Composites Science and Technology 53 ( 1995) 9% 110 Elsevier Science Limited Printed 0266-3538(94)00074-3 in Northern Ireland 0266-3538/95/$09.

50

EFFECT OF AGEING ON THE PHYSICAL AND MECHANICAL PROPERTIES OF SISAL-FIBER-REINFORCED POLYETHYLENE COMPOSITES
Kuruvilla Joseph, Sabu Thomas*
School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills PO, Kottayam, Kerala-686560, India

&

C. Pavithran
Regional Research Laboratory (CSIR), Trivandrum-695019, Kerala, India

(Received 1 August 1994; accepted 22 November 1994) decade cellulose-based natural fibers have found use as a potential resource for making low-cost composite materials, especially in developing tropical countries where these fibers are abundant. Natural fibers possess moderately high specific strength and stiffness and can be used as reinforcing materials in polymeric resin matrices to make useful structural composites materials.* Lack of good interfacial adhesion and poor resistance to moisture absorption make the use of natural fiber-reinforced composites less attractive. This problem can be overcome by treating these fibers with suitable chemicals. The use of natural-fiber-reinforced thermoplastic composites under different environmental conditions has increased during the last few years. Environmental conditions such as humidity or change in temperature and exposure time cause dimensional instability and loss of mechanical properties. It is well established that natural fibers are susceptible to moisture absorption.5 Virtually all properties of plastics are affected by increases in temperature, but in different ways and to different degrees. Many studies have been reported concerning the effect of different ageing conditions on the physical and mechanical properties of natural-fiber-reinforced polymer composites.6*7- Sapieha et al. have studied the kinetics and equilibrium of water sorption in polyethylene/cellulose composites. Other workers8- have studied extensively the effect of different ageing conditions on the and mechanical properties of physical cellulose/polymer composites. There have also been studies on the effect of recycling on the mechanical properties of wood-fiber/polystyrene composites under different ageing conditions.j It has been further reported that the behavior of the recycled composites under all ageing conditions did not change sig99

Abstract
The effects of ageing on the mechanical properties and dimensional stability of cardanol derivative of toluene diisocyanate (CTDZC) treated and untreated sBal/LDPE composites have been studied. The ageing properties of the sisal composites were compared to those of glass-fiber composites aged under identical conditions. The tensile properties and dimensional stability were evaluated under two different ageing conditions. In the first case, samples were immersed in boiling water for 7 h under atmospheric pressure; in the second case, samples were heated at 70C in an air circulating oven for 7 days. The mechanical properties, weights and dimensions of the aged samples were measured. Zt was noted that CTDZC-treated composites showed superior mechanical properties and better dimensional stability compared to untreated composites under identical ageing conditions. The greater resistance of the treated composites under different ageing conditions indicated the existence of an eficient interfacial area between the fiber and the polymer matrix. Keywords: ageing, sisal-fiber-reinforced physical properties, mechanical properties

composites,

INTRODUCTION In recent years polymer composites containing natural fibers have received considerable attention both in the literature and in industry. Since natural fibers are strong, light in weight, abundant, non-abrasive, non-hazardous and inexpensive, they can serve as an excellent reinforcing agent for plastics. Over the past *To whom correspondence should be addressed.

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Kuruvilla Joseph,

Sabu Thomas, C. Pavithran

nificantly. Furthermore, treated wood-fiber-filled thermoplastic composites offer good mechanical and dimensional stability under extreme conditions even after recycling. Sisal fiber is a lignocellulosic fiber obtained from the leaf of the plant Agave-veracruz. Recently, we have successfully used sisal fibers as potential fillers for thermosets, elastomers and thermoplastics. Processing characteristics, tensile properties, dynamic mechanical properties and rheological behavior of the resulting composites have been reported.2- This paper presents the results of studies on the effect of different ageing conditions on the physical and mechanical properties of low-density polyethylene (LDPE) filled with untreated, and isocyanate treated sisal fiber. The ageing properties of the sisal-filled composites were compared to those of glass-fiber composites aged under identical conditions.

