Composites: Part A 40 (2009) 687694

Contents lists available at ScienceDirect

Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Mechanical property improvement of unsaturated polyester composite reinforced with admicellar-treated sisal bers
Supranee Sangthong a, Thirawudh Pongprayoon a,*, Nantaya Yanumet b
a b

Department of Chemical Engineering, Faculty of Engineering, King Mongkuts University of Technology North Bangkok, 1518 Pibulsongkram Road, Bangsue, Bangkok 10800, Thailand The Petroleum and Petrochemical College, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand

a r t i c l e

i n f o

a b s t r a c t
Sisal ber was treated by admicellar polymerization with a poly(methyl methacrylate) lm coating in order to enhance the interfacial adhesion of the ber/polymer composite for mechanical property improvement. Properties of the admicellar-treated sisal ber were investigated by measuring its moisture absorption and electrostatic charge. Thermal stability study by thermogravimetric analysis and lm identication by FTIR was also carried out. The treatment was shown to improve the tensile and exural properties, impact strength, and hardness of the composite. SEM micrographs of the tensile fracture surface of sisal/unsaturated polyester composites also show interfacial adhesion improvement of the composite prepared with admicellar-treated sisal. 2009 Published by Elsevier Ltd.

Article history: Received 28 January 2008 Received in revised form 3 December 2008 Accepted 4 December 2008

Keywords: A. Sisal ber surface treatment E. Admicellar polymerization A. Reinforced unsaturated polyester composite B. Mechanical property

1. Introduction The mechanical properties of a plant ber-polymer matrix composite are controlled to a large extent by the efciency of the bonding at the ber-matrix interfacial boundary. The principal function of the interface is to facilitate the transfer of stress from ber to ber, across the matrix. Cellulose ber is, however, known to exhibit poor bonding characteristics with a polymeric matrix. This is mainly due to the presence of organic and inorganic substances on the ber surface, and the hydrophilic nature of cellulose, which prevents effective adhesion between the ber surface and the polymer matrix. The surface of plant ber such as sisal ber is usually not suitable for creating a strong bond with a polymeric matrix. The bond strength has, however, been successfully improved by modifying the ber surface with either chemical or physical surface treatment [1]. Sisal ber is one of the most widely used plant bers. It is obtained from the leaves of the Agave sisalana plant, which is largely available in tropical zone countries. During the past decade, sisal ber has raised great interest for use as an economical and environmentally friendly reinforcement for polymeric composites. To improve the interfacial adhesion of the ber/polymer composite, the sisal ber must be modied to make it more compatible with the polymer matrix. Many researchers have applied different techniques to modify the cellulose ber surface [110]. A special
* Corresponding author. Tel.: +6689 182 6168; fax: +662 587 0024. E-mail addresses: thp@kmutnb.ac.th, tpongprayoon@yahoo.com (T. Pongprayoon). 1359-835X/$ - see front matter 2009 Published by Elsevier Ltd. doi:10.1016/j.compositesa.2008.12.004

review of sisal ber treatment for improving the mechanical properties of its composites has been presented by Li et al. [1]. For using sisal ber as reinforcement in the polymeric composite, unsaturated polyester is one of the most widely used for the polymer matrix. Sreekumar et al. studied the mechanical properties of a sisal ber-reinforced polyester composite [9]. They observed the tensile and exural behavior of the sisal ber/polyester composite as a function of ber length and ber loading. The surface characteristics of natural ber are also widely investigated in order to improve the adhesion of the natural ber/polymer composite. To investigate the hydrophilicity/hydrophobicity of the ber surface, several techniques, such as the measurements of wetting and spreading phenomena, moisture absorption, and electrostatic charge, have been used [2,9,1113]. In the present study, admicellar polymerization was studied as an alternative method to improve the interfacial adhesion between the ber and the polymer matrix. The surface characteristics of the admicellar-treated sisal ber and the mechanical properties of the treated sisal ber composite were investigated. Admicellar polymerization is an innovative technique used to improve the material surface with an ultrathin polymeric lm coating. This novel method offers several advantages over the conventional methods for surface coating. The process is simple with minimal chemical usage as the coated lm is ultrathin, in nanoscale [14,15]. It is also environmental friendly as it can be carried out in an aqueous solution with no need for any organic solvents. In addition, the hydrophobic polymer lm formed by admicellar polymerization has been shown to adhere tenaciously to the hydrophilic substrate [16] due to the presence of the surfactant

