European Polymer Journal 42 (2006) 23692378 www.elsevier.

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Structural and mechanical studies on modiWed reused tyres composites

X. Colom
a

, J. Caavate a, F. Carrillo a, J.I. Velasco b, P. Pags b, R. Mujal c, F. Nogus a

a,

Department of Chemical Engineering, Technical University of Catalonia, Colom 1, 08222 Terrassa, Barcelona, Spain b Department of Materials Science, Technical University of Catalonia, Colom 11, 08222 Terrassa, Spain c Department of Electrical Engineering, Technical University of Catalonia, Colom 1, 08222 Terrassa, Spain Received 7 April 2006; received in revised form 29 May 2006; accepted 3 June 2006 Available online 27 July 2006

Abstract Reused tyres powder was used as reinforcement in HDPE-reused tyre composites. In order to improve the compatibility between both components, several pre-treatments performed over the rubber tyres were applied: sulphuric acid etching, use of a silane coupling agent and chlorination with trichloroisocyanuric acid (TCI). Mechanical properties of the resulting materials (e.g. tensile strength, Youngs Modulus, toughness and elongation at break) were studied and compared. Chemical modiWcations on the surface of reused tyres were monitored by FTIR and physical modiWcations and behaviour to fracture were followed by means of SEM. The inXuence of rubber pre-treatment was assessed by comparing the results of treated and untreated composites with those for neat HDPE. Reused tyre rubber, added to the HDPE in small quantities, acts as a Wller, improving the stiVness and providing a more brittle behaviour. Pre-treatment with TCI gave poor results in terms of mechanical properties obtaining lower values than neat HDPE in some cases and always worst properties than sulphuric or silane coupling agent. Treatments with H2SO4 and silane coupling agent improve the ability of rubber to interact with the HDPE, increasing the materials stiVness and its tensile strength. Sulphuric acid modiWcates chemical and physically the particles surface improving mainly mechanical adhesion, whereas silane acts as a compatibilizer developing chemical matrix-reinforcement interactions. 2006 Elsevier Ltd. All rights reserved.
Keywords: Recycling (A); Interface (B); Mechanical properties (B); Surface analysis (D)

1. Introduction The concern among the scientiWc community about the increasing number of tyres (about 250 mil* Corresponding author. Tel.: +34 937398044; fax: +34 937398225. E-mail address: xavier.colom@upc.edu (X. Colom).

lion tyres in Europe only) [1] that end up in landWlls at the end of their life has impulsed initiatives that include ways of integrating these residues as a Wller in a number of products as: concrete [24], rubber vulcanizates [5] or polymer blends [6]. PolyoleWnic matrix composites including reused tyres as reinforcement may constitute a new way to recycle rubber wastes and minimize environmental problems.

0014-3057/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2006.06.005

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Polymeric composites are usually formed by a biphasic structure where an elastomer is dispersed in a thermoplastic matrix [7]. This structure provides to the material a high impact resistance and toughness. For this reason, the combination of a brittle matrix with an elastomer that acts as energy dissipater, has been very useful in many applications. Properties and performance of these materials are strongly inXuenced by the nature of the components and their compatibility at interfacial level. In many cases when interfacial adhesion is not enough, some pretreatments are applied in order to achieve better results. In case of tyres, some acids have proved to be functional in order to achieve a porous surface [8]. These treatments, designed initially to exploit other characteristics of the tyre reinforcement may also be useful to improve mechanical interlock with the matrix because of the high porosity developed. Chlorination has been also reported as a way to increase the adhesion in SBR rubber, because it favours the migration of wax to the rubber surface and subsequent elimination. The paraYn wax is mainly responsible for the lack of adhesion of rubber [9]. Other approaches to the compatibilization in similar materials include grafting of polymers [10] and use of coupling agents. In case of HDPE/tyres, some pre-treatment based on the modiWcation of the rubber with acrylamide have been reported [11]. The use of silanes could improve the matrix-reinforcement interface properties by the development of chemical interactions. To achieve an optimisation of these composite materials properties is important in order to determine their applications. In this context, pretreatments become very important to improve interfacial adhesion. However, in order to obtain an useful Wnal product and to produce an economically competitive material, is important to take into account the cost of the general procedure that should avoid complex processes. The pre-treatments studied and compared in this work have been preformed using: (a) sulphuric acid, (b) trichloroisocyanuric acid (chlorination) and (c) silane as a coupling agent. The composites performance was monitored by determining its mechanical properties. Chemical and physical modiWcations related to the material behaviour were studied by means of Fourier transform infrared (FTIR) spectroscopy and scanning electronic microscopy (SEM), respectively.

