Article

Journal of Thermoplastic Composite

Materials
Properties of low-density 26(1) 3–15
! The Author(s) 2011

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shell composites: DOI: 10.1177/0892705711417028

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Effect of polyethylene
co-acrylic acid
H Salmah1, A Romisuhani1 and H Akmal2

Abstract
Palm kernel shell (PKS)-filled low-density polyethylene (LDPE) composites was studied.
The polyethylene co-acrylic acid (PEAA) was used as compatibilizer. The tensile prop-
erties, thermal analysis, water absorption, and morphology of LDPE/PKS composites
were investigated. The results show that increasing of PKS loading have decreased the
tensile strength and elongation at break but Young’s modulus and water absorption of
composites increased. The higher tensile properties (such as tensile strength and
Young’s modulus) and lower water absorption with addition of compatibilizer was
due to the improvement in the filler-matrix interaction and adhesion of composites
as evidence from scanning electron microscopy studies. The presence of PEAA also
increased the crystallinity of LDPE/PKS composites.

Keywords
Low-density polyethylene, palm kernel shell, compatibilizer, composites

Introduction
Growing environmental awareness has resulted in renewed interest in the use of
natural material for different application. Considering the serious environmental
problems caused by the growing consumption of synthetic polymers, it is

1
School of Materials Engineering, University Malaysia Perlis, Taman Muhibah, 02600, Jejawi, Perlis, Malaysia
2
School of Bioprocess Engineering, University Malaysia Perlis, Taman Muhibah, 02600, Jejawi, Perlis, Malaysia

Corresponding author:
H Salmah, Division of Polymer Engineering, School of Materials Engineering, University Malaysia Perlis, 02600
Jejawi, Perlis, Malaysia.
Email: irsalmah@unimap.edu.my
4 Journal of Thermoplastic Composite Materials 26(1)

potentiated to minimize the use of the synthetic polymers derived from petroleum
and also to maximize the use of renewable resources. The considerable attention
to the natural fibers has picked up momentum both in the literature and in
the industry in recent years. Advantages of natural fibers over conventional
reinforcement such as glass or carbon fibers are of lower cost, low density,
low biodegradability, as well as high specific properties. Natural organic fibers
from renewable natural resources often have the potential to act as a biodegrad-
able reinforcing material alternative for the use of glass or carbon fiber and
inorganic fillers.1–4
Low-density polyethylene (LDPE) is an important thermoplastic because of
having a good combination of properties, such as fluidity, flexibility, transparency,
and a glossy surface. LDPE is used as a food-packing material, sheet and film.5 In
general, the utilization of lignocellulosic material in the production of plastic com-
posites is becoming more attractive, particularly for low-cost and high-volume
applications. Lignocellulosic-derived filler possess several advantages compared
to inorganic fillers, that is lower density, greater deformability, less abrasiveness
to equipment, and lower cost. More importantly, lignocellulosic-based fillers are
derived from a renewable resource, available in relative abundance, the potential of
which has not been really tapped. Intrinsically, these fillers have a number of inter-
esting mechanical and physical properties. Palm kernel shell (PKS) is one of the
lignocellulosic biofibers derived from waste PKS.6
However, in producing good lignocellulosic composites, the main obstacle to be
resolved is the compatibility between the filler and matrix. The properties of the
lignocellulosic composites are dominated by the interfacial interaction between the
lignocellulosic filler and the polymer matrix.7 Several comprehensive reviews about
improvement in interfacial adhesion between cellulosic fillers and thermoplastics
have been the focus of a large amount of research during the past two decades and
have been published recently.8,9 Cellulosic fillers can be modified by physical and
chemical methods. Among various ways of chemical modification for polyolefin/
natural fiber composites,7,10–19 the functionalized polyolefins are most often tested
because of their efficiency and commercial availability. In our previous study, we
reported the effect of acrylic acid on tensile properties of PKS-filled LDPE
composites.20

Table 1. Properties of low-density polyethylene (LDPE).

Physical properties G811

Tensile strength at Break 11.8 MPa
Elongation 600%
Stiffness 180 MPa
Melting point 106 C
Salmah et al. 5

This research was focused to study the effect of PKS content and polyethylene
co-acrylic acid (PEAA) as a compatibilizer on the properties of PKS-filled LDPE
composites. The addition of PEAA efficiently was improved by the fiber-matrix
bonding due to the formation of covalent linkages and hydrogen bond between the
acrylic acid and hydroxyl group of the PKS thus enhanced the compatibility and
properties of LDPE/PKS composites.