688

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

layer which interacts with the substrate on one side and the polymer lm on the other. Whereas in some other conventional coating methods, such as coating by an emulsion of PMMA, the polymer merely deposit on the substrate surface with no special binding force. Therefore, admicellar-treated ber can be expected to improve the mechanical properties of the composite better than ber treated by other conventional techniques. The admicellar polymerization process generally consists of three main steps: admicelle formation, monomer adsolubilization, and polymer formation. After the polymeric lm formation, the upper layer of the surfactant is usually removed by washing to expose the layer of polymer coating on the substrate surface. The steps in the admicellar polymerization process are shown in Fig. 1. The polymeric lm formation of this process is controlled by several parameters, including the characteristics of the substrate surface, the type of surfactant and monomer, and the conditions used such as pH, and the amount of electrolyte. Admicellar polymerization has been applied to improve the interfacial adhesion of composite in various systems such as precipitated silica with polystyrene [17] and a copolymer of styrenebutadiene and styreneisoprene [18], and glass bers with polystyrene [19], polyethylene [20], and a copolymer of isoprenestyrene [21]. In previous work, admicellar polymerization has been used to treat inorganic reinforcement only. This study is the rst to apply admicellar polymerization to modify plant ber surface for use as reinforcement for polymeric composite. In this work, the sisal ber surface was treated by admicellar polymerization using hexadecylpyridinium chloride as the surfactant to form a PMMA lm for enhancement of the sisal ber/unsaturated polyester matrix composite adhesion. Since cellulose, which is the main component in the sisal ber, acts as a weak acid in aqueous solution with the ionization of the primary hydroxyl group as shown in the following equation [22]:

Fig. 2. The ion pairing mechanism between the cellulose anions and the pyridinium cations in admicelle formation.

rated polyester composite and the mechanical properties of the composite were investigated. 2. Experimental 2.1. Materials Sisal bers (diameter 0.220.27 mm) were purchased from growers in Petchaburi Province, Thailand. Hexadecylpyridinium chloride (HDPyCl, 98% purity), methylmethacrylate (MMA, 99% purity) and sodium persulphate (98% purity) were purchased from Fluka (Switzerland). Unsaturated polyester resin (UP) was purchased from Thai Mitsui Specialty Chemical (Thailand). Cobalt naphthenate (65% in mineral spirits) and methyl ethyl ketone peroxide (MEKP) were supplied by Merck (Germany). 2.2. Sisal surface treatment by admicellar polymerization

Whereas the cationic surfactant, hexadecylpyridinium chloride, ionizes in the aqueous solution to give a pyridinium cation as shown in the following equation:

Hence, there will be an adsorption of the surfactant cations on the ber surface through the ion pairing mechanism between the cellulose anions and the pyridinium cations, leading eventually to the admicelle formation as shown in Fig. 2. After the formation of PMMA lm on the ber surface through admicellar polymerization, the treated ber was used to prepare the ber-reinforced unsatu-

The sisal bers were preliminarily soaked in 6% NaOH at 30 C for 48 h for wax removal. The bers were then washed and put in an oven at 110 C until dry. In the experiment, the three main steps of admicellar polymerization; admicelle formation, adsolubilization, and in-situ polymerization, were carried out in succession. In the rst step, 20 g sisal bers was placed in a ask containing 400 mL HDPyCl at the concentration of 800 lM in aqueous solution, which is close to the CMC of HDPyCl [23] to ensure high surfactant adsorption. The system was left at room temperature for 24 h to reach the equilibrium surfactant adsorption on the sisal ber surface. Then MMA was added to the system and left at room temperature for 48 h to reach the equilibrium MMA adsolubilization into the admicelle. The MMA concentration was varied from 0.025%, 0.05%,

Admicelle formation

Monomer adsolubilization

Polymer formation

Outer-layer surfactant removal

Fig. 1. Steps in the admicellar polymerization process.