2. Methodology 2.1. Materials High-density polyethylene (HDPE), supplied by REPSOL-YPF, with a melt Xow index of 1.35 g/min and a density of 960 kg/m3, and reused tyres supplied by Alfredo Mesalles-Spain was used to prepare the composites. Two acids: sulphuric and Trichloroisocyanuric (TCI) and a coupling agent supplied by Dow Corning: -methacriloxypropyltrimethoxysilane (silane A-174), were used as reagents for surface pre-treatment of the reused tyre rubber. 2.2. Preparation of composites The tyre rubber was previously micronized (400 600 m average particle size) and dried in an oven at 100 C for 24 h. Four rubber-HDPE composites of varying rubber content (5, 10, 20 and 40 wt%) were then prepared from untreated and treated rubber. All composites were prepared by melt mixing the components in a Collin W100T. The roller temperature was kept at 153 C during mixing. To minimize the polymers degradation, the mixing was carried out for no longer than 10 min for each sample. Neat HDPE samples were subjected to the same process in the two-roll mill so that they had the same thermal history as the rubber-reinforced polymer. Composite sheets (150 150 2 mm) were randomly prepared by hot press moulding at 100 kN and 170 C for 15 min. The cooling step was carried out under pressure and water was employed as a refrigerant. 2.3. Pre-treatments of micronized rubber The rubber was treated with sulphuric acid (96%) following these steps: (a) immersion in concentrated acid for 1 min; (b) removal from the acid bath and reaction in air for 2 min; (c) neutralisation of the acid using hot distilled water and ammonium hydroxide (15 wt% ammonia); and (d) washing with distilled water at room temperature until pH 7. Chlorination treatment was performed by: (a) wiping of the rubber with a tissue paper immersed in ethyl acetate, (b) 15 min later the wiped rubber was treated with TCI ethyl acetate solution (2,5 wt%) and (c) 1 h later, an ethanol/water solution (25 wt%) was applied to the chlorinated tyre surface. Pre-treatment using silane as a coupling agent was carried out as follows: every 5 g of oven-dried

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reused tyre Wller, and the corresponding proportion of Silane A-174 were added to 50 ml. of diethylic ether. The resulting mixture was heated for 1 h at 60 C until total evaporation of the solvent. 2.4. Mechanical testing Tensile tests were carried out to determine the evolution of Youngs modulus, toughness, tensile strength and the percentage of ultimate elongation versus tyre-rubber content and surface modiWcation. For this purpose, the ASTM-D-412-98 Standard was applied using a universal machine Adhamel Lmargy DY-34. It was Wtted with an extensometer laser type Class B-2 (HounsWeld 500 L). The testing speed was 20 mm/min, the samples were 4 mm wide and measures were taken as indicated in the aforementioned standard, at a temperature of 23 2 C and a relative humidity of 50 5%. Toughness was calculated from area measurements. Statistical analysis was conducted on the mechanical testing data to determine the signiWcance of the values (p > 0.05) for Youngs Modulus, toughness, tensile strength and the percentage of ultimate elongation. Five replicate samples were analysed, and average and standard deviation percentages were calculated. 2.5. Fourier transform infrared spectroscopy Fourier transform infrared (FTIR) spectra were obtained by means of a Nicolet 510 M spectrometer with CsI optics. Samples of the powdered rubber (400600 m average particle size) were ground and dispersed in a matrix of KBr (9 mg Wnely divided rubber in 300 mg KBr), followed by compression at 167 MPa to consolidate the formation of the pellet. Reduced absorbance values were used in order to avoid the spectral diVerences arising from the preparation of KBr pellets. To calculate the reduced absorbance, the absorbance value of a given band of the spectra is divided by that of an invariable band. 2.6. Scanning electron microscopy Scanning electron microscopy (SEM) was used to qualitatively examine the surface etching of the powdered rubber produced by the acids. The surfaces of the samples were examined with a JEOL 5610 scanning electron microscope. Dry samples were coated with a thin layer of gold palladium alloy before observation under the microscope, in order to increase the samples electrical conductivity.

