Natural Fiber Polymer Composites: A Review

D. NABI SAHEB and J. P. JOG

Polymer Engineering Group, Chemical Engineering Division, National Chemical Laboratory, Pune 411 008, India
Received: May 3, 1999 Accepted: May 19, 1999

ABSTRACT: Natural ber reinforced composites is an emerging area in

polymer science. These natural bers are low cost bers with low density and high specic properties. These are biodegradable and non-abrasive. The natural ber composites offer specic properties comparable to those of conventional ber composites. However, in development of these composites, the incompatibility of the bers and poor resistance to moisture often reduce the potential of natural bers and these draw backs become critical issue. This review presents the reported work on natural ber reinforced composites with special reference to the type of bers, matrix polymers, treatment of bers and ber-matrix interface. 1999 John Wiley & Sons, Inc. Adv in Polymer Techn 18: 351 363, 1999

Introduction

ver the past few decades, we nd that polymers have replaced many of the conventional metals/materials in various applications. This is possible because of the advantages polymers offer over conventional materials. The most important advantages of using polymers are the ease of processing, productivity, and cost reduction. In most of these applications, the properties of polymers are modied using llers and bers to suit the high strength/high modulus requirements. Fiber-reinCorrespondence to: J. P. Jog

forced polymers offer advantages over other conventional materials when specic properties are compared. These composites are nding applications in diverse elds from appliances to spacecrafts. Natural bers have recently attracted the attention of scientists and technologists because of the advantages that these bers provide over conventional reinforcement materials, and the development of natural ber composites has been a subject of interest for the past few years.1 4 These natural bers are low-cost bers with low density and high specic properties. These are biodegradable and nonabrasive, unlike other reinforcing bers. Also, they are readily available and their specic properties are comparable to those of other bers used

Advances in Polymer Technology, Vol. 18, No. 4, 351 363 (1999) 1999 by John Wiley and Sons, Inc.

CCC 0730-6679/99/040351-13

NATURAL FIBER POLYMER COMPOSITES for reinforcements. However, certain drawbacks such as incompatibility with the hydrophobic polymer matrix, the tendency to form aggregates during processing, and poor resistance to moisture greatly reduce the potential of natural bers to be used as reinforcement in polymers. In this article, we shall review the reported work on various aspects of natural ber reinforced composites and address some of the basic issues in development of such composites. higher specic properties are one of the major advantages of using natural ber composites for applications wherein the desired properties also include weight reduction.

MICROSTRUCTURE OF THE FIBERS

Natural bers themselves are cellulose ber reinforced materials as they consist of microbrils in an amorphous matrix of lignin and hemicellulose. These bers consist of several brils that run all along the length of the ber. The hydrogen bonds and other linkages provide the necessary strength and stiffness to the bers.

Natural Fibers
Before discussing the methods of the preparation of these composites and their performance, we describe the types of natural bers, their microstructure, and their chemical composition.

CHEMICAL COMPOSITION OF NATURAL FIBERS

The chemical composition of natural bers varies depending upon the type of ber. Primarily, bers contain cellulose, hemicellulose, pectin, and lignin. The properties of each constituent contribute to the overall properties of the ber. Hemicellulose is responsible for the biodegradation, moisture absorption, and thermal degradation of the ber as it shows least resistance whereas lignin is thermally stable but is responsible for the UV degradation. The percentage composition of each of these components varies for different bers. Generally, the bers contain 60 80% cellulose, 5 20% lignin, and up to 20% moisture.

TYPES OF NATURAL FIBERS

Natural bers are grouped into three types: seed hair, bast bers, and leaf bers, depending upon the source. Some examples are cotton (seed hairs), ramie, jute, and aax (bast bers), and sisal and abaca (leaf bers). Of these bers, jute, ramie, ax, and sisal are the most commonly used bers for polymer composites. Natural bers in the form of wood our have also been often used for preparation of natural ber composites. The properties of these bers are presented in Table I. As can be seen from Table I, the tensile strength of glass bers is substantially higher than that of natural bers even though the modulus is of the same order. However, when the specic modulus of natural bers (modulus/specic gravity) is considered, the natural bers show values that are comparable to or better than those of glass bers. These

NATURAL FIBER COMPOSITES

The matrix phase plays a crucial role in the performance of polymer composites. Both thermosets and thermoplastics are attractive as matrix materials for composites. In thermoset composites, formulation is complex because a large number of compo-

TABLE I
Mechanical Properties of Natural Fibers Fiber Jute Sisal Flax Sunhemp Pineapple Glass Fiber-E Specic Gravity 1.3 1.3 1.5 1.07 1.56 2.5 Tensile Strength (MPa) 393 510 344 389 170 3400 Modulus (GPa) 55 28 27 35 62 72 Specic Modulus 38 22 50 32 40 28

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NATURAL FIBER POLYMER COMPOSITES nents are involved such as base resin, curing agents, catalysts, owing agents, and hardeners. These composite materials are chemically cured to a highly cross-linked, three-dimensional network structure. These cross-linked structures are highly solvent resistant, tough, and creep resistant. The ber loading can be as high as 80% and because of the alignment of bers, the enhancement in the properties is remarkable. Thermoplastics offer many advantages over thermoset polymers. One of the advantages of thermoplastic matrix composites is their low processing costs. Another is design exibility and ease of molding complex parts. Simple methods such as extrusion and injection molding are used for processing of these composites. In thermoplastics most of the work reported so far deals with polymers such as polyethylene, polypropylene, polystyrene, and poly(vinyl chloride). This is mainly because the processing temperature is restricted to temperatures below 200 C to avoid thermal degradation of the natural bers. For thermoplastic composites, the dispersion of the bers in the composites is also an important parameter to achieve consistency in the product. Thermoplastic composites are exible and tough and exhibit good mechanical properties. However, the % loading is limited by the processability of the composite. The ber orientation in the composites is random and accordingly the property modication is not as high as is observed in thermoset composites. Properties of the bers, the aspect ratio of the bers, and the ber matrix interface govern the properties of the composites. The surface adhesion between the ber and the polymer plays an important role in the transmission of stress from matrix to the ber and thus contributes toward the performance of the composite. Another important aspect is the thermal stability of these bers. These bers are lignocellulosic and consist of mainly lignin, hemicellulose, and cellulose. The cell walls of the bers undergo pyrolysis with increasing processing temperature and contribute to char formation. These charred layers help to insulate the lignocellulosic from further thermal degradation. Since most thermoplastics are processed at high temperatures, the thermal stability of the bers at processing temperatures is important. Thus the key issues in development of natural reinforced composites are (i) thermal stability of the bers, (ii) surface adhesion characteristics of the bers, and (iii) dispersion of the bers in the case of thermoplastic composites. TABLE II
Reported Work on Natural Fiber Composites Fiber Wood our/ber Matrix Polymer PE PP PVC PS Polyurethane PP SBR, nitrile rubber Epoxy Polyester Phenolformaldehyde PE Natural rubber Polyester epoxy Epoxy PE, polyester Polyester, PP Rubber PE, PP Natural rubber Polyester PP PP Epoxy References 5 12 13 28 29 31 32 34 35 36 40 50, 51 41, 42 43 49 52 53 55 58 61 56, 57, 62 72 67 69 76 80 63 66 75 73 74 70 71 70 78

