Composites Science and Technology 63 (2003) 283293 www.elsevier.

com/locate/compscitech

Dynamic mechanical analysis of banana ber reinforced polyester composites

Laly A. Pothana, Zachariah Oommenb, Sabu Thomasc,*
Department of Chemistry, Bishop Moore College, Mavelikara 690110, Kerala, India b Department of Chemistry, CMS College, Kottayam, Kerala, India c School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills PO 686560 Kottayam, Kerala, India Received 13 November 2001; received in revised form 10 September 2002; accepted 24 September 2002
a

Abstract The dynamic mechanical analysis of banana ber reinforced polyester composites was carried out with special reference to the eect of ber loading, frequency and temperature. The intrinsic properties of the components, morphology of the system and the nature of interface between the phases determine the dynamic mechanical properties of the composite. At lower temperatures (in the glassy region), the E0 values are maximum for the neat polyester whereas at temperatures above Tg, the E0 values are found to be maximum for composites with 40% ber loading, indicating that the incorporation of banana ber in polyester matrix induces reinforcing eects appreciably at higher temperatures. The loss modulus and damping peaks were found to be lowered by the incorporation of ber. The height of the damping peaks depended on the ber content. When higher ber content of 40% was used, an additional peak in the tan  curve, pointing to micro mechanical transitions due to the immobilized polymer layer was evident. The glass transition temperature associated with the damping peak was lowered up to a ber content of 30%. The Tg values were increased with higher ber content. ColeCole analysis was made to understand the phase behavior of the composite samples. A master curve was constructed based on timetemperature super position principle, which allows the prediction of long-term eects. Apparent activation energy of the relaxation process of the composites was also analyzed. The value was found to be maximum for composites with 40% ber content. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Banana ber

1. Introduction Manufacturing high performance engineering materials from renewable resources is one ambitious goal currently being pursued by researchers across the world. The ecological benets of renewable raw materials are clear: they save valuable resources, are environmentally sound and do not cause health problems. Natural bers have already established a track record as simple ller material in automobile parts. Natural bers like sisal, jute, coir, oil palm ber have all been proved to be good reinforcement in thermoset and thermoplastic matrices [14]. Our earlier studies have proved banana bers to be an eective reinforcement in polyester matrix [5].
* Corresponding author. Tel.: +91-481-598303; fax: +91-481561190. E-mail address: sabut@md4.vsnl.net.in (S. Thomas).

Dynamic mechanical test methods have been widely employed for investigating the structures and viscoelastic behavior of polymeric materials for determining their relevant stiness and damping characteristics for various applications. The dynamic properties of polymeric materials are of considerable practical signicance when determined over a range of temperature and frequencies. Composite damping property results from the inherent damping of the constituents. This can be represented as [6] tanc Vf tanf 1 Vf Tanm 1

where tan c, tan f, and tan m are the damping values of the composite, the ber and the polymer, respectively and Vf and Vm are the volume fraction of the ber and the matrix, respectively. In the transition region, the molecular chains begin to move and every time a frozen segment begins to move its excess energy is dissipated as

0266-3538/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved. PII: S0266-3538(02)00254-3

284

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

heat. A segment, which is completely frozen in or is free to move, gives rise to a low damping value. The rule of mixtures, which is used in predicting composite mechanical properties, can be used in analyzing the composite damping property as well, [7] According to Nielsen, the damping of a composite, tan c is given by the proportional contribution of the matrix according to its relative content. tan c tan m 1 f 2

where tan m is the damping value of the matrix and f is the volume fraction of the ller. Around Tg, the ller particles are not deformed and damping is purely due to the polymer. But, a specic interaction between the ller and the polymer layer will create a layer of immobilized polymer in between the ller and the polymer. In such cases the Eq. (2) can be rewritten as tan c tan m 3

In the present communication we report on the inuence of banana ber on the viscoelastic properties of polyester. The eect of ber content, frequency and temperature on the viscoelastic properties is reported. The elevation of Tg is taken as a measure of the interfacial interaction and the eect of ber content on the Tg values is reported. The Tg is usually interpreted as the peak of the tan  or the loss modulus curve that is obtained during a dynamic mechanical test conducted at a low frequency. The Tg values of the dierent samples and the shift in Tg were determined from the loss modulus and the tan  curves to have more insight into the ber/matrix adhesion. The eect of interlayer on the micro mechanical transitions is also reported.