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

689

0.075%, to 0.1% by volume. The initiator, 0.02 g of sodium persulphate, was nally added to the system and the temperature was raised to and maintained at 60 C for 1 h for the polymerization reaction of MMA. After that the system was cooled to room temperature. The treated bers were then taken out and washed with distilled water and immersed in a mixture of 70/30 v/v water/ethanol for 24 h to remove the outer-layer surfactant and any unreacted monomer, while the inner-layer surfactant trapped between the ber surface and the coated polymer lm was not removed by this washing process. Finally the treated bers were dried in an oven at 60 C for 5 h. 2.3. Fiber-reinforced unsaturated polyester composite preparation The admicellar-treated sisal bers coated with PMMA and untreated bers were chopped to the desired lengths of 10, 20, 30, and 40 mm to be used as reinforcement for composite preparation. Unsaturated polyester resin was rst mixed with 1 wt.% cobalt napthenate (accelerator) and 1 wt.% methyl ethyl ketone peroxide (curing agent) for the matrix preparation of the composite. Composite sheets were made by hand lay-up technique using a 13 17 0.3 cm stainless steel mold. Polyvinyl alcohol (releasing agent) was coated onto the mold surface before the laying of the matrix and bers. The desired ber loading (10%, 20%, 30%, and 40% v/v) of the desired ber length was randomly laid, and 70 mL of unsaturated polyester resin was carefully poured onto the bers in the mold. The mold was then closed by screwing the cover plate onto the base as tightly as possible. This closing of the mold helped to force the resin to penetrate into the spaces between the bers while the excess amount of resin was forced out in between the cover plate and the base. The mixture was left to cure for 12 h at room temperature [8]. 2.4. Fiber surface characterization The surface characterization of admicellar-treated and untreated sisal bers was carried out by measuring their moisture absorption and electrostatic surface charge to observe the surface hydrophilicity/hydrophobicity. In addition, thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) were used to analyze and identify the PMMA lm on the sisal surface. Moisture absorption of the treated and untreated bers was determined by holding 3 g of dried bers under the ambient conditions of 27 C and 65% specic humidity overnight. After that, the moisture absorption of the bers was determined by a moisture analyzer (Mettler, Toledo model LJ16). The surface charge or zeta (f) potential at pH 7 and pH of f potential = 0 or point of zero charge (PZC) of the untreated and treated bers were determined by Laser Doppler Electrophoresis (LDS) (Malvern model Zetasizar 3000). The measurements were carried out in a 0.001 M KClelectrolyte solution. The PZC was observed by varying pH from 1 to 10. The thermal behavior of the sisal bers was investigated by TGA (NETZSCH STA 409 C) over the temperature range of 30 C to 450 C with a 5 C/min heating rate under nitrogen atmosphere. For each experiment, about 1-mg sisal ber sample was used. The PMMA lm formed on the sisal ber surface was also identied by FTIR, (PerkinElmer Model 2000) using the KBr disc technique. 2.5. Mechanical property testing Tensile and exural tests of the composite samples were carried out on a Universal Testing Machine, Model LR 10 K, according to the standard test ASTM D638 and D790, respectively. Five samples were tested in each experiment. Tensile strength and modulus

testing was conducted using dumbbell-shaped specimens of 115 mm long with a crosshead speed of 10 mm/min and a gauge length of 50 mm. For the exural tests, 62 12.7 3 mm rectangular test specimens were tested with a crosshead speed of 1.28 mm/min in three-point loading, tted by a 100 kN load cell. Impact tests were performed on an Izod Impact Tester, model 258-D, in accordance with ASTM D256. Hardness tests were performed on a Durometer Type D in accordance with ASTM D2240. Five test specimens were used for each study. 2.6. Morphology study of the tensile fractured surface The cross-section of the fractured surface of the sisal ber composite specimens after tensile testing was studied by scanning electron microscopy (SEM), a Joel SEM 5200. The adhesion between the sisal ber and polymeric matrix was explained from these SEM micrographs. 3. Results and discussion 3.1. Surface modication by admicellar polymerization 3.1.1. Surface behavior The hydrophilicity/hydrophobicity of the admicellar-treated sisal ber surface was investigated by moisture absorption and f potential measurement. The moisture absorption of the sisal bers was reduced by almost a half from 7.98% to 4.48% after treatment, as shown in Fig. 3. The moisture absorption decreased sharply after treatment with 0.025% v/v MMA, but the decrease leveled off at higher MMA concentrations.

