Composites: Part A 37 (2006) 14131422 www.elsevier.

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Short palm tree bers Thermoset matrices composites

Hamid Kaddami a, Alain Dufresne b,*, Bertine Kheli b, Abdelkader Bendahou a, Moha Taourirte a, Mustapha Raihane a, Nathalie Issartel c, Henry Sautereau c, Jean-Francois Gerard c, Noureddine Sami d
a

Universite Cadi Ayyad, Laboratoire de chimie bioorganique et macromoleculaire, Faculte des Sciences et Techniques Gueliz, av. A. El Khattabi, BP 618, Marrakech, Morocco b ` Ecole Francaise de Papeterie et des Industries Graphiques (EFPG-INPG), BP 65, F38402 St. Martin dHeres Cedex, France c INSA, Laboratoire des Materiaux Macromoleculaires/IMP, 21 av. Albert Einstein, Villeurbanne 69621, France d Societe Excelsa, Appentis Hangar 67, Aeroport Casablanca Anfa, Casablanca, Morocco Received 28 June 2004; received in revised form 29 June 2005; accepted 29 June 2005

Abstract The use of short palm tree lignocellulosic bers as a reinforcing phase in polyester and epoxy matrices has been reported. The morphology and the mechanical properties of the resulting composites were characterized using scanning electron microscopy analysis, differential scanning calorimetry, dynamical mechanical analysis and three-point bending tests. It was shown that the interfacial adhesion was better in the case of epoxy-based composites. In order to improve interfacial adhesion the esterication of the lignocellulosic ller in alkaline medium was performed using acetic and maleic anhydrides. Such type of chemical modication, which led to a change in the chemical composition of the ller, only succeeded to improve mechanical properties of the epoxy-based composites. 2005 Elsevier Ltd. All rights reserved.
Keywords: A. Thermosetting resin; B. Mechanical properties; B. Interface/interphase; D. Electron microscopy

1. Introduction Natural bers reinforced composites combine good mechanical properties with a low density. Such composites oer a number of well-known advantages which include low cost, availability of renewable natural resources, biodegradability, etc. The use of natural polysaccharides as a ller in polymers has been gaining acceptance in commodity polymers applications for many years. Enhanced properties have been obtained by using natural cellulosic bers such as sisal [1,2], cotton [3], bamboo [4], straw [5], jute [6], kenaf [7], banana [8] and wood [9,10]. Only few studies were reported on polymers reinforced with lignocellulosic bers obtained from palm tree [1121]. These studies were

Corresponding author. Tel.: +33 4 76 82 69 95; fax: +33 4 76 82 69 33. E-mail address: Alain.Dufresne@efpg.inpg.fr (A. Dufresne).

mainly performed by research teams from Malaysia and India and concerned oil-palm bers. Polyolens, such as polypropylene (PP), are the most widely used matrices for the processing of natural ber based composites [12,2225]. Other thermoplastic polymers were also used including poly(vinyl alcohol) [26], polyvinyl chloride [27], polystyrene [28], or natural rubber [14,15, 20,21]. Thermoset polymers can also be used as matrices in the processing of natural ber composites. Polyester matrices [11,2935] were more widely used compared to epoxy [3638]. For both thermoplastic and thermoset based composites, the applications concern mainly automotive industry or domestic objects [39,40]. Unfortunately, the use of natural bers can be limited in industrial applications due to some well-known drawbacks which may lead to composites with poor nal properties. In fact, the inherent polar and hydrophilic nature of lignocellulosics and the non polar characteristics of most of the