3. Results and discussion 3.1. Mechanical properties The eVect of the diVerent pre-treatments on the mechanical properties of treated and untreated reference samples are shown in Fig. 1. The tensile strength values (Fig. 1) show a signiWcant decrease in all cases when using chlorination. The results of the study show that, in all compositions, the chlorination pre-treatment provides substantially poorer tensile strength values than the any other pre-treatment and even than untreated composites. Looking to the values obtained versus the concentration of reused tyre, a diVerence in the behaviour of composites comprised between 020% and 30 40% can be observed. When the content of tyre reinforcement is below 20%, the sulphuric and silane pre-treatments tend to provide the materials a higher tensile strength than the obtained for the untreated composites. Especially silane coupling agent seems, in these range of compositions, to produce good results, better than sulphuric acid pre-treatment. Concentrations of tyres higher than 20% show poor results in all cases, obtaining higher values when treating the materials with sulphuric. Silane provides, for 30% and 40% rubber composition, poor tensile strength values, only higher than chlorination treatment. The higher tensile strength is obtained at 10% of tyre content when using sulphuric acid or silane as pre-treatment. Fig. 2 shows the evolution of Youngs Modulus. In this case, sulphuric pre-treatment provides a high value in all cases, being the rigidity clearly improved

Fig. 1. Tensile strength versus tyre content for untreated, treated with H2SO4, chlorination process and coupling agent in HDPEreused tyre composites.

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Fig. 2. Youngs Modulus versus tyre content for untreated, treated with H2SO4, chlorination process and coupling agent in HDPE-reused tyre composites.

when comparing with the untreated material. Silane and chlorination provide good results, especially silane, increasing the modulus in front of the untreated composite at compositions below 20%. In this case the highest modulus values are obtained at 5% reused tyre by using sulphuric acid as pre-treatment. Toughness values are shown in Fig. 3. Only pretreatment with silane improves this mechanical property in the composite at compositions lower than 30%. At contents of 3040% of tyre, the results are equal to those of the untreated material. Chlorination and sulphuric pre-treatments produce a decrease of the values in all cases. The eVect of adding the tyre reinforcement to the HDPE aVect critically to this property, showing an important drop when incorporating only a 5% of reused tyres. As it is shown in Fig. 4, elongation at break depends strongly of the addition of tyre particles. This property decreases also drastically when incorporating a 5% of tyre reinforcement. The highest values in all compositions are obtained in case of

Fig. 4. Elongation at break versus tyre content for untreated, treated with H2SO4, chlorination process and coupling agent in HDPE-reused tyre composites.

