Polymer Testing 22 (2003) 335341 www.elsevier.

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Material Properties

Flexural and impact properties of oil palm empty fruit bunch (EFB)polypropylene compositesthe effect of maleic anhydride chemical modication of EFB
H.D. Rozman , M.J. Saad, Z.A. Mohd Ishak
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia Received 22 June 2002; accepted 14 August 2002

Abstract This study focused on the effect of chemical modication of oil palm empty fruit bunch (EFB) ller on the exural and impact properties of EFB-lled polypropylene (PP) composites. EFB ller has been chemically modied with maleic anhydride (MAH). The modication involved the reaction of EFB and MAH (dissolved in dimethylformamide) at 90C. The composites with MAH-treated EFB showed higher exural and impact strength than those with untreated EFB. The modication had signicantly improved the exural modulus and toughness of the composites. This may be attributed to the enhanced adhesion between the MAH-treated EFB and PP matrix, as shown in the scanning electron microscopy (SEM) study. Fourier Transform Infra-Red analysis (FTIR) showed evidence of C=C and C=O groups from MAH at 1630cm 1 and 1730cm 1, respectively. The analysis also showed a reduction of absorption at 1630cm 1 for MAH modied EFBPP composites which indicated the reaction of C=C from MAH with PP. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Oil palm empty fruit bunch; Composite; Chemical modication

1. Introduction Several studies have been carried out to improve the mechanical and physical properties of lignocellulosic lled-thermoplastics composites [13]. One of the areas of interest is the compatibility between lignocellulose ller and thermoplastic matrix. The compatibility and interfacial bond strength between these two components are expected to be poor in this kind of composite. This is due to the difference in nature between lignocellulosic ller and polymer matrix. Lignocellulosics are hydrophillic (contributed by hydroxyl groups in cellulose, lignin and hemicellulose), whereas, thermoplastics such as polypropylene (PP) and polyethylene (PE) are hydrophobic. In spite of the advantages contributed by the lig-

Corresponding author. E-mail address: rozman@usm.my (H.D. Rozman).

nocellulosic materials, the lack of good interfacial adhesion and poor resistance to moisture absorption render the use of lignocellulosic lled-composites less attractive [4]. These problems can be alleviated to some extent by treating the lignocellulosic bres with suitable chemicals. Various chemicals have been employed to enhance the compatibility between the constituent materials, these include maleic anhydride modied-polypropylene [1], poly[methylene (polyphenyl isocyanate) [2], poly (propylene-acrylic acid) and silane [3]. In this research, maleic anhydride (MAH) is used to chemically modify the lignocellulosic bre prior to incorporation with polypropylene (PP). The anhydride group is expected to be sufciently reactive with the hydroxyl groups of lignocellulosic. MAH which is chemically attached to the lignocellulosic surface may serve as a bridge between the former and the PP matrix. This study looks into the effect of MAH modication on the compatibility of EFB and PP and subsequently on the mechanical properties, i.e. exural and impact properties.

0142-9418/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. doi:10.1016/S 0 1 4 2 - 9 4 1 8 ( 0 2 ) 0 0 1 0 9 - 5

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2. Experimental 2.1. Materials EFB in bre form was obtained from Sabutek (M) Sdn. Bhd., Teluk Intan, Perak, Malaysia. PP homopolymer used was purchased from Polypropylene (M) Sdn. Bhd., Malaysia with MFI and density of 12.0 g/10 min and 0.903 g/cm3, respectively. MAH supplied in solid form was purchased from Komita (M) Sdn. Bhd., Penang, Malaysia. 2.2. Methods 2.2.1. Preparation of bre EFB ller was obtained in the form of long strands of bres. The bres were ground into small particles. An Endecotts sieve was used to sieve the ller into three sizes, i.e. mesh 60 (250 m), 80 (180 m) and 100 (150 m.) 2.2.2. Extraction of ller The ller was extracted with a solution mixture consisting of toluene, ethanol and acetone (4:1:1, vol./vol.), for about 3 h. The extracted ller was dried in an oven for approximately 16 h at 105C. 2.2.3. Filler treatment MAH was dissolved in dimethylformamide (DMF) (3:7, vol./vol.), followed by the addition of 5% of hydroquinone (based on the weight of MAH). Approximately 90 g of the extracted ller was placed in a round bottom ask. The solution of MAH was added into the ask with constant stirring and heated at 90C for 1 h. The treated ller was then ltered and rinsed with acetone to remove the unreacted MAH. The ller was then washed by reuxing with fresh acetone for 3 h. The treated ller was dried at 105C for 16 h. The weight percentage gain (WPG) of treated ller was calculated using a formula as given below: WPG (%) W2 W 1 100 W1