1359-835X/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesa.2005.06.020

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conventional industrial polymers (PP, unsaturated polyester, etc.) result in a lack of compatibility which leads to difculties in achieving a high level of dispersion of the reinforcing phase within the host polymer matrix and causes a poor interfacial adhesion. These two factors determine to a large extent the nal performances of the composite. Several methods have been tested to enhance adhesion between the lignocellulosic ller and the polymer matrix. They generally involve ber and/or matrix modication by physical or chemical methods. In chemical methods, for apolar thermoplastic matrices such as PP, several coupling agents have been used to modify the nature of the interactions at the ber surface. Among these coupling agents, maleic anhydride graft PP homopolymers or copolymers have been widely used [23,24]. On the other hand, silicon alkoxides such as alkyl triethoxysilanes [8,29,36,41] or pure organic coupling agents [32,42] have been widely used to modify lignocellulosic bers for processing with thermosets/lignocellulosic bers composites. These modications allow to enhance properties of the composite materials such as the mechanical properties and the water uptake. It is well known in date producing countries that the date palm trees need to be maintained each year after the fruit harvesting. The upkeep of the date palm trees results in the production of a huge renewable amount of palms. These renewable resources are used as biofuel for domestic purposes. The valorization of this abundant lignocellulosic residual source as reinforcement in polymer composites worth to receive attention during the last three years. The aim of the present study is to process thermoset matrix/ palm tree lignocellulosic bers composites and characterize their morphological, thermal, and mechanical behavior. For such a purpose, two thermosetting matrices have been used: (i) an unsaturated polyester and (ii) an epoxy/amine. Moreover, the inuence of the chemical modication of the palm tree lignocellulosic bers on the composites performances was also studied. 2. Experimental 2.1. Materials 2.1.1. Polymer matrices The polyester used for the study was an unsaturated polyester resin G154TB (containing 31 wt% of styrene monomer and having a gelation time at 25 C for 30 min). It was obtained from Cray Valley/Total. Methyl ethyl ketone peroxide, MEKP, and cobalt octanoate, used as initiators, were obtained from Aldrich. 0.2 wt% of cobalt octanoate and 2 wt% of MEKP were added to the UP resin before introducing the palm tree bers. The poly epoxy matrix was obtained by the polymerization reaction of epoxy prepolymer (50 vol%) and amine as a curing agent was HV 953U. The epoxy resin and the curing agent were supplied by CIBA-GEIGY. For both matrices, the curing was done at room temperature for 24 hours. Post curing was per-

formed according to the following cure schedule: 60 C for 2 hours, 90 C for 1.5 hour, 120 C for 1 hour, and 150 C for 30 min. 2.1.2. Filler preparation The lignocellulosic ller was obtained by cutting the palm tree leafs into pieces of about 1.5 cm long and 1 mm width. The ller was then extracted for 24 h in the soxhlet reux of a solvent mixture composed of acetone/ ethanol (75/25). The bleached bers were then dried at 80 C for 2 h. The resulting bers were denoted as unmodied bers. The modication of bers was done with acetic anhydride (Aldrich) and maleic anhydride (Aldrich) for 30 min according to the protocol detailed in Scheme 1. The resulting bers were denoted as modied bers. The modied bers were then dried under vacuum at 60 for 24 h. The chemical modication of the ber was checked by FT-IR in a transmission mode. 2.1.3. Chemical composition of the ller The chemical compositions of the dried palm bers were determined according to the French Standards (NF T 12011). It allows to determine the weight fraction of cellulose, hemicelluloses, lignin, extractible and ashes. 2.1.4. Composites processing Both the acetate-modied and maleic anhydride-modied bers were used as a reinforcing phase for composite preparation. The former was used to reinforce the epoxy matrix and the latter was used in association with the unsaturated polyester matrix. Unmodied bers were also used to reinforce both matrices and the properties of resulting composites were used as references to display the eect of the chemical modication. Therefore, four composites were prepared. The ller content was xed at 17 wt% for all the composite materials. The composites were prepared using the classical contact method which consists on the deposition of the bers in a rectangular mold and its physical impregnation with the liquid resin. At the end of the stratication the mold was closed and a pressure of 2 bars was applied for 24 h.
MODIFICATION WITH ACETIC ANHYDRIDE unmodified fibers NaOH (18%) activated fibers MODIFICATION WITH MALEIC ANHYDRIDE unmodified fibers NaOH (18%) activated fibers

activated fibers in NaOH 5% acetic anhydride acetate modified fibers

activated fibers in DMF/N(C2H5)3 maleic anhydride maleic anhydride modified fibers

Scheme 1. Description of the chemical modication of the lignoceullulosic bres.