from Fluka, Switzerland. Dibutyl tin dilaurate and sodium hydroxide were obtained from Scientific and Industrial Supplies Corporation, Bombay, India. Alkali treatment The chopped fibers were placed in a stainless steel vessel. A 10% solution of NaOH was added to the vessel and stirred well; this was kept for 1 h with subsequent stirring. The fibers were then washed thoroughly with water to remove the excess NaOH. Final washings were carried out with distilled water containing a small amount of acid. The fibers were then air dried. Preparation of urethane derivative of cardanol The synthesis of urethane derivative of cardanol was carried out using a 1: 1 molar ratio of cardanol and TDI containing a free isocyanate group. Cardanol (30 g, O-1 mol) was placed in a pressure equalising funnel and diluted with Ccl, (SOml) and the required amount of dibutyl tin dilaurate as catalyst. TDI (17.4 g, 0.1 mol) was placed in a round bottomed flask of capacity 500 ml. The cardanol solution was added dropwise to the TDI with constant stirring until the addition of cardanol was completed. The stirring was continued for 1 h to complete the reaction. The product formed contained one free isocyanate group for further reaction. The mechanism of preparing urethane derivative of cardanol is given in Scheme I. The IR spectrum of the cardanol derivative of toluene diisocyanate (CTDIC) exhibited the characteristic urethane peaks at 3350cm-l for -NH and 1720cm- for -C=O stretching vibrations. The introduction of the cardanol moiety was indicated by the presence of -C=C peak at 1620cm-1, -CH aromatic at 3020cm- and -C-H aliphatic at 2980cm-. The IR spectrum of the CTDIC also showed peaks at 1440 aromatic ring and 1590 cm- due to the -C=C stretching. The product obtained was used for further reaction.

EXPERIMENTAL Materials LDPE granules obtained from M/s. Indian Petrochemical Corporation Ltd, Baroda, were used. The properties of LDPE are given in Table 1. Sisal fiber (Agave-veracruz) was obtained from local sources; the properties of sisal fiber are given in Table 2. The diameter of the fiber varied from 100 to 300 pm. The average diameter of the fiber calculated from the fraction of fibers of different diameter in a sample was about 190 pm. The tensile strength, modulus, and failure strain of the fiber were 400-700 MPa, 9-20 GPa and 5-14%, respectively. Cardanol, the principal component of cashew nut shell liquid (CNSL) obtained from Anacardium occidentale, is a plant-source raw material abundant in tropical countries like southern India and Vietnam. Cardanol was supplied by Satya Chemicals, Madras, India. Toluene-2,4-diisocyanate (TDI) was obtained

Table 1. Physical and mechanical properties of low density polyethylene (LDPE-Iodothene 16 MA 400) Melt flow index w;; 40 0.916 Density (g/cm) Tensile strength at break (kg/cm*) 90 Elongation at break (%) Modulus of elasticity (kg/cm) Vicat softening point (0 85 Crystalline melting point fC) 104

200

1400

Table 2. Properties of sisal fiber Fiber diameter (cLm) 100-300 Lignin content (%) 4-5 Cellulose content (%I 8.5-88 Tensile strength (MPa) 400-700 Tensile modulus Pa) 9-20 Elongation at break (%) 5-14

Effect of ageing on the properties of sisallLDPE Preparation

composites sheets

101

N=C:O

L
Carda nol
Dibutyl tin dilaurate I catalyst1

of composite

Toluene

2, L- diisownate

[TDICI

Sisal/polyethylene composites prepared by both melt mixing and solution mixing were used for making the randomly oriented fiber composites. Composite specimens of dimensions 120 mm X 12.5 mm X 3 mm were prepared by injection molding of the composites at 115 + 5C using a hand operated ram type injection molding machine. Glass/polyethylene composites were prepared by a similar procedure adopted as in the case of sisal/LDPE composites.
Mechanical testing

Urethane

derivative

of cmdaml

I CfDICl

Scheme I.