9 8 7 6 5 4 3 2 1 0 0 0.025 0.05 Amount of MMA (% v/v) 0.075 0.1

Fig. 3. Moisture absorption of the admicellar-treated bers with various MMA concentrations in solution (% v/v).

Moisture Absorption (%)

-8 -10 Potential (mV) -12 -14 -16 -18 -20 0 0.02 0.04 0.06 0.08 0.1 Amount of MMA (% v/v)
Fig. 4. The f potential at pH 7 of the admicellar-treated bers with various MMA concentrations in solution (% v/v).

690

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

4 3.5 3 2.5

2 1.5 1 0.5 0

0.025

0.05 0.075 Amount of MMA (% v/v)

0.1

The f potential of the untreated and admicellar-treated sisal bers was studied to determine the hydrophilicity/hydrophobicity of the treated surface. The f potential at pH 7 of the untreated sisal and the admicellar-treated sisal using various amounts of MMA are shown in Fig. 4. The results show that the f potential increased sharply from 17 to 10 mV when the MMA concentration increased from 0% (untreated ber) to 0.075% v/v MMA, but the f potential value leveled off after this. When studying the PZC or the pH values at f potential = 0, the results showed that the PZC increased from 2 to 3.5 with varying MMA concentration from 0% to 0.075% v/v. At higher MMA concentration, the PZC reached the constant value of 3.5 which is close to the PZC of 3.8 obtained for pure PMMA in previous work [24] (see Fig. 5). 3.1.2. Coated lm characterization Differential thermogravimetric (DTG) curves of PMMA, and the untreated and admicellar-treated bers are shown in Fig. 6. It was found that the thermal stability of the treated sisal ber was higher than that of the untreated sisal ber, and was close to the thermal stability of pure PMMA, proving that the polymeric lm was coated on the sisal ber. The thermal stability increased as PMMA content increased, when using higher amount of MMA. The PMMA lm coating on sisal ber was also identied by FTIR. Fig. 7 shows the FTIR spectra of pure PMMA, untreated sisal ber, and admicellar-treated sisal ber. The admicellar-treated sisal ber spectrum, Fig. 7(c), shows the peaks at 1734 cm1 (C@O) and 1457 cm1 (OCH3), which are the characteristic peaks of pure PMMA as shown in Fig. 7(a), whereas the spectrum of bare sisal ber, Fig. 7(b), shows the characteristic peaks of cellulose at 3421 cm1 (OH) and 1430 cm1 (CH2OH). These results clearly indicate that PMMA lm was successfully coated on the sisal ber surface by admicellar polymerization. The SEM micrographs of the untreated and admicellar-treated surfaces are shown in Fig. 8. It can be seen that admicellar-treated sisal ber shows deposition of a thin lm, while the untreated surface looks bare.

Fig. 5. The PZC of the admicellar-treated bers with various MMA concentrations in solution (% v/v).

PZC
Rate of weight loss (%/min)

2 0 -2 -4 -6 -8 -10 0 50 100 150 200 250 300 350 400 450 Temperature (C)
PMMA 0.050 %v/v MMA Untreated fiber 0.075 %v/v MMA 0.025 %v/v MMA 0.100 %v/v MMA

Fig. 6. DTG curves of PMMA, untreated ber, and admicellar-treated bers with various MMA concentrations in solution (% v/v).

Fig. 7. FTIR spectra of (a) PMMA, (b) untreated sisal ber, and (c) admicellar-treated sisal ber.

