RJTA Vol. 10 No.

3 2006

Studies on the Properties of Sisal Fibre/Phenol Formaldehyde Resin In-situ Composites

JIAN L1, 2, JIN-BIAO ZHONG2 and CHUN WEI1, 2
1

Key Laboratory of Nonferrous Materials and New Processing Technology, Ministry of Education, Guilin 541004, P. R. China 2 Department of Material and Chemical Engineering, Guilin University of Technology, Guilin 541004, P. R. China gllvjian@yahoo.com.cn

ABSTRACT
In this paper sisal fibre (SF) was pretreated by alkali, KH-550, and steam explosion. Then sisal fibre/phenol formaldehyde (SF/PF) composites were prepared through compression molding. The effects of the sisal fibre addition mode and sisal/glass (SF/GF) hybrid phenol formaldehyde composites with glass/sisal weight ratio on mechanical properties, thermal properties, water absorption properties and electrically insulating properties were studied. Meanwhile, the effects of sisal treatments were also examined. Results indicate that polymerization-filling is a novel synthesizing method and KH-550 treatment is an ideal method for the modification of SF. The SF/PF composites made by the polymerization-filling method increased by 17.61%, 7.16% and 12.25% in impact strength, bending strength and bending modulus respectively compared with using the conventional physical blending method. SF/GF/PF composites showed higher mechanical properties when SF/GF was 1/1, and thermal properties improved with the addition of GF; sisal fibre and glass fibre exhibited positive hybrid effect in water absorption properties while negative hybrid effect in insulating properties. A study of fibre-matrix interaction and fracture behavior of the fractured surfaces of the composites was also made by scanning electron micrographs. Keywords: sisal fibre; phenol formaldehyde resin; surface treatment; reinforcement; mechanical properties; in-situ composite

1.

Introduction

Phenol formaldehyde resin was the first industrialization resin in the world. As one of the most important thermosetting polymers, phenol formaldehyde resin exhibits high stiffness, electrically insulating properties, dimension stability and excellent chemical corrosion resistance; however, its structure results in significant brittleness. Natural-fibre-reinforced composites have attracted increasing attention (Bledzki & Gassan, 1999; Li et al., 2000). In recent years, thanks to their high breaking strength, sisal fibre becomes an excellent reinforcing element for the preparation of polymer composite materials (Albano et al., 2002; Mishraa & Mohantyb, 2003; Niu et al., 2005; Zhong et al., 2006). The application of vegetable fibre to bio-composite is, however, limited by
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poor resistance to high temperatures and weak bonding to synthetic polymers. Disadvantages associated with the use of natural fibre as a reinforcement in thermoplastics are the result of a lack of a good interfacial adhesion and a poor resistance to humidity absorption, since cellulose fibre are of hydrophilic nature and thermoplastics are of hydrophobic nature. Now many scientists are working for this field, and a lot of methods are preferred, including the modification of the surface of the fibre (Albano & Ichazo, 2001; Paul et al., 1997). Effects of sisal fibre treatment on the properties of sisal fibre/phenol formaldehyde resin composites were studied in this paper. Studies show that polymerization filling is a novel modification method. In this method the filler is modified first, followed by the monomer polymerize with the modified filler. Finally the

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composites with particular properties can be obtained. In this work we introduce a novel method - the polymerization-filling method for sisal fibre reinforced phenol formaldehyde resin. Similar studies were not found in the literature.

Sisal fibre was immersed in a solution with 5% NaOH for 4 hours at room temperature, in which the fibre-to-solution weight ratio was 1:25. The fibre was then washed thoroughly with water to remove the excess NaOH, then air dried at 80. Sisal fibre was soaked in a solution of 2% amimosilane (KH550, -amine propyl triethoxysilane) in 95% alcohol. The treatment was carried out for 5 minutes at a pH value of 4.5~5.5, then the fibre was kept in air for 30 minutes to hydrolyze the coupling agent. Consequently, the reaction between hydroxyl groups of sisal fibre and silanols of KH550 was induced in an oven at 100 for 2 hours. SF was treated at 170 and was 180 pressed for 4 minutes with steam explosion instrument. 2.2 Investigations

