Composites: Part B 36 (2005) 597608 www.elsevier.

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A study of the mechanical properties of short natural-ber reinforced composites

lez P.J. Herrera-Franco*, A. Valadez-Gonza
n Cient ca, de Yucata n A.C., Division de Materiales, Calle 43 # 130, Col. Chuburna de Hidalgo, C.P. 97200 Me rida, Yucata n, Me xico Centro de Investigacio Received 10 January 2005; accepted 10 April 2005 Available online 22 June 2005

Abstract The degree of bermatrix adhesion and its effect on the mechanical reinforcement of short henequen bers and a polyethylene matrix was studied. The surface treatments were: an alkali treatment, a silane coupling agent and the pre-impregnation process of the HDPE/xylene solution. The presence of SiOcellulose and SiOSi bonds on the lignocellulosic surface conrmed that the silane coupling agent was efciently held on the bres surface through both condensation with cellulose hydroxyl groups and self-condensation between silanol groups. The bermatrix interface shear strength (IFSS) was used as an indicator of the bermatrix adhesion improvement, and also to determine a suitable value of ber length in order to process the composite with relative ease. It was noticed that the IFSS observed for the different ber surface treatments increased and such interface strength almost doubled only by changing the mechanical interaction and the chemical interactions between ber and matrix. HDPE-henequen ber composite materials were prepared with a 20% v/v ber content and the tensile, exural and shear properties were studied. The comparison of tensile properties of the composites showed that the silane treatment and the matrix-resin pre-impregnation process of the ber produced a signicant increase in tensile strength, while the tensile modulus remained relatively unaffected. The increase in tensile strength was only possible when the henequen bers were treated rst with an alkaline solution. It was also shown that the silane treatment produced a signicant increase in exural strength while the exural modulus also remained relatively unaffected. The shear properties of the composites also increased signicantly, but, only when the henequen bers were treated with the silane coupling agent. Scanning electron microscopy (SEM) studies of the composites failure surfaces also indicated that there is an improved adhesion between ber and matrix. Examination of the failure surfaces also indicated differences in the interfacial failure mode. With increasing bermatrix adhesion the failure mode changed from interfacial failure and considerable ber pull-out from the matrix for the untreated ber to matrix yielding and ber and matrix tearing for the alkaline, matrix-resin pre-impregnation and silane treated bers. q 2005 Elsevier Ltd. All rights reserved.
Keywords: (C)Resin; Fibermatrix

1. Introduction Cellulosic bers, like henequen, sisal, coconut ber (coir), jute, palm, bamboo, wood, paper in their natural condition, as well as, several waste cellulosic products such as shell our, wood our and pulp have been used as reinforcement agents of different thermosetting and thermoplastic resins [18]. During the decortication of the henequen leaves, and also during the transformation of the raw bers into cordage,
* Corresponding author. E-mail address: pherrera@cicy.mx (P.J. Herrera-Franco).

1359-8368/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesb.2005.04.001

approximately a 10% of waste is produced. These waste bers could be protably used in the manufacture of shortber polymer reinforced composites because they posses attractive physical and mechanical properties [9]. These waste bers are composed of w60% of cellulose pulps which are easily obtained and could also be used to reinforce polymeric materials. Unlike the traditional engineering bers, e.g. glass and carbon bers, and mineral llers, these lignocellulosic bers are able to impart the composite certain benets such as low density, less machine wear during processing than that produced by mineral reinforcements, no health hazards, and a high degree of exibility. The later is especially true because these bers, unlike glass bers, will bend rather than fracture during processing. Whole natural bers

