American Journal of Applied Sciences (Special Issue): 34-39, 2005 ISSN 1546-9239 2005 Science Publications

Tensile Behavior and Morphological Studies of TPNR-KF-CF Hybrid Composite

H. Anuar, S. H. Ahmad, R. Rasid and S. Zakaria School of Applied Physics, Faculty of Science and Technology University Kebangsaan Malaysia, 43600 Bangi, Selangor Darul Ehsan, Malaysia
Abstract: Synergistic effect on hybrid system of thermoplastic natural rubber (TPNR)-kenaf fiber (KF)-carbon fiber (CF) was investigated. It was found that tensile strength reduced drastically with the incorporation of KF. However, the domination of KF content prior to CF directing to the enhancement of tensile modulus of the hybrid. It was also found that hybridization of 50:50 CF to KF has yield in lower cost and moderate loss in tensile property. In order to enhance the tensile property of the hybrid, fibers were treated with the used of MAPP on KF and sulfuric acid surface treatment on CF. However, the treatment applied resulted in rather poor tensile strength and low Youngs modulus. From the morphological observation, it was clearly seen that KF cross-section is not uniform as compared with synthetic CF. Both fibers were randomly orientated. Oxidative treatment via sulfuric acid had roughened the CF surface and pittings were clearly observed. Key words: Hybrid composite, carbon fiber, kenaf fiber, tensile properties INTRODUCTION Hybrid composites have proven to create a balance effect within the fibers incorporated. The types of fibers can be natural fibers or man-made based synthetic fibers. There are many reported studies on hybridization of natural fiber-natural fiber, natural fiber-synthetic fiber and synthetic fiber-synthetic fiber in a single matrix[1-7]. Yet it is hard to find in open literature or more or less none attempt on the combination of natural fiber-short carbon fiber reinforced thermoplastic. The used of carbon fiber is popular especially in high-end applications due to its superiority and excellent properties. The used of carbon fiber in the composite system is more effective, more dominated and resulted in better mechanical properties as compared to the used of glass fiber. Basically, PAN (polyacrylonitrile) based carbon fiber consists of graphitic layer planes which are chemically stable and inert. Unfortunately, this layer will potentially reduce the possible chemical bonding in between fibers and the polymer matrices. Thus surface treatment is believed to increase surface roughness and producing pits to enhance the adhesion in between fibers and the matrix[8-9]. Recently, lignocellulosic fiber such as kenaf bast fiber has gaining much attention in the making of composite material. The fibers are normally blends with thermoplastic materials. The primary advantages of lignocellulosic fibers are its low densities, non abrasiveness, and biodegradable[10]. In spite of the abovementioned advantages, there are some disadvantages of using the lignocellulosic fibers. This is due to its low processing temperature permitted (up to
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200C), thus limit the type of thermoplastic that can be blend with natural fibers. The second drawback is the high moisture contents[10]. Matrix based on polymer is popular due to its simple fabrication process. The polymer, either thermoplastic or thermoset can be fabricated at low processing temperature[11]. Incorporation of short fibers into thermoplastic materials can impart greater strength and stiffness to the polymeric matrix. The mechanical properties of short fiber composites are governed by length to diameter ratio, fiber orientation and fibermatrix interaction[12]. The applied load is transmitting between matrix and fiber through the interphase[13-14]. The mechanical behavior of composite materials reflects the interactions between the elements. This study discuss the effect of oxidative surface treatment of short carbon fiber, the effect of compatibilizer agent on kenaf fiber and the effect of fiber loading at various fraction of CF to KF on the tensile properties of the TPNR. The morphological analysis of the tensile fractured samples will also be discussed. MATERIALS AND METHODS Kenaf bast fiber (KF) was obtained from MARDI, Serdang. PAN type carbon fiber (CF) was procured from Toray, Japan with 6 mm in length. Polymers used were SMR-L grade natural rubber (NR) purchased from Rubber Research Industries Malaysia with density of 0.92 g cm3, polypropylene (PP) with density of 0.905 g cm3 was supplied by Polipropilinas (M) Sdn. Bhd. and maleic anhydride polypropylene (MAPP) with density of 0.95 g cm3 was from Alderich Chemical Co.