Cellulose

-OH

0 H ~~~&-_-_____.,
CTDIC Dtbutyl tin dilaurate
tCOtOlY;f 1

Tensile testing of rectangular specimens of size 120 mm X 12.5 mm X 3 mm was carried out in an Instron universal testing machine model 1190 at a cross-head speed of 200 mm min- and a gauge length of 50mm. The tensile modulus and elongation at break of the composites were calculated from the load/displacement curve. At least five specimens were tested for each set of samples and the mean values were reported.
Thermal ageing

cellulose

-0

-,I

ok-i$

Scheme II. Treatment of sisal fiber with CTDIC

Test samples were heated at 80C in an air-circulating oven for 1, 3, 5 and 7 days. After being cooled down and conditioned at room temperature, the weights and dimensions of each specimen were measured. The tensile properties of these samples were determined in an Instron universal testing machine as mentioned above.
Exposure to boiling water

The alkali-treated dried fibers were placed in a flask and soaked with an appropriate quantity of CCL and a small amount of dibutyl tin dilaurate catalyst. The flask was fitted with a pressure equalising funnel containing the urethane derivative. The urethane derivative was added into the flask dropwise with sufficient stirring. After the complete addition of urethane, the reaction was allowed to continue for 1 h. The possible reaction between the free isocyanate groups in CTDIC and cellulose is as given in Scheme II. The urethane-treated fibers were purified by refluxing with acetone for 8 h in a Soxhlet apparatus followed by repeated washing with distilled water. Finally the fibers were oven dried at 80C.
Preparation of LDPE/sisal composites

Samples were immersed in boiling water for periods of 1, 3, 5 and 7 h, at atmospheric pressure. These samples were then dried between two sheets of filter paper and the weight and dimensions of each specimen were measured. The samples were then subjected to tensile property measurements.
Transcrystallinity studies

The LDPE/sisal composites for molding composites were prepared by a solution mixing technique. In this method, the previously cut (5.8 mm length) fiber was added to a viscous slurry of polyethylene in toluene which was prepared by adding toluene to a melt of the polymer. The mixing was carried out manually in a stainless steel beaker using a stainless steel stirrer. The temperature was maintained at 110C during mixing for about 10 min. The mix was then transferred into a flat tray as lumps and kept in a vacuum oven at 70C for 2 h to remove the solvent.

A few granules (5-7) of LDPE were placed on a clean glass slide. One or two fibers were placed over the LDPE granules and then covered with a cover glass. The total system was heated above the melting point of LDPE (125C) in a hot stage which can be programmed for annealing studies. The sample was kept at 125C for about 10 min. The temperature of the system was brought down to the crystallization temperature of LDPE (110C). The transcrystallization process was followed as a function of annealing time under a polarised microscope.

RESULTS

AND

DISCUSSION

Effect of ageing on tensile strength

Figure LDPE

la shows the tensile properties of unaged composites containing randomly oriented

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Kuruvilla Joseph, Sabu Thomas, C. Pavithran

Fig. lc. SEM photomicrograph of the tensile fracture surface of sisal-fiber/LDPE composites showing better dispersability of sisal fiber in LDPE matrix. Fig. la. Effect of fiber content on the tensile strength of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites before ageing.

untreated sisal fiber, isocyanate-treated (CTDIC) sisal fiber and glass fiber as a function of fiber loading (fiber length = 5.8 mm). It can be seen that tensile strength values of all the composites increase with fiber loading, but in glass-fiber composite, the tensile strength shows a decreasing trend beyond 20% fiber loading. This may be due to the reported poor dispersion of glass fiber in the polyethylene matrix at higher fiber loading. Figures lb and lc are the SEM photomicrographs of the tensile fracture surface of glass-fiber/LDPE and sisal-fiber/LDPE composites respectively. The poor dispersibility of glass fiber in LDPE matrix is readily seen from Fig. lb.