2. Experimental 2.1. Materials Banana ber was obtained from Sheeba Fibers and Handicrafts, Poovancode, Tamil Nadu. Unsaturated polyester HSR 8131 based on isophthalic acid was obtained from Bakelite Hylam, Hyderabad. Methyl ethyl ketone peroxide and cobalt naphthenate were of commercial grade and obtained from Sharon Engineering Enterprises, Cochin. The details of the material are given in Table 1. 2.2. Preparation of composites Banana bers were neatly separated by hand; adhering pith, if any, were removed and the bers were cut to uniform size of 30 mm length. The bers were then evenly arranged, in a mold measuring 1501503 mm3 and pressed into a mat. Composite sheets were prepared by impregnating the ber with the polyester resin to which 0.9 volume percent cobalt naphthenate and 1% methyl ethyl ketone peroxide was added and the air bubbles were removed carefully with a roller. The closed mold was kept under pressure for 12 h; samples were cured at room temperature for 12 h, and then taken out of the mould. The demolded samples were post cured

Work done on the dynamic mechanical properties of brous composite materials are mainly aimed at two objectives. 1. To study the chemical or physical modication of the matrix by the introduction of ber. 2. To study the behavior as a function of the properties of each phase. Gassan and Bledzki [8] carried out dynamic mechanical analysis of jute/epoxy composites and observed an improvement in dynamic modulus by the incorporation of treated jute ber in epoxy. Finegan and Gibson [9] in their investigation on the enhancement of damping in polymer composites have suggested analyzing dierent ber matrix combinations. Saha et al. [10] made comparative studies on the damping of unmodied and chemically modied jute- polyester composite samples. Valea et al. [11] investigated the inuence of cure conditions and the exposure to various chemicals on the dynamic mechanical properties of several vinyl ester and unsaturated polyester resins containing glass ber. Exposure to aromatic solvents was found to modify the viscoelastic character of these materials. Amash and Zugenmaier [12] reported the eectiveness of cellulose ber in improving the stiness and reducing the damping in poly propylenecellulose composites. The eect of adsorbed water on the storage modulus and loss tangent of wood was analysed by Obataya et al. [13] Adsorption of water was found to increase the modulus value up to 8% moisture content and to decrease the values thereafter. The dissolved water was found to decrease modulus values by plasticizing matrix molecules. Extensive research work is being carried out by Thomas and co-workers in this laboratory regarding the viscoelastic behavior of various polymer composites and blends [1418].

Table 1 The mechanical properties of banana ber Sample Diameter Initial Youngs SDInitial Tensile % number of ber modulus (GPa) Youngs strength Strain (mm) modulus (GPa) (MPa) 1 2 3 4 5 50 100 150 200 250 32.703 30.463 29.748 27.698 29.904 8.190 4.689 8.561 7.083 4.059 779 711 773 789 766 2.7 2.4 3.5 3.3 3.2

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

285

for a further period of 24 h at room temperature and samples of dimension 100153 mm3 were cut. A dynamic mechanical thermal analyzer M K I I of Polymer Laboratories was employed for dynamic mechanical property evaluation of the composites. The experiment was performed under tensile mode at a frequency of 0.1, 1 and 10 Hz. The sample dimension was 23 cm2 and the gauge length of the sample 1.5 cm. The testing temperature ranged from 20 to 160  C and the heating rate was 2 K/min. Composites with dierent ber loading were examined using scanning electron microscope (SEM) model Jeol JSM-35 C and Cambridge 250 MK3 stereo scan.

3. Results and discussion 3.1. Eect of temperature Fig. 1 shows the eect of temperature on the dynamic modulus of the neat polyester and various composites with dierent ber content. Variation in modulus occurs due to the eect of the incorporated bers. In the case of neat isophthalic polyester cured with MEK peroxide and cobalt naphthenate, it is seen that the dynamic modulus is higher than the ber lled system in the glassy region. The lowering of the modulus values occurs due to dilution of the polymer. However, the dynamic modulus curve showed an increase in the E0 value above the Tg region in the rubbery plateau. The increase of E0 in the rubbery plateau is maximum for the composites with 40% ber loading. The eectiveness of llers on the moduli of the composites can be represented by a coecient C such as [19] Eg =Er comp C 4 Eg =Er resin Where E0 g and E0 r are the storage modulus values in the glassy and rubbery region respectively. The higher the value of the constant C, the lower the eectiveness of the ller. The measured E0 values at 45 and 130  C

