Composites Science and Technology 63 (2003) 375387 www.elsevier.

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Durability of bamboo-glass ber reinforced polymer matrix hybrid composites

Moe Moe Thwea, Kin Liaob,*
b a School of Materials Engineering, Nanyang Technological University, Singapore 639798, Singapore School of Mechanical & Production Engineering, Nanyang Technological University, Singapore 639798, Singapore

Received 4 July 2001; accepted 22 March 2002

Abstract The resistance of bamboo ber reinforced polypropylene composite (BFRP) and bamboo-glass ber reinforced polypropylene hybrid composite (BGRP) to hygrothermal aging and their fatigue behavior under cyclic tensile load were studied. Injection molded samples were exposed in water at 25  C for up to 6 months and at 75  C for up to 3 months. Tensile strength and elastic modulus of BFRP and BGRP samples have shown moderate reduction after aging at 25 C after 6 months, however, they were reduced considerably after aging at 75 C for 3 months. Moisture absorption and tensile strength degradation are suppressed by using maleic anhydride polypropylene (MAPP) as a coupling agent in both types of composite systems. BFRP and BGRP samples were also loaded cyclically at maximum cyclic load of 35, 50, 65, and 80% of their ultimate tensile stress. Results suggest that BGRP has better fatigue resistance than BFRP at all load levels tested. # 2002 Published by Elsevier Science Ltd.
Keywords: A. Natural ber composites; B. Durability; Aging; Fatigue

1. Introduction Cellulosic ber reinforced plastics materials are low cost, light-weighted, have enhanced mechanical properties, free from health hazard, and thus have the potential for structural applications. Despite the attractiveness of natural ber reinforced polymer matrix composites, they suer from lower modulus, lower strength, and relatively poor moisture resistance compared to synthetic ber reinforced composites such as glass ber reinforced plastics (GFRP). Because of the presence of hydroxy and other polar groups in various constituents of natural ber, the moisture uptake is high which lead to weak interfacial bonding between bers and the relatively more hydrophobic polymer matrices, thus compromising the mechanical properties of the composites. Therefore, data on the eects of moisture on retention of mechanical properties of natural ber reinforced composites during long-term environmental exposure are crucial for them to be utilized in outdoor applications. Studies on the environmental eect on the mechanical
* Corresponding author. Tel.: +65-6790-5835; fax: +65-6790-1859. E-mail address: askliao@ntu.edu.sg (K. Liao).

properties of some natural bers such as jute, sisal, wood our etc., composites have been reported [17]. It is shown by previous studies that moisture causes degradation of mechanical properties of natural ber reinforced composites to a larger extent when compared to synthetic ber reinforced composites, as a consequence of the higher moisture sorption behavior, and the organic nature of the natural bers [811]. It is necessary to enhance the hydrophobisity of the natural ber by chemical treatments with suitable coupling agents or by coating with appropriate resin in order to develop composites with better mechanical properties and environmental performance. Hybridization of natural ber with stronger and more corrosion-resistant synthetic ber, for example, glass or carbon ber, can also improve the stiness, strength, as well as moisture resistance of the composite. Using a hybrid composite that contains two or more types of dierent bers, the advantages of one type of ber could complement what are lacking in the other. As a consequence, a balance in performance and cost could be achieved through proper material design. However, only a few studies on the mechanical properties of natural and synthetic ber reinforced polymer matrix hybrid composites are available to

0266-3538/02/$ - see front matter # 2002 Published by Elsevier Science Ltd. PII: S0266-3538(02)00225-7

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date and in most cases durability issues are not addressed [1214]. Although there have been numerous studies of fatigue and environmental fatigue of composite materials [15,16], only a few references are available on fatigue behavior of natural ber and their composites [1719]. In this work, the behavior of composites and hybrid composites of short bamboo and glass bers in a polypropylene (PP) matrix under hygrothermal aging and under tensiletensile cyclic load were studied, with the considerations of the eects of ber length, ber content, and coupling agent.