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undergo some breakage while being intensively mixed with the polymeric matrix, but this is not as notorious as with brittle or mineral bers. Also, natural bers impart the composite high specic stiffness and strength, a desirable ber aspect ratio, biodegradability, they are readily available from natural sources and most important, have a low cost per unit volume basis. It should also be mentioned that the hollow nature of vegetable bers may impart acoustic insulation or damping properties to certain types of matrices. One difculty that has prevented a more extended utilization of the henequen bers is a lack of a good adhesion to most polymeric matrices. The hydrophilic nature of natural bers adversely affects adhesion to a hydrophobic matrix and as a result, it may cause a loss of strength. To prevent this, the ber surface has to be modied in order to promote adhesion. Several methods to modify the natural ber surface such as: graft copolymerization of monomers onto the ber surface, the use of maleic anhydride copolymers, alkyl succinic anhydride, stearic acid, etc. have been proposed. It is also known that the use of coupling agents such as silanes, titanates, zirconates, triazine compounds, etc. also improves bermatrix adhesion [1014]. Furthermore, is has been proven that pre-impregnation of the ber with the polyolen solution will also improve bermatrix adhesion [15]. The mechanical properties of a ber-reinforced polymer composite depend not only on the properties of constituents, but also on the properties of the region surrounding the ber known as the interphase. Stress transfer from the matrix to the ber takes place at such interphase and, therefore, it is important to characterise its properties to better understand the performance of the composite. In this paper, the degree of mechanical reinforcement for a thermoplastic matrix that can be achieved with short-natural bers by modifying the ber surface by different treatments and the optimization of the composite material properties is studied. The chemical surface modication of henequen bres was carried out using an organofunctional silane coupling agent in a methanol/water medium. Heat treatment (curing) was applied after reaching the equilibrium adsorption of the pre-hydrolysed silane onto the lignocellulosic substrate. The modied bers were then characterised by diffuse reectance infrared spectroscopy (DRIFT). 1.1. Characteristics of the henequen bers (Agave fourcroydes) Depending on their origin, natural bers can be grouped into bast (jute, banana, ax, hemp, kenaf, mesta), leaf (pineapple, sisal, henequen, screw pine) and seed or fruit bers (coir, cotton, oil palm). Cellulose is the main component of the henequen bers and the elementary unit of a cellulose macromolecule is anhydro d-glucose, which contains three hydroxyl (OH) groups. These hydroxyl groups form hydrogen bonds inside the macromolecule

itself (intramolecular) and between other cellulose macromolecules (intermolecular). The characteristics of henequen bers have been studied by several authors. The chemical analysis of the bers indicated that their main component is cellulose (60%), hemicellulose (28%), lignin (8%), extractives (4%). The structural arrangement of these components in the ber, as in other natural hard bers, is in such a way that lignin acts as a cementant matrix for the cellulosic bers, which posses their own structure. The mechanical properties of the henequen bers are a consequence of such structural arrangement. The mechanical properties of the henequen bers are: tensile strength, 500G70 MPa, strain at break, 4.8G1.1% and Youngs modulus, 13.2G3.1 GPa.

2. Materials and experimental procedures High density polyethylene, HDPE (Petrothene) extrusion grade, was supplied by Quantum Chemical Inc. A melt ow index (MFI) for the HDPE of 0.33 g/10 min was determined following the ASTM standard D-1238-79 at 190 8C and using a weight of 2160 g. A density for the HDPE of 0.96 g/cm3 was determined following the ASTM standard D-792-86, using benzene as an immersion liquid. The melting point (135 8C) was determined in a DSC-7 Perkin Elmer calorimeter. Henequen bers with an average diameter of 180 mm, approximately, were used in the form of short bers (6 mm long) and it was supplied by Desbradora Yucateca, S.A. rida, Yucata n, Me xico. (DESFIYUSA Co.) of Me Sodium hydroxide and xylene, reagent grade from cnica Qu mica S.A., were used for the various surface Te treatments. As a coupling agent, vinyltris (2-methoxyethoxy) silane (Silane A-172) from Union Carbide was used. Dicumyl Peroxide from Polyscience was used as catalyst to the reaction between the silane coupling agent and the polymer. 2.1. Fiber surface treatments The nomenclature for the different henequen ber surface treatments used is shown in Table 1.
Table 1 Nomenclature used for the different bre surface treatments Keyword Fib FIBNA FIBPRE FIBNAPRE FIBSIL FIBNASIL Description Fiber without treatment Fiber treated with a NaOH aqueous solution Fiber pre-impregnated with dissolved HDPE Fiber treated with a NaOH aqueous solution and then pre-impregnated with dissolved HDPE Fiber treated with a silane coupling agent Fiber treated with a NaOH aqueous solution and then with a silane coupling agent