Jute

Sisal

Abaca Pineapple Sunhemp Oil palm Kenaf Coir Banana Flax Wheat straw Bamboo

Numerous reports are available on the natural ber composites. Table II summarizes the reported work on natural ber composites. As can be seen from the table, the majority of the work is on wood our, with a few reports on other bers such as jute, sisal, and kenaf.

Major Issues in Development of Composites

THERMAL STABILITY OF NATURAL FIBERS
Natural bers are complex mixtures of organic materials and as a result, thermal treatment leads to a variety of physical and chemical changes. The thermal stability of natural bers can be studied by thermogravimetric analysis (TGA). A typical TGA for jute bers is shown in Figure 1. As can be seen from the gure, the natural bers start degrading at about 240 C. The thermal degradation of lignocellulosic materials has been reviewed by Nguyen

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NATURAL FIBER POLYMER COMPOSITES Sridhar et al.43 have studied the thermal stability of jute bers at temperatures ranging from 150 to 300 C both in air and under vacuum. The degradation was monitored by measuring the weight loss, change in chemical structure, and mechanical properties. It was observed that heating under vacuum at 300 C for 2 h resulted in 60% decrease in the tensile strength, which was ascribed to the depolymerization and oxidation of bers. In actual practice, processing is carried out under atmospheric conditions and the possibility of thermal degradation leading to inferior mechanical properties cannot be ruled out. Gonzalez and Myers86 87 have studied the effect of thermal degradation on the mechanical properties of wood/polymer composites. The temperature range of study was from 220 to 260 C and the exposure time was varied from 4 to 4096 min. It was observed that although, in general, the mechanical properties deteriorate, as a result of thermal degradation of wood our, toughness and bending strength were more affected. It was also pointed out that the changes in the surface chemistry might cause changes in the wood/polymer bonding that is responsible for the inferior properties of the composites. In another study of PP/wood our composites, similar loss in properties has been reported after extrusion at 250 C.88 The thermal degradation of the bers also results in production of volatiles at processing temperatures 200 C. This can lead to porous polymer products with lower densities and inferior mechanical properties.

FIGURE 1. Typical TGA thermogram of cellulose ber

(jute powder).

et al. in detail for modied and unmodied materials.81,82 The thermal degradation of natural bers is a two-stage process, one in the temperature range 220 280 C and another in the range 280 300 C. The low-temperature degradation process is associated with degradation of hemicellulose whereas the high-temperature process is due to lignin. The apparent activation energies for the two processes are about 28 and 35 kcal/mol, which correspond to the degradation of hemicellulose and lignin, respectively. The degradation of natural bers is a crucial aspect in the development of natural ber composites and thus has a bearing on the curing temperature in the case of thermosets and extrusion temperature in thermoplastic composites. For improvement of thermal stability, attempts have been made to coat the bers and/or to graft the bers with monomers. Grafting is possible since the lignin can react with the monomers. Mohanty et al.83 have reported that grafting of acrylonitrile on jute improved the thermal stability as evidenced by the increase in the degradation temperature from 170 to 280 C. Sabaa84 has also reported improved thermal stability for acrylonitrile-grafted sisal bers as evidenced by the increased initial degradation temperature, lowering of the rate of degradation, and the total weight loss. In another study by Yap et al.,85 the polymer wood composites were prepared by in situ polymerization of various monomers and it was observed that the maximum rate of degradation was substantially reduced for phosphonate-treated wood our. The degradation of natural bers leads to poor organoleptic properties such as odor and color and also deterioration of their mechanical properties.

MOISTURE CONTENT OF THE FIBERS

Cellulosic bers are hydrophilic and absorb moisture. The moisture content of the bers can vary between 5 and 10%. This can lead to dimensional variations in composites and also affects the mechanical properties of the composites. During processing of composites based on thermoplastics, the moisture content can lead to poor processability and porous products. Treatment of natural bers with chemicals or grafting of vinyl monomers can reduce the moisture gain.

BIODEGRADATION AND PHOTODEGRADATION OF NATURAL FIBERS

Natural bers (lignocellulosics) are degraded by biological organisms since they can recognize the

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NATURAL FIBER POLYMER COMPOSITES carbohydrate polymers in the cell wall. Lignocellulosics exposed outdoors undergo photochemical degradation caused by ultraviolet light. Resistance to biodegradation and UV radiation can be improved by bonding chemicals to the cell wall polymers or by adding polymer to the cell matrix. pounding PP/wood composites. It was observed that tensile strength varied nonlinearly with rpm, mixing temperature, and time, indicating that ber length and dispersion need to be optimum to obtain enhanced properties.

Dispersion of the Fibers in the Matrix

The incorporation of cellulosic bers in thermoplastics leads to poor dispersion of the bers due to strong interber hydrogen bonding, which holds the bers together. Treatment of the bers and/or use of external processing aids can reduce this problem. Various processing aids/coupling agents such as stearic acid, mineral oil, and maleated ethylene have been used. The concentration of the additive is approximately 1% by weight of bers. The stearic acid is highly effective in dispersing, reducing ber to ber interaction. Mineral oil functions as a lubricant that is adsorbed by the bers and this facilitates the disentanglement of individual bers.