2. Materials and method 2.1. Sample fabrication and preparation Polypropylene block copolymer (Cosmoplene) with a density of 0.9 g cm3 and melt ow index of 5 and maleic anhydride polypropylene (MAPP) with a density of 0.902 g cm3 (melting temperature at 140  C) were obtained for this study. Bamboo ber extracted from locally grown bamboo, and E-glass ber with the density of 2.25 g cm3 were used to fabricate short ber reinforced composite samples. Bamboo bers of dierent lengths were obtained using a laboratory scale extraction technique. Cylindrical bamboo culms deprived of nodes were cut into smaller pieces of 11.5 m in length and soaked in water for 24 h. After soaking the culms were manually sliced into 1 cm wide strips with a knife. Thin bamboo rods approximately 1 mm in diameter were obtained by passing the wider strips through an extruder. Small chips of bamboo 1 mm 10 mm in dimension were then obtained from cutting the longer rods. Short bamboo bers were obtained by grinding bamboo chips with a high-speed blender for approximately half an hour. The

extracted bers were dried in an oven at 105  C for 72 h in order to remove moisture. E-Glass bers 3 mm in length were obtained by cutting from continuous ber roving using an electronic ber-cutting machine. These short glass bers were also dried in an oven at 105  C for 24 h to remove surface moisture. Bamboo ber reinforced polypropylene composite (BFRP) and bamboo-glass ber reinforced polypropylene hybrid composite (BGRP) samples were prepared by rst melt mixing the constituents using a torque rheometer (Hakkae rheocord 90) at 190  C and a rotor speed of 40 rpm for 810 min. After mixing, the mixture of bamboo ber, glass ber, and PP (with or without MAPP) was transferred to injection molding machine. The resultant material coming out from injection molding was a randomly oriented short ber composite or hybrid composite. The sample code and their contents are listed in Table 1. 2.2. Tensile testing Injection molded, dog-bone shaped samples of PP, BFRP and BGRP with dimension 100 mm 10 mm 3.5 mm were tested according to ASTM standard D638. Samples were tested to failure under tension at a crosshead speed of 1.5 mm s1 using an Instron1 tensile tester. An extensometer was attached to the gauge section of the sample for strain measurement. Five samples were tested for each type of composite. Tensile strength, failure strain, and tensile modulus were recorded. 2.3. Environmental aging BFRP and BGRP samples described in the previous section were immersed in water at 25  C for up to 6 months and at 75  C for up to 3 months. Mass change of the samples was recorded using an electronic balance at regular time intervals. Tensile tests were performed at

Table 1 Sample code for BFRP and BGRP samples No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Sample type PP BFRP BGRP BGRP BFRPM BGRPM-1 BGRPM-2 BGRPM-20 BGRPM-30 BGRPM-40 BGRPM-L1 BGRPM-L2 BGRPM-L3 Sample code PP B H1 H2 BM HM1 HM2 HM1-20 HM1-30 HM1-40 HM1-L1 HM1-L2 HM1-L3 Total ber content (wt.%) 20 20 20 20 20 20 20 20 20 20 20 20 Bamboo ber content (wt.%) 0 20 15 10 20 15 10 15 25 35 15 15 15 Glass ber content (wt.%) 0 0 5 10 0 5 10 5 5 5 5 5 5 Bamboo ber length (mm) 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 0.250.5 16 612 Material used for modication MAPP MAPP MAPP MAPP MAPP MAPP MAPP MAPP MAPP Gass ber length 3 3 3 3 3 3 3 3 3 3 3

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the end of 3 and 6 months for samples aged at 25  C, and after 3 months for those aged at 75  C, respectively, to determine the residual tensile strength and elastic modulus. 2.4. Fatigue testing Cyclic tests were conducted at ambient temperature in air using an Instron micro force tester under a loadcontrolled mode. Tensiontension cyclic load was

applied with a sinusoidal wave with R=0.1 and a frequency of 5 Hz. Four cyclic load levels, 35, 50, 65 and 80% UTS, were chosen to test PP, B (BFRP), and H1 (BGRP) samples. At least three samples were tested at each load level. Cyclic tests were interrupted at regular intervals to record the elastic modulus of the sample. Samples survived 1 million cycles were loaded subsequently to failure in tension to determine residual strength. Fatigue fracture surfaces of selected samples were examined under scanning electron microscope (SEM) for damage and failure characteristics.