2.
2.1

Experimental
Materials and Preparation Methods

Sisal fibre, served by Guangxi Sisal Company, was treated by alkali and then chopped. Phenol solution and 37% (wt) formaldehyde solution with oxalic acid were used to prepare phenol formaldehyde resin. The different blends of samples in the present work were coded with the mode of sisal fibre addition: A, traditional blending mode with the fibre and resin blended directly; B, polymerization-filling mode; C, mixed mode which is a combination of A and B, i.e., half of the fibres were added through polymerization and half were added by the traditional blending method; D, the addition after the polymerization of phenol formaldehyde resin. The preparation methods of mode B were as follows. Phenol, formaldehyde solution and oxalic acid were placed into a flask at a certain proportion and stirred at 50oC for about 15 minutes. Then the mixture was incorporated with treated sisal fibre. The blends reacted for 5 hours at 1022; at the end of the reaction, the blends were poured into a stainless steel plate. After being smashed, the blends were blended with fillers and some other additives for further blending using a roller machine. Then the materials were smashed and sisal/phenol formaldehyde composites were prepared through compression molding for 4 minutes at 150~165 and 5.5 Mpa. In addition, sisal fibre was pretreated by alkali, KH-550, and steam explosion. After being smashed, the treated sisal fibre was added into phenol formaldehyde resin at a certain ratio and the mixture was blended; the phenol formaldehyde/sisal fibre composite (SF/PF) was then made through compression molding for 4 minutes at 150~165 and 5.5Mpa.

Impact testing of the composite specimens was carried out using an impact tester (XJJ-5), Chengde tester company, China. The sample size was 10mm4mm120mm. Bending tests were performed in the instrument according to AG-201, Shimadzu Corporation, Japan, at a pressing speed of 1mm/min and a gauge length of 60mm. The sample size was the same as the above. All the impact and bending result data were the average of three successful tests. A JSM-5610LV, JEOL Company, Japan, scanning electron microscope (SEM) was used to observe the morphology of fractured surfaces of the composite samples. The non-conducting composite samples were gold coated. A thermo gravimetric analysis was carried out in a NETZSCH STA 449 C thermo gravimetric instrument, in an inert atmosphere at a heating rate of 20/min. Thermal dilatability was obtained in the NETZSCH DIL 402 C thermal dilatometer at a heating rate of 10/min.

3.
3.1

Results and Discussion

Influence of SF adding Mode and Surface Treatment on the Mechanical Properties of SF/PF Composites

Table 1 lists some mechanical property parameters of pure phenol formaldehyde resin and sisal/phenol formaldehyde composites. It is clear that the polymerization-filling mode is the best

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RJTA Vol. 10 No. 3 2006

one. Compared to the traditional normal blending mode, the polymerization-filling mode increases the impact strength, bending strength and bending modulus of the composites by 17.61%, 7.16% and 12.25% respectively. As the densities of the Table 1.

samples are close, the variation of the specific strength and specific modulus are close to the bending strength and bending modulus respectively.

The mechanical properties of phenol formaldehyde resin and SF/PF composites Pure resin 4.23 77.72 7091.6
3

Sisal addition modes Impact strength (KJ/m2) Bending strength (MPa) Bending modulus (MPa) Specific strength (MPacm /g) Specific modulus (MPacm /g) Density (g/cm3)
3

A 4.26 76.67 7137.3 53.62 4991.1 1.430

B 5.01 82.16 8011.3 56.62 5521.2 1.451

C 4.17 77.70 7405.0 53.55 5103.4 1.451

D 5.16 79.38 7750.8 55.20 5390.0 1.438

53.79 4907.6 1.445

Various treated SF/PF composites were prepared through compression molding and the impact, bending strength and modulus of the composites were studied (Table 2). The properties of pure

resin were taken as control for comparison ((A) control; (B) alkali treatment (10%); (C) KH-550 Treatment; (D) steam explosion treatment).