Man-made fibers like glass are relatively straight and smooth surfaced, whereas the surface of the CTDIC-treated sisal fiber is irregular or rough.7 This leads to strong physical interaction between fiber and matrix in natural fiber composites. Therefore, treated natural fibers are likely to offer greater resistance to pullout from the matrix than man-made fibers and this results in superior mechanical properties.5 However, the untreated sisal fiber composites show inferior properties. Figure 2 shows the tensile strength of the composites as a function of exposure time in boiling water. In these composites, the fiber loading was

ZD

. I

IS

CTDK Treated GIOSS Untreated

Fig. lb. SEM photomicrograph of the tensile fracture surface of glass-fiber/LDPE composites showing poor dispersability of glass fiber in LDPE matrix.

Fig. 2. Effect of exposure time (h) in boiling water on the tensile strength of untreated sisal fiber, CTDIC-treated sisal fiber, and glass-fiber-filled LDPE composites. (Fiber content = 20 wt%.)

Effect of ageing on the properties of sisal/LDPE composites 20 wt% and the average fiber length was 5.8 mm. It is interesting to note that except for glass fiber composites, all other composites showed a decrease in properties with exposure time. From Fig. 2, it can be seen that the tensile strength values of both untreated and CTDIC-treated sisal/LDPE composites decrease steadily with exposure time in boiling water. The in the case of untreated decrease is sharper composites. This can be attributed to the fact that the rate of diffusion of water into the composite is time and temperature dependent. Swelling of the fiber increases with exposure time in boiling water. As a result of the swelling of fibers, which are surrounded by the polymer matrix, cracks may be formed at the matrix for the flapping of the swollen fibers. This may also contribute to the penetration of more water into the composite during prolonged exposure in boiling water. This leads to a reduction in the fiber/matrix adhesion and a consequent decrease in tensile strength with exposure time in boiling water. It is interesting to note that the decrease in properties are marginal in the case of CTDIC-treated composites, because the CTDIC treatment reduces water absorption. In the case of CTDIC-treated sisal fibers, the functional group -N=C==O, reacts with the cellulose -OH group and thereby the hydrophilic nature of the cellulose fiber is reduced.16 The retention of tensile strength of glass/LDPE composites when exposed to boiling water may be due to the reported plasticizing effect of water.5 Since the glass fiber does not absorb water, the penetrated water at the interface may act as a plasticizing agent. The retention of tensile properties of these composites up to an exposure time of 5 h, again indicated that a small amount of water can offer a better plasticizing effect. Moreover, when glass-fiber-filled LDPE composites were immersed in boiling water (close to the softening temperature of LDPE) for a limited period, the fiber/matrix adhesion is improved due to the transcrystallization phenomenon at the interface. However, long-time exposure in boiling water leads to the deterioration of tensile strength due to the penetration of large amounts of water at the interface and the consequent reduction of the fiber/matrix adhesion. On the other hand, in untreated naturalfiber composites, the fiber absorbs water very quickly even with a short exposure time (1 h) in boiling water. The behavior of CTDIC-treated composites is comparable to that of glass-fiber composites. Figure 3a shows the tensile strength of the composites immersed in boiling water for 7 h, as a function of fiber loading (average fiber length = 58 mm). It can be seen that, after exposure for 7 h in boiling water, the tensile strength of untreated sisal-fiber/LDPE composites is unaffected by fiber loading. At all levels of fiber loading the tensile strength is almost the same. However, the CTDIC-

103

.
I .

