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C. K. Hong1, N. Kim2, S. L. Kang2, C. Nah*2, Y.-S. Lee3, B.-H. Cho4 and J.-H. Ahn5
The effect of maleic anhydride (MA) modification of jute fibre on the mechanical properties of jute/ polypropylene (PP) composites was studied. Jute fibre, an environmental friendly, low-density renewable material was chemically modified with MA before the incorporation with PP to improve interfacial adhesion between them. Fourier transform infrared (FTIR) study showed that the C5C groups of MA attached to jute cellulose reacted with the PP matrix. Jute fibre/PP composite treated with MA displayed higher Youngs modulus and dynamic storage modulus owing to the enhanced interfacial adhesion between the fibre and PP matrix. A scanning electron microscopy (SEM) study showed evidence of the enhanced adhesion and bridging in the interfacial region of the composite as the result of MA modification of jute fibre.
Keywords: Jute fibre, Polypropylene, Maleic anhydride
Introduction
As a result of the increasing demands for environmentally friendly materials and the desire to reduce the cost of traditional bres, bio-composites reinforced with natural bres have been developed.1,2 Natural bres such as banana, cotton, coir, sisal and jute have attracted the attention of scientists and technologists for applications in consumer goods, low-cost housing and other civil structures.3 Natural bres exhibit many advantageous properties as reinforcement for composites. They are lowdensity materials yielding relatively lightweight composites with high specic properties. Natural bres also offer signicant cost advantages and benets associated with processing, as compared with synthetic bres. Also, they are highly renewable resources, which reduce the dependency on petroleum oil. One difculty that has prevented a more extended utilisation of natural bres is the lack of a good adhesion to most polymeric matrices.4 The hydrophilic nature of natural bres adversely affects adhesion to a hydrophobic polymer matrix and, as a result, it may cause a loss of strength. The inherent high moisture sorption of natural bres brings about dimensional changes in the composites. Decient adhesion leads to a weak load transfer from the matrix to the bres, and this, in turn, induces a low reinforcing effect. The mechanical properties of a bre-reinforced polymer composite depend not only on the properties of constituents, but also on the
School of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, South Korea BK-21 Polymer BIN Fusion Research Team, 3Division of Chemical Engineering, Nanomaterials Processing Research Center, 4Jeonbuk Cancer Center, Chonbuk National University, Jeonju 561-756, South Korea 5 Department of Chemical & Biological Engineering, Engineering Research Institute, Gyeongsang National University, 900 Gajwa-dong, Jinju 660701, South Korea
2 1
interfacial adhesion between the bre and the polymer matrix. Poor interfacial bonding leads to composites with rather poor durability and toughness. In order to reduce the hydrophilic character of natural bres and to improve their adhesion properties, it is necessary to undertake a modication of the surface of the bre.5 Several methods to modify the natural bre surface, such as alkali treatment,69 plasma treatment,1012 preimpregnation of the bre,13 the use of silanes4,5,1418 and the use of maleic anhydride (MA) copolymers,17,1923 have been proposed. Recently, natural bres have been used to reinforce traditional thermoplastic polymers in automotive applications.24 Polypropylene (PP) has often been used as the matrix material. Among all the natural bre-reinforcing materials, jute appears to be a promising material because it is relatively inexpensive and commercially available in the required form. Jute bre has higher strength and modulus than plastic25 and is a good substitute for conventional bre in many applications. In this study, MA is used to chemically modify the surfaces of jute bre before incorporation with PP for improving interfacial adhesion between the bre and the matrix. The anhydride group is expected to be sufciently reactive with the hydroxyl groups of jute bre. The MA that is chemically attached to the surface of the jute bre may serve as a bridge between the bre and the polymer matrix.23 The reinforcing capability of the jute bre modied with MA on the PP composites was investigated. The modied jutePP composites were characterised by various experimental techniques.
Experimental
Materials
The natural bre used in this experiment was Bangladesh jute bres. Commercial-grade PP (J-170 homopolypropylene, Honam Petrochemical Corp.) was
2008 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 11 May 2007; accepted 28 March 2008 DOI 10.1179/174328908X314334
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selected as a polymer matrix. The density of PP was 0?9 g cm23 and the melt ow index (MI) was 2?8 g min21. MA (Aldrich) supplied in powder form was used.
where w1 and w2 represent the weight of bre before and after MA treatment, respectively. The WPG in this experiment was 11?57%.