(for polyester) were employed as E0 g and E0 r respectively. The values obtained for the dierent systems at frequency 0.1 Hz are given in Table 2. In this case the lowest value has been obtained for 40% ber loading and the highest value for 20% ber loading. The eectiveness of the ller is the highest at 40% ber loading. It is important to mention that modulus in the glassy state is determined primarily by the strength of the intermolecular forces and the way the polymer chains is packed. Fig. 2 shows the variation of log E0 with ber volume fraction at dierent temperatures of 40,60,90 and 145  C. In all the cases, the E0 value decreases up to a volume fraction of 0.25 and then increases. There is a large fall in modulus with increasing temperature in the unlled system, the stiness at high temperature being determined by the amorphous regions, which are very compliant above the relaxation transition. The drop in the modulus on passing through the glass transition temperature is comparatively less for reinforced composites than for un-reinforced resin. In other words, banana bers have larger eect on the modulus above Tg than below it. However the dierence between the moduli of the glassy state and rubbery state is smaller in the composites than in the neat polyester. This can be attributed to the combination of the hydrodynamic eects of the bers embedded in a viscoelastic medium and to the mechanical restraint introduced by the ller at the high concentrations, which reduce the mobility and deformability of the matrix. Other authors have also reported similar observations. [20]. At low temperature, E0 values of matrix and composite are found to be close to each other emphasizing
Table 2 The value of the constant C Sample 10% 20% 30% 40% C 0.97 0.97 0.96 0.91

Fig. 1. The eect of temperature on the dynamic modulus of the neat polyester and various composites with dierent ber content.

Fig. 2. The variation of log E0 with ber volume fraction.

286

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

that at low temperatures bers do not contribute much to imparting stiness to the material. At higher temperatures any water molecules adhering on to the ber will get evaporated making the ber stier. Air-dried cellulose is rather resistant to mechanical impact and a large amount of mechanical energy has to be spent in order to destroy the macroscopic and microscopic structure [21]. This ultimately contributes to the improved modulus of the composite at high temperatures. Tan  is a damping term that can be related to the impact resistance of a material. Since the damping peak occurs in the region of the glass transition where the material changes from a rigid to a more elastic state, it is associated with the movement of small groups and chains of molecules within the polymer structure, all of which are initially frozen in. In a composite system, damping is aected through the incorporation of bers. This is due mainly to shear stress concentrations at the ber ends in association with the additional viscoelastic energy dissipation in the matrix material. Another reason could be the elastic nature of the ber. Fig. 3 delineates the eect of temperature on tan d. Improvement in interfacial bonding in composites occurs as observed by the lowering in tan d values. The higher the damping at the interfaces, the poorer the interface adhesion. SEM photographs of banana polyester composite with ber volume fraction of 10, 20 and 40% are shown in Fig. 4a b and c. It is interesting to note that there is better ber/matrix bonding in composites with 40% ber loading. Whereas ber/matrix de-bonding is evident in composites with 10 and 20% ber loading, composites with 40% ber loading show no gap between the ber and the matrix because of the stronger bonding. When the ber concentration is lower, the packing of the bers will not be ecient in the composite. This leads to matrix rich regions and thereby easier failure of the bonding at the interfacial region. When there is closer packing of the bers crack propagation will be prevented by the neighboring bers. The eective stress transfer occurs in the case of composites with

