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World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia

Conference on Advanced Processes and Materials

CAPM1
EFFECTS OF COUPLING AGENTS AND FIBRE PRE-TREATMENT ON OIL PALM
EMPTY FRUIT BUNCH REINFORCED POLYPROPYLENE COMPOSITES
S. S. Suradi1, R. M. Yunus1, A. K. Lovely2 and M. D. H. Beg*1
1
Faculty of Chemical and Natural Resources Engineering, 2Faculty of Technology Management
Universiti Malaysia Pahang (UMP), Lebuhraya Tun Razak, 26300 Kuantan, Pahang Darul Makmur, Malaysia
*Email: mdhbeg@ump.edu.my, Phone: +649 5492881, Fax: +64 549 2889

ABSTRACT
Nowadays, there are competing product development based on natural fiber which renewable, environmentally
acceptable, and biodegradable reinforcing fiber. Also, combine acceptable mechanical properties with a low
density. The major challenge for natural fiber composites is their inherent poor adhesion between fiber and the
matrix, high moisture absorption and UV degradation. Lignin and hemicelluloses are the components of natural
fiber which are mostly responsible for moisture absorption and UV degradation. In this study the lignocelluloses
(Oil Palm Empty Fruit Bunch) were treated with alkaline peroxide to remove lignin and hemicelluloses. Composites
were produced with treated and untreated fiber using up to 45% fiber with polypropylene (PP) matrix using Twin-
screw extruder followed by injection molding. Composites were characterized using tensile and flexural testing,
SEM and TGA. The tensile and flexural modulus were found to be higher for alkaline peroxide treated fiber
composites compared to untreated fiber composites. To improve interfacial bonding, addition of coupling agents
also found to provide higher strength and modulus of composites.

Keywords: Oil palm fibre, alkali treatment, coupling agents, thermal analysis.

INTRODUCTION

Nowadays, enormous studies were developed on potential of natural fibers as reinforcement in thermoplastics which
has been shown in important industries such as automotive, construction or packaging industry. Natural fibers
present some advantages such as lower density, lower price, less abrasive to the processing equipment, harmless,
biodegradable, renewable, and their mechanical properties can be comparable to those of inorganic fibers
[1,2].Almost more than 30 million metric ton of entire oil palm production in the world and about 8 million metric
ton is empty fruit bunch materials. A viable solution is to combine the petroleum and bio resources (plant and
agriculture stock) to produce a useful product having the requisite cost-performance properties for real world
applications [3].However, the main disadvantage of natural fibers/plastic composites is the poor compatibility
between the mainly hydrophobic polymer-matrix and the hydrophilic fibers. This leads to the formation of a weak
interface, which results in poor mechanical properties; where the stress transfer at the interface between two
different phases is determined by the degree of adhesion. A strong adhesion at the interfaces is needed for an
effective transfer of stress and load distribution throughout the interface. Thus, enhanced interfacial adhesion for
composites containing natural fibers can be achieved either by fiber and matrix modification with chemical/physical
treatments or by use of interfacial additives such as delignition, bleaching and chlorination [4,5,6].
Due to the utilization of chlorine and chlorine derivatives in conventional bleaching processes, large
amounts of chlorinated organic compounds are generated, which presents serious environmental problems.
Therefore, the use of chlorine-free bleaching processes has become increasingly important. A few studies have been
performed on delignication of lignocelluloses materials with alkaline hydrogen peroxide [6, 7,8].
The present paper is focused on study of new fabrication method of fibers by alkaline peroxide treatment.
Within the framework, the role interfacial morphology and exothermal reactions between fiber and biocomposite by
means of Thermogravimetric Analyzer (TGA-DTA) and Scanning Electronic Microscopy (SEM) and influence of
matrix-fibers on the mechanical properties of prepared composite were analyzed.