Infrared spectroscopy
The MA modication of jute bre and the composites were identied by Fourier transform infrared spectroscope (FTIR, Abb Bomem MB100), using a KBr pellet method.
Mechanical properties
Instron UTM 8872 (load cell capacity 5 25kN) was used for the tensile property measurements according to ASTM D638. All tests were performed at room temperature with a crosshead speed of 5 mm min21. The dynamic mechanical properties of the jute bre/PP composites were measured by using a dynamic mechanical analyzer (DMA938, TA Instruments) at a heating rate of 5 uC min21 and a frequency of 10 Hz. The temperature range of the test was from 220 to 140 uC. The dimension of a sample was 50?0 6 12?3 6 3?0 mm.
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in natural bre reinforced polymer composites. The increased adhesion brought by the chemical 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.
Mechanical properties
Figure 3 shows the tensile modulus of untreated and MA-treated jute bre/PP composites as a function of bre concentration. The tensile properties were investigated with respect to the reinforcement effect of the untreated and MA-treated jute bres. The tensile modulus of the composites increased with increasing jute bre concentration. It is also seen that the tensile modulus of a jute bre/PP composite was signicantly increased by MA treatment of jute bre. Table 1 gives the Youngs modulus of untreated and MA-treated jute
bre/PP composites. The MA-treated composites exhibited improved Youngs modulus compared with the untreated composite at the same weight percent of bre content. The composite prepared at 15 wt% bre content showed a 22?4% increase in the Youngs modulus after MA treatment. This increase is probably caused by improved interfacial adhesion or chemical bonding between the jute bre and the PP matrix. Generally, Youngs modulus reects the capability of both bre and matrix material to transfer the elastic deformation in the case of small strains without interface fracture.20 Improved adhesion between jute bre and PP makes it possible for stress transfer from the weaker plastic matrix to the stronger jute bre during loading, thereby improving the modulus of the composites.15 The improved interfacial adhesion could be caused by some chemical reaction between MA attached on the bre and PP matrix or van der Waals forces between them. Moreover, covalent bonding between jute cellulose and PP matrix can also improve the adhesion between the phases. Figure 4 shows the tensile strength of untreated and MA-treated jute bre/PP composites as a function of bre concentration. It was observed that the tensile strength of untreated jute bre/PP composite increased slightly at 2 wt% bre content and decreased at 15 wt% bre content. The tensile strength of MA-treated jute bre/PP composites decreased with increasing bre content. It may be attributed to a change from ductile to brittle fracture behaviour with increasing bre content. Also, this decrease in tensile strength of the composites might imply non-uniform stress transfer in the matrix owing to bre agglomeration. Table 1 gives the tensile strength of untreated and MA-treated jute bre/PP composites. It is seen that at 15 wt% bre content the MA treatment of jute bre yielded a stronger
Table 1 Tensile properties of untreated and MA-treated jute bre/PP composites Fibre, wt% 0 2 2 15 15 Treatment of fibre Pure PP Untreated MA-treated Untreated MA-treated Youngs modulus, MPa 1383.4 1542.7 1641.5 1890.1 2314.1 Tensile strength, MPa 26.5 27.6 25.3 16.2 18.7
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5 Storage modulus of PP, untreated and MA-treated jute bre/PP composites with 15 wt% bre content
7 Tan d of PP, untreated and MA-treated jute bre/PP composites with 15 wt% bre content
tensile strength of the composites. In order to obtain natural bre composites with satisfactory mechanical properties, strong interfacial adhesion and effective wetting of bre by matrix are required.