40% loading. The variation of tan  with temperature of the composites has been analyzed with respect to ber loading and frequency. Incorporation of bers reduces the tan d peak height by restricting the movement of the polymer molecules. Magnitude of the tan  peak is indicative of the nature of the polymer system. In an unlled system, the chain segments are free from restraints. Addition of bers above 30% show two peaks making the two phases, ber and matrix distinct. The appearance of two peaks can also be explained as due to a microgel structure cross-linked to a general matrix structure. The micro gel particles could develop at hot spots where there were initially small excesses of the cross-linking agent or catalyst reagent. Addition of ber decreases the Tg value at low ber loading, showing that the addition of ber below 30% has only a plasticising eect. However, at 40% ber loading, the Tg values show a positive shift, stressing the eectiveness of the ber as a reinforcing agent i.e. the high polymer- ller interaction. The result is consistent with the E0 values obtained. However, the introduction of ller reduces the magnitude of the tan  peak more, than shifting the temperature. The shifting of Tg to higher temperatures can be associated with the decreased mobility of the chains by the addition of bers. Elevation of Tg is taken as a measure of the interfacial interaction. In addition, the stress eld surrounding the particles induces the shift in Tg. Chua [22] concluded based on his studies that a composite with poor interface bonding tends to dissipate more energy than that with good interface bonding. At high ber content when strain is applied to the composite, the strain is controlled mainly by the ber in such a way that the interface, which is assumed to be the more dissipative component of the composite, is strained to a lesser degree [23]. The width of the tan d peak also becomes broader than that of the matrix. The behavior suggests that there are molecular relaxations in the composite that are not present in the pure matrix. The molecular motions at the interfacial region generally contribute to the damping of the material apart from those of the constituents [24]. Hence the width of the tan  peak is indicative of the increased volume of the interface. Table 3 shows the peak width at half height of the samples from the damping curve. The peak width
Table 3 Peak height and peak width at half height of the tan  curves Sample Poly 10% 20% 30% 40% Peak height (cm) 10 5.9 6.3 5.3 4 Peak width (cm) 6.4 6.5 6.5 6.4 9

Fig. 3. Eect of temperature on the tan d value of the composite at dierent ber loading.

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

287

Fig. 4. (a) SEM of the composite with 10% ber loading showing ber/matrix debonding and ber pull out. (b) SEM of the composite with 20% ber loading showing ber/matrix debonding and matrix cracking. (c) SEM of the composite with 40% ber loading showing good ber/matrix adhesion.

Table 4 Peak height and peak width at half height of the E00 curves Sample Gum 10% 20% 30% 40% Peak height (cm) 7 5.8 5.4 5.2 4.8 Peak width (cm) 8.5 8 8 8.3 12

is found to be maximum for composites with 40% ber loading. Increase in the concentration of the ller increases the interface [25]. Stress induced motions may also occur in the composite. The hydrogen bonds between segments may rupture under stress. After such a bond is broken, a small amount of molecular motion can occur which makes it dicult for the same bond to reform. As a result, a new hydrogen bond forms, which initially carries little, if any stress. The net result is energy dissipation and mechanical damping [26].

Fig. 5. The variation of loss modulus with temperature of composites with dierent ber loading.

The loss modulus E00 is dened as the stress 90  C out of phase with the strain divided by the strain; it is a measure of the energy dissipated or lost as heat per cycle of sinusoidal deformation, when dierent systems are compared at the same strain amplitude. It is in fact the viscous response of the material. The loss factors are

288

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

most sensitive to the molecular motions. Fig. 5 shows the variation of loss modulus with temperature of composites with dierent ber loading. It can be seen from the gure that the loss modulus peak values decrease with increase of ber content at temperatures below the glass transition. The eect of the ller is prominent above the glass transition temperature in this case also. The modulus values increase with ber content above the glass transition temperature. Another interesting result that is observed is the broadening of the loss modulus curve when the ber content is increased to 40%. Fig. 6 shows the plot of peak height vs. ber volume fraction. The peak height shows a regular decrease with increase of ber content. At a ber loading of 40%, the most pronounced eect of the ller has been the broadening of the transition region as the ber concentration increases. The observed broadening may be explained as due to the dierence in the physical state of the matrix surrounding the bers to the rest of the matrix ber, matrix and immobilised polymer layer matrix [27]. As reported by other authors, a shell of immobilised polymer surrounds the bers [28]. Fig. 7 shows schematic diagram of ber, matrix and the immobilised polymer layer. The higher the volume fraction of matrix, the more restraint at the interfaces. The dierent physical state of the matrix surrounding the ber hinders the molecular motion. This can be taken as the inter layer which causes the additional

transition [29]. The increase in width of the loss modulus curve is taken to represent the presence of an increased range of order. The greater constraints on the amorphous phase could give rise to a higher or broader glass transition behaviour. The peak width at half height of the composites with dierent ber volume fraction is given in Table 4. The maximum peak width is found to be for the composites with maximum ber content (40%) 3.2. Eect of frequency The storage modulus, loss modulus and damping peaks have been found to be aected by frequency. The variation of E0 with frequency of neat polyester as a function of temperature is shown in Fig. 8. Increase of frequency has been found to increase the modulus values. Fig. 9 shows the eect of frequency on the dynamic modulus of samples with 40% ber loading. Frequency has a direct impact on the dynamic modulus especially at high temperatures. The modulus values are

Fig. 8. The variation of E0 with frequency of neat polyester as a function of temperature.