3. Results and discussion 3.1. Tensile behavior of BFRP and BGRP Typical stressstrain curves of PP, BFRP and BGRP samples are shown in Fig. 1. In general, the stressstrain behavior of these samples is non-linear. The strain at maximum tensile stress for all types of composite samples ranged from 3 to 8%. The results of tensile tests of unlled PP, BFRP and BGRP samples (without MAPP) are shown in Fig. 2 a, b. In this case the ber content was kept at 20% by mass. The average tensile strength and modulus of H1 samples has increased by 4 and 18%, respectively, compared with B samples. An increase in glass ber content in

Fig. 1. Typical tensile stressstrain curves of BFRP and BGRP samples.

Fig. 2. (a) Tensile strength (without MAPP), (b) tensile modulus (without MAPP), (c) tensile strength (with MAPP), (d) tensile modulus (with MAPP) of BFRP and BGRP samples. Error bar represents standard deviation.

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BGRP results in an increase in tensile properties. Tensile strength and modulus of H2 samples (bamboo to glass ber ratio 1:1) has increased by 10 and 30%, respectively, compared to H1 samples (bamboo to glass weight ratio 3:1). Although the tensile strength of BFRP is slightly lower than that of the PP samples, enhancement was found by inclusion of glass ber in BFRP. A signicant improvement in tensile modulus of BFRP and BGRP is observed compared to unlled PP. Tensile modulus of B samples is increased by more than 100% compared to unlled PP whereas up to 200% increment is found for H2 samples. Tensile properties of BFRP and BGRP samples are further improved by using MAPP as a compatibilizer, shown in Fig. 2c, d. MAPP acts as a compatibilizer in BGRP as the maleic anhydride group can be bonded with bamboo ber and glass ber, resulting in an improved interfacial adhesion between the matrix and both types of bers [20], thus allowing a more ecient transfer of stress along the ber/matrix interface. As a consequence, an increase in tensile strength of the samples with MAPP of about 11% is seen compared to samples without MAPP, although the dierences in tensile modulus between the two systems is not obvious. The inuence of ber content on the tensile properties of BGRP (with 5% MAPP) is shown in Fig. 3. The glass ber content of all BGRP samples was kept at 5% by mass. Tensile strength and modulus have increased almost linearly with an increase in ber content. A 44 and 7% increase in tensile modulus and strength, respectively, is seen at 40% (by mass) total ber content, compared to the case of 20% (by mass) ber content in HM1-20 samples. HM1-40 samples with 40% (by mass) exhibit the highest tensile strength of about 24.4 MPa whereas their tensile modulus has increased to 4.8 GPa. The eects of ber length on the tensile strength and modulus for the BGRP (with PP-MAPP matrix) samples

are summarized in Fig. 4. The tensile strength was not signicantly aected by changing the bamboo ber length from L1 (0.250.5 mm) to L2 (16 mm) in the composites whereas the tensile modulus of sample of L2 bers has increased by 10% compare to those with L1 bers. Increased modulus with ber length is easily understood because longer bers are carrying more tensile loads as a result of increased transfer length. Further increased in bamboo ber length did not result in an increase in tensile strength and modulus, on the contrary, a slight drop in tensile strength and modulus is seen. Therefore, BGRP composite with MAPP system oers the maximum tensile load transfer when using bamboo ber length 16 mm and glass ber length 3 mm. Lowering in tensile strength and modulus of the HM1-L1 samples may be attributed to the insucient ber length to receive proper tensile loads transferred from the matrix. It has been shown that the tensile strength,  c, of an uniaxially oriented short ber composites tends to increase with ber length and ber matrix adhesion according to the equation: c f Ef m Em "c f E 2 f 4q

where  is the volume fraction, E the modulus, " the composite strain,  the interfacial shear stress, and q the aspect ratio; and the subscripts f and m designate ber and matrix, respectively.

Fig. 3. Eect of ber content on tensile strength and tensile stiness of BFRP and BGRP. Error bar represents standard deviation.