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2.2. Treatment with NaOH The bers were treated with a NaOH aqueous solution (2% w/v) for 1 h at 25 8C, then, they were washed with distilled water until all the sodium hydroxide was eliminated, that is, until the water no longer indicated any alkalinity reaction. Subsequently, the bers were dried at 60 8C for 24 h. 2.3. Treatment with a silane coupling agent For the ber surface treatment with the coupling agent, 1% silane and 0.5% dicumyl peroxide (Polyscience), weight percentage with respect to the ber, were dissolved for their hydrolysis in a mixture of methanolwater (90/10 w/w) at 25 8C. The pH of the solution was adjusted to 3.5 with acetic acid with continuous stirring for 10 min. Then, the bers were immersed in the solution and left for 1 h under agitation. Afterwards, the bers were dried at 60 8C for 24 h and at 120 8C for 2 h. 2.4. Surface pre-impregnation with a polyethylene dilute solution The henequen bers were pre-impregnated with a 1.5% w/w HDPE/xylene solution as follows: HDPE in powder form was dissolved in xylene at 110 8C in a Kettle reactor by continuously stirring it with a magnetic bar. The natural bers were placed in a stainless-steel basket and carefully immersed in the hot solution and stirred continuously for 1 h. Then, the basket was removed and the lumps of bers were transferred to a at tray and kept in an oven at 60 8C for 24 h to allow evaporation of the solvent. The lumps of impregnated bers were dispersed before blending them with the matrix. 2.5. Composites processing A 20% v/v ber content HDPE-henequen ber composite was chosen in order to determine the effect of the different surface treatments on its mechanical properties. The henequen bers were incorporated into the HDPE matrix, at 180 8C using a Brabender Plasticorder intensive mixer, model PL330. The mixing process was performed in the following order. First, one half of the HDPE was placed inside the mixing chamber for about 1 min at 30 rpm; then henequen bers were added over a period of 3 min. Then, the other half of the HDPE was placed inside the mixing chamber and the mixing speed was increased to 60 rpm for 5 min. The total mixing time process was 10 min. The resulting material was compression molded at a pressure of 1 ton using a Carver laboratory press and a temperature of 180 8C. The specimens for the mechanical test were obtained from these laminates according to ASTM standards.

2.6. Fibermatrix adhesion characterization 2.6.1. Fiber pull-out Is a direct method used for the characterization of the bermatrix interphase and relies on the use of single ber matrix adhesion and detection of failure modes. In this test the ber is pulled out of the matrix (Fig. 1), which can be

Fig. 1. Schematic representation of the micromechanical techniques used for the determination of the interfacial shear strength measurement: (a) pull-out test; and (b) single ber fragmentation test.

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a block of resin, a disc, or a droplet [16]. In this case, one end of the ber was embedded in the middle plane of a plate made from the resin. The bers were rst aligned on a plate and a second one was used to complete the assembly. The samples were made using compression molding at a pressure of 1 ton using a Carver laboratory press and a temperature of 180 8C. The load and displacements were monitored continuously and upon ber pull-out, the load (P) registered at debonding was converted into an average interfacial shear strength (t) by tZ P pdL

25 8C. The Iosipescu shear test specimens were cut from the laminates obtained previously, and the dimensions of specimens were 76 mm of length, 19 mm of wide, 2 mm of thickness and the distance between the two 908 notches was 12 mm. The cross-speed used was 0.5 mm/min. 2.8. Infrared spectroscopy (FTIR) The FTIR analysis was performed using a Nicolet model Protege 460 Magna IR spectrometer. Diffuse reectance spectroscopy (DRIFTS), with a deuterated triglycine sulphate (DTGSKBr) detector, was used. In order to obtain a good resolution spectra it was necessary to mill the henequen bers to an average length of 0.2 mm. The milled bers were then mixed with an analytical grade KBr and the spectra were recorded with a 2 cmK1 resolution and 200 scans. 2.9. Scanning electron microscopy The failure surfaces of shear for specimens will be used to illustrate the effect of the different ber surface treatments and their effect on the effective properties of the composite. This analysis was performed using a Zeiss DSM 940A Scanning Electron Microscope (SEM). Fracture surfaces of the composite samples were coated with gold and then analyzed using the SEM operated at 20 keV.