Fig. 3. Toughness versus tyre content for untreated, treated with H2SO4, chlorination process and coupling agent in HDPE-reused tyre composites.

samples untreated and treated with the silane coupling agent. In all cases the lower mechanical properties results are obtained by chlorination pre-treatment. This is attributed to the morphology changes produced on the tyre particles after the pre-treatment and to the generation of polar groups, mainly chloro-derivates that increase the surface energy and reduce the adhesion properties with the HDPE matrix. The tensile strength and Youngs Modulus of the untreated composites only are better than neat HDPE when compositions are lower than 10%. Toughness and elongation at break are always lower than neat HDPE when including tyres. The fact of including tyre particles, in concentrations high enough to collapse and agglomerate and that have poor interfacial adhesion to the matrix, produce a decrease of the mechanical properties in general. The use of sulphuric acid and silane improve the studied properties, especially when the content of tyres is below 30%. The eVect of the dispersion of reused tyre in the HDPE matrix aVects tensile strength and Youngs Modulus (Figs. 1 and 2) in a diVerent way that Toughness and Elongation at break (Figs. 3 and 4). This could be explained because, instead of the typical behaviour of toughened materials [7,12], the reused tyre is very rigid and exhibits a more brittle behaviour than the HDPE matrix. In this case, the tyre content tends to increase rigidity and tensile strength, provided that the interfacial adhesion is good. For instance, in pre-treatments with sulphuric acid both properties are higher than those obtained

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for neat HDPE, which is attributed to an quite eYcient interlocking of the disperse phase with the matrix. The same occurs with silane pre-treatment that for most of the compositions an improvement of rigidity and tensile strength is observed in front of neat HDPE composites. As it was observed previously, elongation at break (Fig. 4) and toughness depend basically on the reused tyre content. Rigidity of the particles, aVect drastically to these properties and makes them drop to values 11 times lower (toughness) and 50 times lower (elongation) even in case of the best pre-treatment provided by the silane coupling agent. 3.2. Scanning electronic microscopy of reused tyre surfaces SEM pictures of fracture surfaces of several composites are shown in Figs. 58. Figs. 5a and 5b show a microphotograph of the untreated composite materials. Untreated particles show a smooth surface, which is not suitable for mechanical adhesion. When the composite is fractured, the surface of the reinforcement appears completely Xat and free of any adherences of matrix segments. The rubber particles are clean and easily extracted from the matrix (Fig. 5b). That means that adhesion is poor because the fracture has taken place through the interface. These results agree with the mechanical properties discussed previously in the sense that adding the
Fig. 5b. SEM Microphotographs of fracture surface of untreated composite (magniWcation 300).

reinforcement to the matrix, the properties of HDPE are not signiWcantly improved. The compatibilizing eVect of the silane is clearly observed in Figs. 6a and 6b. The surface appears delaminated and stretched, because of the adhesion of the rubber to the matrix. In case of sulphuric acid, the pre-treatment produces a very porous surface (Fig. 7a), full of microcavities that are suitable for mechanical interlocking and adhesion. Also, the rough surface helps to improve the interfacial contact and the link between

Fig. 5a. SEM Microphotographs of fracture surface of untreated composite (magniWcation 50).

Fig. 6a. SEM Microphotographs of fracture surface of composite pretreated with coupling agent (magniWcation 2000).

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Fig. 6b. SEM Microphotographs of fracture surface of composite pretreated with coupling agent (magniWcation 50).

Fig. 7b. SEM Microphotographs of fracture surface of composite pretreated with H2SO4 (magniWcation 200).

Fig. 7a. SEM Microphotographs of fracture surface of composite pretreated with H2SO4 (magniWcation 2000).

the matrix and disperse particles. This eVect has been reported in previous works [8,13] and provides a morphology where the HDPE is able to penetrate into the holes produced by the acid and, through a physical mechanism, Wx the reinforcement to the matrix (Fig. 7b). The microroughness achieved with this treatment is related to the ability of the acid to partially degrade and remove some components of the reused tyre from the surface of the particle. Chlorination pre-treatment produces a poor compatibility. Figs. 8a and 8b show a hole where the particle has been clearly extracted and a particle without any sign of being adhered to the matrix, respectively. No traces or segments of HDPE are

Fig. 8a. SEM Microphotographs of fracture surface of composite pretreated with TCI (magniWcation 2000).

