Composites Science and Technology 63 (2003) 12551258 www.elsevier.

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An investigation on the processing of sisal bre reinforced polypropylene composites

K.L. Funga, X.S. Xinga, R.K.Y. Lia,*, S.C. Tjonga, Y.-W. Maib
a

Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong b Department of Manufacturing Engineering and Engineering Management, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong Accepted 21 February 2003

Abstract In this paper, a pre-impregnation technique has been introduced for the injection moulding of sisal bre reinforced polypropylene (PP/SF) composites. The major advantasge of the pre-impregnation technique is that the PP/SF composites can be injection moulded with relatively lower barrel temperature, and therefore signicant thermal degradation of the sisal bres could be avoided. The resulting injection mouldings possessed lighter colour and no odor. # 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Sisal bre; Polypropylene; A. Short-bre composites; B. Interface; E. Injection moulding

1. Introduction Polymer matrix composites using natural plant bres as reinforcement has attracted a lot of interest in recent years. The main reasons are that these natural bres can be harvested from renewable resources, possess long aspect ratio for ecient stress transfer, and certain aspects of their mechanical properties are comparable to existing inorganic glass bres. With these plant bres, sisal, jute, ax, hemp, banana and coconut have attracted particular attention [17]. Early research studies on natural plant bre reinforced composites have been focused on thermosetting matrix composites, and detailed references can be found in two recent review articles [2,3]. For fabrication of thermosetting matrix composites, matrix impregnation into the reinforcing bres is facilitated by the low viscosity of the uncured resin. Furthermore, if low cure temperature resin is used, the matrix can be cured without causing thermal degradation to the reinforcing natural bres. Thermoplastics are alternative candidate matrix materials that possess a number of obvious advantages over thermoset matrices. These include shelf-life, post* Corresponding author. Tel.: +852-2788-7785; fax: +852-27887830. E-mail address: aprkyl@cityu.edu.hk (R.K.Y. Li).

forming, toughness and recycling considerations. Polypropylene (PP) is a thermoplastic matrix material that received attention for the production of natural bre reinforced thermoplastic composites [5,711]. Concerning injection moulding of sisal bre reinforced polypropylene (SF/PP) composites, the problems encountered are (i) increased melt ow viscosity as sisal bres were introduced [8,11]; and (ii) poor interfacial bonding between sisal bre and PP. To overcome the high melt viscosity of the SF/PP composites, high injection temperature is needed. The elevated injection temperature can cause severe thermal degradation of the reinforcing sisal bres. This gives rise to the darkening colour and odor emission of the moulded SF/PP composites. To overcome the poor interfacial bonding between sisal bre and PP, a number of bre pre-treatment techniques, such as alkaline treatment, heat treatment, and coupling agent treatment are possible solutions. However, some studies have indicated that maleic anhydride can serve as an eective compatibilizer for cellulosic bre and polyolen matrices [1113]. By using a maleic anhydride grafted polypropylene (MA-gPP) as the compatibilizer for SF/PP composites, the melt blending torque could also be reduced [11]. The above observations point to the possibilities of using MA-g-PP as a compatibilizer and processing aid for SF/ PP composites.

0266-3538/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0266-3538(03)00095-2

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The main objective of this study is to introduce a new technique of applying MA-g-PP as a compatibilizer for the injection moulding of SF/PP composites.

2. Experimental method Isotactic polypropylene (PP, grade Pro-fax 6331, Montell) was used as the matrix, and maleic anhydride grafted polypropylene wax (MA-g-PP, grade Epolene G-3003 WAX, Eastman Chemical) was used as the compatibilizer in this investigation. The sisal bres used were obtained from a local supplier in P.R. China (Huari Natural Fibre Products Co., Ltd.). Sisal bres with diameter ranging from 100 to 200 mm were supplied as a roll of sisal bre yarns. The thermal degradation behaviour of the sisal bres was characterized using a Seiko thermal gravimetric analyser (model SSC/5200) under pure helium and helium/oxygen (50/50 ratio) gas ow conditions. The weight loss against temperature plots were measured at a heating rate of 5  C/min. Injection moulded ASTM type-I dumb-bell shaped tensile bars were tested using a universal tensile tester (Instron model 4206). A clip-on extensometer was used to measure the tensile strain to give accurate measurements for the calculation of Youngs modulus.

diameter was EXIT=3 mm. MA-g-PP was extruded by the extruder (the extruder screw rotated at a speed of 1 rpm) and came to intimate contact with the dry sisal bre yarns (which were pulled at a speed of 5 mm/min). The temperature settings for the four temperature control zones of the extruder were:     Zone Zone Zone Zone 1=175 2=170 3=120 4=100
 