PROCESSING OF THERMOSET COMPOSITES

Thermosets are processed by simple processing techniques such as hand layup and spraying, compression, transfer, resin transfer, injection, compression injection, and pressure bag molding operations. A few other methods such as centrifugal casting, cold press molding, continuous laminating, encapsulation, lament winding, pultrusion, reinforced reaction injection molding, rotational molding, and vacuum forming are being used for composites but use of these methods for natural ber composites is hardly reported. In thermoset polymers, the bers are used as unidirectional tapes or mats. These are impregnated with the thermosetting resins and then exposed to high temperature for curing to take place.

FIBER MATRIX INTERFACE PROCESSING OF THERMOPLASTIC COMPOSITES

The processing of natural ber thermoplastic composites involves extrusion of the ingredients at melt temperatures followed by shaping operations such as injection molding and thermoforming. Fiber ber interactions as well as ber matrix interactions play a crucial role in determining the properties of such composites. Many times, it is observed that these bers do not function as an effective reinforcement system due to poor adhesion at the ber matrix interface. Cellulose bers also tend to aggregate and therefore the bers do not disperse well in a hydrophobic polymer matrix and thus pose difculties in achieving a uniform distribution of ber in the matrix. The surface characteristics of the reinforcing ber are important in the transferring of stress from the matrix to the ber. The pretreatment of the ber with suitable additives prior to processing leads to good dispersion and signicantly improved mechanical properties of the composites. The properties of the composites are also inuenced by the processing parameters in the case of thermoplastic composites. Takase and Shiraishi88 have reported the effect of processing parameters such as mixing time, rpm, and temperature in comThe incorporation of hydrophilic natural bers in polymers leads to heterogeneous systems whose properties are inferior due to lack of adhesion between the bers and the matrix. Thus the treatment of bers for improved adhesion is a critical step in the development of such composites. The treatment of the bers may be bleaching, grafting of monomers, acetylation, and so on. In addition to the surface treatment of bers, use of a compatibilizer or a coupling agent for effective stress transfer across the interface can also be explored. The compatibilizer can be polymers with functional groups grafted onto the chain of the polymer. The coupling agents are tetrafunctional organometallic compounds based on silicon, titanium, and zirconium and are commonly known as silane, zirconate, or titanate coupling agents. Table III presents the structures, functional groups, and applications of a few commercial coupling agents. (The coupling mechanism for the silane coupling agent is illustrated in the Appendix.)

MODIFICATION OF NATURAL FIBERS

Natural bers are incompatible with the hydrophobic polymer matrix and have a tendency to form aggregates. These are hydrophilic bers and thus

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NATURAL FIBER POLYMER COMPOSITES TABLE III

Some Typical Representative Commercial Coupling Agents115 Sl. No. 1 2 3 Functional Group Vinyl Chloropropyl Epoxy Chemical Structure CH2 " CHSiCl3 CH2 " CHSi(OC2H5 )3 ClCH2CH2CH2Si(OCH3 )3 O CH2CHCH2O(CH2)3Si(OCH3)3 4 Methacryl CH3 CH2 " C 9 COO(CH2)3Si(OCH3)3 5 6 7 8 9 Amine Cationic styryl Phenyl Mercapto Phosphate (titanate) H2N(CH2 )3Si(OC2H5 )3 HN(CH2 )2NH(CH2 )3Si(OCH3 )3 CH2CHC6H4CH2H H2(CH2 )3Si(OCH3 )3Cl C6H5Si(OCH3 )3 HS(CH2 )3Si(OCH3 )3 HS(CH2 )2Si(OC2H5 )3 O O C3H7OTi[O 9 P 9 O 9 P(OC8H17)2]3 OH 10 Neoalkoxy (zirconate) O O Polyolens, ABS, phenolics, polyesters, PVC, polyurethane, styrenics Applicable Polymera Elastomers, polyethylene, silicone elastomers, UP, PE, PP, EPDM, EPR EP Elastomers, especially butyl elastomers, epoxy, phenolic and melamine, PC, PVC, UR Unsaturated polyesters, PE, PP, EPDA, EPM Unsaturated polyesters, PA, PC, PUR, MF, PF, PI, MPF All polymers PS, addition to amine silane EP, PUR, SBR, EPDM Polyolens, ABS, phenolics, polyesters, PVC, polyurethane, styrenics

neoalkoxy-Ti[O 9 P 9 O 9 P(OC8H17)2]3 OH

Abbreviations according to ASTM 1600.

exhibit poor resistance to moisture. To eliminate the problems related to high water absorption, treatment of bers with hydrophobic aliphatic and cyclic structures has been attempted. These structures contain reactive functional groups that are capable of bonding to the reactive groups in the matrix polymer, e.g., the carboxyl group of the polyester resin. Thus modication of natural bers is attempted to make the bers hydrophobic and to improve interfacial adhesion between the ber and the matrix polymer.89 103 Chemical treatments such as dewaxing (defatting), delignication, bleaching, acetylation, and chemical grafting are used for modifying the surface properties of the bers and for enhancing its performance. (The mechanisms of these reactions are discussed in detail in the Appendix.) Chemical modication of natural bers has been reviewed by Rowell.90 Table IV summarizes the various chemical treatments and coupling agents used so far for the modication of the ber surface. Delignication (dewaxing) is generally carried

out by extracting with alcohol or benzene and treatment with NaOH followed by drying at room temperature.93 Many oxidative bleaching agents such as alkaline calcium or sodium hypochlorite and hydrogen peroxide are commercially used. Bleaching generally results in loss of weight and tensile strength.94 These losses are mainly attributed to the action of the bleaching agent or alkali or alkaline reagent on the noncellulosic constituents of bers such as hemicellulose and lignin. Acetylation of jute is reported to impart resistance to fungal attack and hydrophobicity. The change in properties is attributed to the decrease in moisture sorption in the cell walls and blocking of the hydroxyl group of the wall components in such a way that enzymes of the wood-degrading microorganisms cannot recognize them as attachable substrates. Acetylated jute is considerably more hydrophobic than unmodied jute.95 The acetylated jute shrinks much less than unmodied jute when exposed to water and thus exhibits improved dimensional stability.

