LLDPE-g-PAA.
3.6. Morphology analysis (SEM)
The porosity of a hydrogel can affect its water absorbency
[31]. Therefore, the hydrogel microstructure morphology is
an important property to investigate. SEM micrographs of
LLDPE-g-PAA and LLDPE–PAA/OMMT composites contain-
ing 3, 5, 7, 9, and 11% OMMT are shown in Fig. 7. These im-
ages show that the samples have a porous structure. The
LLDPE-PAA/OMMT composites (see Fig. 7b–f) show a loose
surface and are more porous (higher pore density) than that
of LLDPE-g-PAA. It can be concluded from the SEM images
that the OMMT particles were well dispersed in the com-
posites; therefore, there was good interaction between the
OMMT particles and the polymer chains. However, by
increasing the OMMT content to more than 7%, some
29
Fig. 5. Si solid-state NMR spectrum of (a) OMMT and (b) LLDPE-g-PAA/OMMT1.
507
aggregated clay particles were characterized with SEM. This
means that the aggregation tendency of OMMT particles
increased with increasing OMMT content. Several aggre-
gated clay particles are shown in the circles drawn (see
Fig. 7d–f). Furthermore, these pores would provide regions
for water penetration into the polymeric network and give
more interaction sites for the hydrophilic groups of the
polymer network and external stimuli [18,27].
3.7. XRD
Fig. 8 shows the wide angle X-ray diffraction patterns of
LLDPE and LLDPE-g-PAA. The XRD pattern of LLDPE shows
two main peaks at 21.5 and 23.6 of 2q; which correspond to
the (110) and (200) planes [32]. Compared with LLDPE, the
intensity of the peak located at 21.5 decreased sharply and
shifted slightly to 21.37 for the (110) plane, and the peak
located at 23.6 of 2q disappeared from the XRD pattern of
LLDPE-g-PAA. It is suggested that, when acrylic acid was
grafted onto the LLDPE, the original crystallinity of the
LLDPE was destroyed, leading to diminishing peak in-
tensity. Several references [33,34] reported that PAA
showed a wide peak at around 19 of 2q (from 10-30 of 2q).
Therefore, the peak from PAA should overlap with the main
peaks of LLDPE in XRD pattern of LLDPE-g-PAA.
The X-ray diffraction (XRD) patterns of OMMT and
LLDPE-g-PAA/OMMT hydrogel composites are shown in
Fig. 9. An intense reflection at 2q ¼ 4.32 was observed for
OMMT, which was attributed to the (001) plane of OMMT
[35]. In comparison with OMMT, the d001 peak of OMMT
disappeared in the XRD pattern of LLDPE-g-PAA/OMMT
composites, thus indicating the exfoliation of OMMT in the
hydrogel composites. Therefore, the delaminated layers of
OMMT were individually dispersed in a continuous polymer
matrix.
508 M. Irani et al. / Polymer Testing 32 (2013) 502–512

Fig. 6. A proposed mechanism for the synthesis of the LLDPE-g-PAA/OMMT superabsorbent hydrogel composite.