where d is the ber diameter, L is the embedded length of the ber. The force was applied by holding one end of the resin plate xed and pulling from the free end of the ber using an Instron Universal Testing Machine Model 1125, equipped with a 50 kg load cell, after conditioning at 25 8C and a loading speed of 0.02 mm/min was used. 2.6.2. Single ber fragmentation In this method, a single-ber coupon is loaded in tension to determine the stress transfer efciency at the bermatrix interphase. Upon load application, the tensile stress on the ber (sf) increases and fragmentation occurs at points where its tensile strength is reached. This fragmentation process continues as the applied stress is continuously increased. At some point, the ber fragments become so short that stress transferred to the ber though the interface is no longer high enough to cause any further ber breakage. When this occurs, it is said that a critical ber fragment length (lc) has been reached [16]. To a rst approximation, the interface shear strength (t) is calculated from a simple relationship obtained from a force balance on a ber fragment and the recognition of the random nature of the ber-fragmentation process as:   sf 1 t Z G 1K a 2b here G is the gamma function, a and b are Weibull shape and scale parameters. 2.7. Mechanical properties Both, tensile and exural tests were performed using an Instron Universal Testing Machine Model 1125, equipped with a 500 kg load cell, after conditioning at 25 8C according to ASTM standards D638 and D790, respectively. The cross-head speed used for the type IV tensile specimens was 5 mm/min. For the Flexural test (three point bending) a specimen with nominal dimensions of 50!25!2 mm3, a span of 32 mm and a cross-head of 1 mm/min were used. The Iosipescu Shear Test was carried out following the ASTM D-5379 standard using a Wyoming Shear Test Fixture adapted to the Instron machine, after conditioning at

3. Results and discussion 3.1. Surface treatments 3.1.1. Alkaline treatment Alkaline treatments, similarly as with other lignocellulose bers, induced variation in the physicochemical n bers. Valadez et al. using [18] properties of henerque FTIR and TGA pointed out that these lignocellulosic bers can experience a signicant weight loss due to the partial dissolution of hemicellulose, lignin and pectin. They clearly identied that the band around 1730 cmK1, corresponding to hemicellulose, disappears when the ber is treated by a dilute NaOH aqueous solution. The DRIFT spectra of FIB and FIBNA and their subtraction in the region between 1500 and 650 cmK1 are shown in Fig. 2. It could be appreciated that the strong band at 1240 cmK1 disappears whereas two bands become evident, the doublet at 1200 and 1230 cmK1. These behavior has been associated to the mercerization of lignocellulosic bres [19,20]. Mercerization removes waxy epidermal tissue, adhesive pectins and hemicelluloses that bind ber bundles to each other and to the pectin and hemicellulose rich sheats of the core [21]. In Fig. 3, features of the bers surfaces are shown. A comparison between the native ber and the alkaline treated one reveals topographical changes because of the removal of low molecular weight compounds resulting in a formation of a rougher

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Fig. 2. Fourier Transform Infrared (FTIR) spectra for untreated henequen bers (FIB) and a Na(OH) aqueous solution treated bers (FIBNA).

surface. One of the consequences of the topographical change is an increment of the surface area. 3.2. Silane treatment The spectra in the 1500600 cmK1 range, for FIBSIL and FIBNASIL and their subtraction spectra are shown in Fig. 3. The broad intense bands around 1200 was assigned to the stretching of the SiOcellulose and the absorption bands at 700 and at 765 cmK1, were assigned to the SiO Si bonds [18,19,2325]. It should be noted that the intensity of these bands was more evident after the curing at 120 8C, suggesting that both the grafting of silane onto cellulose and the intermolecular condensation between adjacent adsorbed SiOH groups had been substantially enhanced. The peaks near 1060 cmK1 are related to residual unhydrolysed Siethoxymethoxy groups and their small intensity, compared to those of the spectrum of the hydrolysed A-172 (not shown), suggested that most of the silane adsorbed under our conditions had been hydrolysed. These peak assignments are in agreement with those reported in other studies dealing with glass surfaces treated with the same coupling agents [26,27]. These ndings suggest that the condensation reaction between the hydrolysed silane and the henequen ber was carried out in a greater extent in FIBNASIL than FIBSIL (see Fig. 4). 3.3. Stress transfer at the interface between the short ber and the matrix Generally, the best mechanical properties in a composite depend mainly on ber orientation, but the adhesion between the ber and the matrix is also important. This is especially true for short ber reinforced composites. The bers are loaded through the matrix and for good performance, the load must be transferred effectively to the ber, and a strong ber/matrix bond is required.