Table 2. Effects of different treatment methods on the impact properties of the SF/PF composites Treatment methods A B C D Impact strength (KJ/m2) 3.70 4.49 5.11 4.99 Bending strength (MPa) 75.71 82.16 83.27 73.64 3.2 Bending Modulus (MPa) 8087.0 8011.3 7424.3 5430.7

Among different treatments, KH-550 treated sisal fibre reinforced phenol formaldehyde shows higher impact strength and bending strength. KH-550 treated sisal fibre reinforced PF increases by 38.11% and 9.99% in impact strength and bending strength respectively compared with the untreated SF/PF composites. Investigation indicates that KH-550 treatment on sisal fibre changes the structure of fibre, and improves the agglutinating effect between matrix and fibre, which is favorable for the dispersion of fibre and finally improve the mechanical properties than any other treated fibre composites. This contributes to the combination of the interface, and results in comparatively greater energy absorption.

Influence of SF/GF Weight Ratio on Mechanical Properties of SF/GF/PF Composites

Table 3 shows that the impact strength of composites with 0 share of glass fibre is 5.23KJ/m2. With an increase of glass fibre from 0 to 1.5 shares, the impact strength increases by about 8.6%. In addition, the sisal/glass (1.5/1.5) leads to maximum impact strength (5.68 KJ/m2) of hybrid composites. The bending strength of composites at 0 share glass fibre was found as 81.89Mpa. By the addition of 1.5 share of glass fibre, the bending strength of composites increases by about 11.1%. With further increase of glass fibre, there is no significant increase in the bending strength. As a
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RJTA Vol. 10 No. 3 2006

result of observation, among different values of sisal/glass, sisal/glass (1.5/1.5) leads to maximum bending modulus (9262 MPa). The variation of Table 3. Sisal/Glass Impact strength (KJ/m2) Bending strength (MPa) Bending modulus (MPa) Specific strength (MPacm /g) Specific modulus (MPacm3/g) Density (g/cm3) 3.3
3

specific strength and specific modulus of hybrid composites are also close to the bending strength and bending modulus respectively.

The effects of SF/GF on the mechanical properties of composites 3/0 5.23 81.89 6652.1 55.63 4519.1 1.472 2/1 5.32 88.38 8667.5 58.72 5759.1 1.505 1.5/1.5 5.68 90.98 9261.9 60.86 6195.3 1.495 1/2 5.20 88.25 8545.3 58.06 5621.9 1.520 0/3 5.56 88.96 8611.2 57.95 5609.9 1.535

Influence of SF/GF Weight Ratio and SF Treatment on Tg and Td of Composites The thermo-gram for PF with SF/GF is presented in Figure 2. When SF/GF are 0/3, 1/2, 1/1, 2/1, 3/0, the corresponding degradation temperatures (Td) are 677, 658, 631, 583, 484 respectively. With the increase in sisal fibre, Td and Tmax decrease, which can be explained by GF, an inorganic fibre which has higher thermal stability and can improve the Td of composites.

From the results of the thermal dilatability experiments, the glass transition temperatures (Tg) of composites were obtained. Figure 1 lists the thermal dilatability plot and results of Tg. When SF/GF are 0/3, 1/2, 1/1, 2/1, 3/0, the corresponding Tg are 188, 192, 189, 191, 180 respectively. The addition of GF improves Tg but the content of GF has little effects on the Tg of composites.
240 210 180

Loss mass ( % )

dL ( m )

1----0/3 2----1/2 3----1/1 4----2/1 5----3/0

100

5 3 4 2 1
90 80 70

1----0/3 2----1/2 3----1/1 4----2/1 5----3/0

150 120 90 60 30 120 140 160 180 200

5
60 50 100 200 300 400 500 600 700

1 2 3 4
800

Tem perature ( )

Temperature ( )

Fig. 1. The thermal dilatability of SF/GF/PF composites From the results of the thermal dilatability experiments, glass transition temperatures (Tg) of composites were obtained. Figure 3 lists the thermal dilatability plot and results of Tg. When SF is treated by alkali treatment, KH-550
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Fig. 2. The thermal decomposition plot of SF/GF/PF composites Treatment and steam explosion, the corresponding Tg are 167, 187, 190 respectively. It is evident that treatments on SF improve the Tg of composites, especially the KH-550 treatment.