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

691

Fig. 8. SEM micrographs of (a) untreated and (b) admicellar-treated sisal ber surfaces.

a
Tensile strength (MPa)

65 60 55 50 45 40 35 0 10 20 30 Amount of fiber (%v/v) Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA 40 50

was observed that both tensile properties increased with increasing ber loading, up to 30 vol%. After that the tensile properties slightly decreased at 40 vol% ber loading for all types of sisal bers. Several workers have found the same trend [5,9,2527]. It is generally agreed that, at high ber loading, it is more difcult for the resin to penetrate the decreasing spaces between the bers, leading to poor wetting, and hence, a reduction in the stress transfer efciency across the ber-resin interface. The treated sisal ber gave higher tensile properties when higher amount of MMA was used. The results show that the coated lm helps to

a
Flexural strength (MPa)

100 90 80 70 60 50 40 Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

b
Tensile modulus (MPa)

1600

1400

1200

1000

800 0 10

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA 20 30 Amount of fiber (%v/v) 40 50

10

20 30 Amount of fiber (%v/v)

40

50

b
Flexural modulus (MPa)

4500 4000 3500 3000 2500 2000 1500 Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

Fig. 9. Effect of untreated and admicellar-treated ber content on (a) tensile strength and (b) tensile modulus of the composites (using 10-mm ber length).

3.2. Mechanical properties of the composites 3.2.1. The effect of ber loading The mechanical properties (tensile, exural, impact, and hardness) of ber-reinforced unsaturated polyester composites were investigated by varying the ber loading, as shown in Figs. 912, respectively. Fig. 9(a) and (b) shows the effect of ber loading on the tensile strength and tensile modulus of the composite, respectively. It

10

20

30

40

50

Amount of fiber (%v/v)

Fig. 10. Effect of untreated and admicellar-treated ber content on (a) exural strength and (b) exural modulus of the composites (using 10-mm ber length).

692

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

13 12 11 10 9 8

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

improve the ber-matrix adhesion leading to higher tensile properties. The exural properties were also investigated, as shown in Fig. 10. The results show the same trend as with the tensile properties. From the studies of both the tensile and exural properties, it can be concluded that the optimum ber loading was at 30 vol% for all sisal ber types. Similar results were also observed by Sreekumar et al. [9]. Figs. 11 and 12 show the impact strength and hardness of the sisal/unsaturated polyester composites. It was observed that both impact and hardness properties increased with increasing ber loading. Higher amounts of MMA were also found to give higher impact and hardness properties.

Impact strength (J/m)

10

20 30 Amount of fiber (%v/v)

40

50
3.2.2. The effect of ber length The effect of ber length of untreated and admicellar-treated bers on the mechanical properties was also investigated, as shown in Figs. 1316. The ber length was varied from 10 to 40 mm. The results of tensile and exural properties are shown in Figs. 13 and 14, respectively. They show that the tensile and exural properties in both strength and modulus increased with increasing ber length for both untreated and admicellar-treated sisal bers up to the ber length of 30 mm. Further increase in ber length to 40 mm showed a decreasing trend. At the same ber loading, as the ber length increased, the space distribution between bers can be expected to decrease leading to poorer mixing between the bers and the polymer matrix, and hence lower mechanical properties. Other workers have found the same trend [9,25]. The results also show that the tensile and exural properties of composites prepared from admicellar-treated sisal bers were better than the composites prepared from untreated ber, and they also increased with increase in the MMA concentration used.

Fig. 11. Effect of untreated and admicellar-treated ber content on the impact strength of the composite (using 10-mm ber length).

73 72.5 Hardness (Shore D) 72 71.5 71 70.5 70 0 10 20 30 Amount of fiber (%v/v) Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA 40 50

Fig. 12. Effect of untreated and admicellar-treated ber content on the hardness of the composite (using 10-mm ber length).

a
Tensile strength (MPa)

80 75 70 65 60 55 50 45 0 10 20 30 Fiber length (mm) Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA 40 50

a
Flexural strength (MPa)

110 105 100 95 90 85 80 75 70 65 0 10 20 30 Fiber length (mm)

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

40

50

b
Tensile modulus (MPa)

Flexural modulus (MPa)

2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 0 10 20 30 Fiber length (mm)

5500 5000 4500 4000 3500 3000 0 10 20 30 Fiber length (mm)

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

40

50

40

50

Fig. 13. Effect of untreated and admicellar-treated ber length on (a) tensile strength and (b) tensile modulus of the composite (using 30% v/v ber loading).