Fig. 6. The plot of peak height vs. ber volume fraction.

Fig. 7. Schematic diagram showing the ber, matrix and the immobilised polymer layer.

Fig. 9. The eect of frequency on the dynamic modulus of samples with 40% ber loading.

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

289

found to drop at a temperature around 60  C. The drop in modulus value continues steadily till a temperature of 120  C is reached. The molecular motion can be believed to be set in at 60  C. The glass transition temperature of the neat polyester is around 130  C and the modulus value remains unchanged after that. The change in dynamic properties is also associated with crazing and formation of microscopic cracks and voids. At high temperature breaking up of the ber agglomerates and breaking up of the bond between the ber and polymer phases may also occur [26]. The lowering of the modulus peak is maximum for the neat polyester due to the development of microscopic cracks in the unlled resins. Frequency is seen to have a direct impact on the tan  values as well. The viscoelastic properties of a material are dependent on temperature, time and frequency. If a material is subjected to a constant stress, its elastic modulus will decrease over a period of time. This is due to the fact that the material undergoes molecular rearrangement in an attempt to minimize the localized stresses. Modulus measurements performed over a short time (high frequency) result thus in higher values whereas measurements taken over long times (low frequency) result in lower values [26]. In this system also, the modulus measurements over a range of frequencies have been studied. Higher values were observed for measurements made over a short time. The tan d values measured over a range of frequencies for the neat polyester samples are shown in Fig. 10. The tan d peak is found to shift to higher temperature with increase of frequency. The damping peak is associated with the partial loosening of the polymer structure so that groups and small chain segments can move. The tan d curve peak, which is indicative of the glass transition temperature, is also indicative of the degree of cross-linking of the system. Fig. 11 shows the eect of frequency on the tan  curve of samples with

40% loading. The nature of the tan  curve is aected by the incorporation of ber. Eklind and Maurer [30,31] have reported on an interlayer model to simulate the dynamic mechanical properties of lled blends. The ller particles have been reported to be surrounded by an interlayer attached to the ller surface. This phenomenon could give rise to ller structure in the matrix able to alter the dynamic mechanical modulus. The bound polymer results in a layer with properties dierent from the bulk properties of the pure polymer. This micro mechanical transition caused by the interlayer resulted in a new tan  peak occurring at a temperature lower than the Tg of the pure matrix. The tan  curve in this system is found to have two peaks at 40% ber loading. This can be believed to be due to the micromechanical transition arising from the immobilised polymer layer, which acts as the interlayer. The eect of the interlayer becomes prominent only at high ber loading. Increase of frequency is found to have a broadening eect on the tan delta curve. Broadening of

Fig. 11. Eect of frequency on the tan delta curve of composites with 40% loading.

Fig. 10. Eect of frequency on the tan d curve of neat polyester.

Fig. 12. Eect of frequency on the loss modulus curve of neat polyester.

290

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293 Table 5 Values of tan  maximum E00 maximum and Tg values of neat polyester and banana ber reinforced polyester composites at dierent ber loading Fibre loading Tan  Max Frequency (Hz) 0.1 Poly 10% 20% 30% 40% 0.421 0.248 0.262 0.228 0.220 1 0.423 0.241 0.257 0.207 0.214 10 0.452 0.253 0.277 0.233 0.224 Tg from tan  Max Frequency (Hz) 0.1 104.92 99.44 102.619 93.5 118.49 1 114.38 106.25 112.21 106.95 125.27 10 125.22 119.231 122.22 120.02 133.36 108.70 103.62 108.48 101.02 122.22

Fig. 13. Eect of frequency on the loss modulus curve of composites with 40% ber loading.