RJTA Vol. 10 No. 3 2006

The thermo-gram for PF with different treatments of SF is presented in Figure 4; Table 4 is the plot results of thermal decomposition. After being treated by the alkali treatment, KH-550 treatment

and steam explosion, the corresponding degradation temperatures (Td) of SF/PF composites are 478 , 530 , 518 , 500 respectively.

300
200

250

A
200

190

dL( m)

150

100

Tg ( )
180 200 220

180

C
50

170

160

0
150

20

40

60

80

100

120

140

160

Temperature ()

Surface treatment of SF

Fig. 3.

The thermal dilatability of SF/PF composites

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Weight Remain (%)

90 80 70
A

60 50 100 200 300 400 500

C D

600

700

Temperature ( )

Fig. 4. Table 4. Samples A B C D T0 198 227 230 300

The thermal plot of SF/PF composites

The thermal stability of SF/GF/PF composites W1% 96.9 92.9 95.3 95.7 Td 478 530 518 500 W2% 65 65 65 68 Tmax 373 372 366

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3.4

Influence of SF/GF Weight Ratio on Water Absorption Properties and Electrically insulating Properties of SF/GF/PF Composites

a barrier and prevent the contact between water and the hydrophilic sisal fibre, which explains the lower water absorption properties of these composites. The effects of sisal/glass weight ratio on volume resistance v of sisal/glass hybrid phenol formaldehyde composites are shown in Figure 6. Contrary to the mechanical and water absorption properties, it was found that sisal fibre and glass fibre exhibit negative hybrid effect in insulating properties.

Figure 5 indicates that sisal/glass hybrid phenol formaldehyde composites show lower water absorption as compared to that of pure resin. Sisal fibre and glass fibre exhibit positive hybrid effect in water absorption properties. Fibres in these composites are arranged in a close-packed manner in which the water impermeable glass fibre acts as

2.4 2.2 2.0

(10 /cm)

2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8

G( ) ( 3d)

1.8 1.6 1.4 1.2 1.0 0.8 3/0 2/1 1/1 1/2

14

3/0

2/1

1/1

1/2

0/3

sisal/glass

sisal/glass

Fig. 5.

The effects of sisal/glass on the water absorption properties of composites Fractured Surfaces of

Fig. 6.

The effects of SF/GF on the electric properties of composites

3.5

SEM of Composites

Scanning electron micrographs of the fractured surfaces of the composites were taken to study the fibre-matrix interaction and fracture behavior. Figure 7(a) shows the fractured graph of pure phenol formaldehyde resin. The photo shows poor fracture surface; the smooth and orderly surface
a b

indicates the significant brittleness of the resin. Yet in the case of polymerization-filling sisal/phenol formaldehyde (Fig. 7 (b)) composites, the interfacial adhesion between the fibres and matrix is comparatively stronger. The sisal/glass (Fig. 7(c)) hybrid phenol formaldehyde composite indicates better dispersion of the two fibres and well adhesion of fibre-matrix.

Fig. 7. SEM micrographs of the fractured surface of composites (a) Pure phenol formaldehyde resin, (b) SF/PF composites, (c) SF/GF/PF composites

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Figure 8 (a) shows the fractured graph of untreated SF/PF composites, and it shows poor fracture surface. Yet in the case of treated SF/PF

(Fig. 8 (b, c, d)) composites, the interfacial adhesion between the fibres and matrix is comparatively stronger.