adhered to the rubber, displaying lack of interaction between the components and being the cause of the poor mechanical behaviour achieved by this pretreatment. 3.3. FTIR spectroscopic characterization 3.3.1. Pre-treatment with silane The spectroscopic study has been carried out by comparing the spectrum of a sample of rubber treated with silane with the references of the spectrum of untreated rubber and the spectrum

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Fig. 8b. SEM Microphotographs of fracture surface of composite pretreated with TCI (magniWcation 150).

obtained by the theoretical weighed addition of the spectra of rubber and silane. DiVerences observed with the theoretical spectra are due to the changes of the vibration modes of the groups belonging to silane and rubber that are involved in interactions that produce a change in the frequency of vibration.

Fig. 9a shows the spectra corresponding to the rubber treated with 1% silane. The theoretical spectrum, as result of the addition of only a 1% of silane is similar to that of the rubber alone, due to the small quantity of silane added (although there are some diVerential bands). The real spectrum of rubber shows several diVerences and changes in the frequencies that suggest interactions with participation of the groups assigned to these bands. The dipoles related to the methyl and methylene groups of the polymer and the double bonds (13901457 and 875 cm1) are aVected by the presence of silane. In the same Wgure, it can be seen an increase in the silane bands at 1260, 1095 and 815 cm1, which indicates also participation of this group in the interactions with rubber. A good interaction of rubber with silane means an eVective compatibilizer eVect because the coupling agent described here has already been studied in terms of HDPE-silane interactions with positive results [14]. Table 1 describes the bands involved in interactions between rubber and silane. 3.3.2. Pre-treatment with sulphuric acid EVects of the pre-treatment with sulphuric acid are shown at Fig. 9b. Several chemical and degradative

1457 1390

875

815

1260 1095
1800 1600 1400 1200 1000 800

Wavenumbers (cm-1)

Fig. 9a. Spectra of rubber in 1800600 cm1 area: (dotted line) theoretical spectrum addition 1% silane to rubber, (dashed line) real spectrum of rubber treated with 1% silane, (continuous line) real spectrum of rubber treated with 2% silane.

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Table 1 Bands involved in interactions between rubber and silane Band (cm1) 815 875 1260 1095 1390 1426 Assignation SiC stretch CBCH in plane CH bend SiCH3 stretch SiOC stretch CH3 bend CBCH in plane CH bend Component Silane Silane and rubber Silane Silane and rubber Silane and rubber Silane and rubber

that causes carbonization. These results are in agreement with previous studies by a range of authors [1719]. 3.3.3. Pre-treatment with TCI Spectra of the rubber pre-treated with TCI appear at Fig. 9c. The chlorination pre-treatment causes also chemical modiWcation that can be summarized as follows: (a) removal of paraYns and other weak layers present in rubber (decrease of 29552985 cm1 bands, not shown), (b) chlorination of hydrocarbon chains (increase of 534 cm1 band and weak increase of 1420 cm1 band), (c) decrease of double bonds due to the reaction with TCI (decrease of 1629 cm1 band), (d) formation of oxidized species as CBO and OBSBO (increase of 1715 and 1400 cm1 bands), (e) generation of some nitrogenated residua (slight increase of 3213 cm1 band, not shown). These results agree with other previous works [9]. The described processes increase the energy surface and have negative inXuence in adhesion with HDPE. The eVect of elimination of weak layers is by far less intense that in case of sulphuric acid, giving a physical surface modiWcation that is not enough to achieve a better interlocking with the matrix.

modiWcations on the tyre surface can be observed. The main eVects are: (a) decrease in double bonds (1640 cm1) due to the degradation process of polybutadiene and other unsaturated components of the tyre, (b) a decrease in content in minor components related to the disappearance of the weak bands at 1739 and 1540 cm1 and the decreasing of bands at 1430 and 875 cm1 and (c) formation of sulphonic acid indicated by the appearance of new bands at 1402, 1121 and 618 cm1, assigned to the OBSBO stretching absorptions [15,16]. Physical changes observed by SEM above (Figs. 7a and 7b), such as the formation of microporosities, are due to the partial degradation of several components that was observed. Chemical modiWcations are related to the strong dehydrating power of sulphuric acid

1640

1430 1402 1382

1540 1739

875

1121

1800

1600

1400 Wavenumbers (cm-1)

1200

1000

Fig. 9b. Spectra of rubber in 1900400 cm1 area: (continuous line) rubber treated with sulphuric acid, (dotted line) rubber untreated.