E00 Max107(Pa) 7.982 7.979 8.005 7.822 7.802 7.825 7.822 7.768 7.762 7.751 7.717 7.713 7.753 7.683 7.729

Tg from E0 ( C) 85.42 95.08 85.95 95.82 85.95 97.35 85.95 95.82 85.95 116.29

the curve is due to some kind of heterogeneity in the network structure. This broadening is more prominent in composites with high ber content. Addition of ber increases the free volume between monomeric units. The introduction of bers, which in turn aects the curing reaction, aects the molecular motions and diffusion, as well. Fig. 12 shows the eect of frequency on the loss modulus values of neat polyester samples. The peak of the loss modulus curve is seen to be shifted to higher temperatures with increase of frequency. Fig. 13 shows the eect of frequency on the loss modulus curve of the samples with 40% ber loading. The E00 peak of the composite is broader revealing the morphological rearrangement resulting in a highly plasticized amorphous region and also the improved interaction between the ber and matrix. The loss modulus curves in addition show two peaks. These very well support the micro mechanical transition observed in the tan  peaks. Eklind and Maurer [31] have reported on glass transition peak on the low temperature side for both loss modulus and tan  curves. It is interesting to note that the micro mechanical transition becomes prominent only at relatively high ber content indicating the critical ber volume fraction and the related interlayer responsible for the micro mechanical transition. Table 5 shows the tan max and E00 max values and the corresponding Tg values for the dierent composites. The values of Tg obtained from the loss modulus peaks are found to be lower than that obtained from the damping peaks. The plasticization results from the addition of ber within the polyester matrix. The loss modulus peak has a double humped nature when bers are incorporated. At lower frequencies the peak of the curve is around 120  C. With increase in frequency, the peak of the loss modulus peak, which corresponds to the glass

transition temperature, is also found to be shifted to higher temperature. Since the response of the sample changes with both temperature and frequency of oscillation, it was decided to make a three dimensional thermo gram for composites with dierent ber loading. Fig. 14 shows the three-dimensional thermo gram. The dierent peaks are clearly visible in the thermo gram. 3.3. ColeCole plots The magnitude of polarisation within a material is represented by dielectric constant, which can be represented by the Debye and Onsager [32] equations. The single relaxation peaks are inadequate to describe the viscoelastic response of polymers. ColeCole is a particular treatment of dielectric relaxation data obtained by plotting E 00 against E00 , each point corresponding to one frequency [32]. Structural changes taking place in cross-linked polymers after ber addition to polymeric matrices can be studied using the ColeCole method. The dynamic mechanical properties when examined as a function of temperature and frequency are represented on the Cole Cole complex plane, E fE0 5

Fig. 15 shows the ColeCole plot, where the loss modulus data log E00 are plotted as a function of the storage modulus log E0 . The nature of the ColeCole plot is reported to be indicative of the nature of the system. Homogeneous polymeric systems are reported to show a semi circle diagram [26]. The ColeCole diagram presented in the gure are imperfect semi circles the shape of the curve points towards the relatively good bermatrix adhesion.

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

291

Fig. 14. Three dimensional thermogram of composites with 40% ber loading.

Fig. 15. ColeCole plot of the composites with dierent bre loading. Fig. 16. Master curve of the composites with 40% ber loading.

3.4. Master curve Polymers obey the superposition principle, i.e.; dynamic modulus is a function of temperature as well as frequency (time). The storage modulus of the composite sample with 40% ber loading as a function of time at dierent temperatures was determined. Time t is related to the frequency f by the following equation t 1=2f 6 ence temperature will be able to cover times outside the range easily accessible by practical experiments. The curve made by superposition is called a master curve. On a logarithmic plot, the storage modulus at a reference temperature, TR and frequency !R equals the storage modulus at temperature T and frequency !. E0 log !R ; TR Glog !; T 7

Because changes in time appear to be equivalent to changes in frequency or time, the process of developing a master curve is called timetemperature superposition. Curves obtained at dierent temperatures were superposed by horizontal shifts along a logarithmic time scale to give a single curve covering a very large range of time. Such curves made by superposition, using a refer-

The dierence between log !R and log ! is constant equal to log aT where aT is called the temperature shift factor. In the log E0 vs. log t graph, the shift factor was calculated as follows log aT log t log t0 8

where t0 is the reference temperature i.e. in the current case 100  C.

