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Polymer-Plastics Technology and Engineering, 49: 1–5, 2010 Copyright # Taylor & Francis Group, LLC ISSN: 0360-2559 print=1525-6111 online DOI: 10.1080/03602550903283075

A Decorative Construction Material Prepared by Making Use of Marble Waste Granules and PMMA/SiO2 Nanocomposites
S. M. El-Bashir and A. Hindi

Physics Department, Science College, King Saud University, Riyadh, KSA




Innovative nanocomposite acrylic sheets incorporated with marble waste granules (MWG) were prepared by free radical polymerization of methyl methacrylate (MMA). The study of physicomechanical properties showed an improvement of adhesion between PMMA/SiO2 nanocomposites and (MWG). The introduction of SiO2 nanoparticles induced an extraordinary improvement of the abrasion resistance of PMMA matrix. The modulii of elasticities, maximum strain, impact absorbed energy and scratch resistance are explained on the basis of (MWG) porosity and adhesion. The manufactured nanocomposite sheets are cost effective in comparison with natural marble and possess the ability to have wide range of wonderful colors due to the inclusion of marble stones in a polymer matrix. In addition, the sheets display other specific properties such as light weight, color stability, electric insulation, low flammability, low water absorption and excellent mechanical properties. Keywords &

have several applications in architectural uses such as counter tops and more complex shapes. Moreover, the nanocomposite sheets incorporated with colored (MWG) as decorative materials and contain significant amounts of 45 alumina trihydrate (ATH) as a flame retardant material. ATH is the most frequently used flame retardant and very effective smoke suppressant in the world, due to its thermodynamic properties that absorb heat and release water vapor. Moreover, it is non-toxic and non-corrosive 50 so that it can be safely used in various elastomeric applications[5]. Our work contemplates an innovative nanocomposite material that can be considered as a cheap replacement of natural marble. This artificial marble have somewhat 55 the glossy appearance of the acrylic matrix, and the decorative effect of colored marble. EXPERIMENTAL TECHNIQUES Methylmethacrylate (MMA) monomer (Merck, Darmstadt, Germany) was freed from inhibitors by distillation at 50 C under reduced pressure (1 m bar) using rotary evaporator (BUCHI ROTAVAPOR R-114, Switzerland). The polymer syrup (PMMA-MMA) was prepared by adding 0.1 wt% AIBN initiator (DuPont, USA). The solution was refluxed at 100 C for 1 h to increase the monomer viscosity and subsequently reduce the polymerization time. The viscosity of the resulting syrup was determined using a rotational viscometer (BROOK FIELD DV-IIþ, USA) and was equal to 200 cP[6]. Afterwards, hydrophilic nanosilica (Aldrich, USA) was added as a thixotropic agent, with a concentration about 2% of the as-prepared PMMA-MMA syrup, the viscosity of the syrup reached 800 cP. Alumina trihydrate (ATH) (Albemarle Corp.) was added with concentration about 20 wt%. Ethylene glycol dimethacrylate was added as a cross-linking agent with a concentration 0.5%[7]. After that marble waste granules (MWG) having maximum diameter about 5 mm were produced by successive sieving of pulverrized natural marble (calcite). 1






INTRODUCTION Nanocomposite materials are of great interest due to their physical properties and suitability in a wide range of technological applications[1]. It has been significantly important to develop the technology to treat or recycle the waste from natural marble due to enormous production of them as the industry and economy of the world are growing[2]. There have been several ways to treat the stone wastes such as land fills, incineration, chemical recycling and the utilization of energy from combustion[3]. Particulate materials are of great interest due to their physical properties and suitability upon wide-range technological applications. Recently the importance of how to recycle or reuse of marble waste granules (MWG) became an important issue in reference[4]. This study relates to the manufacture of acrylic nanocomposite sheets made of poly(methylmetacrylate) (PMMA), SiO2 nanoparticles and MWG. These nanocomposite sheets





Address correspondence to S. M. El-Bashir, Physics Department, Science College, King Saud University, Riyadh, KSA. E-mail: elbashireg@yahoo.com