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Post curing was made following the temperature schedule given previously. 2.2. Experimental methods 2.2.1. Scanning electron microscopy (SEM) Scanning electron microscopy (SEM) was used to investigate the morphology of the dierent types of materials and the ller/matrix interface by using a ABT-55 microscope. The specimens were frozen under liquid nitrogen, fractured, mounted, coated with gold/palladium and observed using an applied tension of 10 kV. 2.2.2. Dierential scanning calorimetry (DSC) A Mettler TA 3000 calorimeter was used to measure the glass transition temperature, Tg. It was taken as the onset temperature of the specic heat increment. The heating rate was xed at 10 C min1 and scans were recorded under argon atmosphere between 100 and 200 C. 2.2.3. Dynamic mechanical analysis (DMA) Dynamic mechanical analysis (DMA) experiments were performed with a Rheometric viscoelasticimeter, RDA II, equipped for rectangular samples and working in the shear mode testing to measure shear storage and loss moduli, i.e., G 0 and G00 , respectively. This apparatus is especially dedicated to the study of lms and composite materials. The average typical dimensions of the composite samples were 20 4 1 mm3. Tests were performed in isochronal conditions at 1 Hz and each sample was heated from 120 to 200 C at a heating rate of 2 K min1. The maximum shear strain was equal to 0.2%. 2.2.4. Non linear mechanical properties Three-point bending tests were performed according to the international standard ISO 178, to determine the stress at break (MPa), the exural modulus (GPa) and the total absorbed energy (J). The testing machine was a 2/M type supplied by MTS (load cell: 10 kN). Specimens were parallelepipedic bars with dimensions close to 60 10 5 mm3 and the distance between supports was xed at 50 mm. Tests were carried out at the glassrubber transition (Tg) of the corresponding neat matrix and at Tg 40 K. The results were averaged from data collected on ve tested samples. 3. Results and discussion 3.1. Chemical analysis of the bers Results of the chemical composition of the dierent bers are presented in Table 1. It can be clearly seen that the solvent extraction step (purication treatment) results in the elimination of CH2Cl2 extractibles. The surface chemical modication induces a signicant decrease of the hemicelluloses content and an increase of the cellulose content. The former observation results from the high solubility of hemicelluloses in alkaline solution. The amount

Table 1 Chemical composition of the palm tree bers before (raw dried palm tree ber) and after purication treatment (unmodied bers) and chemical modication (modied bers) Constituent Raw dried palm tree ber (wt%) 33.9 1.9 26.1 2.0 27.7 1.2 6.9 0.1 3.5 1.0 Unmodied ber (wt%) 33.5 0.5 28.5 1.5 26.5 0.5 6.5 0.5 0 Modied ber (wt%) 43.0 0.5 20.3 1.2 26.0 1.0 5.2 0.2 0

Cellulose Hemicelluloses Lignine Ashes CH2Cl2 extractibles

of lignin and ashes also decreases but not signicantly. This modication induces a shortening and a thinning eect of the ller as can be clearly seen after the bers chemical modication (not shown). It should have an inuence on the mechanical properties of the resulting composites. This ` shortening and thinning eect was also reported by Angles et al. [23] and Kallavus and Gravitis [43]. 3.2. Morphological investigation of the interfaces Figs. 1 and 2 show SEMs of freshly fractured surface for composite materials based on unsaturated polyester and epoxy matrices, respectively. Both unmodied and modied bers reinforced materials were investigated. For each composite material, two dierent magnications were used to evidence the eect of the ber treatment on the interfacial adhesion. For unlled materials, i.e., thermoset matrices, the fracture surface is rather smooth as expected for brittle polymers, especially for the polyester matrix. By comparing these micrographs with those of the composite materials, the bers can be clearly identied. The SEM micrographs in Fig. 1 clearly indicate that the interfacial adhesion between the ller and the matrix is poor for unsaturated polyester based materials. This can be readily seen from the absence of any physical contact between both components. The bers are pulled out from the UP matrix and their surface remains practically clean. On the other hand fracturing the samples did not lead to break the palm tree ber. Holes result from debonding occurring along the ber due to the lack of interactions at the interface. It results in a poor stress transfer between the matrix and the ller. It is also well known that unsaturated polyester networks display a large shrinkage after curing [4850]. This shrinkage reduces the specic volume of the matrix, and due to the weak interfacial interactions it results in free spaces between the matrix and the ller. On the other hand, the SEM analysis shows that the chemical modication did not succeed to improve the adhesion between the polymer and the palm tree ller. Other coupling agents, i.e., organo functional alkoxysilane like vinyl silane or acrylate silanes, should be used for this purpose. The silanols resulting from the hydrolysis of the silanes are expected to react with the hydroxyl groups from the cellulosic ber surface as reported previously [51].