292

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293

Table 6 Activation energy values of neat polyester and banana polyester composites under dierent loading Fibre loading Poly 10% 20% 30% 40% Activation energy (kJ/mol) 25.708 21.031 23.836 22.75 41.16

The method of relating the horizontal shifts along the log time scale to temperature changes as developed by Williams, Landel and Ferry is known as the W-L-F method [32]. The amount of horizontal shift of the time scale is given by aT. Use of the master curve and the variations of the shift factors with temperature allow the prediction of the storage modulus at frequencies and temperatures that are not experimentally accessible. In developing the master curve, the reference temperature was randomly chosen as 100 and aT values were found out. Fig. 16 shows the master curve. Any increase in vibrational frequency causes the glass transition temperature to rise and the amplitude of the damping peak to increase. The shift of the transition temperature allows one to calculate the apparent activation energy of the relaxation process for each of the samples assuming a linear equation of the type [33]. log f log f0 H=2:303RT 9

ulus shows a decrease with incorporation of ber below the glass transition temperature and has a positive eect on the modulus at temperatures above Tg. The maximum improvement in properties is observed for composites with 40% ber loading, which is chosen as the critical ber loading. Increase of frequency shifts the Tg to higher temperatures supporting the good ber/matrix interaction, which is clear from the SEM. At the maximum possible ber loading in this study i.e. 40% loading, the loss modulus peak gets broadened emphasizing the improved ber/matrix adhesion. Moreover, an additional peak occurs at high ber loading in the tan  curves, due to the interlayer eect. Addition of ber lowers the tan  peak height, which again points to the improved ber/matrix adhesion. The glass transition temperature is shifted positively on the addition of ber. ColeCole plots show an imperfect semicircle showing the heterogeneity of the system as well as the good interfacial adhesion at high ber loading. Activation energies calculated for the dierent systems show the highest value for 40% loading. Use of master curve and the relationship of the shift factors are useful in predicting the long-term behavior of the composite.

Acknowledgements One of the authors (L.A. Pothan) would like to thank the Science engineering and Technology Department of the Government of Kerala for nancial assistance received for carrying out the project.

Where f0 is an experimental constant, f and T are the measuring frequency and the temperature for the dispersion peak respectively, and R is a gas constant, and H the activation energy. By means of extrapolation, the glass transition temperature Tg can be calculated. Activation energy of the dierent composite samples was calculated from the Arrhenius relationships [26]. The activation energy values are given in Table 6. The activation energy values of the composites with 40% ber loading are the maximum. The activation energy values for neat polyester samples are 25.7 kJ/mol. At low ber loading, as is evident from the SEM of the samples, the ber/matrix adhesion is low and the activation energy is also low. However, incorporation of the critical ber volume fraction brings about high interfacial interaction and eective stress transfer. This increases the activation energy value.

References
[1] Joseph K, Thomas S, Pavithran C. Eect of chemical treatment on the tensile properties of short sisal ber-reinforced polyethylene composites. Polymer 1996;37:513945. [2] Varma IK, Ananthakrishnan SR, Krishnamoorthi S. Comp of glass/modied jute fabric and unsaturated polyester. Composites 1989;20:383. [3] Geethamma VG, Thomas Mathew K, Lakshminarayanan R, Thomas S. Composite of short coir bers and natural rubber: eect of chemical modication, loading and orientation of ber. Polymer 1998;39:1483. [4] Sreekala MS, Kumaran MG, Thomas S. Oil palm bers: morphology, chemical composition, surface modication and mechanical properties. J Appl Poly Sci 1997;66:8821. [5] Pothan LA, Thomas S, Neelakantan NR. Short banana ber reinforced polyester composites: mechanical, failure and aging characteristics. J Reinf Plast Comp 1997;16:744. [6] Richardson MOW, Polymer engineering composite. Applied Science Publishers 1977. [7] Nielsen LE. Mechanical properties of polymers and composites. New York: Marcel Dekker; 1974. [8] Gassan J, Bledzki AK. Possibilities of improving the mechanical properties of jute/epoxy composites by alkali treatment of bers. Compos Sci Technol 1999;59:13039. [9] Finegan IC, Gibson RF. Recent research on enhancement of damping in polymer composites. Comp Strs 1999;44:8998.