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World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

MATERIALS AND METHODS

Materials
Homopolymer polypropylene (PP) grade G452 (Melt flow Index 45g/10min, density 0.90g/cm3) was supplied by
MTBE (M) Sdn Bhd, Empty fruit bunch fibers (EFBF) was obtained from Felda Palm Oil Berhad and other
chemicals supplied from Merck.

Methods
Alkaline Peroxide pre-treatment of Empty fruit bunch (EFB)
Generally, first stage is physical treatment where empty fruit bunch was dried minimum three days, then were cut
using hammer mill, crusher machine and was passed through 500 µm seive to obtain uniform size of empty fruit
bunch fiber. After that, untreated fibers were soaked with hot distilled water at 70°C at least for 4-6 hrs to remove
impurities and large particles. Then, fiber was treated with alkaline peroxide by placing about 25 g fibers in 500 ml
Erlenmeyer flask of distilled water containing 15% (w/v) of sodium hydroxide (NaOH) solution. These
delignificated fibers were then soaked and maintained at 75°C about 4 hrs to active the OH group of the cellulose.
The fiber treatment method is commonly known as mercerization [9]. After two hours treatment EFB fibers were
taken out and washed with distilled water. Then, was treated with 2% of hydrogen peroxide (H 2 O 2 ) solution in
water bath at 45°C with a speed of 40 rpm for 8 hour, other the excess NaOH present in treated fiber residue was
neutralized by using 10% (v/v) acetic acid (at room temperature) for 30min. The washings were repeated until
cellulose residue is free from acid. Then, the treated fiber was dried in an oven at 70°C for 48 hours.

Preparation of composite
The compounding of polypropylene with untreated and treated EFB fibers, was carried out using twin screw
compounder Scientific (MODEL: LTE26-40) at 180°C at a roller speed around 50 rpm and pressure about 48 bar. A
composite was molded into tensile and bend test specimen, respectively by using injection molding machine
Toshiba (MODEL: IS 80 EPN) at 190°C. After molding, test specimens were conditioned at 23 ± 2°C, 50 % relative
humidity for at least 40 h according to ASTM D618-99.

Characterization of fiber (EFB)


The Characteristic of fiber was determined by using SEM and TGA-DTA. Surface of fibers before and
after pre-treatment as well as fracture surface of composites was observed with a scanning electron
microscope (SEM) (Model OXFORD). Samples of air-dried cellulose fibers were fixed to a metal-base
specimen holder using double-sided sticky carbon tape and then coated with gold using a vacuum sputter-
coater to make them conductive prior to SEM observation. TGA measurements were carried out using
thermogravitmetric analyzer (TA instruments, TGA Q500). Each specimens weighed about 10mg (±5mg)
at scanning temperature range of 25ºC-600ºC and heating rate of 10ºC/min. TGA was conducted with the
compounds placed in platinum crucible in nitrogen atmosphere at flow rate of 40ml/min to avoid
unwanted oxidation.

Characterization of composite
The mechanical properties of composite were characterized using tensile and flexural tests. The tensile tests were
conducted according to ASTM D638-03 using SHIMADZU (MODEL AG-1) Universal Testing Machine with load
cell of 5 kN, using crosshead speed of 10 mm/min and with a gauge length of 115 mm. Test was performed until
tensile failure occurred. The flexural test was carried out using SHIMADZU (MODEL AG-1) Universal Testing
Machine in accordance with ASTM D790-97 standard. The support was 51 mm while the crosshead speed utilized
was 1.26 mm/min. Eight specimens were tested and at least five replicate specimens were presented as an average of
tested specimens for all tests. These tests were carried out at 25ºC.