lets were placed into a mould with the dimensions of 17.017.00.3 cm. The pellets were preheated for 10 min at 180C followed by hot pressing at the same temperature for another 10 min. Cooling was carried out for 5 min under pressure. 2.3. Testing 2.3.1. Bending test Bending tests were conducted according to ASTM D790. The sheet produced was cut into test samples with dimensions of 1501503 mm (length width thickness). The test was carried out using Universal Testing Machine at a cross-head speed of 4 mm/min. 2.3.2. Impact test Impact tests were conducted according to ASTM D256. The Izod method was carried out using unnotched samples with dimensions of 60153 mm (length width thickness), using a Zwick Impact Pendulum Tester model 5101. 2.3.3. Scanning Electron Microscopy (SEM) study The fracture surfaces of the composite samples were studied with a Scanning Electron Microscope (model Leica Cambridge S-360). The samples were mounted on an aluminum stub using double-sided tape and then goldcoated with a Polaron SEM coating unit to prevent electrical charging during examination. 2.3.4. Fourier Transform Infra Red (FTIR) analysis Fourier transmission infrared spectroscopy (FTIR) analysis was carried out by using a Nicolet FTIR spectrophotometer (Avatar system 360) and KBr method. All spectra were recorded in transmittance in the 4000 400cm 1 range, with a resolution of 4 cm 1. There were 32 scans for each spectrum.

3. Results and discussion Figure 1 shows the FTIR spectra of the untreated and MAH-treated ller. It is clear that there are some differences for the peak at approximately 3420 cm 1, which corresponds to OH stretching vibration. The MAHtreated sample shows a narrower peak as compared to the untreated. The difference may indicate that some changes have occurred as the result of the reaction between MAH and the ller. Dimethylformamide (DMF) which serves as a catalyst for the reaction as well as swelling agent for the lignocellulosic material would have swelled the cell wall and subsequently exposed lignocellulosic OH groups freed from the hydrogen bonding. The difference in the absorption at 3420 cm 1 may be caused by the freed hydroxyl groups which are not reacted with MAH [5]. MAH-treated samples also

where, W1 and W2 represent weight of ller before and after treatment, respectively. 2.2.4. Compounding and processing The compounding of MAH-treated and untreated llers was carried out in a Haake twin-screw extruder (counter-rotating). 2% of dicumyl peroxide (based on the WPG of treated ller) was added during the compounding process. The mixing was carried out at temperatures from 165C to 180C from feeding zone to the die zone, respectively, and with screw speed at 35 rpm. The mixture was then extruded and pelletised. The pel-

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Fig. 1.

FTIR spectra for the untreated and MAH-treated EFB.

showed an increased absorption in the carbonyl (C=O) region (about 1730 cm 1). This is good evidence for the formation of ester linkages as a result of the reaction between MAH and hydroxyl groups from EFB. Notably, MAH-treated samples also show an increased absorption at 1630 cm 1, which may be attributed to the presence of C=C bonds of MAH. Figure 2 shows two spectra, i.e. MAH-treated ller before and after being compounded with PP in making composites. It can be seen that the

peak at approximately 1630 cm 1 shows a signicant reduction in the transmittance. This indicates that the C=C groups of MAH (attached to EFB) may undergo further reaction (in the presence of dicumyl peroxide) upon heating during mixing in the extruder and also during hot-pressing. The opening up of the C=C groups coupled with the abstraction of hydrogen from PP as the result of free radical reaction of dicumyl peroxide may result in the copolymerization of these two components.

Fig. 2.

FTIR spectra for the MAH-treated ller before and after being incorporated with PP.

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Fig. 3. The effect of chemical loading of MAH and ller loading on the exural strength; ller size=mesh 60.

Fig. 5. The effect of chemical loading of MAH and ller loading on the exural strength; ller size=mesh 80.

This in turn would enhance the adhesion between the PP matrix and the EFBmaleic anhydride treated surface. It is known that compatibility, in general, between polymer matrix and reinforcing agent is one of the main criteria to produce a good mechanical characteristic of a composite [610]. Hence, the increased adhesion brought by the C=C groups reaction with the PP matrix, together with other means of enhancing compatibility such as Van der Waals interaction, should be reected in the mechanical properties, which will be discussed later. The effects of MAH chemical modication of EFB ller on the exural properties of the EFBPP composites are shown in Figs 3 and 511. Generally it can be seen that, irrespective of the ller loading, the exural strength increases with the increase of MAH chemical loading on the EFB surface (Fig. 3). The results show that as more and more surface is covered with MAH, the exural strength is increased. This indicates that the modication of EFB with MAH has enhanced the efciency of stress transfer from the matrix to the EFB. This may come about as the result of better bridging

Fig. 6. The effect of chemical loading of MAH and ller loading on the exural strength; ller size=mesh 100.