3.8. Thermogravimetric analysis (TGA)
Fig. 10 depicts the TGA curves of LLDPE-g-PAA and
LLDPE-g-PAA/OMMT with various OMMT contents.
The thermal decomposition temperatures of 10 and 50%
weight loss, and char yield of the samples are shown in
Table 3. It was found that the thermal decomposition
temperature of LLDPE-g-PAA with OMMT was higher than
that of LLDPE-g-PAA without OMMT. This indicates that the
incorporation of OMMT particles in the polymer network
leads to increase of thermal stability. This phenomenon
occurs due to the heat barrier effect of OMMT.
Furthermore, the thermal decomposition temperature
of hydrogel composites (LLDPE-g-PAA/OMMT) increases
with increase of OMMT content when the OMMT content is
less than 7%. This phenomenon is possibly due to the effect
of dispersion on the thermal stability of the samples. With
increasing OMMT content, the aggregation of OMMT also
increases. Therefore, thermal decomposition temperature
of 10 and 50% weight loss of the samples decreases as the
OMMT content increases from 7 to 11%. The same result
was reported by Zhu et al. [36]. They prepared a hybrid of
organo-soluble polyimide and MMT, and found that dis-
persion of MMT affected the thermal stability of the sample,
and that increased, as the MMT content increased.
3.9. Water absorbency in various saline solutions
The effect of saline solution on water absorbency is
shown in Fig. 11. The swelling capacity of the hydrogel
 M. Irani et al. / Polymer Testing 32 (2013) 502–512
Fig. 7. Scanning electron micrographs of (a) LLDPE-g-PAA, (b) LLDPE-g-PAA/OMMT1, (c) LLDPE-g-PAA/OMMT2, (d) LLDPE-g-PAA/OMMT3, (e) LLDPE-g-PAA/
OMMT4, and (f) LLDPE-g-PAA/OMMT5.
composites in saline solutions was lower than it was in
distilled water. This phenomenon could be due to a charge
screening effect of the excess cations. These excess cations
can shield the carboxylate anions and reduce the effective
anion-anion repulsion; thus resulting in a decrease in the
osmotic pressure (ionic pressure) difference between the
hydrogel network and the external solution [31]. Fig. 11
shows that the swelling capacity of the prepared hydrogel
composite in the saline solutions is Naþ > Ca2þ > Feþ3. The
absorbency of the superabsorbent composites in the salt
solutions is monovalent > divalent > trivalent cations; the
degree of ionic crosslinking increases with increasing cat-
ion charge and, consequently, swelling reduces [27]. The
reduced water-absorbing capacity observed in multivalent
Fig. 8. X-ray diffraction patterns of LLDPE and LLDPE-g-PAA.
509
cationic solutions could be attributed to the carboxylate
groups, which can induce the formation of the complexes
with the cations in saline solutions that form ionic crosslink
points in the polymer network. As a result, the network
crosslink density would increase [37]. The order of the
ability of the carboxylate group to form a complex with the
three cations is Fe3þ> Ca2þ > Naþ, based on their formation
constants for ethylenediaminetetraacetic acid (EDTA) [38].
Furthermore, water absorbency reduces with increasing
concentration of different external saline solutions. This
phenomenon may be due to the presence of cations in the
different salt solutions. The osmotic pressure between the
external saline solution and the polymeric network reduces
Fig. 9. X-ray diffraction patterns of (a) LLDPE-g-PAA/OMMT1, (b) LLDPE-g-
PAA/OMMT2, (c) LLDPE-g-PAA/OMMT3, (d) LLDPE-g-PAA/OMMT4, (e) LLDPE-
g-PAA/OMMT5, and (f) OMMT.
510 M. Irani et al. / Polymer Testing 32 (2013) 502–512

Fig. 10. TGA curves of LLDPE-g-PAA, and LLDPE-g-PAA/OMMT with various Fig. 11. Water absorbency of LLDPE-g-PAA/OMMT1 in NaCl, CaCl2, and FeCl3
OMMT content at a heating rate of 10  C/min. in aqueous solutions with various salt concentrations.

with increasing concentration of the saline solution [39].
The penetration of counter ions (Feþ3, Ca2þ, and Naþ1) in
the polymeric network can have a screening effect on the
carboxylate groups (–COO), which results in water ab-
sorbency of the superabsorbent composites [31].
3.10. Gel strength
The gel strength variation versus speed of the visc-
ometer spindle for LLDPE-g-PAA and LLDPE-g-PAA/OMMT
with various OMMT contents is illustrated in Fig. 12. The
gel strength of all samples declined with increased speed.
By increasing the amount of OMMT in the hydrogel com-
posites from 3 to 7 wt%, the gel strength also increased. It
can, therefore, be concluded that OMMT had an effective
role in enhancing gel strength. However, when the OMMT
content exceeded 7 wt%, the gel strength decreased
slightly. This may have been due to aggregation of OMMT.
3.11. Swelling kinetics
The swelling rates of the LLDPE-g-PAA and LLDPE-g-
PAA/OMMT superabsorbents are illustrated in Fig. 13. It
can be seen from Fig. 13 that the swelling rates of LLDPE-g-
PAA and LLDPE-g-PAA/OMMT were higher for 0-45 mins
and that the water absorbency of LLDPE-g-PAA and LLDPE-
g-PAA/OMMT reached 260 and 400 g/g within 45 mins,
respectively. Then, the swelling rates decreased slowly, and
equilibrium of water absorbency for LLDPE-g-PAA and
LLDPE-g-PAA/OMMT was reached within 165 and
135 mins, respectively. Compared with the swelling rate of
LLDPE-g-PAA/OMMT, the LLDPE-g-PAA superabsorbent
took longer to reach equilibrium. The swelling rate of
a superabsorbent is determined by surface area, swelling
ability, polymer density, and particle size [40]. The
enhanced swelling rate with the introduction of OMMT
particles into the polymer network of the prepared
hydrogel could be due to OH groups on the surface of
OMMT increasing the affinity of the polymeric network to
water molecules. Another reason for this behaviour may be
because LLDPE-g-PAA/OMMT1 has more porosity than the
free clay hydrogel (LLDPE-g-PAA) (see Fig. 7) which can
provide more free volume for the penetration of water
molecules into the polymeric network. As a result, the af-
finity of the hydrogel network to the water molecules is
higher for LLDPE-g-PAA/OMMT than it is for LLDPE-g-PAA.
Swelling kinetics can be illustrated using the Voigt-
based viscoelastic model (Eq. 2) [41–43].