CTDIC
GIOSS

Treated

untreated

Fig. 3a. Effect of fiber content on the tensile strength of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites after exposure in boiling water for 7 h. treated and glass-fiber composites showed a different trend, i.e. tensile strength increases with fiber loading. It has been reported that the water absorption of cellulose-fiber composites depends on the concentration of the fiber and temperature. When the fiber/matrix interface is accessible to moisture from the environment, the wood fibers tend to swell. This results in the development of shear stress at the interface, which leads to the ultimate debonding of the fibers. But in the case of CTDIC-treated sisal fibers, the functional group -N=C%O, reacts with the cellulose -OH group and thereby the hydrophilic nature of the cellulose fiber is reduced.j Comparing Figs la and 3a, it is seen that the CTDIC-treated sisal fiber and glass-fiber-filled composites show good retention of tensile strength. However, in the untreated composites the retention is very poor. This clearly indicates that there is excellent interfacial contact between the CTDIC-treated fiber and matrix even in a humid environment. A possible hypothetical chemical structure of cellulose-fibreCTDIC-polyethylene in the interfacial area is given in Scheme III. On the other hand, the decrease in strength with increasing fiber loading and exposure time observed in untreated sisal/LDPE composite again indicated its greater affinity towards moisture. The differences in the tensile properties can be further understood from the SEM photomicrographs of the fracture surfaces of CTDIC-treated and untreatedsisal/LDPE composites as shown in Figs 3b and 3c respectively. However, in glass/LDPE composites, the tensile strength values at all levels of fiber loading

104 Cellulose fibre

Kuruvilla Joseph, Sabu Thomas, C. Pavithran

-CH2-CH2-CH2-CH2-CH2 LDPE

-CH,-CH,-CH,-CH,-CH1 Matrix

Where

Fig.

0 0

3c. SEM photomicrograph of the tensile fracture surface of untreated sisal-fiber/LDPE composites.

Scheme III.

Fig. 3b. SEM photomicrograph of the tensile fracture surface of CTDIC-treated sisal/LDPE composites. (Figs la and 3a) remain almost constant due to the fact that glass fiber has little affinity towards water. Figure 4a shows the tensile strength of the above composites as a function of exposure time at 80C. It is seen that all the composites showed a general tendency to increase their strength up to a limited time of exposure (1 day). This may be due to the fact that the fiber/matrix adhesion will be increased due to softening of the polyethylene matrix. It has been reported that short-time ageing at high temperature improves the mechanical properties of thermoplastic composites. This can be explained by an additional process of annealing the thermopressed composites at the softening temperature.17 Therefore a transcry-

Fig. 4a. Effect of exposure time (days) at elevated temperature (SOT) on the tensile strength of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites. (Fiber content = 20 wt%.)

stalline region will be developed at the fiber/matrix interface even at this temperature and time, as shown in Figs 4b and 4c. The photographs were taken after an annealing period of 12 h at 100C. Our studies have shown that transcrystallization is possible even at 80C on prolonged heating which enhances the tensile properties. Figure 5 shows the tensile strength of the composites after an exposure time of 7 days at an elevated temperature (WC) as a function of fiber loading. It can be seen that in all cases tensile strength increases with fiber loading. It is also seen that the tensile strength values of all the composites except

Effect of ageing on the properties of sisallLDPE

composites

105

Fig. 4b. Optical

micrograph of sisal/LDPE showing transcrystallinity.

composites

that of glass-fiber composites, are inferior to unaged samples (Fig. la) due to the poor fiber/matrix interface adhesion on prolonged exposure at an elevated temperature (SOC) for 7 days. However, a deterioration of strength was observed in all the composites except glass/LDPE composites after an exposure time of 1 day at an elevated temperature (SOC). This may be due to the loss of strength of sisal fiber during prolonged exposure at elevated temperatures (SOY) caused by the decomposition of volatile extractives present in the sisal fiber surface.18 Although the components of cellulose are supposed to remain stable up to 16OC, the degradation reaction may initiate slowly for prolonged heating at 80C.7,8 The decomposition of fiber will develop voids at the interface and this leads to poor fiber/matrix adhesion. In the case of glass/LDPE composites, the tensile strength was almost retained or remained constant even after an exposure time of 7 days. This is due to the fact that in glass/LDPE composites, no decomposition takes place at this temperature. Effect of ageing on modulus Figure 6 shows the tensile modulus of the unaged composites as a function of fiber loading. It can be seen that the modulus increased steadily with fiber loading. Since the modulus of the matrix is constant, the relative packing efficiencies of the fiber and the fiber matrix adhesion are the important factors in determining the modulus of the composite.5 At higher fiber loading (>20%), the CTDIC-treated composites exhibit the maximum modulus values. As expected the untreated composites show the lowest modulus values.