Experimental
Materials
Low-Density Polyethylene. LDPE grade Injection Molding G811 was supplied by
Polyolefin Company (Singapore) Pvt Ltd. Table 1 shows the properties of LDPE.
Palm kernel shell. PKS was used as filler in LDPE. PKS was obtained from
Malpom Industries Sdn.Bhd., Penang, Malaysia. PKS was dried in vacuum oven at
80 C for 24 h to remove moisture and later grinded to become powder. A Malvern
particle size measurement used to measure average particle size of PKS was 63 mm.
Compatibilizer. PEAA was used as compatibilizer. The amount used was 3 php
based on weight of LDPE. The composition of PEAA was 80 wt% polyethylene
and 20 wt% acrylic acid. This PEAA was supplied by Aldrich Chemical
Company Inc.

Methodology
Mixing process. The composite was mixed using Z-Blade mixer from Malaysia, at
temperature 180 C with rotor speed 50 rpm. LDPE was charged into the chamber
for 10 min until it completely melted. Then filler was added and mixing continued
for another 10 min. The whole mixing process was conducted for 25 min. The
composites were discharged from chamber and sheeted through a laboratory mill
at 2.0 mm nip setting. The formulation for uncompatibilized and compatibilized
LDPE/PKS composites is shown in Table 2.
The 1 mm thickness sheet sample was prepared by molding process. This process
was done by using compression molding machine model GT 7014 A – Gotech,

Table 2. Formulation of uncompatibilized and compatibilized low-density polyethylene

(LDPE)/palm kernel shell (PKS) biocomposites with polyethylene co-acrylic acid (PEAA).

Materials Uncompatibilized biocomposites Compatibilized biocomposites

LDPE (php) 100 100

PKS (php) 0, 10, 20, 30, 40 10, 20, 30, 40
PEAA (php)a - 3
a
3 php from weight LDPE.
6 Journal of Thermoplastic Composite Materials 26(1)

Taiwan, with temperature 180 C and pressure 170 kg/cm2. The samples were pre-
heated for 8 min. After 7 min of preheating, the samples were fully compressed for
5 min to produce a uniform flat surface. The samples are quickly cooled for 4 min.
After compression molding, the samples were cut into dumbbell shapes by using
Wallace Dumbbell Cutter, Gotech, Taiwan.

Measurement of mechanical properties

Measurement of tensile properties. Tensile test was carried out according to
ASTM D-638 on an Instron 3366, USA. A cross-head speed of 50 mm/min was
used and the test was performed at 25  3 C. An average of five samples for each
formulation was tested. Tensile strength, elongation at break, and Young’s mod-
ulus were recorded and calculated by the instrument software.
Water absorption test. LDPE/PKS biocomposites sample of approximate dimen-
sions (25 mm  20 mm  1 mm) were used for the measurement of water absorption
according to ATM D570. The samples were dried at 80 C for 24 h and immersed in
distilled water at room temperature until a constant weight was reached. The speci-
mens were periodically taken out of the water, wiped with tissue paper to remove
surface water, and weighed. At least three specimens for each sample were used. A
Mettler balance type AX 200, Shimadzu, Japan, was used with precision of 1 mg.
The percentage of water absorption, (Mt), was calculated according to the follow-
ing formula:

Wn  Wd
Mt ¼  100 ð1Þ
Wd

where
Wd = original dry weight
Wn = weight after immersed.

Morphology study
Studies of the morphology of tensile fracture surface of composites were carried
out by using a scanning electron microscopy (SEM) model JOEL JSM-6460LA,
Japan. The fracture ends of specimens were mounted on aluminium stubs and
sputter-coated with a thin layer of paladium to avoid electrostatic charging
during examination.

Differential scanning calorimetric

Thermal analysis measurements of selected systems were performed using a Perkin
Elmer DSC-7 analyzer, USA. About 10–25 mg of the sample was heated from 20 to
250 C using a nitrogen air flow of 50 mL/min with a heating rate of 20 C/min. The
melting and crystallization behavior of selected composites were also performed
Salmah et al. 7

using a Perkin Elmer DSC-7. The crystallinity (Xcom) of composite was determined
using the following relationship:

xcom ð% crystallinityÞ ¼ Hf =Hf  100 ð2Þ

where Hf and Hof are enthalpy of fusion of the system and enthalpy of fusion of
perfectly (100%) crystalline PE, respectively. For Hof (PE) a value of 285 J/g was
used for 100% crystalline PE homopolymer.