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NATURAL FIBER POLYMER COMPOSITES TABLE IV

Chemical Treatments Used for Modication of Natural Fibers Fiber Wood our Chemical Treatments Succinic acid, EHMA, styrene, ureaformaldehyde, m-phenylene bismaleimide, acetic anhydride, maleic anhydride, itaconic anhydride, polyisocyanate, linoleic acid, abietic acid, oxalic acid, rosin Phenol formaldehyde, malemineformaldehyde, cardanol formaldehyde NaOH, isocyanate, sodium alginate, N-substituted methacrylamide p-phenylene diamine Sodium alginate Sodium alginate, sodium carbonate Coupling Agents/Compatibilizers Maleated PP, acrylic acid grafted PP, Silane A-174, Epolene C-18, Silane A-172, A-174, and A-1100, PMPPIC, zirconates, titanates

Jute Sisal Pineapple Banana Coir

Chemical modication through graft copolymerization provides a potential route for signicantly altering their physical and mechanical properties. Chemical grafting involves attaching to the surface of a ber/ller a suitable polymer with a solubility parameter similar to that of the polymer matrix, which acts as an interfacial agent and improves the bonding between the ber and the matrix. Graft copolymerization of vinyl monomers such as methyl methacrylate, acrylamide, and acrylonitrile onto cellulose, cellulose derivatives, and lignocellulosic bers has been well established and has been extensively studied over the past few decades.96 98 Impregnation with monomer followed by its polymerization has also been one of the most common methods used for treatment of bers. Samal and coworkers99 have reviewed various methods of graft copolymerization onto cellulose bers. Graft copolymerization onto cellulose takes place through an initiation reaction involving attack by macrocellulosic radicals on the monomer to be grafted. The generation of the macrocellulosic radicals is accomplished by a variety of methods such as (1) diazotization, (2) chain transfer reactions, (3) redox reactions, (4) photochemical initiation, and (5) radiation-induced synthesis. The effect of treatments with other chemicals, for instance, sodium alginate and sodium hydroxide, has been reported for coir, banana, and sisal bers by Mani and Satyanarayan.100 The treatment resulted in an increase in debonding stress and thus improved the ultimate tensile strength up to 30%. Basak et al.39 have reported that treatment of jute with polycondensates such as phenol formaldehyde, malemine formaldehyde, and cashew nut

shell liquid formaldehyde improved the wettability of jute bers and reduced the water regain properties. Treatment with cardanol formaldehyde was also found to reduce water absorption and improved the mechanical properties of a jute/polyolen composite.37 The chemical treatment of jute bers with ethylenediamine and hydrazine results in formation of complexes with the hydroxyl group of the cellulose and thus reduces the moisture absorption of the ber.46,47 Samal and Ray102 have studied the chemical modication of pineapple leaf ber using alkali treatment, diazo coupling with aniline, and cross-linking with formaldehyde and p-phenylenediamine. These chemical treatments resulted in signicant improvements in mechanical properties, chemical resistance, and reduced moisture regain. A study by Yap et al.103 has shown that the treatment of wood with vinyl monomers improved termite and funogal resistance and they also imparted ame retardancy to polymer wood composites.

Mechanical Properties of Natural Fiber Composites

The properties of natural ber reinforced composites depend on a number of parameters such as volume fraction of the bers, ber aspect ratio, ber matrix adhesion, stress transfer at the interface, and orientation. Most of the studies on natural ber composites involve study of mechanical properties as a function of ber content, effect of various treat-

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NATURAL FIBER POLYMER COMPOSITES ments of bers, and the use of external coupling agents.104 108 Other aspects include the prediction of modulus and strength using some well-established models for two-phase systems and comparison with experimental data.104 Both the matrix and ber properties are important in improving mechanical properties of the composites. The tensile strength is more sensitive to the matrix properties, whereas the modulus is dependent on the ber properties. To improve the tensile strength, a strong interface, low stress concentration, ber orientation is required whereas ber concentration, ber wetting in the matrix phase, and high ber aspect ratio determine tensile modulus. The aspect ratio is very important for determining the fracture properties. In short-ber-reinforced composites, there exists a critical ber length that is required to develop its full stressed condition in the polymer matrix. Fiber lengths shorter than this critical length lead to failure due to debonding at the interface at lower load. On the other hand, for ber lengths greater than the critical length, the ber is stressed under applied load and thus results in a higher strength of the composite. For, good impact strength, an optimum bonding level is necessary. The degree of adhesion, ber pullout, and a mechanism to absorb energy are some of the parameters that can inuence the impact strength of a short-ber-lled composite.105 The properties mostly vary with composition as per the rule of mixtures and increase linearly with composition. However, it has been observed that this linear dependence on percentage of ber content does not hold at high percentage ( 80%) of the ber, probably due to lack of wetting of the ber surface by the polymer. ester composites, it was noted that the mechanical properties were dependent on the secondary chemical bonding between jute ber and polyester.45 Sanadi et al.76 have studied the mechanical properties of sunhemp ber reinforced polyester. The tensile strength and modulus increased linearly with increasing ber content following the rule of mixtures. The improved toughness was ascribed to the ber pullout mechanism in the composite. In banana/ polyester composites, the improvement in the properties was observed only when the ber weight fraction was more than 19%. At 30% ber content, the exural strength was 97 MPa and elastic modulus was 6.5 GPa.73 Jain et al.78 have studied bamboo/ epoxy composites up to a volume fraction of 0.85. It was noted that the composites with banana ber exhibited better tensile, impact, and exural strength compared with the properties of other natural ber composites. Ismail and Rosnah79 have studied the curing characteristics of oil/palm ber reinforced rubber composites. It was noted that the presence of bonding agents prolonged the curing time; however, the mechanical properties were better due to improved interfacial bonding as evidenced by SEM studies. Tobias and Ibarra74 have studied the effect of cure temperature on exural strength of polyester-based composites. The exural strength increased with increasing cure temperature and maximum strength was obtained for abaca/polyester composites compared to banana/polyester and rice hull/polyester composites. The incorporation of pineapple leaf bers in polyester resulted in an increase of 2.3 times in the specic exural stiffness at 30 wt% content of the ber.68 The use of Silane A-172 further improved the properties of the composites. For sisal/polyester composites, the effect of treatments of bers with silane, titanate, and zirconate coupling agents and N-substituted methacrylamide was investigated by Singh et al.56 The treatments resulted in improved strength retention properties of the composites and thereby the composites exhibited better properties in humid as well as dry conditions. Similar improved moisture resistance was reported by Bisinda et al.62 For natural rubber composites with sisal bers, treatment with resorcinol and hexamethylenetetramine resulted in a better storage modulus. The relaxation process for the composites was altered and the composites exhibited a two-stage relaxation process corresponding to the matrix and the interface. The process was sensitive to the type of bonding agent used.60,61