a c

Fig. 8. SEM micrographs of the fractured surface of (a) Untreated SF/PF composites, (b) Alkali treated SF/PF composites, (c) KH-550 treated SF/PF composites, (c) Steam explosion treated SF/PF composites The superior mechanical properties may be attributed to the fact that KH-550 treatment results in an improvement in the interfacial bonding by giving rise to additional sites of mechanical interlocking, hence, promoting more resin-fibre interpenetration at the interface. KH-550 hydrolyzation and form tri-hydroxyl coupling agent, the hydroxyl reaction with the OH of SF and steady structure are formed. At the same time, the organic groups in KH-550 react with phenol formaldehyde resin and make cross-linking structure, which improve the mechanical properties of composites. The microstructure analysis is consistent with the impact and bending results. properties of sisal fibre were studied. Experiment results indicate that KH-550 treatment is an ideal modification method. KH-550 treated sisal fibre reinforced PF increases by 38.11% and 9.99% in impact strength and bending strength respectively compared with untreated SF/PF composite. And the thermal stability of composites improves evidently after SF being treated. Additionally, as expected, SEM reveals that KH-550 treated SF/PF show complex fracture surface than that of untreated SF/PF composites. On the other hand, sisal fibre was pretreated by alkali treatment, and then sisal fibre/ phenol formaldehyde (SF/PF) composites were prepared through compression molding. The effects of sisal fibre addition mode and sisal/glass (SF/GF) hybrid phenol formaldehyde composites with glass/sisal weight ratio on mechanical properties, thermal properties, water absorption properties and electrically insulating properties were studied. Experiment results indicate that polymerization filling is a novel synthesizing method. The SF/PF composites made by this method increase by 17.61%, 7.16% and 12.25% in impact strength,
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4.

Conclusions

Sisal fibre (SF) was pretreated by alkali, KH-550, and steam explosion. Sisal fibre/ phenol formaldehyde (SF/PF) composites were prepared through compression molding. The effects of the treatments on the mechanical and thermal

RJTA Vol. 10 No. 3 2006

bending strength and bending modulus respectively compared with the conventional physical blending method. SF/GF/PF composites show higher mechanical properties when SF/GF is 1/1, and thermal properties improve with the addition of GF; Sisal fibre and glass fibre exhibit positive hybrid effect in water absorption properties while negative hybrid effect in insulating properties. In this present work we introduce a novel method the polymerization-filling method for sisal fibre reinforced phenol formaldehyde resin; this original study, reporting some novel outcomes, may serve as a stepping-stone for future investigations of SF.

[3]

[4]

[5]

[6]

Acknowledgements
The financial support by National Natural Science Foundation (Grant No.: 50473060) and the Guangxi education bureau (Grant No.: 2004[20]) are gratefully acknowledged.

[7]

REFERENCES
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Bledzki, A.K. and Gassan, J., 1999, Composites reinforced with cellulose fibre, Progress in Polymer Science, vol. 224, pp. 221-224. Li, Y., Mai, Y.-W. and Ye, L. 2000, Sisal fibre and its composites: a review of recent developments, Composites Science and Technology, vol. 60, pp. 2037-2055. Mishraa, S. and Mohantyb, A.K. 2003, Studies on mechanical performance of biofibre/glass reinforced polyester hybrid composites, Composites Science and Technology, vol. 63, pp. 1-9. Niu, Y.-L., Zhong, J.-B., Yang, X.-W., Yu, X.-B. and Wei, C. 2005, Effect of sisal fibre contents on wear resistance of sisal fibre/phenol formaldehyde resin in-situ composites, Proceedings of 2005 International Conference on Advanced Fibres and Polymer Materials, Shanghai, China, pp. 411-414. Paul, A., Joseph, K. and Thomas, S. 1997, Effect of surface treatments on the electrical properties of low-density polyethylene composites reinforced with short sisal fibres, Composites Science and Technology, vol. 57, no. 1, pp. 67-79. Zhong, J.-B., Niu, Y.-L., L, J. and Wei, C., 2006, Effect of steam explosion treatment on mechanical properties of sisal fibre/phenol-formaldehyde resin composite, China Plastics Industry, vol. 34, no. 7, pp. 53-55.

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