Fig. 4. Eect of ber length on (a) tensile strength, and (b) tensile modulus of BFRP and BGRP. Error bar represents standard deviation.

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During injection molding both bamboo and glass bers suer from fragmentation, resulting in reduced average ber length of the product. The tensile stress transfer to the ber increases when the aspect ratio of the ber increases. However, at the critical aspect ratio when the tensile stress in the ber reaches a maximum, any further increase in the ber length leads to no further increase in the transferred stress. Mechanical properties are improved when the axis of the orientation of the bers is parallel to the loading direction compared to the other two mutually perpendicular directions. Longer bers will orient less readily than shorter ones because of the greater intertwining. Moreover, larger average size (diameter) of longer bamboo ber may lead to poorer compatibility with the matrix. In the case of longer bers, although they can carry more tensile load within the critical stress transfer length, ber failures may readily occur in a brittle manner. These aforementioned factors may all contribute to reduced tensile

properties of the composites with longer ber length [9]. To illustrate, SEM micrographs of the fracture surface of HM1-L1 and HM1-L2 samples shown in Fig. 5a indicate that shorter bers tend to be more evenly distributed, and thus results in desired bermatrix interaction. However, ber agglomeration, ber attrition, and holes on the fracture surface of composite with longer ber length suggest poor interface region leading to reduced strength (Fig. 5b). 3.2. Sorption behavior The moisture uptake expressed in percent mass gain, M(t), is: Mt Mt M 0 100 M0

where M0 andMt are the masses of the sample before and during aging, respectively. The sorption curves of BFRP and BGRP samples after soaking in water at 25  C for 6 months are shown in Fig. 6a, where mass change of the samples is plotted against the square root of soaking time. The moisture absorption level (about 1.2%) for BFRP samples is substantially higher than that of most glass ber reinforced polymer composites. Moisture absorption during aging can be reduced considerably by replacing bamboo ber with glass ber

Fig. 5. (a) SEM image of HM1-L1 sample showing well distributed bers and good bonding of short bers in the matrix; (b) SEM image of HM1-L3 sample. Double-headed arrow indicates ber agglomeration, arrow with V-shaped tail indicates holes on matrix because of pulled out bamboo ber, and thin arrow points to a broken ber.

Fig. 6. (a) Sorption behavior of BFRP and BGRP at 25  C; (b) sorption behavior of BFRP and BGRP at 75  C.

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(with a negligible moisture uptake of about 0.1%) in the samples. As expected, moisture uptake decreases with an increase of glass ber content in the composite. The moisture absorption level for B, H1, and H2 samples are 1.2, 0.9, and 0.7%, respectively, while PP samples only show little moisture uptake after aging in water for 6 months at 25 C. Use of PP-MAPP matrix further reduces water uptake for both BFRP and BGRP samples. This reduction in moisture level is attributed to the improved interfacial adhesion that reduces water accumulation in the interfacial voids and prevents water from entering the bamboo ber. A saturated moisture level has not been reached for all types of sample within the aging period. Water sorption behavior of BFRP and BGRP samples at 75 C displayed a pseudo-Fickian behavior where a saturated moisture level had not been attained at the end of the 3-month aging period, as shown in Fig. 6b. A plausible cause is that internal degradation continues to occur with soaking time. Sorption rate during the initial stage is signicantly higher compared to those aged at 25 C. Moisture contents of about 3.6 and 2.79% are seen for BFRP and BGRP samples, respectively, after 3 months. The mass gain during aging also decreases with an increase of glass ber content and with the use of MAPP-PP matrix, a trend that is seen previously for samples aged at 25  C. 3.3. Tensile properties after aging Tensile strength and modulus of all of the samples measured after aging in water at 25  C for 6 months are summarized in Fig. 7a, b. The tensile strength of all types of samples did not change signicantly after aging in water at 25  C for 3 months, while a slight increase in tensile modulus is observed. A 219% reduction in tensile modulus is seen after 6 months. The results show that property retention of BGRP (with no MAPP) is better than BFRP (with no MAPP). For example, reduction in tensile strength of B samples is 19% after 6 months whereas it is 10% for H2 samples. It is also seen that property retention for systems with PP-MAPP matrix is, in general, better than those systems with pure PP matrix (no MAPP). However, the extent of reduction is trivial. Results of tensile tests for samples after aging in water at 75 C for 3 months are also shown in Figs. 7a,b. Tensile strength of the both BFRP and BGRP samples only drops slightly whereas moderate reduction in tensile modulus is observed. Similar to the previous case at 25 C, BFRP samples showed a greater reduction in tensile strength and modulus than those of BGRP samples, and retention in mechanical properties of the composites is enhanced by using the MAPP-PP matrix. The reduction in tensile strength and modulus for samples B, H1, and H2 are found to be about 16 and 61%,