St ¼ P 1  et=r (2)
where St is the swelling capability (g/g) at any time (min), p
is the power parameter (g/g) denoting the theoretical

Table 3
TGA data of prepared samples.

Samples T10% T50% Char yield (%)

LLDPE-g-PAA 156 342 22.095
LLDPE-g-PAA/OMMT1 191 418 25.075
LLDPE-g-PAA/OMMT2 200 449 26.27
LLDPE-g-PAA/OMMT3 205 455 26.25
LLDPE-g-PAA/OMMT4 192 434 24.00 Fig. 12. Variation of swollen gel strength with rotation rate of the spindle of
LLDPE-g-PAA/OMMT5 171 362 22.89 a Brookfield viscometer for LLDPE-g-PAA and LLDPE-g-PAA/OMMT with
various OMMT content.
 M. Irani et al. / Polymer Testing 32 (2013) 502–512
Fig. 13. Swelling rate in distilled water for LLDPE-g-PAA, and LLDPE-g-PAA/
OMMT1.
equilibrium of water absorbency, t is time (min), and r is the
rate parameter (time required to reach 63% of its ultimate
swelling) (min). To calculate the r value, using the equation
and a little rearrangement, Ln[1(St/P)] versus time t was
plotted. The slope of the straight line (slope ¼ 1/r) gave the
r value. The lower p values reflect lower water absorption
and the lower r values reflect a higher swelling rate [41].
The results show that the rate parameters for the LLDPE-
g-PAA and LLDPE-g PAA/OMMT1 samples were 61.34 and
53.19 mins, respectively. The p-value was found to be 585
and 798 g/g for LLDPE-g-PAA and LLDPE-g-PAA/OMMT1,
respectively. Based on this data, it can be concluded that
incorporating of OMMT into the sample can provide
a higher swelling rate and higher water absorbency.
4. Conclusions
A superabsorbent hydrogel (LLDPE-g-PAA) without clay,
and superabsorbent hydrogel composites (LLDPE-g-PAA/
OMMT) with clay particles incorporated, were synthesized
by the graft copolymerization of AA onto waste linear low
density polymer chains (LLDPE) through emulsion poly-
merization. The incorporation of OMMT particles resulted
in an increase in water absorbency. The maximum water
absorbency under optimum conditions for superabsorbent
hydrogel composite was 800 g/g in distilled water (LLDPE-
g-PAA/OMMT1).
FTIR, 13C NMR, and Si NMR results, indicated that there
are interactions between the –OH groups of OMMT and,
COOH and –COO groups of AA. The SEM results showed
that the OMMT particles can disperse into the polymer
network. However, by increasing OMMT content to more
than 7% some aggregated clay particles were evident. The
XRD analysis showed that exfoliation of OMMT within the
hydrogel composites occurs.
TGA results show that the introduction of OMMT into
the polymeric network results in an increase in the thermal
decomposition temperatures of the superabsorbent
hydrogel composites compared to that of the clay free
hydrogels.
511
The effect of saline solutions on the water absorbency of
LLDPE-g-PAA/OMMT1 depended on the concentration of
saline solution and valence of cations. The swelling capacity
of the prepared hydrogel composite in the saline solutions
(NaCl, CaCl2 and FeCl3) was in the following order:
Naþ > Ca2þ > Feþ3. The investigation of LLDPE-g-PAA and
LLDPE-g-PAA/OMMT1 superabsorbent swelling rates
showed that LLDPE-g-PAA/OMMT1 had a higher swelling
rate than that of the hydrogel free clay.
The gel strength of the samples was also investigated,
and it was found that the swollen gel strength of the
superabsorbent hydrogel composites was higher than that
of the clay free hydrogel (LLDPE-g-PAA).
Acknowledgments
The authors wish to acknowledge the financial support
provided by a USM short- term grant (Ac No.: 8044043).
Maryam Irani would like to thank Universiti Sains Malaysia
for its financial support under the USM fellowship scheme
for her PhD study. The authors wish to acknowledge Mr.
Zahari Othman for his contribution to the NMR
measurements.
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