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Fig. 3. SEM photomicrographs of henequen bers for (a) untreated henequen bers (FIB) and (b) Na(OH) aqueous solution treated bers (FIBNA), showing their surface features.

The micromechanical events that occur for a long ber reinforced composite are not the same as those observed for a short reinforced composite. In a short ber there are variations in stress distribution along the bermatrix interface, and end effects can be neglected in the case of long bers, but they can be very important in the case of short ber reinforced composites. Additionally, because the bers are not oriented parallel to the applied loads, ber matrix adhesion should be studied more carefully. Table 2
Table 2 Fiber critical length and ber aspect ratio obtained for the different surface treatments Fiber surface treatment FIB FIBPRE FIBNA FIBNAPRE FIBSIL FIBNASIL Critical length (mm) 12.96 11.40 9.25 6.00 5.45 3.50 Fiber aspect ratio (lc/df) 72 63.33 51.38 33.33 30.27 19.44 IFSS pullout (MPa) 2.5 4.2 3.5 4.0 3.75 5.0 IFSS SFFT (MPa) 5.4 5.0 6.0 9.2 11.9 16.0

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fib fibna fibnapre fibnasil

shows ber critical lengths and ber aspect ratios obtained for the different ber surface treatments, obtained using the single ber fragmentation test. For all the surface-treated bers there was a noticeable decrease of the ber critical length as compared to that measured for the untreated bers. For the untreated bers (FIB), an average critical length value of 12.96 mm was obtained, 6 mm for the pre-impregnated ber (FIBNAPRE) and 3.5 mm for the silane treated ber (FIBNASIL). The dimension of the ber critical length is important from several points of view. First, it is convenient to select a suitable ber length in order to allow for an adequate ow of the molten composite material during processing. This will avoid the development of excessive temperature in the composite. Especially during injection or extrusion, extremely high pressures are developed, and consequently, very shear stresses can produce ber breakage or splitting. The increase in the respective calculated IFSS values were 5.4 MPa (FIB), 9.2 MPa for FIBNAPRE and 16.0 MPa in the case of FIBNASIL. The initial treatment with the aqueous solution of NaOH removed some lignin and hemicelluloses from the ber surface, thus, the ber surface area also increased. Such ber surface increase resulted in a larger area of contact between the ber and the matrix. Then, the hydroxyl groups on the cellulose bers could better react with the silane-coupling agent because a larger number on possible reaction sites were available. It is interesting to note that even though a pre-impregnation of the ber with a solution of the matrix ensures a better ber wetting, there was a decrease of the measured ber critical length, and the corresponding increase of the IFSS, does not seem to improve considerably. Typical curves of average interfacial shear stress versus displacement are shown in Fig. 5. It can be noted that all the curves shown in this gure exhibit the non-linear behavior characteristic of a ductile matrix. However, once the load
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reaches its maximum value there are clearly signicant differences in the way of these curves drop. It can be seen that during the pull-out process the debond force follows a linear behavior but the slope differs between them depending on the bermatrix interactions. For the untreated and the alkaline solution treated henequen bers, it can be seen that after reaching the maximum force value, then, there is a smooth transition and a decrease in a linear fashion until the total embedded length of ber is pulled-out. This behavior agrees well with the behavior of a poor interphase that results as a consequence of the incompatibility of the hydrophilic ber and hydrophobic matrix. In the case of a combination of the alkaline solution and the matrix-pre-impregnation treatment, the pull-out force was higher than that observed for the previous ber treatments. After reaching a maximum the pull-out process takes place more rapidly but some frictional effects could be mentioned. That is, after failure of the interphase, the ber can be extracted in a controlled way and the friction measured up to the nal point [14]. In the case of the ber treated with the alkaline solution and the silane coupling agent, the pull-out force was higher that the previous treatments, but the interphase failed and pull-out process occurred catastrophically. From the load-embedded length curve two characteristics should be noted: the initial portion of the curve is linear only in a very small portion and that the slope varies for each surface treatment. The rst is indicative of a ductile interphase behavior and the second that the interaction between ber and matrix is different for each treatment. Several authors [15,28,29] have pointed out that the silanization of the natural bers modies the surface properties and increases the bermatrix interaction. The silane used in this study has two functional groups: an ethoxymethoxy group able to react with hydroxil groups of