H. Anuar ,School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor Darul Ehsan, Malaysia. Phone: ++6019-2605527

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Am. J. Applied Sci., ., (Sp. Issue): 34-39, 2005 Chemicals used were sodium hydroxide and sulfuric acid supplied by MERCK, Germany, liquid natural rubber (LNR) was synthesis using photochemical oxidation technique on natural rubber in our laboratory[15]. Kenaf fiber preparation: Kenaf bast fibers were flakes and then sieved at 300 m to 500 m aperture sizes based on the optimum tensile results. The density of the kenaf fiber was measured to be 1.13 g cm3 and the moisture content was 4.1%. Carbon fiber treatment: Sulfuric acid surface oxidative treatment was employed on carbon fiber. Firstly sulfuric acid of 1M concentration was heated to 70oC. This is followed by soaking the fibers into the acid solution for 90 min. Reflux of the carbon fiber was later followed using 1M sodium hydroxide for 60 min. Then, the carbon fibers were re-soaked in distilled water for subsequent 5 days. Finally, rinsing of carbon fibers were carried out using distill water and later dried for 3 hours at 110oC. The dried carbon fibers were kept in a dessicator to minimize the moisture content prior to use[16]. Thermoplastic natural rubber matrix preparation: Thermoplastic natural rubber (TPNR) was melt blended using an internal mixer, Thermo Haake 600p. The mixtures of NR, LNR and PP at ratio of 20:10:70 were used in this work. The blending was carried out at 175oC and a rotor speed of 40 rpm for 12 min. Hybrid composite preparation: TPNR-KF-CF hybrid composite was prepared using the same internal mixer. Prior to mixing, the TPNR and KF were pre-mixed at various loading compositions. MAPP was pre-mixed together with TPNR and KF whenever the used of coupling agent required. TPNR and KF were allowed to mix for 5 min before CF was charged into the mixer. Based on optimum processing parameters determination, the mixing was carried out at 175oC for 12 min at a rotation speed of 9 rpm. The compound was compression moulded into a dumbbell shape for 16 min. Composite characterization: Tensile property was measured using Testometric 350 according to ASTM D638 at crosshead speed of 50 mm min1. The gauge length was 70 mm. 5 samples were tested for each compositions and a mean of these samples were taken for stress and strain calculations. The tensile fractured surfaces of the composites with overall fiber content of 15% were observed under scanning electron microscope (Philips XL 30). RESULTS AND DISCUSSION Untreated hybrid of TPNR-KF-CF composite: Figure 1 shows tensile strength of untreated hybrid TPNR-KF-CF composites. It is clear from the graph 35
40 35 30 25 20 15 0/100 30/70 50/50 70/30 100
Ratio of KF/CF (%)

TPNR = 18.8 MPa

Tensile Strength (MPa)

5%

10%

15%

20%

Fig. 1: Effect of KF loading on tensile strength

1000 Tensile Modulus (MPa) 900 800 700 600 500 400 300 0/100 30/70 50/50 70/30 100/0 Ratio of KF/CF (% ) 5% 10% 15% 20% TPNR = 315 MPa

Fig. 2: Effect of KF loading on tensile modulus that the incorporation of CF resulted in the highest strength of composite up to 10% fiber loading. By making comparison at 10% fiber loading, an addition of KF, even at lower fraction will reduced the tensile strength. From the Fig. 1, single type of KF composite shows 39% reduction in tensile strength compared to single type of CF composite. However composite of 50:50 ratio of KF:CF shows only 6% dropped in strength than single type CF composite. Thus, this show synergistic effect at partial replacement of KF/CF. This has a close agreement with Rozman et al.[1] work on hybrid PP reinforced oil palm empty fruit bunch-glass fiber whereby the hybrid strength decreases as natural fiber content increases. However at higher loading (20% fiber loading), the inconsistency and fluctuation of tensile strength occurred. This could be related to fiber agglomeration and localized from uneven fibers distribution. These tend to reduces fibers-matrix interaction. In the end, it may creates stress concentration area. Studies by Maya Jacob et al.[4] reported that the fibers has a tendency to agglomerate and limits a stress transfer from the