Fig. 7. (a) Tensile strength and (b) tensile modulus of BFRP and BGRP before and after aging in water at 25  C for 6 months and at 75  C for 3 months. Error bar represents standard deviation.

11 and 55%, and 9 and 29%, respectively. It is worth mentioning that reduction in tensile strength and modulus of sample B is about twice that of sample H2 under accelerated aging in water for 3 months. From the sorption curves, it is found that the moisture content of samples H2 and H1 is about 2.85 and 3.7%, respectively, after soaking in water for 3 months. Reverting to data on tensile properties, it reveals that the mechanical properties are inuenced by the amount of water absorbed. Degradation of mechanical properties of the BFRP and BGRP composites depend on the amount of water uptake, soaking time, and temperature at which aging is carried out. Water diusion through the matrix results in stress corrosion of glass bers (even under stress free condition) and degradation of the bamboo ber, as well as weakening the adhesion between the bers and the matrix [21]. Swelling and shrinkage of bers and matrix may also help in uncoupling the interfacial adhesion. These factors are believed playing a major role in degradation of mechanical properties of the composite. Environmental aging has no notable eect on the tensile properties of PP samples within the temperature range and time of aging of the present study, possibly related to the hydrophobic nature of the polymer, although it is

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known that moisture absorption will lead to reduction in the elastic modulus of polymers, presumably through a plasticizing process [22]. Accelerated aging is generally carried out in order to shed light on the long-term performance of material without actually carrying out long-term test. Temperature is the key factor for accelerated aging in the processes of water diusion and chemical degradation. Accelerated test is justiable if the accelerating parameter does not cause an change in the aging mechanism. To understand the detrimental eects of water on mechanical properties of the composite, it is necessary to study its eect on the constituents of the composite, the ber, the matrix, and the ber/matrix interphase region. Because it has been known from previous studies that each of these components are degraded under environmental aging in water. 3.4. Fiber degradation Degradation of the reinforcements plays an important role in strength and stiness reduction of ber-reinforced composites as they are the major load-carrying constituents. It has been proposed that decrease in the tensile strength of glass ber is caused by breaking of the SiOSi bond on the ber surface by the attacking water molecules, and the process is accelerated at higher temperatures, which can be described by a kinetic crack growth equation. Apparently, as suggested by most available data, temperature has no eect on altering the mechanism of crack growth [23]. In our case, no apparent morphological changes on glass ber was observed in both aging conditions (Fig. 8). Morphological features of bamboo ber before and after aging in water at 25  C are shown in Figs. 9 and 10, respectively. The ultra-structure of the bamboo ber consists of alternating broad and narrow lamellae with dierent brillar orientation. Each layer is made up of lignin, pentosan, and cellulose compound, and cellulose

Fig. 9. SEM fracture surface of a BGRP (H1) sample before aging. An arrow shows a clean bamboo ber surface.

Fig. 8. SEM image showing bamboo and glass ber surface after aging in water for 6 months. No noticeable damage is seen on the glass ber throughout the sample.

Fig. 10. (a) SEM fracture surface of BGRP (H1) after aging in water at 75  C for 3 months. Thin arrow shows a weaker bamboo ber where a bril is transported out from inside. Arrow with V-shaped tail points to weaken interface between ber and matrix. (b) SEM fracture surface of a BFRP (B) sample after aging in water for 6 months. An arrow indicates a bamboo ber with holes due to attacking of water during aging.