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Fig. 1. Scanning electron micrograph of freshly fractured surface for an unsaturated polyester lm lled with (a) 0 wt%, (b,c) 17 wt% of unmodied and (d,e) 17 wt% of acetate modied palm tree bers.

On the contrary, for epoxy-based composites, the micrographs in Fig. 2 evidence a good adhesion between the matrix and the ller. One can observe the absence of holes around the llers on the fractured surface, i.e., no debonding occurs, and the break of bers during fracture. On the other hand, the region surrounding the cellulosic ller seems to be continuous with the matrix phase. No evidence of the changes in the interfacial adhesion was observed by comparing SEM micrographs of the fractured composites based on modied or unmodied palm tree llers. This dierence in interfacial adhesion between the unsaturated polyester-based materials and the epoxy-based ones is the result of the dierence in the nature of physico-chemical interactions which can be created at the interface. This dierence can be explained from the values of the solubility parameters of the two polymers. In fact the polarity of the

epoxy resin [48], which is expressed by it high solubility parameter, makes easier its adsorption on the lignocellulosic bers. As a consequence, the wettability of the ber surface with the epoxy resin which is a necessary condition for good interfacial adhesion, is better for the epoxy-amine reactive mixture. On the contrary the low solubility parameter of the unsaturated polyester resin [49] makes more difcult its adsorption at the lignocellulosic ber surface whatever the ber treatment is. It results in a poor interfacial adhesion. 3.3. Thermal behavior of palm tree ber-based composite materials As mentioned in Section 2 the thermal behavior of palm tree bers based composites was investigated using DSC.

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Fig. 2. Scanning electron micrograph of freshly fractured surface for an epoxy lm lled with (a) 0 wt%, (b,c) 17 wt% of unmodied bers and (d,e) 17 wt% of maleic anhydride modied palm tree bers.

The glass transition temperatures, Tg, of these materials are collected in Table 2. Tg of the unlled epoxy matrix is close to room temperature and the one of the unsaturated polyester matrix is slightly higher. Table 2 clearly shows that Tg of the unsaturated polyester matrix is almost not aected by the presence of unmodied bers, whereas the surface chemical modication of the ller with acetate results in a signicant decrease of Tg down to 35 C. It could be ascribed to a hindering of the cross-linking process of the matrix in the vicinity of the modied ller/matrix interface. It can be noticed that the free radical polymerization process of such unsaturated polyester matrix is very sensitive to the reactive mixture composition. In fact, the components, i.e., polyester resin, styrene monomer, initiator, etc, can have specic interac-

Table 2 Glass transition temperature, Tg, determined from DSC measurements, main relaxation temperature, Ta, storage shear modulus in the rubbery state, G0c , of the composite materials and relative modulus, G0c =G0m (G0m refers to the storage shear modulus of the neat matrix in the rubbery state) determined from DMA experiments Tg (C) Ta (C) G0c (MPa) 12.5 G0m 5.5 5.4 3.2 G0m 5.2 8.2 G0c =G0m 1.00 0.44 0.43 1.00 1.63 2.56

Unsaturated polyester-based materials Neat matrix 46 95 Unmodied ller 49 93 Modied ller 35 93 Epoxy-based materials Neat matrix 24 Unmodied ller 32 Modied ller 38 51 57 61