Fig. 4c. Optical photomicrograph of sisal/LDPE composites showing transcrystallinity: magnified view.

.
I

Untrshc! Gloss . ultreoted

I

Gloss CTDlC Treokd

r/.//l

Fig. 5. Effect of fiber content on the tensile strength of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites atier 7 days exposure at elevated temperatures (80C).

Fig. 6. Effect of fiber content on the tensile modulus of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites before ageing.

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Kuruvilla Joseph,

Sabu Thomas, C. Pavithran

e
I

nfreated

Gloss CTDIC Treated

.
I

untreated GIOSS
CTDlC Treated

Expcmre time I hrsl

Fibre content

I %I

Fig. 7. Effect of exposure time (h) in boiling water on the tensile modulus of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites. Tensile modulus values of the composites containing 20% fiber as a function of exposure time in boiling water are presented in Fig. 7. In sisal/LDPE composites (both CTDIC-treated and untreated), the modulus showed a decreasing tendency with exposure time, whereas in glass-fiber composites, the modulus was found to be almost independent of exposure time, although a slight decrease is observed after an exposure time of 1 h. The decrease in modulus with exposure time observed in sisal/LDPE composites is associated with water absorption, i.e. the natural fibers absorb more water than inorganic fibers like glass because of their hydrophilic nature. Therefore, due to the high water content after exposure in boiling water, the stiffness of the cellulose fiber drops considerably. This has been explained as being due to the softening of the desorbed zones of the cellulose microfibrils, whereas the situation is different in glass-fiber composites. In this case, since the fiber does not absorb water, the degree of water mobility at the interface is greatly reduced. So the modulus remains almost constant even after an exposure of 7 h in boiling water. Figure 8 shows the variation in modulus with fiber content after an exposure of 7 h in boiling water. It is seen that the modulus values of CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites increase with fiber loading, whereas untreated sisal-fiber-filled LDPE composites showed a decreasing tendency. This is because of the variation in hydrophilic nature of the fibers. As mentioned earlier, the CTDIC-treated sisal fibers are more hydrophobic than untreated fibers, so the hydrophobicity varies in the order: plain

Fig. 8. Effect of fiber content on the tensile modulus of untreated sisal fiber, CIVIC-treated sisal fiber and glass-fiber-tiled LDPE composites after exposure in boiling water for 7 h.

polymer > glass fiber > CTDIC-treated sisal fiber > untreated sisal fiber. Therefore, the degree of water absorption is lower in CTDIC-treated and glass-fiberfilled composites than in untreated composites. However, when the fiber loading increases, the degree of water absorption increases correspondingly. In other words, at higher fiber loading, the water content in untreated sisal-fiber composites is much higher than that of CTDIC-treated and glass-fiber-filled composites. In fact, because of the excessive absorption of water, the intermolecular hydrogen bonding in the cellulose fiber might be reduced by the formation of intermolecular hydrogen bonding between cellulose molecules and water molecules which lead to the deterioration of the modulus. Figure 9 shows the effect on the modulus with exposure time at elevated temperature (SOC). It is interesting to note that the modulus of all composites increases steadily after an exposure time of 1 day and then remain constant. These results suggest that heating of a thermoplastic composite for a short period close to its softening temperature improves the modulus considerably due to its better interfacial adhesion at this temperature. This may be associated with the development of a transcrystalline region, as discussed earlier. The modulus of the composites as a function of fiber content aged at elevated temperatures (SOC) for 7 days is shown in Fig. 10. It can be seen that in all cases the modulus increases with fiber a significant improvement in loading. However, modulus with fiber content was observed in CTDIC-treated sisal fiber and glass-fiber-filled LDPE

Effect of ageing on the properties of sisal/LDPE composites

107

of exposure time (days) at elevated temperature (SOT) on the tensile modulus of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites.