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1629

1400 1450 1020

1715

530
1500 Wavenumbers (cm-1) 1000 500

Fig. 9c. Spectra of rubber in 20001000 cm1 area treated with TCI at several concentrations. Rubber untreated corresponds to dotted line.

4. Conclusions In order to achieve a suitable and useful composite material, one of the most important aspects is the study of its behaviour in terms of mechanical properties. From the study performed with tyre rubber HDPE composites we can summarize that: (i) the addition of micronized reused tyre rubber to the HDPE in small quantities (5%) as a Wller improves the stiVness and provides a more brittle behaviour; (ii) treatment with H2SO4 improves the rubbers ability to interact with HDPE, thus providing the materials with a greater stiVness, which is also a consequence of the rigidity of the rubber after the acidic treatment because of the extraction of additives and degradation; (iii) treatment with silane improves the ability of interacting of both components obtaining better results than neat HDPE at concentrations lower than 30%. In terms of tensile strength the use of a coupling agent gives higher values than any other pre-treatment at compositions below 30%. On the other hand, stiVness is not so high as the observed for sulphuric acid pretreated rubber because the silane does not aVect the rigidity of the particles of rubber. This could be also related to the fact that silane provides better results than any other treatment when measuring toughness and elongation. TCI only provides better results than neat HDPE for Youngs Modulus values. The results

obtained are clearly poorer than any other pre-treatment studied. SEM micrographs show diVerences depending on the treatment followed. Treatments with H2SO4 produce a rough surface that is more suitable for mechanical adhesion, whilst TCI does not seem to aVect the rubber surface. The fracture surfaces indicate that there is interfacial adhesion of the rubber particles to the matrix due mainly to a physical modiWcation of the particles. The increase of the mechanical properties observed when using coupling agent is due to chemical interactions that produce also an increase in compatibility. The particles appear as quite coupled to the matrix. TCI pre-treatment leads to particles not properly linked to the HDPE. The results obtained for mechanical properties are justiWed in the light of these considerations. By studying the FTIR spectral bands, the main results obtained were the following: (i) every acid treatment studied produces a speciWc chemical modiWcation on the rubber, thus inducing the formation of speciWc groups; (ii) several degradative eVects appear in a similar way and do not depend on the acid used in the treatment (mainly the decrease in double bonds and the elimination of minor components and moieties); (iii) TCI acid seems to produce by far fewer modiWcations than sulphuric acid, and (iv) the coupling agent, by its own nature acts in a diVerent way, developing interactions with the