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1.00E+10

tion with the cellulosic ber surface leading to changes in local concentrations and formation of microgels. For the epoxy matrix based materials, a signicant increase of Tg from 24 to 32 C is reported upon palm tree bers addition. Modifying the ller with maleic anhydride results in a further increase of Tg. It could be ascribed to strong interactions between both components and possible etherication reactions between carboxylic groups of the esteried cellulosic bers and epoxy groups of the epoxyamine reactive mixture. As a consequence, the segmental motion of the epoxy chains is reduced. This result is particularly interesting because to our knowledge such an eect was never observed even with polar matrices. 3.4. Mechanical behavior The mechanical behavior of all specimens was investigated in both linear (DMA measurements) and non linear conditions (three-point bending experiments). 3.4.1. Dynamical mechanical analysis The dependence of log G 0 , i.e., logarithm of the storage shear modulus, and tan d, the loss factor, vs. temperature at 1 Hz are displayed in Figs. 3 and 4, for unsaturated polyester based materials and epoxy based materials, respec1.00E+10

Shear Modulus (G' / Pa)

1.00E+09

1.00E+08

1.00E+07

1.00E+06

1.00E+05

1.00E+04 -50

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-10

10

30

50

70

90

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150

Temperature (C)
1 0.9 0.8

Tan (delta)

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -110 -60 -10 40 90 140

Temperature (C)
a

Shear Modulus (G'\Pa)

1.00E+09

Fig. 4. (a) Storage shear modulus G 0 , and (b) loss factor tan d vs. temperature at 1 Hz for epoxy based composites lled with () 0, () 17 wt% of non-modied and () 17 wt% of maleic anhydride modied palm tree bers.

1.00E+08

1.00E+07

1.00E+06 -110

-60

-10

40

90

140

Temperature (C)
1 0.9 0.8

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -110 -60 -10 40 90 140

Temperature (C)
Fig. 3. (a) Storage shear modulus G 0 , and (b) loss factor tan d vs. temperature at 1 Hz for unsaturated polyester based composites lled with () 0, () 17 wt% of non-modied bers and () 17 wt% of acetate modied palm tree bers.

tively. All materials exhibit a relaxation process which is associated to the glassrubber transition of the matrix. It is displayed through a sharp modulus decrease and the concomitant maximum of the loss factor. This relaxation process, denoted a, involves the release of cooperative motions of the chains between crosslinks. The relaxation temperature values, Ta, corresponding to the maximum of the loss factor are collected in Table 2. It is about 9395 C for the unsaturated polyester-based materials and 5161 C for epoxy based materials. An increase of Ta is observed for epoxy-based composites in the presence of the lignocellulosic ller, especially as its surface is chemically modied. This increase conrms the previous conclusions given from the increase of Tg observed from DSC measurements. The magnitude of the main relaxation process of the epoxy matrix is also strongly reduced in composite materials. This is due to strong interfacial phenomena. On the contrary the magnitude of the loss factor is almost unaected by the incorporation of the lignocellulosic ller within the unsaturated polyester matrix. In the temperature range between 100 and 10 C a secondary relaxation, denoted b relaxation, can be observed for the epoxy-based materials. This relaxation process was reported for numerous epoxy polymers and is associated with the motions of hydroxyether groups. In

Tan (delta)