Impact strength measurements have been carried out according to (ASTM D 256) using charpy impact tester (43-02 monitor=impact. M. It is noticed that the for all nanocomposites the values of E and rm are increased by increasing soaking time of 130 MWG and much higher than that of pure PMMA. USA). was examined according to ASTM (D1037-87.1% AIBN) for different durations 3. UK). So the incorporation of MWG and SiO2 nanoparticles deduced the molecular motion of PMMA. The abrasion resistance test was performed according to ASTM (D 1034-98) by using (Taber1 Abrasion Tester models 5130. It is noticed that the impact resistance increased from 2. Messmer instruments.90 kJ=m2 for pure PMMA to 20. The values of E.2 S. The hardness of PMMA and PMMA=SiO2=MWG was estimated according to (ASTM D 256) and plotted in Figure 4. Water swelling test of PMMA=SiO2=MWG nanocomposites. Stress-strain curves of PMMA and PMMA=SiO2=MWG nanocomposites. the moisture adsorbed on the surface of MWG was removed by heating it at 150 C for 24 h. HINDI 85 Q2 90 95 100 105 110 Before preparing PMMA=SiO2=MWG nanocomposites. The mixture was poured into a rectangular glass mold of dimensions 50 Â 50 Â 0. 18. for PMMA=SiO2=MWG nanocomposites is increased by increasing soaking time of MWG to about 162% over pure PMMA. The electrical conductivity r is measured for all the nanocomposite samples by (conductivity meter Model 1116 SLD. em. Figure 5 illustrates the percentage sample weight loss for 135 140 145 150 155 160 165 . 100). The excellent compatability and strong adhesion prevent the separation of MWG from PMMA=SiO2 matrix and subsequently reduce the formation of cavities and promote the absorption of impact energy. which is the reciprocal of E. RESULTS AND DISCUSSION Figure 1 illustrates the flexural stress-strain curves of 115 pure PMMA and PMMA=SiO2=MWG nanocomposites obtained by ASTM (D638. It is apparent that the long soaking time provides strong adhesion between PMMA and MWG in addition to the excellent compatability between PMMA and CaCo3. UK). The hardness of the samples was measured using a shore tester model (Shore1 S1 Portable Digital Durometer. FT-IR spectra for all samples were recorded in the wave number range (4000– 400 cmÀ1) with an FT-IR spectrophotometer (Genesis Series. 12. This can be attributed to the reduction of nanocomposite matrix free volume by increasing soaking time of MWG and subsequently. at a rate 15 mm=min. 24 hrs. UK). In addition the maximum strain. 1. Five sheets of PMMA=SiO2=MWG nanocomposites were produced by adding MWG to PMMA= SiO2 syrup with a concentration ratio 50%. Thermal conductivity of the samples was measured using thermal conductivity apparatus (PASCO TD-8561. kept at 65 C for 10 hrs followed by final curing at 100 C for 6 hrs[8]. Wolpert Wilson. FIG. and left in open air atmosphere to dry at room temperature to prepare different nanocomposite samples. It is clear that the compliance of PMMA=SiO2=MWG nanocomposites is lower than that of pure PMMA. D3039). It is noticed that the hardness increased from 200 Mpa for PMMA to 400 Mpa for nanocomposites having MWG soaked for 24 hrs. yield (maximum) stress rm and maximum strain em are listed in Table 1. 6. The values of the compliance D. Messmer instruments. This can be attributed to the increase of the chain stiffness in the polymer due the absorption of polymer chains at the filler surface. which is the major component of MWG.74 kJ=m2 for nanocomposites having MWG soaked for 24 hrs.5KN 84-02. USA). Messmer instruments. The impact strength of PMMA and PMMA=SiO2= MWG nanocomposites is plotted in Figure 3. 120 The modulus of elasticity E has been estimated according to Hook’ s law relation[9]. has been calculated for pure PMMA and all PMMA=SiO2=MWG nanocomposites and plotted in Figure 2. The elected MWG were soaked in a solution of (nano-SiO2=MMA= 0. EL-BASHIR AND A. It is noticed that the stress-strain curve of PMMA changed from hard and brittle to that of hard and strong material[9]. USA). UK) at rate of 1 mm=min. The mechanical properties were tested using tensile machine (UNIVERSAL Tester AT 2.6 cm3 and then immersed in a water bath. The surface abrasion of PMMA=SiO2=MWG nanocomposites was estimated according to ASTM (D 1034-98). e is the strain and E is the modulus of elasticity which is clearly a measure of material 125 resistance to deformation. r ¼ Ee where r is the flexural stress. good adhesion between PMMA=SiO2 and MWG.