C; C;  C;  C;

3. Sample preparation To prepare the materials for injection moulding, a pre-impregnation process was developed in our laboratory. Before processing, sisal bre and MA-g-PP were dried in an air-circulating oven at 80  C for 24 h. In the pre-impregnation process, dry sisal bre yarns were fed into a special die assembly (Fig. 1), which was connected to a Brabender single screw extruder. The die assembly consisted of an inlet die, an exit die, and the connector for the two dies. In the process, it was observed that to achieve good impregnation, a larger inlet die diameter had to be used. The inner diameter for the inlet die was INLET=5 mm, and the exit die inner

with Zone 1 being nearest to the die assembly, and zone 4 being nearest to the hopper. Due to the strong wettability between MA-g-PP and sisal bres, the sisal bres were now well impregnated with MA-g-PP as they were drawn out from the exit of the die assembly. Fig. 2 shows the cross-sectional view of a MA-g-PP/sisal bre pre-preg. It can be seen that the sisal bres were well coated by MA-g-PP. The MA-g-PP/SF pre-pregs were cut into 5 mm long pellets. These pellets were then dry mixed with PP homopolymer pellets in a ratio such that the sisal bre content was kept at 10 wt.%. The two types of pellets were then melt blended using the Brabender single screw extruder with the same temperature settings as described earlier. The extruded PP/MA-g-PP/SF extrudate was again cut into 5 mm long. These diluted PP/MA-g-PP/ SF pellets were then injection moulded into ASTM type-I tensile bars. Using the current pre-impregnation technique, it has been found that the PP/MA-g-PP/SF pellets could be injection moulded at a temperature setting as shown below:  Zone 1=180  C;  Zone 2=180  C;  Zone 3=170  C;

Fig. 1. Experimental setup for the impregnation of sial bre yarns with MA-g-PP.

Fig. 2. SEM micrograph showing the cross-section of the MA-g-PP/ sisal bre pre-preg.

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with Zone 1 being the heating zone nearest to the injection nozzle, and zone 3 nearest to the hopper. Specimen injection moulded using this temperature prole will be called LT (for low temperature) specimens. The PP/MA-g-PP/SF pellets were also injection moulded using the following temperature prole, which was used in our previous study on the injection moulding of PP/SF composites [11]:  Zone 1=200  C;  Zone 2=210  C;  Zone 3=190  C. Specimens injection moulded using this temperature prole will be called HT (for high temperature) specimens.

4. Results and discussions The stability of sisal bres under high melt processing temperature is of major concern. If serious degradation of the sisal bres took place during melt processing of the composites, the mechanical reinforcement eects of the sisal bres would be lost. This will also give rise to darkening of the composite and giving out serious odour that persists for a long time. Thermal gravimetric analysis (TGA) was employed to study the high temperature decomposition characteristics of the sisal bre under helium and helium/oxygen atmosphere as shown in Fig. 3. Decomposition of the sisal bre in helium atmosphere is a two-stage process as indicated by the two peaks (  295 and 350  C, labelled as A and B, respectively) in the DTG curve. According to Albano et al. [14], the rst decomposition peak (A, 295  C) is due to the thermal depolymerization of hemicellulose and the glycosidic linkages of cellulose. The second decomposition peak (B, 350  C) is due to cellulose decomposition. The decomposition behaviour is modied

slightly when measured under a helium/oxygen atmosphere. The two decomposition processes (which were labelled as A* and B* in order to identify with the two processes A and B, respectively) occurred at reduced temperatures in the presence of oxygen. It is believed that the two processes A* and B* are similar in nature to the two processes A and B, but are both accelerated due to the presence of oxygen. As presented in Section 3, two injection moulding temperature zone settings were used. For HT specimens injection moulded at 210  C serious darkening and the emission of empyreuma odor occurred. The odor stayed for a few months without disappearing. In contrast, the LT specimens injection moulded at 180  C were light in colour and without odor. Fig. 4 compares the appearance of the specimens moulded using the high and low temperature settings. In our previous study [11], the sisal bre reinforced PP composites without MA-g-PP addition could not be injection moulded using the injection moulding machines in our laboratory with barrel temperature setting below 210  C. With the addition of sisal bres into the PP matrix, the increased melt shear viscosity can only be overcome by increasing the moulding temperature. Hence thermal degradation of the sisal bres was unavoidable. With the introduction of the pre-impregnation technique in this study, the sisal bre yarns were coated by MA-g-PP. The MA-gPP used was a low molecular weight PP grafted with maleic anhydride. It functioned as a wax lubricant to enhance the ow and dispersion of the SF inside the PP matrix. Therefore a much lower moulding temperature can be used. This solved the problem of the darkening colour and odor emission. Thin sections were cut from HT and LT tensile bars and compressed into thin lms on a hot-plate. From Fig. 5a, it can be seen that the sisal bres in HT specimens have darkened colour, while the sisal bres inside LT specimens have much lighter colour (Fig. 5b). The darkened sisal bers caused the dark colour of the injection moulded HT tensile bars. Hence, higher injection moulding temperature setting (210  C) plus the possibility of frictional heating caused the thermal depolymerization of hemicellulose and the glycosidic linkages of cellulose [14]. From the TGA measurements, these processes started at about 230  C irrespective of the atmospheric conditions.