Results and discussion

Effect of filler loading on mechanical properties
Tensile Properties. Figure 1 shows the effect of filler loading on tensile strength of
uncompatibilized and compatibilized LDPE/PKS composites. From the figure, it
can be seen that the tensile strength of both composites decreased with increasing
of filler loading. The reduction in tensile strength with increasing the filler loading
was caused by the effective matrix cross-section reduction and stress concentration
increased. On the other hand, a lack of interfacial adhesion between LDPE and
filler due to large surface differences led to decreased tensile strength of composites.
At 10 php of PKS loading show, the uncompatibilized and compatibilized

Figure 1. The effect of filler loading on tensile strength of uncompatibilized and compatibi-
lized of low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites.
8 Journal of Thermoplastic Composite Materials 26(1)

composites have the highest tensile strength. However, at similar filler loading, the
compatibilized composites exhibit higher tensile strength compared to uncompati-
bilized composites. The tensile strength of compatibilized composites had been
increased 55% than uncompatibilized LDPE/PKS composites. The higher tensile
strength of LDPE/PKS composites with the presence of PEAA was attributed to
the better dispersion and adhesion of PKS in the LDPE matrix. The better fillers
matrix interaction was derived from the formation of hydrogen bonding between
the acrylic acid of PEAA and hydroxyl groups at the surface of PKS. The PEAA is
a derivative of PE and it should be compatible with LDPE matrix. A similar result
was found by Yang et al.16 in their study on rice husk flour and wood flour with
HDPE and LDPE matrix using different compatibilizers agents, such as MAPE
and MAPP.
Figure 2 shows the effect of filler loading on elongation at break of uncompa-
tibilized and compatibilized of LDPE/PKS composites. The elongation at break of
both composites decreased steadily with the increasing of filler loading. The
decreases in elongation at break in filled polymer composites was due to the fact
that the deformation of the filler is generally much less than the polymer matrix;
thus, the filler forces the matrix to deform more than the overall deformation of the
composites. At similar filler loading, the elongation at break of compatibilized
LDPE/PKS composites is lower compared to uncompatibilized LDPE/PKS com-
posites. The reduction of elongation at break of compatibilized composites was

Figure 2. The effect of filler loading on elongation at break of uncompatibilized and compati-
bilized of low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites.
Salmah et al. 9

Figure 3. The effect of filler loading on Young’s modulus uncompatibilized and compatibilized
of low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites.

12% than uncompatibilized composites. This indicates that the PEAA imparts a
greater stiffening effect to PKS-filled LDPE composites.
Figure 3 shows the effect of filler loading on Young’s modulus of uncompati-
bilized and compatibilized LDPE/PKS composites. The Young’s modulus of
PKS-filled LDPE composites increased with increasing of filler loading. Young’s
modulus is an indication of the relative stiffness of composites. The addition of
filler increases the stiffness of the composites which in turn decreased the elongation
at break. At similar filler loading, the Young’s modulus of the compatibilized
LDPE/PKS composites is higher compared to uncompatibilized LDPE/PKS com-
posites. The increasing of the Young’s modulus of compatibilized composites was
48% compared to uncompatibilized composites. The presence of PEAA has
enhanced the Young’s modulus and led to increase in the tensile properties of
the composites by improving adhesion across the interface also to overcome the
dispersion problem.
Water absorption. Figure 4 shows the comparison of water absorption between
uncompatibilized and compatibilized LDPE/PKS composites at 0, 20, and 40 php
filler loading. It can be seen that the water absorption of the composites increased
with increasing PKS loading. PKS is polar and contains-OH groups that can form
hydrogen bonds with water molecules. When the filler loading increased, more
hydrogen bonding occurs between hydroxyl group and water molecules. The com-
patibilized composites indicated lower water absorption compared to uncompati-
bilized composites. The reduction in water absorption with the presence of PEAA
10 Journal of Thermoplastic Composite Materials 26(1)

Figure 4. The comparison of water absorption between uncompatibilized and

compatibilized low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites at 0, 20,
and 40 php.