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brils are embedded in the lignin-polyose matrix by hydrogen bonding [7]. The bonding between the layers of the bamboo ber were destroyed during aging by the attacking water, leaving them detached from each other as the chemical constituents were being dissolved (Fig. 10). Consequently, the diameter of the lumen (inner hole) of bamboo ber became larger as the material in the inner layers was dissolved and transported out of the ber. Splitting of cellulose, as is obvious from the holes that are seen on the bamboo ber surface (Fig. 10b). These damaged morphologies were not observed on the fracture surface of unaged sample (Fig. 9). Although similar morphological pattern is also seen from those aged at 75 C, exposure to elevated temperature has a much greater eect in terms of the extent of degraded morphology. Thus it can be concluded, based on morphological comparisons, that there is no fundamental dierence in the degradation mechanism for the bamboo ber at ambient and elevated temperatures. The strength of the hollow bamboo ber is weakened and the load transfer eciency is reduced by these aging-related damages. More will be said on the matrix-related damage of bamboo bers in the following section. 3.5. Matrix degradation Physical and chemical changes may occur in the polymer matrix during hygrothermal aging. As has been discussed earlier, water ingress is controlled by temperature and it follows that matrix plasticization is also controlled, at least in part, by temperature. In addition, temperature also serves as a rate controlling parameter for other degradation mechanisms such as hydrolysis. Chemical changes occur due mainly to the hydrolysis of polymer bonds, dissolution, and leaching of the watersoluble species. Therefore, the extent of degradation of polymeric matrix at elevated temperature is expected to be greater than that at lower temperature [24,25]. However the interrelationship between water ingress, temperature, and matrix plasticization and degradation, cannot be elucidated without extensive experimentation. In our case, degradation of semi-crystalline PP matrix had occurred during aging. A layer of regularly spaced array of thin, short polymer rods deposited on the bamboo surface after aging is clearly seen (Fig. 11a). In Fig. 11b, regularly spaced small holes are seen on the bamboo ber surface, very possibly after separation of the polymer rods from it. This depositionseparation process is described in more detail in a series of SEM micrographs shown in Fig. 12AF. The numerous holes found in some part of the PP matrix on the fracture surface as shown in Fig. 12F, may be formed during a similar degradation process. Various combinations damaging agents such as heat, mechanical stress, moisture, and oxygen may result in

Fig. 11. (a) SEM fracture surface of a BGRP (H1) sample after aging in water for 3 months. An arrow points to a bamboo ber surface covered with a thin polymer layer with well-arranged array of small polymer rods. (b) SEM fracture surface of a BGRP (H1) sample after aging in water for 3 months. An arrow shows a bamboo ber surface covered with a thin polymer layer with an array of small holes.

very complex damage processes. PP could have reacted with oxygen and moisture, changing both the morphology and appearance of the polymer [25]. Various compounds such as additive and impurities, which include catalyst residues and processing aids to cause oxidation of the polymer may present in commercially prepared polymers. Oxidation products may serve as an autocatalyst to cause further oxidation process. PP possesses reactive tertiary hydrogen atoms, which oers higher probability of oxidation reaction to occur, leading to decreased molecular weight and discoloration of the polymer [26,27]. In our case, degradation of the PP matrix could be attributed to oxidation process and it seem to be have occurred at a faster rate in moist environment. Large and small holes (Fig. 13) are seen in some parts of the PP matrix on the fracture surface of all types of samples, but they are not seen in unaged samples (Fig. 9). The color of the aged samples has changed from brown to deep brown and it became even darker in water at 75  C

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Fig. 12. Degrading process of thin polymer layer with small polymer rods covering a bamboo ber surface, observed on the fracture surface of BGRP (H1) samples after aging in water for 6 months: (A) a thin layer of polymer with well-organized array of short polymer rods on the bamboo surface; (B) a closer view of the polymer rod array; (C) growing polymer rods; (D) small polymer rods are about to leave from the polymer surface; (E) well-arranged polymer layer with holes after separation of polymer rods; (F) numerous holes found in the PP matrix.