Fig. 3. TGA and derivative of the TGA (DTG) curves for untreated sisal bres under helium and helium/oxygen atmosphere.

Fig. 4. Tensile bars injection moulded using the high temperature (HT) and low temperature (LT) settings.

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work, the technique can be modied by using MA-g-PP/ PP blends in the pre-impregnation process. This modication will have the advantage of lowering production cost (MA-g-PP is more expensive) and controlling the degree of interfacial adhesion.

Acknowledgements The work described in this paper was supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. Cityll 1033/99E).

References
[1] Joseph K, Thomas S, Pavithran C. Eect of chemical treatment on the tensile properties of short sisal bre-reinforced polyethylene composites. Polymer 1996;37:513949. [2] Bledzki AK, Gasssan J. Composites reinforced with cellulose based bres. Prog Polym Sci 1999;24:22174. [3] Li Y, Mai Y-W, Ye L. Sisal bre and its composites: a review of recent developments. Comp Sci Technol 2000;60:203755. [4] Satyanarayana KG, Sukumaran K, Mukherjee PS, Pavithran C, Pillai SG. Natural Fibre-Polymer Composites. Cement & Concrete Comp 1990;12:11736. [5] Hornsby PR, Hinrichsen E, Tarverdi K. Preparation and properties of polypropylene composites reinforced with wheat and ax straw bres: part II. Analysis of composite microstructure and mechanical properties. J Mater Sci 1997;32:100915. [6] Hepworth DG, Hobson RN, Bruce DM, Farrent JW. The use of unretted hemp bre in composite manufacture. Composites Part A 2000;3:127983. [7] Rozman HD, Tan KW, Kumar RN, Abubakar A, Mohd Ishak ZA, Ismail H. The eect of lignin as a compatibilizer on the physical properties of coconut ber-polypropylene composites. Eur Polym J 2000;36:148394. [8] Joseph PJ, Joseph K, Thomas S. Eect of processing variables on the mechanical properties of sisal-ber-reinforced polypropylene composites. Comp Sci Technol 1999;59:162540. [9] Vazquez A, Dominguez VA, Kenny JM. Bagasse Fiber-Polypropylene Based Composites. J Thermo Comp 1999;12:47797. [10] Ichazo MN, Albano C, Gonzalez J, Perera R, Candal MV. Polypropylene/wood our composites: treatments and properties. Comp Struct 2001;54:20714. [11] Fung KL, Li RKY, Tjong SC. Interface modication on the properties of sisal bre reinforced polypropylene composites. J Appl Polym Sci 2002;85:16976. [12] Tjong SC, Xu Y, Meng YZ. Composites based on maleated polypropylene and methyl cellulosic ber: Mechanical and thermal properties. J Appl Polym Sci 1999;72:164753. [13] Li TQ, Ng CN, Li RKY. Impact behavior of sawdust/recycledPP composites. J Appl Polym Sci 2001;81:14208. [14] Albano C, Gonzalez J, Ichazo M, Kaiser D. Thermal stability of blends of polyolens and sisal ber. Polym Degrad Stab 1999;66: 17990.

Fig. 5. Photographs showing the degradation (and the related darkening) of the sisal bres in the tensile bars injection moulded with (a) high temperature (HT); and (b) low temperature (LT) settings.

The tensile properties for PP, HT and LT specimens are compared in Table 1. It can be seen that the incorporation of 10 wt.% of sisal bres increases Youngs modulus by about 150%, and the tensile strength was increased by about 10%. The reinforcement eciency for LT specimens is slightly higher than HT samples. The major advantages of the pre-impregnation technique introduced in this work include the reduction of injection moulding temperature, and improved interfacial bonding between sisal bre and PP matrix. The lower injection moulding temperature used imparts lighter colour and odorless mouldings. As for future