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World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

RESULTS AND DISCUSSION

SEM of EFB fibers before and after alkaline pre-treatment


From figure 1(a), it can be seen the roughness surface of lignocelluloses EFB which is residual of lignin. While, by
applying alkaline peroxide treatment, residual lignin was eliminated. Elimination of lignin after pretreatment of
cellulose fiber can be seen as per figure 1(b). Alkaline peroxide of fiber treatment can be improves adhesion,
characteristics by removing surface impurities such as lignin content which it was breakdown the fiber bundles led
increasing of porosity, the effective surface area and surface charge exposed further hydroxyl and carboxyl groups,
thus exposing micro-fibrils which tend better packing of cellulose chain [4, 5]. Furthermore, some researchers
reported on the change in the crystallinity through alkaline treatment on sugarcane [9]. The increase in the
percentage crystallinity index of alkali peroxide treated fibers occurs because of the removal on the cementing
materials, which leads to better packing of cellulose chain [9]. In addition, treatment with NaOH leads to decrease in
the spiral angle, i.e. closer to fiber axis, and increase in the molecular orientation. A fair amount of randomness is
introduced in the orientation of the crystallites due to non-cellulosic matter. Hence, these micrographs were
observed the huge superficial area of cellulosic fibers that can promote better contact with matrix after mixing
process. The SEM micrographs confirmed the chemical modification such as alkaline peroxide treatment and it
influence in morphology aspects of fibers strongly affects the mechanical properties [7,8 ].

a) b)

Figure 1: Fiber surface before (a) and and after (b) pre-treatment

Thermal analysis of EFB fibers before and after alkaline pre-treatment


The thermogravitmetric analysis (TGA) and differential thermal analysis (DTA) plots of untreated and treated EFB
fiber can be seen in figure 2. The onset of thermal degradation can be identified be dramatic decrease in sample
weight and increase in the temperature different due to exothermic combustion reaction taking place. The thermal
degradation of untreated EFB fiber begins around 217.90ºC, while treated EFB fiber starts at around 229.19ºC.
Untreated fiber degrades at lower temperature due to presence of thermally unstable fiber constituents such as
hemicelluloses, holocelluloses and ash, whereas the treated fiber is more stable due to the removal of these
constituents [10,3].

b) a) Untreated Fiber
b) Treated Fiber

a)

Figuer 2 : TGA and DTA of empty fruit bunch (EFB) fiber before (a) and after (b) after pre-treatment

There are interactions between these fractions to identify the multiple exothermic degradation reaction of cellulose,
hemicelluloses and lignins. The maximum decomposition rate of untreated at 268ºC is mainly attributed to the
decomposition of hemicelluloses. The much narrower DTA peaks of treated EFB fiber indicated a more
homogeneous composition containing mostly cellulose, with fewer other decomposition reactions taking place

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World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

which can been seen the large peak at 368ºC. This is likely caused by decomposition of cellulose leading to the
formation and volatilization of levoglucosan and other volatile products [15], attributed to quick devolatilization
reaction [11]. Since the decomposition more stable and large exothermic peak at high temperature of treated EFB
fiber rather than untreated EFB fiber, it can be concluded that alkaline treatment increases the thermal stability of
EFB fibers.

Mechanical Properties
The quality of interfacial bonding is determined by several factors, such as the nature of fiber and polymer
components, the fiber aspect ratio, the processing method and the treatment of the fiber [5, 6]. In the case of PP-
lignocelluloses (EFBF) composite without pre-treatment, adhesion between the two materials was expected to be
rather poor than the PP-lignocelluloses (EFBF) composite with application of treated EFBF. EFBF has polar nature
whereas polypropylene is characterized by non-polar groups. Due to the changes in physical structure it was
expected for treated lignocelluloses (EFBF) to show some changes in the overall properties. The tensile and flexural
modulus properties of composites are presented in table. 1.
Table 1: Mechanical properties of lignocellulose based biocomposite
Tensile Strength (MPa) Flexural Modulus (GPa)
(untreated) (Treated) (Untreated) (Treated)
% fibre (untreated) (Treated) (Untreated) (Treated)
with with with with
MAPP MAPP MAPP MAPP
0 38.0 38.0 38.0 38.0 1.50 1.50 1.50 1.50
10 25.0 30.0 27.0 31.0 1.52 1.82 1.73 1.76
20 26.0 31.0 32.0 32.0 1.69 1.85 1.96 2.14
30 22.0 28.0 33.0 40.0 1.58 1.97 2.15 2.35
40 35.0 26.0 35.0 41.0 1.05 1.68 2.52 3.06
45 11.0 24.0 37.0 43.0 0.76 1.51 2.69 3.47