is attributed to improve interfacial adhesion that reduces water accumulation in

interfacial voids and prevents water molecules from entering the composites. The
reduction of water absorption of compatibilized composites was 19% than uncom-
patibilized composites. Figure 5 shows the percentage of equilibrium water absorp-
tion of uncompatibilized and compatibilized LDPE/PKS composites at different
filler loading. The percentage equilibrium of water absorption of compatibilized
composites is lower than uncompatibilized composites.
Morphological study. Figures 6 and 7 show the micrograph of tensile-fractured
surface for LDPE/PKS composites at 20 and 40 php of filler loading. Both the
micrographs show detachment of filler and filler agglomeration at higher filler
loading. This support by result of tensile strength of composites decreased with
increasing of filler loading as discussed previously. The micrograph of tensile-
fractured surface for compatibilized LDPE/PKS composites at 20 and 40 php of
filler loading are shown in Figures 8 and 9, respectively. The fracture of compati-
bilized composites show less evidence of voids. It can be seen that the PKS filler
show better dispersion and adhesion in the LDPE matrix. The filler was coated in
the matrix and the interfacial bonding between filler and matrix was improved. In
the presence of compatibilizer, PEAA has enhanced the interfacial interaction
between filler and matrix.
Salmah et al. 11

Figure 5. The percentage of equilibrium water absorption for uncompatibilized and compati-
bilized low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites at different filler
loading.

Figure 6. The scanning electron microscopy (SEM) micrograph of tensile fracture surface of
uncompatibilized low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposite at
20 php at 200 magnification.
12 Journal of Thermoplastic Composite Materials 26(1)

Figure 7. The scanning electron microscopy (SEM) micrograph of tensile fracture surface of
uncompatibilized low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposite at
40 php at 200 magnification.

Figure 8. The scanning electron microscopy (SEM) micrograph of tensile tensile fracture
surface of compatibilized low-density polyethylene (LDPE)/palm kernel shell (PKS) at 20 php at
200 magnification.
Salmah et al. 13

Figure 9. The scanning electron microscopy (SEM) micrograph of tensile tensile fracture sur-
face of compatibilized low-density polyethylene (LDPE)/palm kernel shell (PKS) at 40 php at
200 magnification.

Figure 10. Differential scanning calorimetric curve of uncompatibilized and compatibilized

low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites at different filler
loading.
14 Journal of Thermoplastic Composite Materials 26(1)

Table 3. Differential scanning calorimetric (DSC) analysis of uncompatibilized and compatibi-

lized low-density polyethylene (LDPE)/palm kernel shell (PKS) biocomposites at different filler
loading.

Biocomposites Tm (oC) Hf (J/g) Xc (% crystallinity)

LDPE/PKS 100/0 129 60.40 21.20

LDPE/PKS 100/20 (uncompatibilized) 128 90.02 31.58
LDPE/PKS 100/40 (uncompatibilized) 127 97.34 34.15
LDPE/PKS 100/20 (compatibilized) 128 94.13 33.02
LDPE/PKS 100/40 (compatibilized) 128 115.4 40.35

Thermal properties
Differential scanning calorimetric. Figure 10 shows the differential scanning calori-
metric (DSC) curve of uncompatibilized and compatibilized LDPE/PKS compos-
ites at 0 and 20 php of PKS loading. The data of DSC measurement was
summarized in Table 3. The Table 3 indicates the value of melting temperature
(Tm), the heat of fusion of composites (Hf (com)), and the crystallinity of the com-
posites (Xc). The melting temperature point (Tm) of uncompatibilized and compa-
tibilized LDPE/PKS composites in range from 127 to 129 C (Table 3). The
enthalpy and crystallinity of uncompatibilized LDPE/PKS composites increased
with increasing of filler loading. At similar filler loading, compatibilized LDPE/
PKS composites exhibit higher enthalpy (Hf (com)) and crystallinity (Xc) compared
to uncompatibilized composites. This is due to the improvement of interfacial
interaction between filler and matrix which increase the compatibility of the
composites.

Conclusion
The tensile properties of LDPE/PKS composites were improved with addition of
PEAA as compatibilizer. The compatibilized composites show higher tensile strength
and Young’s modulus but lower elongation at break and water absorption compared
to uncompatibilized composites. The presence of PEAA had positive effect on the
tensile properties and enhanced the compatibility of composites. SEM studies indi-
cate that the interfacial interaction and adhesion between LDPE and PKS improved
in with presence of PEAA. The crystallinity of composites increased with increasing
of PKS loading and addition of PEAA as compatibilizer.

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