THERMOSET COMPOSITES
For thermoset composites, the bers are combined with phenolic, epoxy, and polyester resins to form composite materials. These thermoset polymers contain reactive groups, which aid the interface development. The reported work on thermoset composites covers the effect of process parameters such as curing temperature and various treatments on the properties of composites. For jute/polyester composites, an increase in modulus and strength was reported up to a volume fraction of 0.6 followed by a decrease. Further increase in volume fraction resulted in a decrease in the properties, which was attributed to insufcient wetting of the ber.44 In another study of jute/poly-

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NATURAL FIBER POLYMER COMPOSITES

THERMOPLASTIC COMPOSITES Polyethylene-Based Composites

The mechanical properties of thermoplastic composites can be improved by improving the compatibility between the ber and matrix. Compatibilizers such as maleated ethylene, maleated propylene, and a few acrylic-grafted linear polymers are reported to enhance the adhesion between the ber and polymer matrix.5 12 For HDPE/cellulose ber composites (at 10 and 30% ber concentration), the best improvement in tensile strength and tensile modulus was achieved with maleated ethylene. The enhancement in the properties was attributed to the coupling reaction (ester linkage) between the maleated ethylene and the hydroxyl group of cellulose, which improves the bonding between the ber and matrix.7 Mechanical properties of HDPE/wood ber composites have been studied by Carrasco et al.11 Two types of coupling agents Epolene C-18 and Silane 174 were evaluated. Use of silane coupling agents resulted in composites with better properties than those of Epolene-treated and untreated wood ber. The inuence of coupling agents on the mechanical properties of HDPE/wood bers has also been studied by Raj et al.4,5 It has been observed that incorporation of wood bers in HDPE resulted in an increase in the stiffness and decrease in tensile strength for untreated wood bers. Treatment of wood bers with silane coupling agent and polyisocyanate resulted in an increase in tensile strength. Raj et al.7 have compared the tensile and impact properties of LLDPE/wood ber composites with mica and glass ber composites and have shown that the potential advantage of using wood bers as reinforcement is in terms of material cost and specic properties. Pretreated wood ber produced a signicant improvement in tensile strength and modulus. Grafting of aspen chemithermomechanical pulp was found to improve the mechanical properties of LLDPE composites as noted by Beshay et al.5 The inuence of various chemical treatments on the properties of sisal/PE composites has been investigated by Joseph et al.55 The chemical treatments included treatments with sodium hydroxide, isocyanate, and peroxide. The enhancement in the properties was ascribed to the bonding between sisal ber and the PE matrix. Treatment with the cardanol derivative of toluene isocyanate was found to be better than other treatments as evidenced by the

decrease in the hydrophilic nature of the composite. The composites exhibited better dimensional stability and retention of properties even after aging, which was ascribed to the improved moisture resistance.54

PP-Based Composites
A systematic study of the effect of surface treatments on the properties of PP/cellulose ber has been carried out by Bataille et al.16 The results indicated an increase in modulus with increase in the ber content. The addition of coupling agents and/ or maleic anhydride PP improved the interfacial adhesion, thereby leading to improved properties. Sain et al.21 have reported that the properties of PP/ wood ber composites were very poor due to the absence of interface modiers. However, it was noted that use of maleated PP, itaconic anhydride, and bismaleimide-modied PP resulted in a stable surface and thus improved tensile strength. An increase in tensile and impact strength was reported when rosin was used in PP/wood our composites.13 Sun and Hawke24 have studied the performance of wood ber composites using polyisocyanate as a bonding material. Sain et al.20 have demonstrated the use of bismaleimide modication for improving the properties of PP/wood ber composites. Write and Mathias18 have reported synergistic reinforcement of balsa wood composites using ethyl- -(hydroxy methyl)acrylate (EHMA) and styrene. The signicant improvements in the properties were ascribed to the strong interaction between the ber and the matrix polymer, conrmed by solid-state NMR and SEM. The composite also exhibited improved dimensional stability. Tibor23 has reported that the properties of electron beam processed PP/ wood ber composites were signicantly better than those of conventionally processed composites. The improvement in the performance was explained on the basis of creation of active sites in the polymer as well as the bers, which resulted in improved adhesion. Signicant improvement in the properties was observed for PP/kenaf ber composites when maleated PP was used for modifying the ber matrix interface.64 66 Dalvag et al.14 used maleic anhydride modied propylene to improve the strength and ductility of PP/wood ber and PP/cellulose our composites. Hydrolytic pretreatment of cellulose bers with oxalic acid was found to improve the homogeneity and mechanical properties of PP, HDPE,