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henequen bers and a vinyl group which reacts with HDPE, so a picture of this interphase is one with silane groups chemically attached to ber surface on one side and bonded with some chains of the matrix in the other one. 3.4. Mechanical properties In order to determine whether any statistically signicant difference existed between the values of mechanical properties as a result of the application of one or more different ber surface treatments, a One Way Analysis of Varianza (ANOVA), was performed. All pairwise multiple comparison procedures were performed following a StudentNewmanKeuls method. Also, all strength values for the different ber surface modications are related to the strength obtained for the untreated bers. 3.5. Tensile test results The tensile strength of the HDPE/henequen bers (80:20 v/v) composites is shown in Fig. 6. When the ber surface was modied with an aqueous NaOH solution (FIBNA) or with the pre-impregnation process (FIBPRE), the tensile strength of the composite did not seem to improve noticeably. With the pre-impregnation process (FIBNAPRE), the tensile properties of the composite showed a small improvement. The tensile strength increases 11% resulting from the pre-impregnation process resulted in an enhancement of the mechanical interlocking. However, when the silane coupling agent (FIBSIL) is used, a 19% increase in the tensile strength was observed. Furthermore, when the henequen bers are rst treated with alkaline solution and then with the silane coupling agent (FIBNASIL) a 30% increase in the tensile strength was observed. This increment is attributed to chemical interactions in

the case of FIBSIL and to both, mechanical and chemical interactions in the case of FIBNASIL. No noticeable effect on the elastic modulus was noticed from the bermatrix interface improvements of the HDPE-henequen bers composites (Fig. 7). Bisanda et al. [22] showed that the mercerization of sisal bres (0.5 N NaOH-solution for 72 h) greatly improved the resin pick-up or wettability of the bres, which resulted in a 21% rise in the compressive strength of the composite. It is believed that this alkali treatment results in an improvement in the interfacial bonding by giving rise to additional sites of mechanical interlocking, hence promoting more resin/bre interpenetration at the interface. It is observed in this study, that the ratio between values of bermatrix interfacial shear strength for the different ber surface techniques with respect to the untreated bers is different from the ratio of material property values obtained from the composites using treated bers and the untreated bers. It is well known that the ber reinforcing effect is most efcient along the ber axis orientation. However, the processing technique will dictate the nal ber orientation distribution, one of the most important characteristics, which will determine the composite mechanical properties. The anisotropy expected from an injection molded part is not the same as that found in extruded or compression molded parts. Furthermore, the mathematical prediction of a composite stiffness is well established for common ber orientation distributions: (1) when all the bers are oriented parallel to the test direction, (2) when all the bers are oriented in a transverse direction, perpendicular to the test direction and (3) when all the bers are randomly oriented. The formulas developed for these different scenarios have been developed for bers, which because of the high stiffness will remain straight after processing. However, in the case of natural

Fig. 6. Tensile strength of a HDPE/henequen-ber (80:20 v/v) composite, plotted as a function of ber surface treatment.

Fig. 7. Elastic modulus of a HDPE/henequen-ber (80:20 v/v) composite, plotted as a function of ber surface treatment.