Am. J. Applied Sci., ., (Sp. Issue): 34-39, 2005

40 Tensile Strength (MPa) 35 30 25 20 15 0/100 30/70 50/50 70/30 100/0 Ratio of KF/CF (% ) 5% 10% 15% 20% TPNR = 18.8 MPa

Fig 3: SEM micrograph of 70CF/30KF

Fig. 6: Effect of KF loading on tensile strength

1000 Tensile Modulus (MPa) 900 800 700 600 500 400 0/100 30/70 50/50 70/30 100/0 Ratio of KF/CF (% ) TPNR = 315 MPa

Fig. 4: SEM micrograph of 50CF/50KF

5%

10%

15%

20%

Fig. 7: Effect of KF loading on tensile modulus varied between 24 to 102. These might be the caused that contributes to the failure in tensile strength which denoted as reduction in strength. Unlike uniform synthetic fibers, irregularly shaped of fillers, their capability to support stress from matrix is rather poor. Studied agreed with Rozman et al. where the effect is obvious at higher KF loading. The micrographs also show that there are no interaction in between fibers and matrix. This could be explained by the incompatibility of the interfacial region due to hydrophobic nature of TPNR matrix and hydrophobic nature of KF. Treated hybrid of TPNR-KF-CF composite: The effect of fiber loading, the effect of surface treatment on carbon fiber and coupling agent on kenaf fiber on tensile strength and Youngs modulus of hybrid TPNR composite are shown in Fig. 6-7. From the Fig. 6, single type CF composite shows the highest tensile strength. The highest strength was obtained at 10% carbon fiber loading. Higher loading of CF leading to reduction in tensile strength. At 20% CF treated composite, the dropped in strength is almost 29% compared to the maximum strength achieved. As compared to untreated CF composite, the improvement was 11%. By comparing Fig. 1 and 6, the optimum tensile strength 36

Fig 5:

SEM micrograph of 30CF/70KF

matrix to the fibers. In this study, the value of strain obtained is too low and thus ignored. Figure 2 illustrates the tensile modulus with various composition of kenaf loading in KF/CF hybrid TPNR composite. The incorporation of kenaf fiber has imparted greater stiffness to the composite, but the value declined at higher fraction of kenaf fiber. The higher value of Youngs modulus seems to be influenced by the single fiber stiffness[2, 4]. From the SEM micrographs in Fig. 3-5, it can be observed that kenaf fiber shows non-uniform crosssection. The length to diameter ratio measured were

