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Influence of Methacrylic Acid Modification on Tensile Properties of

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DOI: 10.1080/03602559.2014.977425

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Influence of Methacrylic Acid Modification on

Tensile Properties of Polypropylene/Cocoa Pod Husk
Biocomposites
a a a
Koay Seong Chun , Salmah Husseinsyah & Hakimah Osman
a
Division of Polymer Engineering, School of Materials Engineering, Universiti Malaysia Perlis,
Jejawi, Perlis, Malaysia
Accepted author version posted online: 03 Jan 2015.Published online: 22 Jan 2015.

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To cite this article: Koay Seong Chun, Salmah Husseinsyah & Hakimah Osman (2015) Influence of Methacrylic Acid
Modification on Tensile Properties of Polypropylene/Cocoa Pod Husk Biocomposites, Polymer-Plastics Technology and
Engineering, 54:3, 296-300, DOI: 10.1080/03602559.2014.977425

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 Polymer-Plastics Technology and Engineering, 54: 296–300, 2015
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ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602559.2014.977425

Influence of Methacrylic Acid Modification on Tensile

Properties of Polypropylene/Cocoa Pod Husk Biocomposites

Koay Seong Chun , Salmah Husseinsyah, and Hakimah Osman

Division of Polymer Engineering, School of Materials Engineering, Universiti Malaysia Perlis,
Jejawi, Perlis, Malaysia

GRAPHICAL ABSTRACT
Downloaded by [Universiti Teknologi Malaysia] at 17:06 22 January 2015

In this research, cocoa pod husk (by-product from cocoa industrial) has been utilized as filler
in polypropylene (PP) matrix biocomposites. The CPH filler was modified with different
contents of methacrylic acid (MAA) and its effect on tensile properties of PP/CPH
biocomposites was investigated. The result showed that 3% of MAA gave the optimum
improvement on tensile strength and tensile modulus of PP/CPH biocomposites. However,
the MAA modification reduced the elongation at break of PP/CPH biocomposites. The
improvement of tensile properties is attributed by the presence of MAA enhancing the
filler-matrix interfacial bonding. The scanning electron microscope results indicated that
the modified CPH exhibited less filler pull-out and was well wetted by the PP matrix,
which indicated better interfacial bonding. Fourier transmission infrared (FTIR) confirm
that the MAA was covalently bonded to the CPH filler surface.

Keywords Biocomposites; Cocoa pod husk; Methacrylic acid; Polypropylene

Address correspondence to Salmah Husseinsyah, Division of Polymer Engineering, School of Materials Engineering, Universiti Malaysia
Perlis 02600, Jejawi, Perlis, Malaysia. E-mail: irsalmah@unimap.edu.my
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpte.