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NATURAL FIBER POLYMER COMPOSITES and PS that contained various amounts of bleached pulp.15 Improvement in the mechanical strength of wood ber lled thermoplastic composites has been achieved with the use of coupling agents. Cellulose bers treated with vinyl chloride, plasticizers, and an isocyanate produced better adhesion with silane coupling agents A-172 and A-174, and A-1100 exhibited better bonding between the bers and PVC matrix.29 31 The physical properties of silane-treated wood/ PMMA composites were studied by Elvy et al.109 As a result of treatment, the compressive strength was found to increase from 180 to 210% for treated wood ber composites. The increased values of stress are attributed to the incorporation of polymer into the void spaces in the wood ber. As discussed earlier, reports on wood ber composites with engineering polymers are scarce. This is mainly because of the high processing temperature ( 250 C) required for processing of engineering polymers. The inuence of the use of jute bers on the mechanical properties of ABS has been studied by Bawadekar and Jog.110 It has been observed that the ABS/jute ber composites show remarkable improvement in the exural modulus from 2000 to 3500 MPa at 30% jute ber content. The composites showed marginal changes in the tensile strength values whereas tensile modulus increased with increase in jute ber content. Surface treatment of jute using coupling agents was found to result in further improvement in the modulus.111 ns are now commercially available. It is reported that these composites offer advantages of 20% reduction in processing temperature and 25% reduction in cycle time in addition to a weight reduction of about 30%.113 The composites provide woodlike appearance without requiring the maintenance. The extruded proles can be used as a wood substitute in various applications such as window systems and decking.114 These developments are conned to polymer composites based on PE, PP, PS, and PVC, for which the processing temperature is about 200 C. The real challenge for the scientist is to improve the thermal stability of these bers so that they can be used with engineering polymers and further the advantage of both the polymers and the bers. Thus improved thermal stability of natural bers and modication of bers for better performance are still an indispensable task for the scientist. Such attempts can widen the applications of natural ber composites

References
1. Schneider, J. P.; Myers, G. E.; Clemons, C. M.; English, B. W. Eng Plast 1995, 8 (3), 207. 2. Reinforced Plastics 1997, 41(11), 22. 3. Colberg, M.; Sauerbier, M. Kunstst-Plast Europe 1997, 87 (12), 9. 4. Schloesser, Th.; Knothe, J. Kunstst-Plast Europe 1997, 87 (9), 25. 5. Beshay, A. D.; Kokta, B. V.; Maldas, D.; Daneault, C. Polym Compos 1985, 6, 261. 6. Maiti, S. N.; Singh, K. J Appl Polym Sci 1986, 32, 4285. 7. Raj, R. G.; Kokta, B. V.; Maldas, D.; Daneault, C. J Appl Polym Sci 1989, 37, 1089. 8. Raj, R. G.; Kokta, B. V.; Grouleau, G.; Daneault, C. Polym Plast Technol Eng 1989, 28 (3), 247. 9. Raj, R. G.; Kokta, B. V.; Grouleau, G.; Daneault, C. Polym Plast Technol Eng 1990, 29 (4), 339. 10. Raj, R. G.; Kokta, B. V.; Daneault, C. J Mater Sci 1990, 25, 1851. 11. Carrasco, F.; Saurina, J.; Arnau, J. J.; Pages, P. 6th European Conference on Composite Materials, France, 1993, p 483. 12. Berenbrok, P. A.; Liles, B. E. Special Areas Annual Technical Conference ANTEC, Toronto, Conference Proceedings, Vol. 3, pp 2931 2933; Society of Plastics Engineers, Brookeld, CT, 1997. 13. Lightsey, G.; Short, P. H.; Klasinsley, K. S.; Mann, L. J Miss Acad Sci 1979, 24, 76. 14. Dalvag, H.; Klason, C.; Stromvall, H. E. Int J Polym Mater 1985, 11, 9.

Recent Developments
A natural ber composite with an outstanding combination of properties is not a dream today. Use of proper processing techniques, ber treatments, and compatibilizers/coupling agents can lead to composites with optimum properties for a particular application. Recently, there has been increasing interest in commercialization of natural ber composites and their use, especially for interior paneling in the automobile industry. These composites with density around 0.9 g/cm3, stiffness around 3000 MPa, impact strength of 25 kJ/m2, and good sound absorption characteristics are being used by a number of leading companies.112 Composites based on polyole-