Fig. 14. Effect of untreated and admicellar-treated ber length on (a) exural strength and (b) exural modulus of the composite (using 30% v/v ber loading).

S. Sangthong et al. / Composites: Part A 40 (2009) 687694

693

13

Impact strength (J/m)

12.5 12 11.5 11 10.5 10 9.5 0 10 20 30 Fiber length (mm)

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

40

50

Fig. 15. Effect of untreated and amicellar-treated ber length on the impact strength of the composite (using 30% v/v ber loading).

73 72.5 72 71.5 71 70.5 0 10 20 30 Fiber length (mm)

Untreated fiber 0.025 %v/v MMA 0.050 %v/v MMA 0.075 %v/v MMA 0.100 %v/v MMA

Hardness (Shore D)

40

50

Fig. 16. Effect of untreated and admicellar-treated ber length on the hardness of the composite (using 30% v/v ber loading).

Fig. 17. SEM micrographs of the treated fractured surface of (a) untreated and (b) admicellar-treated sisal ber-reinforced composite.

Figs. 15 and 16 show the impact strength and hardness of the sisal ber-reinforced composites. It was observed that the impact and hardness properties also increased with increasing ber length and composites prepared from admicellar-treated sisal bers also had higher impact strength and hardness. 3.3. Interfacial adhesion of sisal/unsaturated polyester composite The improvement in the interfacial adhesion between treated sisal bers and unsaturated polyester matrix can be clearly seen from SEM micrographs of the tensile fracture surface, as shown in Fig. 17. With a weak interfacial bond, the fracture is more likely to lead to interfacial debonding and extensive ber pullout, as shown in Fig. 17(a) with untreated bers. However, if the bonding is strong as in the cases when admicellar-treated bers were used, the failure occurs with ber breakage at the fracture point, as shown in Fig. 17(b). 4. Conclusions From this work, it can be concluded that PMMA lm coating on sisal ber surface by admicellar polymerization leads to improved mechanical properties of the sisal ber/unsaturated polyester composite due to the improvement of the interfacial adhesion of the composite. The composite with the best mechanical properties can be obtained by using 30 vol% ber loading with ber length of 30 mm and an MMA concentration of 0.075% v/v.

Acknowledgment This work was nancially supported by the Thailand Research Fund (TRF). References
[1] Li Y, Mai Y, Ye L. Sisal bre and its composite: a review of recent developments. Compos Sci Technol 2000;60(11):203755. [2] Bisanda ETN. The effect of alkali treatment on the adhesion characteristics of sisal bres. Appl Compos Mater 2000;7(56):3319. [3] Gassan J. A study of ber and interface parameters affecting the fatigue behavior of natural ber composites. Composites A 2002;33(3):36974. [4] Roman-Aguirre M, Marquez-Lucero A, Zarsgoza-Contreras EA. Elucidating the graft copolymerization of methyl methacrylate onto wood-ber. Carbohydrate Polym 2004;55(2):20110. [5] Lu X, Zhang MQ, Rong MZ, Shi G, Yang GC. Self-reinforced melt processable composites of sisal. Compos Sci Technol 2003;63(2):17786. [6] Aziz SH, Ansell MP. The effect of alkalization and bre alignment on the mechanical and thermal properties of kenaf and hemp bast bre composites. Part 1: polyester resin matrix. Compos Sci Technol 2004;64(9):121930. [7] Marquez M, Grady BP, Robb I. Different methods for surface modication of hydrophilic particulates with polymers. Colloids Surf A 2005;266(13):1831. [8] Ojah R, Dolui SK. Graft copolymerization of methyl methacrylate onto Bombyx mori initiated by semiconductor-based photocatalyst. Bioresour Technol 2006;97(13):152935. [9] Sreekumar PA, Joseph K, Unnikrishnan G, Thomas SA. Comparative study on mechanical property of sisal leaf bre reinforced polyester composites prepared by resin transfer and compression moulding techniques. Compos Sci Technol 2007;67(34):45361. [10] Tragoonwichian S, Yanumet N, Ishida H. Effect of ber surface modication on the mechanical properties of sisal ber-reinforced benzoxazine/epoxy composites based on aliphatic diamine benzoxazine. J Appl Polm Sci 2007;106(5):292535.