296
 PP/COCOA POD HUSK COMPOSITES
INTRODUCTION
Cocoa (Theobroma Cacao) is one of the important
agricultural crops in Malaysia. Cocoa pod husk (CPH) is a
nonfood part of the cocoa pod, usually accounting for 52 to
76% of the cocoa pod wet weight[1,2]. In the cocoa industry,
the CPH is a by-product of the process of obtaining cocoa bean
from cocoa pod. Usually, the CPH is abundant but does not
have economic value. Therefore, the utilization of CPH as
natural filler in thermoplastic materials will provide a new
application route for CPH and a useful resource for
thermoplastic industry.
Nowadays, natural filler has become a popular choice of the
plastic industry. This is because natural fillers show some
excellent benefits compared to mineral fillers (such as lower
cost), are obtained from renewable resources, present
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a minimal health hazard, have low density, are less abrasive
to processing machinery, and are eco-friendly[3-5]. In our pre-
vious research, an eco-packaging product and eco-tableware
were developed from coconut shell, corn cob and polylactic
acid[5,6]. The new development of CPH-filled polypropylene
biocomposites is applicable to wooden fittings, fixtures, deck
and furniture as well.
Generally, poor adhesion between the hydrophilic natural
filler and the hydrophobic thermoplastic is the main drawback
to producing biocomposites. However, filler modification
can be used to modify the hydrophilic natural filler, which
can improve filler dispersion, wettability, and filler-matrix
adhesion. In previous work, it was found that filler modifi-
cation with acrylic acid[3,7], silane coupling agent[4,8], maleic
acid[5], modified fatty acid[6], sodium dodecyl sulphate[9,10],
and cross-linking agent[11] enhanced the properties of biocom-
posites. In our current work, methacrylic acid (MAA) was
used as a modifying agent for PP/CPH biocomposites. The
influence of various MAA contents on the tensile properties
of PP/CPH biocomposites was studied.
EXPERIMENTAL
Materials
Polypropylene (PP) type co-polymer, grade SM 340 was
supplied by Titan Petchem (M) Sdn. Bhd. Cocoa pod husk
(CPH) was obtained from cocoa plantation at Perak region.
The collected CPH was dried in an oven at 80°C for 24 h.
Then, the dried CPH was crushed into small pieces and further
ground into fine powder. The CPH powder was sieved, and the
average particle size of the CPH powder was 22 µm, measured
using a Malvern Particle Size Analyzer Instrument. The
ethanol and methacrylic acid (MAA) used for filler modification
were obtained from Sigma Aldrich, Penang.
Filler Modification
First, the MAA solution was prepared by dissolving MAA
into ethanol according to the formulation in Table 1. Then, the
CPH powder was added slowly to MAA solution and stirred
297
TABLE 1
Formulation of PP/CPH biocomposites
Materials PP/CPH Biocomposites
PP (phr) 100
CPH (phr) 20
MAA (%) 0, 1, 3, 5*
phr ¼ Part per hundred resin.
*Percentage based on weight of CPH.
continuously for 1 h. Afterwards, the CPH was soaked in
MAA solution and left for 12 h. The modified CPH was fil-
tered and dried in an oven at 80°C for 24 h.
Compounding and Molding Procedures
The PP/CPH composites with various of MAA contents
were prepared using a Brabender Plastrograph intermixer,
Model EC PLUS in counterrotating mode at 180°C and a rotor
speed of 50 rpm. The compounding steps involved were as fol-
lows: i) the PP was added into the mixing chamber for 3 min
until it melted homogeneously; ii) the CPH was added to the
melted PP and continuously compounded for 5 min. All the
compounds were compressed into 1 mm-thick sheets using a
hotpress, model GT 7014A at 180°C. The compression
sequences involved were as follows: i) preheat the compound
for 4 min; ii) compress the compound under a pressure of
100 kgf cm
12 for 1 min; iii) cooling under the same pressure
for 5 min. The PP/CPH composite sheets were cut into tensile
bars using a dumbbell cutter withdimensions according to
ASTM D638 type IV.
Tensile Test
Tensile testing was carried out according to ASTM
D638 using Instron machine model 5569. A cross-head speed
of 30 mm min
1 was used and the tests were performed
at 25  3°C.
Morphological Analysis
The tensile fracture surfaces of the PP/CPH composites
were analysed using a scanning electron microscope (SEM),
model JEOL JSM-6460 LA. The samples were coated with
a thin layer of palladium for conductive purposes and analyzed
at 5 keV.
Fourier Transmission InfrA-Red (FTIR) Spectroscopy
A Perkin Elmer Paragon 1000 FTIR spectrometer was
used to characterize functional groups in unmodified and
modified CPH. The Attenuated Total Reflectance (ATR)
method was used. The sample was recorded with four scans
in the frequency range of 4000–600 cm
1 with a resolution
of 4 cm
1.
 298 K. S. CHUN ET AL.

RESULT AND DISCUSSIONS

Tensile Properties
The increasing of MAA content increased the tensile
strength of PP/CPH biocomposites (Fig. 1). An MAA content
of 3% led to the highest tensile strength. The improved tensile
strength was due to the presence of MAA enhanced interfacial
bonding between CPH and the PP matrix. Modified coconut
shell powder with 3% acrylic acid and maleic acid also
improved the tensile strength of biocomposites[3,5].
In contrast to tensile strength, the elongation at break of PP/
CPH biocomposites decreased with increased MAA content
(Fig. 2). The PP/CPH biocomposites with 3% MAA exhibited
lowest elongation at break. The decrease in elongation at break
can be explained by the strong interfacial adhesion between
modified CPH and PP matrix restraining chain mobility, which FIG. 2. Elongation at break of PP/CPH biocomposites with different MAA
Downloaded by [Universiti Teknologi Malaysia] at 17:06 22 January 2015

reduced the flexibility of the biocomposites. content.