(Fig. 14). Small polymer strings are observed on the fracture surface of samples in both aging conditions, which is believed to be the consequence of polymer matrix deformation due to swelling in moist environment (Fig. 15). It has been shown that the mechanical properties for many commonly used polymer systems for composites do degrade under environmental loads [28]. However, it should be mentioned that in the present case, the tensile strengths and stiness of PP did not show a signicant drop after aging. In addition to the aforementioned factors, dimensional instability of the matrix under the inuence of moisture and temperature may result in

debonding of the ber/matrix interface, discussed as follows. 3.6. Degradation of the ber matrix interface The interfacial adhesion characteristics have a signicant eect on the load carrying capacity of a berreinforced composite. Under environmental aging, interfacial debonding occurs by penetration of water molecule, and water-lled voids or blisters may also develop at the interface. Dierences in both thermal and moisture expansion coecients of bers and matrix also

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contribute to progressive debonding and therefore weakening of the materials and it is more severe at elevated temperatures because of the larger dierences of temperature and moisture content [26]. Obvious debonded ber/matrix interface of the BFRP and BGRP (Fig. 13) is found in both PP or PP-MAPP matrix composite after aging at room temperature for 3 months, compared to those before aging condition (Fig. 9). Damage at the interface is more severe at high temperature as a result of dissolution of components of bamboo ber, and has caused a greater reduction in mechanical properties of the composite. Although ber and interface degradation may occur during processing, ber and matrix degradation similar to those shown in Figs. 10 and 15 were not observed on the fracture surfaces of all types of unaged samples. Therefore, both ber and matrix degradations observed on the surfaces of aged samples are believed to be attributed to the attack of water when the samples were exposed to the moist environment but not as a result of processing.

So far it has been shown that environmental aging do introduce damage to bamboo ber, PP and PP-MAPP matrix, and the bermatrix interface, and that aging at a higher temperature accelerates the process and intensies the extent of those damages. Qualitative comparison on damage modes based on morphology reveals that the fundamental damage mechanisms appear to be the same. While degradation in both tensile strength and stiness are gradual at 25  C, accelerated aging has a stronger eected on the stiness of BFRP and BGRP samples at 75 C compared to that of tensile strength.

4. Fatigue behavior 4.1. SN curves SN curves for PP, B, and H1 samples are shown in Fig. 16. All samples survive 1 million fatigue cycles at

Fig. 13. SEM fracture surface of BGRP (H1) after aging in water at 75  C for 3 months. Thin arrow points out a weak interface between bamboo ber and matrix. Numerous small holes in the matrix indicated by an arrow with V-shaped can be seen.

Fig. 15. SEM fracture surface of a BFRP (B) sample after aging in water at 75  C for 3 months. An arrow points to swelling polymer strings at the interface between bamboo ber and polymer matrix.

Fig. 14. BGRP (H1) samples before and after aging in water at 75  C, the aged sample is darker in color.

Fig. 16. Stresslife data for PP, BFRP (B) and BGRP (H1) samples. Arrow represents run-out.

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dierent load levels except those tested at 80% UTS. These results suggest high fatigue resistance of the PP and their composites with bamboo and glass bers. It is noted that SN curve of the unreinforced PP is above all the other curves for BFRP and BGRP samples. The fatigue resistance of PP comes from the irreversible structural changes associated with nonlinear viscoelastic behavior, which is gradually stored in the sample tested during cyclic fatigue [29]. The reinforcing bers did not show clearly their eects in the fatigue behavior as in the case of quasi-static loading. At 80% UTS, H1 samples longer fatigue lives than B samples on the average, but their life dierence is not as signicant when compared to PP samples. Fatigue life ranged between 5104 and 5105 cycles for both types of composite whereas 7105 to 1106 is seen for PP. Large data scattering associated with fatigue life is common for short ber composites due to the random nature of damage accumulation process [30], and in this case, data scattering is within one decade. Although no visible damages were found on samples loaded at lower stresses levels, micro cracks of various length transverse to the load direction can be seen obviously by naked eye at the surfaces and corner of the sample tested at 80% UTS. The density and size of these micro cracks both increase with load cycles and appeared to be crazes induced by higher stresses. 4.2. Stiness degradation and residual tensile strength Tensile stiness degradation as a result of fatigue is measured to assess damage development in the material. A typical plot of normalized tensile stiness degradation of PP, BFRP and BGRP versus applied cycles at 80% UTS is shown in Fig. 17. In general, these stiness degradation curves are typical of ber reinforced composites, that they decay from its initial values with increasing applied load cycles [2931]. All samples