Thermomechanical properties
Figure 5 represents the storage modulus of pure PP, untreated and MA-treated 15 wt% jute bre/PP composite as a function of temperature. The storage modulus is useful in assessing the molecular basis of the mechanical properties of materials since it is very sensitive to structural changes such as brematrix interfacial bonding28 and is closely related to the load-bearing capacity of composites materials. There was a notable increase in the storage modulus of PP matrix with the incorporation of jute bres over the whole range of the testing temperature. This is probably because of the increase in the stiffness of the matrix with reinforcing effect imparted by the bres that allowed a greater degree of stress transfer at the interface. The storage modulus of the jute bre/PP composites was further improved by MA treatment of jute bre. This behaviour is primarily attributed to improved interfacial adhesion or chemical bonding between jute bre and PP matrix. The C5C groups of MA attached on jute bre can undergo chemical reaction with the PP matrix. These cause better adhesion between the bre and the matrix.
6 Loss modulus of PP, untreated and MA-treated jute bre/PP composites with 15 wt% bre content
Therefore, the stress transfer from the matrix to the bres is improved, leading to the higher modulus. In all the samples the storage modulus decreased with the increase in temperature. Figure 6 shows the loss modulus of pure PP, untreated and MA-treated jute bre/PP composites containing 15 wt% jute bre as a function of temperature. It is known that loss modulus is proportional to the amount of energy that has been dissipated as heat by the material and the loss modulus peak is attributed to the mobility of the resin molecules; this peak occurs at the glass transition temperature (Tg) of the material.29 The loss modulus of jute bre/PP composite is higher than that of pure PP matrix and the loss modulus peak of pure PP is shifted to a higher temperature by addition of jute bre. The higher loss modulus and increased glass transition temperature are probably caused by the presence of jute bres that reduce the exibility of the material by introducing constraints on the segmental mobility of polymeric molecules. The loss modulus peak of jute bre/PP composite also shifted to a slightly higher temperature after MA treatment. This is caused by the segmental immobilisation of the matrix molecular chains near the surface of the jute bres because of the improved interfacial adhesion and chemical bonding. The ratio of viscous (loss modulus) to elastic (storage modulus) property is measured as the mechanical loss factor or tan d. The tan d, the damping energy ratio, is an indication of molecular motions existing in the materials. In a composite, molecular motion at the interface contributes to damping of the composites16 and energy dissipation occurs in the polymer matrix and at the interface with a stronger interface characterised by a lower energy dissipation.21 Figure 7 represents the tan d of pure PP, untreated and MAtreated 15 wt% jute bre/PP composites as a function of temperature. The damping peak in the MA-treated composites showed a decreased magnitude of tan d in comparison to PP matrix and untreated composites. The lowering of tan d values suggests a restraint effect of the bres on the matrix mobility,30 and this restriction is enhanced with the MA treatment of jute bre. The improved interfacial adhesion tends to reduce the mobility of the molecular chain at the interface and hence reduces tan d values.
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8 SEM micrographs of fracture surface of 15 wt% jute bre/PP composites: a untreated, b MA-treated
9 SEM micrographs of bre surface in 15 wt% jute bre/ PP composites: a untreated, b MA-treated
matrix are considerably reduced. The bre failed by tearing but no complete interfacial failure is observed. This may be because of improved interfacial adhesion and better bridging at the interfacial region. The bridging may be formed either by van der Waals interaction or a covalent bond between MA and PP matrix. Covalent bonding between MA attached on jute cellulose and PP could be possible through the opening of C5C group in MA through radical reaction of dicumyl peroxide,23 as indicated by the reduction of peak at 1643 cm21, shown in Fig. 2. The SEM micrograph in Fig. 10 shows clear evidence that the interfacial adhesion and bridging is enhanced as the result of MA treatment of jute bre. These results correspond to the results for mechanical and thermomechanical properties discussed in the previous section.
Conclusions
In this study, MA modication of jute bre and the reinforcing capability of the modied jute bres on the PP composites were investigated. Evidence for reaction between MA and jute bre and PP matrix has been observed by FTIR analysis. The MA-treated jute bre/
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10 SEM micrograph of interface between MA-treated jute bre and PP matrix of 15 wt% jute bre/PP composites
PP composite displayed higher Youngs and storage modulus than untreated composite, because of the enhanced interfacial adhesion and chemical bonding between the jute bre and PP matrix. SEM results showed evidence of improved interfacial adhesion and bridging in the composites as the result of MA treatment of jute bre.