Fig. 9.Effect

Fig. Effect of fiber content on the elongation 11.

at break (%) of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites before ageing.

It is seen that in all cases elongation at break decreased with the increase in fiber loading due to the lower elongation at break values of the fiber than that of LDPE. Moreover, the addition of brittle fiber makes the matrix more rigid by decreasing the flexibility of the polymer chains. The variation in elongation at break as a function of exposure time in boiling water of the composites having a fiber loading of 20 wt% and an average fiber length of 5.8 mm is presented in Fig. 12. It is clear that the elongation at
loading.

.
I A

untreated
GIOSS CTDIC Treated

Fig. 10. Effect of fiber content on the tensile modulus of untreated sisal fiber, CTDIC-treated sisal fiber and
glass-fiber-lllled LDPE composites after 7 days exposure at elevated temperature (80C).

composites. This clearly indicates the retention in properties of these composites even at elevated temperatures.

Exposure time,

hrsl

Effect of age& on elongation Figure 11 shows the elongation at break of the composites before ageing as a function of fiber

Fig. 12. Effect of exposure time (h) in boiling water on the elongation at break (%) of untreated sisal fiber, CIDIC-treated sisal fiber and glass-fiber-filled LDPE composites.

108
r

Kuruvilla Joseph,

Sabu Thomas, C. Pavithran

I
0

I10 IO
30

Fig. W. Effect of fiber content on the elongation at break (%) values of untreated sisal fiber, CTDIC-treated sisal fiber
and glass-filber-filled LDPE composites after exposure boiling water for 7 h. in

Eg. 14. Effect of exposure time (days) at elevated temperature (80C) on the elongation at break (%) of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites.

break values of both CTDIC-treated and untreated sisal-fiber/LDPE composites decrease with exposure time. However, the decrease is sharper in untreated composites than in CTDIC-treated composites. However, in glass-fiber/LDPE composites, the elongation at break is independent of exposure time, i.e. the values remain almost constant. The decrease in elongation at break observed in sisal/LDPE composites (both treated and untreated) is due to the increased water absorption. Figure 13 shows the change in elongation at break with fiber loading after exposure in boiling water for 7 h. It can be seen that at all levels of fiber loading, untreated composites showed the lowest elongation values compared to CTDIC-treated sisal fiber and glass-fiber-filled composites. These results also support the fact that the decrease in elongation with exposure time in boiling water is mainly due to the water absorption of the composites. Figure 14 shows the variation in elongation at break values with exposure time at elevated temperatures (80C). It is clear that in all composites (untreated sisal, CTDIC-treated sisal and glass-fiber-filled LDPE composites) elongation is not affected by the ageing at elevated temperatures. Figure 15 shows the variation in elongation at break values of the aged composites with fiber loading. By comparing Fig. 15 with that of the unaged samples (Fig. ll), it can be seen that the elongation is not very much affected by the ageing at elevated temperatures.

Fig. 15. Effect of fiber (%) of untreated sisal glass-fiber-filled LDPE elevated

content on the elongation at break fiber, CTDIC-treated sisal fiber and composites after 7 days exposure at temperature (80C).

Effect of ageing on dimensional stability Dimensional stability of the composites was studied by measuring the change in weight and cross-sectional area of the composites after exposure in boiling water for different periods. Figure 16 shows the change in weight as a function of exposure time in boiling water. It is obvious that change in weight is almost independent of exposure time when the plain polymer

Effect of age@

on the properties of sisaL/LDPE

composites

109

1
.
, I . treoled

CTDIC

Treoled

.
I /

Unlrwled CTDIC Treated

GlO%
LOPE

1
Fig. 16. Effect of exposure time (h) in boiling water on the increase in weight of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites.

Fig. 18. Effect of exposure time (h) in boiling water on the increase in area of untreated sisal fiber, CIDIC-treated sisal fiber and glass-fiber-filled LDPE composites.

and glass-fiber composites are considered. But in the case of sisal-fiber composites (both treated and untreated), weight increases with exposure time, and it is interesting to note that untreated composites showed the greatest increase in weight, as expected. CTDIC treatment greatly reduces the water absorption, so the water uptake decreases in the order: untreated sisal fiber, CTDIC-treated sisal fiber, glass fiber and plain polymer (LDPE).