The tensile modulus of PP/CPH biocomposites was
increased with the increasing of MAA content (Fig. 3). The
maximum tensile modulus of PP/CPH biocomposites was
achieved with 3% MAA. The improvement of tensile modulus
was due to the presence of MAA enhanced filler-matrix inter-
actions which induced to stiffer biocomposites. Similarly, the
tensile modulus of PP/chitosan biocomposites increased with
3% of acrylic acid used in filler modification[7].
The drop in tensile strength above 3% MAA was probably due
to the surface coverage of MAA on CPH filler. At 3% MAA, the
MAA is chemically reacted and widely attached on CPH filler sur-
face. A moderate surface coverage of MAA on CPH surface leads
to a good filler dispersion and wetting of CPH filler by PP matrix.
Therefore, the PP/CPH biocomposites with 3% MAA exhibited
better filler-matrix adhesion which leads to highest tensile strenght
and modulus but lower elongation at break. However, 5% of
MAA had a large surface coverage on CPH filler.
The MAA presence on CPH filler surface is a closely and
tightly packed layer form that make the CPH surface hard to
wet with the PP matrix. As result, a poor interfacial adhesion
occurs between the PP matrix and modified CPH with 5%
MAA and causes the poor tensile properties of the biocompo-
sites. Moreover, the increased elongation at break of PP/CPH
biocomposites at 5% MAA was probably due to a lubricating
effect, because modified CPH with 5% MAA was fully covered
by MAA and a slipping action might occur between filler-matrix
interfaces. A similar effect has be reported by others[12,13].
FTIR Analysis
The FTIR spectra of unmodified and modified CPH
with MAA are shown in Fig. 4. The broad peak at 3600–
3000 cm
1 was assigned to the –OH groups on the CPH
surface and it also reflected the hydrophilicity of CPH. The
peak at 2922 cm
1 was attributed to C-H stretching. The peak
at 1732 cm
1 was related to C¼O stretching of carboxyl
groups from hemicellulose. The peak at 1604 cm
1 contributed
to C¼C stretching from hemicellulose and a small peak at
1518 cm
1 indicates the conjugated C-O group from aromatic

FIG. 1. Tensile strength of PP/CPH biocomposites with different MAA FIG. 3. Tensile modulus of PP/CPH biocomposites with different MAA
content. content.
 PP/COCOA POD HUSK COMPOSITES 299

FIG. 4. FTIR spectrum of unmodified and modified CPH with different

Downloaded by [Universiti Teknologi Malaysia] at 17:06 22 January 2015

MAA content.

skeletal in lignin. The peak at 1434 cm
1 refers to the –CH2

deformations vibration from cellulose.
The, peak at 1372 cm
1 corresponds to C-H group defor-
mation in cellulose and hemicellulose. The peak at 1247 cm
1
was assigned as C-O groups from acetyl groups in lignin.
Another broad peak 950–1200 cm
1 was C-H group vibration
in cellulose. The other peak at range of 700–900 cm
1
corresponds to the C-H vibration of lignin.
The hydrophilicity of CPH was significantly reduced after
modification with MAA as the intensity of –OH groups
absorption band decreased compared to unmodified CPH.
As discussed before, the presence of MAA reacted with
–OH groups on the CPH surface and conferred hydrophobic
properties to CPH. The intensity of the peak at 1730 cm
1
was increased with increased MAA content, evidence of the
presence of ester bonds between MAA and CPH. The new FIG. 6. SEM micrograph of (a) unmodified and (b) modified PP/CPH
peak at 648 cm
1 in modified CPH is attributed to ¼C-H biocomposites.
bending vibration of bonded MAA on CPH particles. The
schematic reaction of MAA and CPH is shown in Fig. 5. The presence of filler pull-out and detached CPH particles
indicate poor interfacial adhesion between unmodified CPH
Morphology and the PP matrix. In contrast, modified CPH with 3%
Figures 6a and 6b display the SEM micrographs of the MAA exhibited good filler dispersion and the CPH particles
tensile fracture surface of PP/CPH biocomposites without were embedded in PP matrix. This shows that the modified
and with 3% MAA. The SEM micrographs show that the CPH has greater wettability and filler-matrix adhesion with
unmodified CPH has poor filler dispersion in the PP matrix. the PP matrix than the unmodified form.

FIG. 5. Schematic reaction of CPH and MAA.
CONCLUSION
Modified CPH with MAA increased in tensile strength and
modulus, but decreased in elongation at break of PP/CPH bio-
composites. The 3% of MAA was the optimum content for fil-
ler modification of CPH giving the greatest improvement of
tensile properties. The FTIR results showed that the MAA
was covalently bonded with CPH via ester bonding. The
SEM micrograph also demonstrated that the filler modification
with 3% MAA improved interfacial bonding between CPH
and the PP matrix.
 300 K. S. CHUN ET AL.
ACKNOWLEDGMENTS
The authors are thankful to Dr. Alias from Cocoa Research
& Development Center (Hilir Perak), Malaysian Cocoa Board
for supplying the cocoa pod husk for this research.
ORCID
Koay Seong Chun http://orcid.org/0000-0003-2884-6027
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