By applying 100% polypropylene, tensile strength is 38 MPa as benchmark. As per expectation based on table 1, it
can be seen with increase in the filler loading in polymer matrix, PP- EFBF composites were showed a common
phenomenon of decrease tensile strength as shown by conventional lignocelluloses thermoplastic composite [4, 5,
8]. The tensile strength of PP-untreated and treated EFBF composites appeared to have slightly increased as the
filler loading till about 20 wt% about 26MPa and 31MPa respectively, while decrease after above 30 wt% [3].
However, the PP-treated EFBF composite till around 45 wt% loading was still higher by almost 50% enhancement,
24MPa rather than untreated EFBF about 11MPa as per Table 1. With increase of fibers loading, a decrease in
tensile strength was observed. This is due to the introduction of flaws created by fiber ends. These flaws act as stress
concentrations and cause the bond between fibers and matrix to break. When at higher volume fraction, the matrix is
sufficiently restrained and the stress is more evenly distributed led gradually improvement of tensile properties till
they surpass those of the matrix. The corresponding fibers volume fraction at which the strength properties of
composite cease to decline and start to increase is known as critical fiber volume fraction [2]. Hence, the strength of
composites starts to decrease due insufficient filling of matrix materials which can be seen in table 1. Another
explanation is filler incorporation in the polymer matrix caused an interruption in stress transferring along the
applied force. Irregularly shape fillers as in the case EFBF filler, were generally not be able to support stresses
transferred from the polymer and thus weakened the composite material [3, 7].
Modulus (stiffness) is another basic property of composites; the primary intention of filler incorporation is
usually to increase the stiffness of the resultant material. The elastic modulus of bulk natural fibers such as wood
and hemp are about 1.0 ±0.5 GPa [3, 6]. From the table 1, it can be seen modulus of treated composite is better
rather than untreated composite with higher moduli is 2.0 GPa at loading of 30 wt% fiber compared 1.6 GPa.
Nevertheless, it was decreased by increased of filler loading almost 50wt% about 1.5 GPa. This might be due of
weak interfacial bonding between fibers interaction with PP matrix polymer, fibers were not perfectly aligned with
matrix in term of void and dispersion, also degree of molecular orientation of composite was decreased [1,2, 4]. In
contrast, composites prepared with untreated fibers for all set wt% of fiber reinforcement showed matrix failure
followed by fiber fracture and pull out irrespective of increased fiber loading. There are many factors affecting the
modulus of the composites. Those factors are filler content, modulus and aspect ratio. As per expectation, the elastic
modulus of fibers, for instance are expected to increase with increasing degree of molecular orientation. Well-

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World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

oriented cellulosic fibers such as flex have much higher Young’s modulus than fibers with medium orientation, such
as cotton [4, 5].

CONCLUSION

This study showed that pre-treatment of EFB fiber provided better interfacial interaction with polypropylene matrix.
Treated fiber also provided higher thermal stability compared to untreated fiber. The mechanical properties were
also found to be higher with treated fiber composites compared to untreated EFB fiber composites. The tensile
strength and flexural modulus was found to be increased significantly by filler loading till 45 wt% after additional of
coupling agent.

ACKNOWLEDGEMENT

The authors gratefully acknowledge the staffs of Felda Palm Industries Berhad (Felda Lepar Hilir 3), Fiber and
Biocomposite Development Centre (FIDEC) and Polypropylene Laboratory of MTBE (M) Sdn Bhd for their
technical support to carry out this research.

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