4. Conclusions Dynamic mechanical properties of short banana ber reinforced polyester composites are greatly dependent on the volume fraction of the ber. The dynamic mod-

L.A. Pothan et al. / Composites Science and Technology 63 (2003) 283293 [10] Saha AK, Das S, Bhatta D, Mitra BC. Study of jute ber reinforced polyester composites by dynamic mechanical analysis. J Appl Poly Sci 1999;71:150513. [11] Valea A, Gonzalez ML, Mondragon I. Vinyl ester and unsaturated polyester resins in contact with dierent chemicals: dynamic mechanical behaviour. J Appl Poly Sci 1999;71:218. [12] Amash A, Zugenmaier P. Morphology and properties of isotropic and oriented samples of cellulose berpolypropylene composites. Polymer 2000;41:158996. [13] Obataya E, Norimoto M, Gril J. The eects of adsorbed water on dynamic mechanical properties of wood. Polymer 1998;39:14. [14] George S, Neelakantan NR, Varghese KT, Thomas S. Dynamic mechanical properties of isotactic polypropylene/nitrile rubber blends: eects of blend ratio, reactive compatibilization, and dynamic vulcanization. J Poly Sci Part B Polymer Physics 1997; 35:230927. [15] Varghese H, Bhagawan SS, Someswara Rao, Thomas S. Morphology, mechanical and dynamic mechanical properties of blends of nitrile rubber and ethylene vinyl acetate copolymer. Eur Poly J 1995;31(10):95767. [16] George J, Bhagawan SS, Thomas S. Thermogravimetric and dynamic mechanical thermal analysis of pineapple ber reinforced polyethylene composites. J Ther Analy 1996;47:112140. [17] Varghese S, Kuriakose B, Thomas S. Mechanicaland viscoelastic properties of short sisal ber reinforced natural rubber composites: eects of interfacial adhesion, ber loading and orientation. J Adhes Sci Technol 1994;8:234. [18] Joseph K, Pavithran C, Thomas S. Dynamic mechanical properties of short sisal ber reinforced polyethylene composites. J Reinf Plast Comp 1993;12:139. [19] Tan JK, Kitano T, Hatakeyama T. J Crystallisation of carbon ber reinforced polypropylene. Mater Sci 1990;25:33804. [20] Marcovich NE, Reboredo MM, Aranguren MI. Mechanical properties of woodour unsaturated polyester composites. J Appl Poly Sci 1998;70:212131.

293

[21] Klemm D, Philipp B, Heinze T, Heinze U, Wagenknecht W. Comprehensive cellulose chemistry. WileyVCH; 1998. [22] Chua PS. Dynamic analysis studies of interphase. Poly Comp 1987;8:308. [23] Ibarra L, Macias M, Palma E. Viscoelastic properties of short carbon ber thermoplastic (SBS) elastomer composites. J Appl Poly Sci 1995;57:831. [24] Dong S, Gauvin R. Application of dynamic mechanical analysis for the study of the interfacial region in carbon ber/epoxy composite materials. Poly Comp 1993;14:414. [25] Landel RF. Mechanical properties of polymers and composites. New York: Marcel Dekker, Inc; 1994. [26] Murayama T. Dynamic mechanical analysis of polymeric materials. 2nd ed. Amsterdam: Elsevier; 1978. [27] Joshi M, Maiti SN, Misra A. Studies on the thermal, dynamic mechanical and rheological behavior of short-glass-ber-reinforced composite based on poly(butylene terephthalate) high density polyethylene blends. Polymer 1994;35:17. [28] Thomason JL. Investigation of composite interphase using dynamic mechanical analysisartifacts and reality. Poly Comp 1990;11:2105. [29] Maurer FHJ. Controlled interphases in composite materials. New York: Elsevier; 1990. p.491 [Ishida H, editor]. [30] Eklind H, Maurer FHJ. Micromechanical and microdielectric transitions in P(S-g-EO) modied PPO/PMMA blends. Polymer 1997;38:1047. [31] Eklind H, Maurer FHJ. Frequency and temperature dependence of molecular and micromechanical transitions in PPO/ PMMA/(S-g-EO) blends. J Poly Sci Part B Phys Ed 1996;34: 1569. [32] Aklonis J J, MacKnight W J. Introduction to polymer viscoelasticity, (John Wiley, ed.); 1983. [33] Folkes MJ. Short ber reinforced thermoplastics. New York: Wiley; 1982.