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bers, they do not remain straight after processing because they are highly exible. The effect of the ber surface modications on the micro failure mode, the surface of fractured specimens were examined using SEM. Fig. 8 shows representative photomicrographs of fracture surfaces of samples subjected to tensile stresses, for the untreated, NaOH aqueous dilute solution treated, and those which additionally were subjected to a matrix pre-impregnation and to a silane coupling agent. The surfaces of the untreated bers (FIB) are completely devoid of matrix material. This is a clear indication of bermatrix interfacial failure followed by extensive ber pull-out from the matrix. Furthermore, the matrix also shows considerable tearing. The bers subjected to the alkaline aqueous solution bath plus matrix preimpregnation also show interfacial failure but in this case, there is not much indication of ber pull-out, but rather, it shows massive failure of both bers and matrix. The failure mode observed on the bers shows ber splitting and tearing and it is attributed to a better interaction with the matrix, but still such interaction is by friction and mechanical interlocking. Also, when the bers were pre-impregnated with the matrix in a dilute solution form, there were clear indications and many traces of matrix material still surrounding the bers, thus indicating a closer contact between the ber and the matrix and a better wetting of the bers. This is also an indication that was able to fully penetrate into the ber and upon failure of the laminate, it showed tearing and shearing and this explains the presence of traces of matrix material on the bers surface. In the case of the silane treated bers, the failure surface indicates a massive matrix failure and the bers are completely coated with the matrix, and there are no indications of bers pullout. Then, it can be said from these failure modes that the increase of the tensile strength of the composite is an effect of the bermatrix interface increases. It can also be said that a low bermatrix adhesion, results in a failure mode dominated by ber pull-out and matrix failure. As the interfacial shear strength increased, the failure mode is more like matrix tearing and ow and ber tearing. 3.6. Flexural properties The exural strength of the HDPE-henequen ber composites plotted again as a function of the different ber surface treatments are shown in Fig. 9. Also, the observations made earlier for the tensile strength on the effect of bermatrix adhesion are also seen clearly here. The ber surface treatments had a marginal effect on the exural modulus, similarly to the observations made for the tensile properties. The exural strength improved by "
untreated, NaOH, FIB aqueous dilute solution treated, and those subjected to a matrix pre-impregnation and to a silane coupling agent and (b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE. Fig. 8. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v) composite fracture surfaces of a sample subjected to tensile stresses, for (a) the

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TYPE OF FIBER SURFACE TREATMENT

Fig. 9. Flexural strength of a HDPE/henequen-ber (80:20 v/v) composite, plotted as a function of ber surface treatment.

approximately a 3% just by modifying the topography of the ber by an alkaline aqueous solution. The increment of interfacial area of contact was benecial for the exural strength (Fig. 9). Such relative increase was doubled when the bers were pre-impregnated with the matrix-liquid solution even when the ber had no surface modication by any alkaline treatment. When these two surface treatments are combined, and additional increase is observed for the exural strength. This indicates that a better contact and the increase in area of contact between the ber and the matrix are improving the level of adhesion, probably by the incorporation of a mechanical component of adhesion for the matrixber interfacial strength. When the ber is treated with the coupling agent a larger increase in the exural strength is also observed (13% approximately). When the chemical and the mechanical components of the adhesion are combined, a larger increase of strength is observed (20%). The failure modes are discussed to further clarify the relationship between bermatrix adhesion and the exural strength. The specimens for FIB (Fig. 10(a) shows no trace of matrix material on both between and around the bers. The ber treated with NaOH and pre-impregnated with the matrix (Fig. 10(b)) show traces of polymer still adhering into and around the ber. The ber failure mode even shows the cellulose microbrils still surround by the polymer. When the ber was treated with NaOH and the coupling agent, the failure mode changed to matrix failure and the bers are still held by the matrix (Fig. 10(c)). Considerable amount of bers tearing was also noticed.

"
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those subjected to a matrix pre-impregnation and to a silane coupling agent and (b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE. Fig. 10. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v) composite fracture surfaces of a sample subjected to tensile stresses, for

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20 18

SHEAR STRENGTH(MPa)

16 14 12 10 8 6 4 2 0 FIB FIBNA FIBPRE FIBNAPRE FIBSIL FIBNASIL

TYPE OF FIBER SURFACE TREATMENT

Fig. 11. Shear strength of a HDPE/henequen-ber (80:20 v/v) composite, plotted as a function of ber surface treatment.