694

S. Sangthong et al. / Composites: Part A 40 (2009) 687694 surface modied precipitated silicas. J Appl Polm Sci 1996;59(11):174150. Sakhalkar SS, Hirt DE. Admicellar polymerization of polystyrene on glass bers. Langmuir 1995;11(9):336973. Somnuk U, Yanumet N, Ellis JW, Grady BP, ORear EA. Adhesion improvement in glass ber reinforced polyethylene composite via admicellar polymerization. Polm Compos 2003;24(1):17180. Barraza HJ, Hwa MJ, Blakley K, ORear EA, Grady BP. Wetting behavior of elastomer-modied glass bers. Langmuir 2001;17(17):;52885296. Dawson TL. pH and its importance in textile coloration. J Soc Dyers Colour 1981;97:11525. Bou S, Gandini A. Formation of polymeric lms on cellulose surfaces by admicellar polymerization. Cellulose 2001;8(4):30312. Pongprayoon T, Yanumet N, Sangthong S. Surface behavior and lm formation of sisal ber coated by poly(methyl methacrylate) ultrathin lm. Colloids Surf A 2008;320(1-3):1307. Joseph K, Varghese S, Kalaprasad G, Thomas S, Prasannakumari L, Koshy P, et al. Inuence of interfacial adhesion on the mechanical properties and fracture behaviour of short sisal bre reinforced polymer composites. Eur Polym J 1996;32(10):124350. Mishra S, Naik JB, Patil YP. The compatibilising effect of maleic anhydride on swelling and mechanical properties of plant-ber-reinforced novolac composites. Compos Sci Technol 2000;60:172935. Zhang MQ, Rong MZ, Lu X. Fully biodegradable natural ber composites from renewable resources: all-plant ber composites. Compos Sci Technol 2005;65:251425.

[11] Bismarck A, Mohanty AK, Aranberri-Askargorta I, Czapla S, Misra M, Hinrichsen G, et al. Surface characterization of natural bres: surface properties and the water up-take behavior of modied sisal and coir bres. Green Chem 2001;3(2):1007. [12] Stana-Kleinschek K, Kreze T, Ribitsch V, Strnad S. Reactivity and electrokinetic properties of different types of regenerated cellulose bers. Colloids Surf A 2001;195(13):27584. [13] Bellmann C, Caspari A, Albrecht V, LoanDoan TT, Mdar E, Luxbacher T, et al. Electrokinetic properties of natural bers. Colloids Surf A 2005;267(1 3):1923. [14] Lai CL, Harwell JH, ORear EA, Komatsuzaki S, Arai J, Nakakawaji T, et al. Formation of poly(tetrauoroethylene) thin lms on alumina by admicellar polymerization. Langmuir 1995;11(3):90511. [15] Yaun WL, ORear EA, Grady BP, Glatzhofer DT. Nanometer-thick poly(pyrrole) lms formed by admicellar polymerization under conditions of depleting adsolubilization. Langmuir 2002;18(8): 334351. [16] Yaun WL, ORear EA, Cho G, Funkhouser GP, Glatzhofer DT. Thin polypyrrole lms formed on mica and alumina wth and without surfactant present: characterization by scanning probe and optical microscopy. Thin Solid Films 2001;385:96108. [17] OHaver JH, Harwell JH, ORear EA, Snodgrass LJ, Waddell WH. In situ formation of polystyrene in adsorbed surfactant bilayers on precipitated silica. Langmuir 1994;10(8):258893. [18] Thammathadanukul V, OHaver JH, Harwell JH, Osuwan S, Na-Ranong N, Waddell WH. Comparison of rubber reinforcement using various

[19] [20]

[21] [22] [23] [24]

[25]

[26]

[27]