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the case of unsaturated polyester based materials, a shoulder on the low temperature side of the a relaxation can be observed. It is also ascribed to a b secondary relaxation of the unsaturated polyester. This relaxation accounts for the motions of molecular groups in the vicinity of the residual maleic groups [42,43] and the corresponding relaxation temperature depends on the amount of styrene monomer in the unsaturated polyester formulation. On the other hand, at very low temperature (around 100 C) an illdened relaxation process is observed and attributed to a c relaxation which accounts for the restricted motions of the phenyl groups of the styrene cross-links [4446]. From the dependence of log G 0 vs. temperature, it is difcult to observe any signicant eect of the ller at low temperature, i.e., in the glassy state. A simple mixing rule allows accounting for this fact. As it is well known the exact determination of the sample glassy modulus depends on the precise knowledge of the sample dimensions. On the other hand, the water absorption could aect the exact determination of the glassy modulus. Therefore, the reinforcing eect of the ller was estimated in the rubbery region of the polymer matrix. The values of the rubbery shear moduli are reported in Table 2, as well as the relative rubbery modulus values corresponding to the ratio of the rubbery modulus of composites, G0c , divided by the one of the neat matrix, G0m . Because the modulus is not perfectly constant against the temperature, G 0 values reported in Table 2 correspond to an average value. The rubbery shear modulus is lower for the unlled epoxy matrix than the one of the unlled polyester matrix. For the unsaturated polyester matrix based composites, the introduction of the lignocellulosic ller (modied or unmodied) results in a decrease of the rubbery modulus. It could be ascribed to the poor adhesion between both components reported from SEM observations. As a consequence, the composite material can be assimilated to a foam or a polymer matrix lled with holes. As mentioned previously, the introduction of the palm tree bers in the reactive polyester system could also aect the free radical polymerization process. The loss factor is unaected by the lignocellulosic ller introduction. On the contrary a signicant reinforcing eect is observed for epoxy-based composites in the rubbery state. It can be quantied through the relative rubbery modulus, G0c =G0m , which increases up to 1.63 and 2.56 for the unmodied and maleic anhydride modied ller, respectively. It can be ascribed to favorable interactions and possible reactions between the matrix and the ller surface zone which lead to an improved adhesion for chemically-modied bers. This result is in good agreement with SEM observations and the resulting conclusions. The main a relaxation process is shifted towards higher temperatures as already discussed from DSC data. It could be explained by more restricted motions of the epoxy chains in the composite, due to the good adhesion between the polymer and the ller. As mentioned, it could be attributed to the additional hydrogen bounds between the acetyl groups on the ller

surface and the hydroxyl groups of the poly epoxy matrix. This restriction of the organic chains motions is conrmed by the decrease in the main relaxation peak magnitude and its broadening towards higher temperatures in the composite materials compared to the neat epoxy matrix [47]. However, it should be noted that the increased G0c =G0m values for the epoxy-based composites reported in Table 2 could be also due, as least partially, to an increase of the cross-link density. This assumption can be supported by the increase in Tg values. Generally, the expected reinforcing eect depends on the interfacial adhesion between both components, i.e., matrix and ller, which allows an ecient stress transfer from the matrix to the ller. This adhesion restricts the motions of the polymer chains in the vicinity of the ller surface and leads to an increase of their glassrubber transition temperature. Based on this argument we can expect a good adhesion between the lignocellulosic ller (modied or unmodied) and the epoxy matrix and a rather bad adhesion between the lignocellulosic ller (modied or unmodied) and the unsaturated polyester matrix. The lack of adhesion in the last case causes the creation of debonded zones at the polyester matrix/ller interfaces which lower the mechanical properties. Moreover, we should

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Neat Polyepoxyde Matrix Composite with modified fillers Composite withnonemodified fillers

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0 0 4 8 12 16 20 24

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Neat Unsaturated PolyesterMatrix Composite with modified fillers Composite with nonemodified fillers

Force (N)

50 40 30 20 10 0 0 0.5 1 1.5 2 2.5 3 3.5 4

Dplacement (mm)
Fig. 5. Load versus displacement curves obtained from three-point bending tests performed at Tg for (a) epoxy-based composites and (b) unsaturated polyester-based composites.

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Table 3 Mechanical properties of the neat matrices and composite materials lled with the lignocellulosic ller obtained from three-point bending experiments: exural modulus (EF, data into square brackets corresponds to the storage tensile modulus values deduced from DMA experiments and taking a Poissons ratio of 0.35), stress at break (rB), deection at break (F) and energy at break (Eb) (values are given the standard deviation) Temperature of the experiment (Texp) Epoxy-based materials Neat matrix Unmodied ller Modied ller Tg of the neat matrix EF (GPa) 1.30 0.16 [1.55] 1.92 0.27 [1.00] 2.49 0.31 [2.00] rB (MPa) No break 1.27 0.28 1.76 0.13 2.12 0.19 0.86 0.16 0.72 0.06 F (mm) 10.51 11.44 15.48 5.42 5.70 Eb (J) 0.44 0.18 0.72 0.23 0.78 0.14 0.124 0.058 0.118 0.013 Tg of neat matrix 40 K EF (GPa) 1.92 0.06 [2.60] 2.04 0.10 [1.45] 2.23 0.16 [2.60] 3.50 0.64 [2.25] 3.70 0.46 [3.00] 3.69 0.29 [3.00] rB (MPa) No break 1.16 0.25 1.34 0.27 2.11 0.61 0.83 0.09 0.74 0.10 F (mm) 6.64 7.82 3.66 2.28 2.19 Eb (J)