3.7. Iosipescu shear strength The shear strength of the HDPE-henequen ber composites plotted again as a function of the different ber surface treatments is shown in Fig. 11. The shear strength is shown again in a non-dimensionalized format. Similar observations made earlier for both the tensile and exural strength on the effect of bermatrix adhesion are evident here. However, the effect of increased ber surface area of contact with the matrix seems to have a larger effect on the shear strength. Fiber pre-impregnation by itself has no great contribution to the shear strength. The largest increase in shear strength is observed for the ber treated with both the aqueous alkaline solution and the silane coupling agent. From previous observations of the tensile and exural properties for this ber surface treatment combination, increments of approximately a 20 and 30%, respectively, were obtained. In the case of the shear strength, such increase is of the order of a 25%. Observation of failure surface of Iosipescu shear test samples further claries the importance of ber adhesion on shear strength results. Fig. 12 shows a series of Scanning Electron Microscope photographs for the composite for 20% v/v ber content and tested under shear loads. In Fig. 12(a), the untreated bers appear to be free of any matrix material adhering to them, thus indicating poor ber matrix adhesion. In Fig. 12(b), the bers treated with the aqueous NaOH solution and then are pre-impregnated, more tearing of the bers could be observed, together with some cavities left by the pulled-out bers. Despite this fact, there is some ber pull-out but the ber is coated with the matrix "
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those subjected to a matrix pre-impregnation and to a silane coupling agent and (b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE. Fig. 12. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v) composite fracture surfaces of a sample subjected to tensile stresses, for

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polymer. Another feature of this ber treatment is on the matrix failure mode, because appreciable shear yielding rather than tearing is observed. It can be inferred that mechanical interlocking and friction are responsible for the observed composite strength increment. Fig. 12(c) shows the failure surface for the composite with bers treated with the aqueous NaOH solution and the silane coupling agent. It can be observed that the bers are still coated with the matrix and that the matrix failed by shear yield ow and tearing from the ber. If the matrix failure mode of the untreated ber composite is compared to the pre-impregnated ber composite, it can be seen that it changes from tearing mode to shear yielding. Then, from these matrix failure modes, it can be said that there exists a higher force transfer capability at the bermatrix interface in the composites with bers treated by pre-impregnation and a silane coupling agent. It should be pointed out that the matrix properties are an upper bound for the composite strength, especially when the bermatrix adhesion is strong, in this case, such upper bound is given by the yield strength of the matrix.

to matrix failure. The interface failure was mainly a frictional type failure, and only for the pre-impregnated and silane treated bers, matrix tearing and shearing was observed. The silane surface treated bers also showed a layer of polymer covering the bers even after failure. The mechanical properties determined from the tensile, exural and shear tests exhibit a similar behavior for each of the different ber surface treatments but the effect of the ber surface treatment was more noticeable for the shear properties.

Acknowledgements The authors would like to express the support given by a [Grant # the Consejo Nacional de Ciencia y Tecnolog 5116-A9406]. Also, the authors would like to thank Ms S.B. Andrade-Canto for the SEM photomicrographs and M.V. Moreno-Chulim for the FTIR analysis.

4. Conclusions The mechanical behavior of short natural ber reinforced HDPE was studied. The bermatrix interaction was changed by modifying the surface properties of the ber, rst to increase the area of contact and to further expose the cellulose microbrils, and to improve ber wetting and impregnation. Also, a chemical interaction was promoted by using a silane coupling agent. The ratio of IFSS observed between the different ber surface conditions and the untreated bers was interesting because such interface strength almost doubled only by changing the mechanical interaction and the chemical interactions between ber and matrix. The micromechanical techniques allowed the determination of an indicator of the bermatrix interface strength and also a suitable value of ber length, both to improve ber matrix force interactions and to be able to process the composite with a relative ease. One important fact resulting from the ber surface treatment and improved bermatrix adhesion was a considerable reduction of ber (l/d) ratio from 72 to w20. The mechanical properties observed did not increase in the same ratio as those observed for the single-ber interfacial shear strength. This was attributed to the fact that the random ber orientation resulted in lower properties that those observed for uniaxial single-ber reinforced composites. The increase in the mechanical properties ranged between 3 and 30%, for the tensile and exural properties. In the case of the shear strength of this composite, such increase was of the order of 25%. From the micro-photographs, obtained from failure surfaces from the SEM, it was observed that with increasing bermatrix interaction the failure mode changed from interfacial failure

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