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X. Colom et al. / European Polymer Journal 42 (2006) 23692378 [5] Yehia A, Mull MA, Ismail MN, Hefny YA, Abdel-Bary EM. EVect of chemically modiWed waste rubber powder as a Wller in natural rubber vulcanizates. J Appl Polym Sci 2004;93:30 6. [6] Dierkes WK. Rubber recycling. In: Pandalai SG, editor. Recent research developments in macromolecules, vol. 7. Trivandrum: Research Signpost; 2003. p. 26592. [7] Bucknall CB. Toughened plastics. London: Applied Science Publishers; 1997. [8] Manchon-Vizuete E, Macas-Garca A, Nadal Gisbert A, Fernndez-Gonzlez C, Gmez-Serrano V. Preparation of mesoporous and macroporous materials from rubber of tyre wastes. Micropor Mesopor Mater 2004;67:3541. [9] Romero-Sanchez D, Pastor-Blas MM, Martin-Martinez JM. Adhesion improvement of SBR rubber by treatment with trichloroisocyanuric acid solutions in diVerent esters. Int J Adhes Adhes 2001;21:32537. [10] Nakason C, Kaesaman A, Supasanthitikul P. The grafting of maleic anhydride onto natural rubber. Polym Test 2004;23:3541. [11] Kim JI, Ryu SH, Chang YW. Mechanical and dynamic mechanical properties of waste rubber powder/HDPE composite. J Appl Polym Sci 2000;77:2595602. [12] Caavate J, Pags P, Saurina J, Colom X, Carrasco F. Determination of small interactions in polymer composites by means of FTIR and DSC. Polym Bull 2000;44:293300. [13] Colom X, Carrillo F, Caavate J. Composites reinforced with reused tyres: surface oxidant treatment to improve the interfacial compatibility. Composites Part A, in press. [14] Colom X, Carrasco F, Pags P, Caavate J. EVects of diVerent treatments on the interface of HDPE/lignocellulosic Wber composites. Compos Sci Technol 2003;63:1619. [15] Smith BC. Infrared spectral interpretation: a systematic approach. CRC Press; 2004. [16] Coates J. Interpretation of infrared spectra a practical approach. In: Mayers RA, editor. Encyclopedia of analytical chemistry. Chichester: John Wiley and Sons Ltd; 2000. [17] Cepeda-Jimenez CM, Pastor Blas MM, Ferrndiz-Gmez TP, Martn-Martinez JM. Surface Characterization of vulcanized Rubber treated with sulphuric acid and itd adhesion to polyurethane adhesive. J Adhesion 2000;73:13560. [18] Cepeda-Jimenez CM, Pastor Blas MM, Ferrndiz-Gmez TP, Martn-Martinez JM. Surface modiWcations of thermoplastic styrene-butadiene rubber treated with sulphuric acid. Polym Surf ModiWcation. Relevance Adhes 2000;2:30534. [19] Cepeda-Jimenez CM, Pastor-Blas MM, Ferrandiz-Gomez TP, Martin-Martinez JM. InXuence of the styrene content of thermoplastic styrene butadiene rubbers in the eVectiveness of the treatment with sulfuric acid. Int J Adhes Adhes 2001;21:16172.

rubber in which methyl, methylene and silane are involved and interpenetrates with the matrix, improving the ability to establish a link between the materials components. According to these results, in order to achieve a better mechanical performance in terms of rigidity, the sulphuric acid treatment seems to obtain the best results. Tensile strength, which is also inXuenced by the eVect of rigiditization of the particles, also shows good results when using the silane coupling agent. The chemical modiWcation achieved by sulphuric acid, does not inXuence substantially the miscibility of the rubber/HDPE interphase. The diVerences of the mechanical properties are attributed mainly to the bigger increase of the porosity and the surface roughness produced by the acid treatment that facilitates a better interlock between matrix and reinforcement. Instead, silane provides a better chemical adhesion but not the adequate morphology for the mechanical interlocking. Acknowledgements Financial support from the Spanish Ministry of Science and Technology (MAT 2003-00275 Project) is gratefully acknowledged. The authors would also like to thank Josep Palou and Teresa Lacorte from the Department of Materials Science of the Technical University of Catalonia for the SEM analyses of the samples. References
[1] European Tyre Recycling Association (ETRA). [2] Figovslq O, Beilin D, Blank N, Potapo J, Chernyshe V. Development of polymer concrete with polybutadiene matrix. Cement Concrete Comp 1996;18:43744. [3] Segre NP, Monteiro JM, Sposito G. Surface characterization of recycled tire rubber to be used in cement paste matrix. J Colloid Interf Sci 2002;248:5213. [4] Hernandez-Olivares F, Barluenga G, Bollatib M, Witoszekc B. Static and dynamic behaviour of recycled tyre rubberWlled concrete. Cement Concrete Res 2002;32:158796.