Fig. 7. The effect of chemical loading of MAH and ller loading on the exural modulus; ller size=mesh 60.

Fig. 4. Schematic illustration of the reactions involved in producing the MAH-treated EFBPP composite.

between these two components at the interfacial region. The bridging may be formed either by Van der Waals interaction or a covalent bond between MAH and PP. Covalent bonding between MAH which is attached to EFB and PP could be possible through the opening of C=C groups in MAH through radical reaction of dicumyl peroxide, as indicated by the reduction of peak at 1630 cm 1, designated for C=C groups in FTIR spectra in Fig.

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Fig. 8. The effect of chemical loading of MAH and ller loading on the exural modulus; ller size=mesh 80.

Fig. 11. Flexural toughness of composites vs. chemical loading of MAH at different ller loading and ller size of mesh 80.

Fig. 9. The effect of chemical loading of MAH and ller loading on the exural modulus; ller size=mesh 100.

2. The possible mechanism is illustrated in Fig. 4. The SEM study, which will be discussed later, shows clear evidence that the adhesion at the interfacial region is enhanced as the result of MAH treatment of the surface. Figure 3 also depicts the effect of the ller loading on the exural strength. The strength of the composites decreases as the ller loading of EFB is increased. The

same trend has also been observed from previous studies [68]. The irregularity in shape and low aspect ratio of the EFB ller may affect their capabilities to support stress transmitted from the PP matrix. The effect will be amplied if the proportion of EFB is increased. The same behaviour on the exural strength is also displayed for llers with sizes of mesh 80 (Fig. 5) and 100 (Fig. 6). Inspection of Fig. 7 shows that composites with MAHtreated ller display signicantly higher modulus than those with untreated ller (0 WPG). The modulus increases as the WPG is increased. This indicates that the increased adhesion at the interfacial region may increase the stiffness of the composites. The same trend has also been observed for the samples with llers with particle sizes of mesh 80 (Fig. 8) and 100 (Fig. 9). Generally exural modulus increases as the percentage of the ller is increased. This is expected, because the inherent stiffness of the EFB ller may positively contribute to the overall stiffness of the composite. The results show that the exural toughness increases as the WPG is increased (Fig. 10). Thus, it indicates that MAH-treatment has enabled the compatibility between the polar functional groups of EFB and non-polar PP to

Fig. 10.

Flexural toughness of composites vs. chemical loading of MAH at different ller loading and ller size of mesh 60.

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Fig. 12. Flexural toughness of composites vs. chemical loading of MAH at different ller loading and ller size of mesh 100.

Fig. 15. The effect of chemical loading of MAH and ller loading on the impact strength; ller size=mesh 100.

Fig. 13. The effect of chemical loading of MAH and ller loading on the impact strength; ller size=mesh 60.

be improved. The results also demonstrate a similar trend for samples with ller of mesh 80 (Fig. 11) and 100 (Fig. 12). As expected, the exural toughness decreases as the ller loading is increased. The explanation is similar to that given for exural strength. Impact strengths of the MAH-treated samples are signicantly higher than those with untreated llers (Figs

1315). This may be as the result of better bridging formed by the MAH and PP. As expected, as shown by many studies [68], the impact strength decreases as the amount of lignocellulosic ller is increased. The explanation is similar to that presented on the exural properties. Figure 16 shows the micrograph of a composite with untreated EFB. It is clear that the adhesion at the interfacial region is rather poor. However, for samples with MAH-treated llers (Fig. 17), better adhesion is detected, i.e. in the form of a more cohesive interface between the matrix and EFB, and a nicely embedded MAH treated ller in the matrix. Thus, these results serve as clear evidence that the compatibility between the EFB and PP is signicantly enhanced upon reaction of the former with MAH.

Fig. 14. The effect of chemical loading of MAH and ller loading on the impact strength; ller size=mesh 80.

Fig. 16.

Micrograph of composites with untreated ller.

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Acknowledgements The authors would like to thank the Ministry of Science, Technology and Environment (MOSTE) and Universiti Sains Malaysia, Penang, for the IRPA grant that has made this research work possible.

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Fig. 17. Micrograph of composites with MAH-treated ller.

4. Conclusions Evidence of MAH reaction with EFB has been observed from FTIR analysis with the emergence of peaks characteristic of MAH in the EFB llers. Composites with MAH-treated ller displayed higher exural and impact properties. SEM showed evidence of better adhesion and compatibility between the EFB and the PP matrix as the result of chemical modication of the former with MAH.