demonstrated stiness drop during their early lives, followed by a graduate drop, and a steep drop at late lives. At failure nearly half of the initial elastic modulus had lost. It is worth noticing that B samples have relatively steeper slopes in stiness degradation compared to H1 samples, suggesting a better damage resistance of the hybrid composite. Although degradation in elastic modulus of PP samples also shows a decreasing trend, extent of degradation is less than that of B and H1 samples, implying that the rate of damage developed in PP samples is slower than its composites. In addition to the lack of damage initiator such as ber ends, etc., which are stress raisers for introducing micro damages in the material, realignment of polymer chains in the loading direction may also contribute to slow down the stiness degradation. It is shown in Fig. 18a that tensile stiness of all of the samples decreases after 1 million cycles when loaded between 35 and 65% UTS. Higher applied cyclic stress results in greater decrease in stiness. Overall drop in stiness of B samples is higher than that of H1 and PP at all load levels. Therefore, incorporation of glass ber in BFRP composite aects the fatigue response at different load levels and hybrid composite BGRP shows better fatigue damage resistance than BFRP at a same total ber loading. Residual strength for all of the samples survived 1 million cycles are tabulated in Fig. 18b. For all types of samples, their residual tensile strength all show a drop

Fig. 17. Stiness degradation of PP, BFRP (B), and BGRP (H1) samples cyclically loaded at 80% UTS.

Fig. 18. (a) Reduction in tensile stiness of PP, BFRP and BGRP samples after one million cycles at 35, 50, and 65% UTS; (b) residual tensile strength of PP, BFRP, BGRP samples after a million cycles at 35, 50 and 65% UTS.

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at 50 and 65% UTS. However, a slight increase in tensile strength is observed for those tested at 35% UTS, this could be attributed to realignment of PP chains and ber reorientation during fatigue. Several damage modes, such as interface debonding, ber splitting, and matrix cracking are observed on the failure surface of a H1 sample after fatigue failure at 65% UTS for a million cycles (Fig. 19a, b). The reduction in tensile strength does not appear to be related to the number of cracks detected, but crack size seems to be more indicative of residual tensile strength in this particular composite. The detailed observation of various fatigue damages correlated to the number of applied load cycles at dierent stress levels and eect of coupling agents (MAPP, silane) on the fatigue response of bamboo/PP and hybrid composite will be discussed in a subsequent paper.

5. Conclusions Based on the results obtained from this study, the following can be concluded:  Both the tensile strength and modulus of BFRP and BGRP have decreased after aging in water at 25 and 75  C for prolonged period. The extent of strength and stiness loss depends on the aging time and temperature.  BGRP samples showed a better resistance to environmental aging than BFRP in terms of retention of tensile strength and stiness.  Tensile strength and stiness are enhanced by inclusion of a compatibilizer, MAPP, in matrix material as a result of improved interfacial bonding.  Bamboo ber degrades by decomposition into thin brils and detached layers while the PP matrix degrades by dissolution.  The hybrid approach of blending more durable glass ber with bamboo ber is an eective way to improve the durability of natural ber composite under environmental aging.  Unreinforced PP has longer fatigue life than BFRP and BGRP samples at the specied cyclic load levels, and hybrid composite showed better fatigue resistance than all bamboo ber reinforced PP.

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Fig. 19. (a) A typical fatigue fracture surface of a BGRP (H1) sample under SEM; (b) SEM image of the sample surface of BFRP (B) after fatigue loading for a million cycles at 65%UTS. Double-headed arrow shows the debonding at the interphase region, arrow with V-shaped tail points out the matrix cracking and connecting among the agglomerated bers, and arrow represents a splitting bamboo ber.

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