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15. Boldizer, A.; Klason, C.; Kubat, J. Int J Polym Mater 1987, 11, 229. 16. Bataille, P.; Ricard, L.; Sapieha, S. Polym Compos 1989, 10, 103. 17. Raj, R. G.; Kokta, B. V.; Dembele, F.; Sanschagrain, B. J Appl Polym Sci 1989, 38, 1987. 18. Wright, J. R.; Mathias, L. J. J Appl Polym Sci 1993, 48, 2241. 19. Belgacem, M. N.; Bataille, P.; Sapieha, S. J Appl Polym Sci 1994, 53, 379. 20. Sain, M. M.; Kokta, B. V. J Appl Polym Sci 1994, 54, 1545. 21. Sain, M. M.; Kokta, B. V.; Imbert, C. Polym Plast Technol Plast Eng 1994, 133, 89. 22. Minqiu, Lu; Collier, J. R.; Collier, B. J. Annual Technical Conference ANTEC, Conference Proceedings, Vol. 2, p 1433; Society of Plastics Engineers, Brookeld, CT, 1995. 23. Czvikovszky, Tibor. Radiat Phys Chem 1996, 47 (3), 425; Mech Eng 1994, 38, 209. 24. Sun, B. C.; Hawke, R. N. J Adv Mater 1996, 27, 45. 25. Gatenholm, P.; Hedenberg, P.; Karlsson, J.; Felix, J. J Eng Appl Sci 1996, 2, 2302. 26. Kazayawoko, M.; Balatinecz, J. J.; Woodhams, R. T.; Law, V. J Reinf Plast Compos 1997, 16 (15), 1383; Int J Polym Mater 1997, 37 (3 4), 237. 27. Kazayawoko, M.; Balatinecz, J. J.; Woodhams, R. T. J Appl Polym Sci 1997, 66 (6), 1163. 28. Xanthos, M. Plast Rubber Proc Appl. 1983, 3 (3), 223. 29. Kokta, B. V.; Maldas, D.; Daneault, C.; Beland, P. Polym Compos 1990, 11, 84. 30. Maldas, D.; Kokta, B. V. J Vinyl Technol 1993, 15, 38; Kokta, B. V.; Maldas, D.; Daneault, G. C. J. Vinyl Technol 1989, 11, 90. 31. Laurent, M. M.; Park, C. B.; Balatinecz, J. J. J Eng Appl Sci 1996, 2, 1900. 32. Sati, M.; Agnelli, J. A. M. J Appl Polym Sci 1989, 37, 1777. 33. Maldas, D.; Kokta, B. V. J Adhes Sci Technol 1991, 5, 727. 34. Simonsen, J.; Rials, T. G. J Thermoplast Compos Mater 1996, 9, 292. 35. Rials, T. G.; Wolcott, M. P. J Mater Sci Lett 1998, 17 (4), 317. 36. Karmacker, A. C.; Hinrichsen, G. Polym Plast Technol Eng 1991, 30 (5), 609. 37. Tan, T. Th. M. Polym Polym Compos 1997, 5, 273. 38. Karmaker, A. C.; Schneider, J. P. J Mater Sci Lett 1996, 15, 201. 39. Basak, R. K.; Mitra, B. C.; Sarkar, M. J Appl Polym Sci 1997, 67, 103. 40. Gassan, J.; Biedzki, A. K. Compos, Part A: Appl Sci Manuf 1997, 28A, 1001. 41. Mohan Ranarajan; Kishor, K. J Reinf Plast Compos 1985, 4, 186. 42. Kumar, P. Indian J Technol 1986, 24, 29. 43. Sridhar, M. K.; Basavarajjappa, G.; Kasturi, S. Sg.; Balsubramanian, N. Indian J Text Res 1982, 7, 87. 44. Roe, P. J.; Ansell, M. P. J Mater Sci 1985, 20, 4015. 45. Semsarzadeh, M. A. Polym Compos 1986, 7, 23. 46. Pal, S. K.; Muhkhopadhyaya, D.; Sanyal, S. K.; Mukharjea, R. N. J Appl Polym Sci 1988, 35, 973. 47. Pal, S. K.; Sanyal, S. K.; Mukharjea, R. N.; Phani, K. K. J Polym Mater 1994, 1, 69. 48. Varma, I. K.; Ananthakrishanan, S. R.; Krishnamurthy, Z. S. Composites 1989, 20, 383. 49. Mohanty, A. K.; Misra, M. Polym Plast Technol Eng 1995, 34 (5), 729. 50. Murthy, V. M.; De, S. K. J Appl Polym Sci 1984, 29, 1355. 51. Bhagwan, S. S.; Tripathy, D. K.; De, S. K. J Appl Polym Sci 1987, 33, 1623. 52. Ghosh, A. K.; Dey, S. S. Ceram-Matrix Compos 1993, 813. 53. Joseph, K.; Thomas, S.; Pavithran, C.; Brahmakumar, M. J Appl Polym Sci 1993, 47, 1731. 54. Joseph, K.; Thomas, S.; Pavithran, C. Compos Sci Technol 1995, 53 (1), 99. 55. Joseph, K.; Thomas, S.; Pavithran, C. Polymer 1996, 37, 5139. 56. Singh, B.; Gupta, M.; Verma, A. Polym Compos 1996, 17, 910. 57. Joseph, K.; Thomas, S.; Pavithran, C. J Reinf Plast Compos 1993, 12, 139. 58. Kumar, R. P.; Amma, P.; Geethakumari, M. L.; Thomas, S. J Appl Polym Sci 1995, 58, 597. 59. Varghese, S.; Kuriakose, B.; Thomas, S.; Premalatha, C. K.; Koshy, A. T. Plast, Rubber Compos Process Appl 1993, 20 (2), 93. 60. Varghese, S.; Kuriakose, B.; Thomas, S. J Appl Polym Sci 1994, 53, 1051. 61. Varghese, S.; Kuriakose, B.; Thomas, S. J Adhes Sci Technol 1994, 8, 235. 62. Bisanda, E. T. N.; Ansell, M. P. Compos Sci Technol 1991, 41, 165. 63. Chen, H. L.; Porter, R. S. J Appl Polym Sci 1994, 54, 1781. 64. Sanadi, A. R.; Cauleld, D. F.; Rowell, R. M. Plast Eng 1994, 50 (4), 27. 65. Sanadi, A. R.; Cauleld, D. F.; Jacobson, R. E.; Rowell, R. M. Ind Eng Chem Res 1995, 34 (5), 1889. 66. Sanadi, A. R.; Young, A. A.; Clemsons, C.; Rowell, R. M. J Reinf Plast 1994, 13, 54. 67. George, J.; Joseph, K.; Bhagawan, S. S.; Thomas, S. Mater Lett 1993, 18 (3), 163. 68. George, J.; Bhagawan, S. S.; Thomas, S. J Therm Anal 1996, 47 (4), 1121. 69. Devi, L. U.; Bhagawan, S. S.; Thomas, S. J Appl Polym Sci 1997, 64, 1739. 70. Mieck, K. P.; Nechwatal, A.; Knobelsdorf , C. Angew Makromol Chem 1995, 225, 37. 71. Hornsby, P. R.; Hinrichsen, E.; Tarverdi, K. J Mater Sci 1997, 32, 1009. 72. Tobias, B. C. Evolving Technologies for the Competitive Edge, International SAMPE Symposium and Exhibition (Proceedings) 1997, 42 (2), 996; SAMPE, Covina, CA. 73. Zhu, W. H.; Tobias, B. C.; Coutts, R. S. P. J Mater Sci Lett 1995, 14 (7), 508.