Fig. 17. Effect of fiber content on the increase in weight of untreated sisal fiber, CIDIC-treated sisal fiber and glass-fiber-tilled LDPE composites after exposure in boiling water for 7 h.

Figure 17 shows the change in weight as a function of fiber loading at an exposure time of 7 h in boiling water. In glass-fiber composites the weight is almost constant even at higher fiber loading, because glass fiber does not absorb water. However, the situation is different in sisal/LDPE composites. In these composites the change in weight increases with fiber loading. It can be seen that the change in weight of untreated composites is higher than that of CTDIC-treated composites. Figure 18 shows the increase in cross-sectional area as a function of exposure time in boiling water. In this case also glass/LDPE composites showed no area change with exposure time. But in the cross-sectional area sisal/LDPE composites, increases with exposure time. The change in cross-sectional area as a function of fiber loading after an exposure time of 7 h is shown in Fig. 19. It can be noted that in all cases, the cross-sectional area increases with fiber loading. The increase in cross-sectional area observed in glass/LDPE composites is much lower than those of other composites. The absorption of water by LDPE, which is hydrophobic in nature, is negligible, so the increase in weight and cross-sectional area is proportional to the concentration of hydrophilic fibers in the composites. However, by increasing the time of exposure in boiling water, both weight and cross-sectional area of the composites increase due to the absorption of water by the hydrophilic cellulose fiber. The water absorption is high in untreated composites and this leads to a deterioration in mechanical properties as well as dimensional stability. But the situation is different in CTDIC-treated-sisal/LDPE composites. As explained earlier, the high reactivity of the -N=C-rr functional

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Kuruvilla

Joseph, Sabu Thomas, C. Pavithran

matrix. The better dimensional stability offered by glass/LDPE composites is attributed to the hydrophobic nature of glass fibers. Finally, it can be concluded that with a suitable fiber surface treatment, the mechanical properties as well as dimensional stability of sisal-fiber-filled/LDPE composites can be improved. The properties of the treated-sisal/LDPE composites are comparable to those of glass-fiberfilled composites. REFERENCES
1. Lightsey, G. R., Organic fillers for thermoplastics, Vol. 17. Plenum Press, New York, 1983. Bisanda, E. T. N. & Ansell, M. P., Comp. Sci. Technol., 41 (1991) 165. Pavithran, C., Mukherjee, P. S., Brahmakumar, M. & Damodaran, A. D., J. Mater. Sci. Lett., 7 (1987) 882. Varma, I. K., Ananthakrishnan, S. R. & Krishnamoorthy, S., Composites, 20 (1989) 383. McKenzie, A. W. & Yuritta, J. P., Appita, 32(b) (1979) 460. Maldas, D. & Kokta, B. V., Polym. Plast. Technol.
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2. 3. 4.

Fig. 19. Effect of fiber content on the increase in area of untreated sisal fiber, CTDIC-treated sisal fiber and glass-fiber-filled LDPE composites after exposure in boiling water for 7 h. group towards the cellulose -OH groups offers better interfacial contact between the fiber and the polymer matrix. In addition to this improved interfacial bonding, the CTDIC treatment reduces the hydrophilic nature of the cellulosic fiber conisderably and imparts some hydrophobicity on cellulose fibers. So the CTDIC-treated sisal-fiber/LDPE composites are superior as far as mechanical properties and dimensional stability are concerned. CONCLUSIONS The physical and mechanical properties of untreated and CTDIC-treated-sisal/LDPE composites under different ageing conditions were evaluated. These properties were compared to those of short-glassfiber/LDPE composites under identical conditions. It has been demonstrated that CTDIC-treated composites showed superior mechanical properties and dimensional stability as compared to untreated composites due to the existence of an efficient interfacial bond between the fiber and the polymer

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