Am. J. Applied Sci., ., (Sp. Issue): 34-39, 2005 and the minimum values, treated CF composite showed higher than the untreated CF composite which were 29 and 11% respectively. This shows that fiber loading plays great influence over the tensile properties of treated CF composite. The increased in strength of the composite is mainly attributed to the sulfuric acid surface treatment applied. It can be observed from the SEM micrograph shown in Fig. 8-9, that the treatment applied on CF has roughened the fiber surface due to etching activities. This is in agreement with Wu et al.[16] on the CF treated nitric acid. Interpenetrated irregularities surface and molecular contacts may lead to mechanical interlocking mechanism when incorporated with polymer matrix[13]. Besides, it were reported that the oxidative treatment may also remove of weak surface layer, alter the chemical nature of the surface by reducing wetting or increase possibility of hydrogen or covalent bond[17]. reduced tensile strength by almost 11%. Again by comparing Fig. 1 and 6, the gap between the optimum tensile strength achieved and the minimum values of treated KF composite showed higher than the untreated KF composite which were 15 and 4% respectively. Thus this shows that fiber loading plays great influence on the tensile properties of treated KF composite. Maleic anhydride polypropylene have long been used as a coupling agent to improve the mechanical properties of wood-polymer materials[18-20]. The effect of maleated polypropylene on the strength of wood fiber-polypropylene have been attributed to the esterification reaction between hydroxyl group of wood fiber and anhydride functionality of maleated polypropylene. Figure 10 illustrated the hypothetical model of mechanism takes place[21]. Due to esterification reaction, the lignocellulosic became more hydrophobic and thus improved the compatibility interphase and reduced wetting[22]. Although the used of coupling agent has improved the tensile strength of single type of KF composite, it is noted in Fig. 6 that the present of KF and MAPP has reduced tremendously the strength of the treated hybrid composite. This is clearly demonstrated at 30:70 of KF:CF ratio, where the strength dropped up to 34 and 10% overall fiber content (as compared to CF composite). However, further increased in KF fraction does not significantly affect the treated hybrid tensile properties. However, the tensile strength declined at higher fiber loading. This could be explained as the reaction occurred between the MAPP and carbon fibers. Generally the treatment applied had contributed to the negative effect on the hybrid TPNR-KF-CF composite. This may be due to three mechanism postulated. Firstly may be attributed to the roughened surface. It is assumed that maleic anhydride is converted into maleic acid due to moisture and the entrapped water. The acid may react with CF and thus created more pores and might enlarge the pores sizes, simultaneously reduced the fiber diameter. It was reported that extremely exposed to acid may somehow degrade the CF which lead to lower in strength[23]. Secondly it might be due to the induction effect which involved - on carbon fiber pores and - charge from the chain breakage of maleated PP that attached to cellulose on KF. But this effect is true only if the moisture content of the carbon fiber is high. Thirdly is different in polarity. This mechanism is due to the excessive carboxyl content. It is expected there were formation of dicarboxyl acid. The first esterification was between KF hydroxyl group and anhydride on maleated PP. The second carboxyl group present due to OH- from moisture or water content entrapped during fabrication process. These possibilities will be further investigated to identify the actual mechanism occurred. From the SEM micrograph observation, formation of voids at the end of KF pull-out are clearly demonstrated 37

Fig. 8: Carbon fiber before treatment

Fig. 9: Carbon fiber after 90 min sulfuric acid treatment On the other hand, for treated KF composite, the addition of MAPP plays great influence over the tensile properties. From Fig. 6, at 15% KF loading the tensile strength improved 21% compared to the samples without addition of MAPP. Further increased of KF has

Am. J. Applied Sci., ., (Sp. Issue): 34-39, 2005

Fig. 10: Hypothetical model of esterification reaction[22] and does not exhibit any interaction between fiber and matrix. The addition of MAPP should serve as a bridge and thus enhanced fiber-matrix bonding. As for carbon fiber, perhaps most of the interaction are due to the rugosity and pitting formation. Besides the non-uniform size of KF, aspect ratio, and random orientation of both fibers may further affected the mechanical performance of the composite. CONCLUSION It can be concluded, that for the untreated composites, the tensile strength and modulus were in the order of CF>hybrid KFCF>KF composites. However, in treated composites, the trend were CF>KF>hybrid KF-CF composites. The addition of MAPP to KF and sulfuric acid surface treatment on CF reduced the tensile properties. There are no significant improvement in treated hybrid systems. The effect of fiber loading was amplified in treated single type carbon fiber and kenaf fiber composite. In contrast there was no improvement due to fiber loading in treated hybrid system. From the SEM micrograph observation, cross-section of KF was irregular and orientation of both fibers were random. It is observed there is no fibermatrix interaction in untreated hybrid composite, but matrix was adhered to CF in treated hybrid composite and formed a void at the end of KF pull-out. It is postulated either of three mechanism could happened, which were mechanical interlocking, inductive effect or polarity differences. ACKNOWLEDGEMENT The author wish to thank to International Islamic University Malaysia, Public Services Department, National University of Malaysia, 09-02-02-0074 grant under Ministry of Science & Technology and Yayasan Felda for the financial support in making this study success. 38

Fig. 11: SEM micrograph of 70CF/30KF

Fig. 12: SEM micrograph of 50CF/50KF

Fig. 13: SEM micrograph of 30CF/70KF

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