Acknowledgements
This study was supported by a grant (0620220-1) from the National R&D Program for Cancer Control, Ministry of Health & Welfare, Republic of Korea.
References
1. A. ODonnell, M. A. Dwieb and R. P. Wool: Compos. Sci. Technol., 2004, 64, 11351145. 2. M. A. Dweib, B. Hu, A. ODonnell, H. W. Shenton and R. P. Wool: Compos. Struct., 2004, 63, 147157. 3. T. M. Gowda, A. C. B. Naidu and R. Chhaya: Compos. Part A, 1999, 30, 277284. 4. P. J. Herrera-Franco and A. Valadez-Gonzalez: Compos. Part A, 2004, 35, 339345.
5. M. Abdelmouleh, S. Boufi, M. N. Belgacem, A. P. Duarte, A. Ben Salah and A. Gandini: Int. J. Adhes. Adhes., 2004, 24, 4354. 6. D. Ray, B. K. Sarkar, S. Das, and A. K. Rana: Compos. Sci. Technol., 2002, 62, 911917. 7. A. K. Mohanty, M. A. Khan, and G. Hinrichsen: Compos. Part A, 2000, 31, 143150. 8. A. K. Mohanty, M. A. Khan, S. Sahoo and G. Hinrichsen: J. Mater. Sci., 2000, 35, 25892595. 9. A. K. Mohanty, M. A. Khan and G. Hinrichsen: Compos. Sci. Technol., 2000, 60, 11151124. 10. S. G. Lee, S. Choi, W. H. Park, and D. Cho: Macromol. Symp., 2003, 197, 8999. 11. X. Yuan, K. Jayaraman, and D. Bhattacharyya: Compos. Part A, 2004, 35, 13631374. 12. X. Yuan, K. Jayaraman, and D. Bhattacharyya: J. Adhes. Sci. Technol., 2004, 18, 10271045. 13. M. N. Sain and B. V. Kokta: J. Appl. Polym. Sci., 1994, 54, 1545 1559. 14. P. J. Herrera-Franco and A. Valadez-Gonzalez: Compos. Part B, 2005, 36, 597608. 15. M. Bengtsson and K. Oksman: Compos. Part A, 2006, 37, 752765. 16. M. A. Khan and M. M. Hassan: J. Appl. Polym. Sci., 2006, 100, 41424154. 17. M. N. Ichazo, C. Albano, J. Gonzalez, R. Perera and M. V. Candal: Compos. Struct., 2001, 54, 207214. 18. J. George, S. S. Bhagawan and S. Thomas: J. Therm. Anal. Calorim., 1996, 47, 11211140. 19. J. Gassan and A. K. Bledzki: Compos. Part A, 1997, 28, 10011005. 20. T. Doan, S. Gao, and E. Mader: Compos. Sci. Technol., 2006, 66, 952963. 21. S. Mohanty, S. K. Verma and S. K. Nayak: Compos. Sci. Technol., 2006, 66, 538547. 22. M. Tajvidi, R. H. Falk and J. C. Hermanson: J. Appl. Polym. Sci., 2006, 101, 43414349. 23. H. D. Rozman, M. J. Saad and Z. A. Mohd Ishak: Polym. Test., 2003, 22, 335341. 24. A. K. Bledzki and J. Gassan: Prog. Polym. Sci., 1999, 24, 221274. 25. A. N. Shah and S. C. Lakkad: Fibre Sci. Technol., 1981, 15, 4146. 26. C. A. Cruz-Ramos: Natural fibre reinforced thermoplastics, mechanical properties of reinforced thermoplastics, pp. 6581; 1986, Amsterdam, Elsevier. 27. M. S. Sreekala, M. G. Kumaran and S. Thomas: J. Appl. Polym. Sci., 1997, 66, 821835. 28. M. Jacob, B. Francis and S. Thomas: Polym. Compos., 2006, 27, 672680. 29. A. K. Rana, B. C. Mitra and A. N. Banerjee: J. Appl. Polym. Sci., 1999, 71, 531539. 30. C. K. Hong and R. P. Wool: J. Appl. Polym. Sci., 2005, 95, 1524 1538.
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