ADVANCES IN POLYMER TECHNOLOGY

361

NATURAL FIBER POLYMER COMPOSITES

74. Tobias, B. C.; Ibarra, E. Proceedings of the 42nd International SAMPE Symposium, p 181, 1997. 75. Geethamma, V. G.; Thomas, K. M.; Lakshminarayanan, R.; Thomas, S. Polymer 1998, 39, 1483. 76. Sanadi, A. R.; Prasad, S. V.; Rohadgi, P. K. J Mater Sci 1986, 21, 4299. 77. Fimio Goto Kasahara Yasumasa, PCT Int Appl WO 8810286, Dec 29, 1988. 78. Jain, S.; Kumar, R.; Jindal, U. C. Adv Compos Mater 1990, 135, Oxford IBH Publ Comp Pvt Ltd, New Delhi, India. 79. Ismail, H. R.; Rosnah, N. Polymer 1997, 38, 4059. 80. Castano, V. M.; Vazquez, P. G.; Amador, M. A.; Garcia, F. Z.; Martinez, E.; Marquez, A.U.; Altmamirano, M.A. J Reinf Plast Compos 1995, 14 (8), 866. 81. Tinh, N.; Eugene, Z.; Edward, M. B. J Macromol Sci, Rev Macromol Chem 1981, C20, 1. 82. Tinh, N.; Eugene, Z.; Edward, M. B. J Macromol Sci, Rev Macromol Chem 1981, C21, 1. 83. Mohanty, A. K.; Patnaik, S.; Singh, B. C. J Appl Polym Sci 1989, 37, 1171. 84. Sabaa, M. W. Polym Degrad Stab 1991, 32, 209. 85. Yap, M. G. S.; Que, Y. T.; Chia, L. H. L.; Chan, H. S. O. J Appl Polym Sci 1991, 43, 2057. 86. Gonzalez, C.; Myers, G. E. Int J Polym Mater 1993, 23, 67. 87. Mayer, G. E.; Chahyadi, I. S.; Gonzalez, C.; Coberly, C. A.; Ermer, D. S. Int J Polym Mater 1991, 15, 171. 88. Takase, S.; Shiraishi, N. J Appl Polym Sci 1989, 37, 645. 89. Rowell, R. M. ACS Proceedings, Polym Mater Sci Eng 1992, 67, 461. 90. Rowell, R. M.; Clemson, C. M. Proceedings of the 26th International Particleboard/Composites Symposium, WA, p 251, 1992. 91. Bledzki, A. K.; Reihmane, S.; Gassan, J. J Appl Polym Sci 1996, 59, 1329. 92. Mohanty, A. K.; Singh, B. C. J Appl Polym Sci 1987, 34, 1325. 93. Muzumdar, P.; Sanyal, S.; Dasgupta, B.; Shaw, S. C.; Guha, R. Indian J Fibre Technol 1994, 19, 286. 94. Andersson, M.; Tillman, A. M. J Appl Polym Sci 1989, 37, 3437. 95. Sahoo, P. K.; Samantaray, H. S.; Samal, R. K. J Appl Polym Sci 1986, 32, 5693. 96. Samal, R. K.; Samantaray, H. S.; Samal, R. N. J Appl Polym Sci 1986, 37, 3085. 97. Mannan-Kh., M.; Latifa, B. L. Polymer 1980, 21, 777. 98. Huque, M. M.; Habibuddowla, Md.; Mohamood, A. J.; Jabbar Mian, A. J Polym Sci, Polym Chem Ed 1980, 18, 1447. 99. Samal, R. K.; Sahoo, P. K.; Samantaray, H. S. J Macromol Sci Chem, Rev Macromol Chem Phys 1986, C26, 81. 100. Mani, P.; Satyanarayan., K. G. J Adhes Sci Technol 1990, 4, 17. 101. Liao, B.; Huang, Y.; Cong, G. J Appl Polym Sci 1997, 66, 1561. 102. Samal, R. K.; Ray, M. C. J Polym Mater 1997, 14, 183. 103. Yap, M. G. S.; Chia, L. H. L.; Teoh, S. H. J Wood Chem Technol 1990, 10, 1. 104. Garcia, Z. F.; Martinez, E.; Alvarez, C. A.; Castano, V. M. J Reinf Plast Compos 1995, 14, 641. 105. Tobias, B. C. Proceedings of the International Conference on Advanced Composite Materials; Minerals, Metals & Materials Society (TMS), Warrendale, PA, 1993, p 623. 106. Vollenberg, P. H. Th.; Heiken, D. Polymer 1990, 30, 1652. 107. Felix, J. M.; Gotenholm, P.; Schreiber, H. P. Polym Compos 1993, 14, 449. 108. Mukharjea, R. N.; Pal, S. K.; Sanyal, S. K.; Phani, D. K. J Polym Mater 1984, 1, 69. 109. Elvy, S. B.; Dennise, G. R.; Ng, L. T. J Mater Proc Technol 1995, 48, 365. 110. Bawadekar, A. A.; Jog, J. P. Private communication. 111. Vasa, D.; Jog, J. P. Private communication. 112. Mod Plast Int, May 1997, p 39. 113. Mod Plast Int, May 1997, p 14. 114. Plast Technol, Jan 98. 115. Information collected from Union Carbide and Kenrich company data sheets.

Appendix
I. Macromolecule of Cellulose
H HO H OH H CH2OH OH H O H H O H CH2OH O H OH O H H H OH H CH2OH H O
n

OH H O

CH2OH O H OH H H OH H

OH

OH

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II. Bleaching Process

In industry, the most common process of bleaching the cellulose/jute uses oxidizing agents such as sodium hypochlorite, calcium hypochlorite, or hydrogen peroxide. In the reaction process, nascent oxygen is also reported.93 The nature of the coloring matter and the reaction mechanism have not been reported so far. (a) With sodium hypochlorite NaOCl H2O !: NaOH HOCl !: H HOCl (b) With H2O2 H2O2 !: HOO H H Cl !: Cl2 HOCl

Two macrocellulosic radicals might couple to yield a dimerized product 2CellD !: dimerized polymer (c) Grafting of monomer on acetylated cellulose92 O Cell 9 O 9 C CH3 R O Cell 9 O 9 C CH2 O Cell 9 C 9 O CH M RH N

OCl H2O

IV. Coupling Agents

Most of the silane/titanate/zirconate coupling agents can be represented as R 9 (CH2 ) 9 X(OR )n , where X Si, Ti, or Zr, n 0 3, OR is the hydrolyzable alkoxy group, and R and R are the functional organic groups (Table III). For example, for triazine coupling agents, triazine derivatives form a covalent bond with cellulose bers, schematically represented as91 Cl N N N Cl
cellulose ber
H2Np

III. Grafting of Monomer on Cellulose Macromolecule95

(a) Formation of the macromolecule radical Cell 9 H R
D

RD !: CellD OH or SO
D D 4

R 9 H;

(b) Grafting the monomer Initiation CellD Propagation Cell 9 M Cell 9 M n Termination Cell 9 MD n
D Cell 9 Mn !:

M !: Cell 9 MD Cl

M
1

Cell 9 M2 M Cell 9 Mn

R HN N N N Cl O

R HN N N N Cl

graft copolymer

Cl

Dimerization

cellulose ber

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