0.22 0.12 0.34 0.13 0.13 0.06 0.043 0.014 0.050 0.012

Unsaturated polyester-based materials Neat matrix 1.70 0.17 [1.55] Unmodied ller 1.92 0.25 [2.20] Modied ller 1.71 0.15 [2.20]

consider the change in the chemical composition of the bers after the chemical modications. In fact the chemical modication of the lignocellulosic bers lead to the dissolution of the hemicelluloses, thus direct interactions between the polymer matrix and the crystalline cellulose are possible. As a consequence, the possibility of stress transfer from the matrix to the ber is better and the mechanical properties are improved. 3.4.2. High strain behavior (three-point bending test) Typical load versus displacement curves obtained from the three-point bending experiments are given in Fig. 5(a) and (b) for epoxy and unsaturated polyester based materials, respectively. These curves were obtained at the glass transition temperature of the unlled matrix, i.e., 46 and 24 C for the unsaturated polyester and epoxy-based materials, respectively. The mechanical properties derived from these experiments as well as those performed at Tg 40 K are presented in Table 3. Storage shear modulus values measured from DMA experiments were determined at these temperatures (Tg and Tg 40 K). Storage tensile modulus values were deduced assuming a Poissons ratio of 0.35. Values are reported in Table 3 and show good correlation with the elastic modulus. In the case of the epoxy-based materials, a signicant eect of the ller on the modulus is reported as the test is performed at a temperature, Texp, equal to the Tg of the matrix, Tg(matrix), or to Tg(matrix) 40 K. As expected, the neat matrices and the composite materials are brittle at low temperatures. The composite material reinforced with the modied ller displays higher mechanical properties compared to the composite lled with the non-modied ller. In fact, the elastic modulus determined in bending mode, the deection and the energy at break are higher for the composites based on treated palm tree bers. For unsaturated polyester based materials, a signicant deterioration in the mechanical properties is obtained by the introduction of the lignocellulosic ller. Even if the bending modulus of the neat matrix and the composite materials was of the same order of magnitude, the stress at break, the deection and the energy at break are seriously lowered upon the introduction of the ller. On the

other hand, no signicant dierence in the mechanical properties, between the composite materials reinforced with unmodied and chemically-modied lignocellulosic ller, was reported. These results are in good agreement with the DMA measurements. In fact, the reinforcing eect obtained for the epoxy-based composites is conrmed by the higher mechanical performances at dierent temperatures. This results from the good interfacial adhesion and as a consequence from the better dispersion of the ller within the epoxy-amine reactive mixture, i.e., the improved wettability. 4. Conclusions Thermosets reinforced with lignocellulosic bers extracted from palm tree were processed. Two matrices, namely unsaturated polyester and epoxy, were used. To improve the interfacial adhesion the ller esterication was done. The surface of the ller was treated with acetate when using a polyester matrix and maleic anhydride when using an epoxy matrix. All the results lead to the conclusion that good interactions exist between the ller and the epoxy matrix. These interactions can be improved by the chemical treatment of the ller. Improved thermomechanical properties, bending modulus, stress at break and maximum absorbed energy were reported. These strong interactions and/or reactions occurring at the epoxy/lignocellulosic ber interface result in a signicant increase of the glassrubber transition temperature of the neat matrix. On the contrary, the adhesion level is very weak when using an unsaturated polyester as matrix. The chemical treatment of the ller with acetate does not improve the interfacial adhesion. It results in very low mechanical properties. Other coupling agent should be tested such as vinylsilane and/or acrylatesilane. Acknowledgments The authors thank the Moroccan National Center of Technical and Scientic Research (CNRST) for its nan-

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cial support in the frame of a PROTARS program and PICS program (# 824). References
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