USING WASTE MARBLE GRANULES AND SIO2 NANOCOMPOSITES FOR CONSTRUCTION 3 TABLE 1 The physical properties of PMMA=SiO2=MWG nanocomposites at different soaking time of MWG compared to PMMA and natural marble Composition PMMA 3 hrs 6 hrs 12 hrs 18 hrs 24 hrs Marble rm (MPa) 72.cm. of PMMA=SiO2=MWG nanocomposites.17 1.29 93.38 168. D.30 4. FIG. 3.67 74.50 111.20 Â 10À3 rdc (XÀ1 Á cmÀ1) 5 Â 10À18 5 Â 10À19 2 Â 10À19 9 Â 10À20 3 Â 10À20 10À20 10À18 q (gm=cm3) 1. The hardness nanocomposites.72 1.00 Â 10À4 5. FIG. The impact strength of PMMA and PMMA=SiO2=MWG nanocomposites.20 6.80 1.76 1. 5. of PMMA and PMMA=SiO2=MWG FIG. C) 4. The surface abrasion of PMMA and PMMA=SiO2=MWG nanocomposites. The relationship between soaking time of MWG and the compliance.70 4.00 189.70 1.62 85.20 Â 10À4 4.83 Â 10À4 6. .00 8.50 4.93 Â 10À4 4. 2.00 em (%) 3.70 Â 10À4 8. 4.00 FIG.70 5.84 3.00 K (Cal=s.90 Â 10À4 4.

M. This indicates that the polymerization of MMA is not decelerated by introducing the inorganic phase. The disappearance C=C stretching mode (1650–1610 cmÀ1) characterizing MMA. It is observed that although the vibrational peaks of C=O stretching mode have the same position (1728 cmÀ1). Water absorption was measured for PMMA. marble. 8. Figure 7 shows FT-IR transmission spectra of PMMA and the optimum PMMA=SiO2=MWG nanocomposite in the wavenumber range (2000–500 cmÀ1). It is noticed that the abrasion loss of PMMA=SiO2=MWG nanocomposites is much lower than pure PMMA. FT-IR spectra for (a) PMMA and (b) PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs. FIG. MWG and PMMA=SiO2=MWG nanocomposites after 24 hrs of soaking according to ASTM (D1037-87. pointing to the complete polymerization of monomer for the two samples. HINDI 170 175 180 185 190 195 pure PMMA and all the as prepared PMMA=SiO2=MWG nanocomposites. SiO2 nanoparticles and ATH are excellent non-corrosive materials so that they provide a large increase in the scratch resistance. EL-BASHIR AND A.4 S. Expanded FT-IR spectra in the range (1800–1500 cmÀ1) for (a) PMMA and (b) PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs. 100). It is also clear that the water absorption in case of the optimum PMMA=SiO2=MWG nanocomposite is equal to 7%. Moreover. our results are plotted in Figure 6. . In addition it is noticed that the abrasion resistance increases by increasing the soaking time of MWG. which is very low compared to natural marble 54% for the same period of soaking at the same atmospheric conditions. position of ester carbonyl groups (C=O stretching mode) 200 expanded in the band (1800–1500 cmÀ1). The water absorption for PMMA. as shown in Figure 8. the band width (FWHM) is reduced from 50 cmÀ1 for 205 PMMA to 43 cmÀ1 for the PMMA=SiO2=MWG nanocomposite. 6. This can be attributed to the fact that polymer solution fills the pores of MWG and protects them from water penetration after the complete polymerization of nanocomposites. natural marble and PMMA= SiO2=MWG nanocomposites. One notes that the water absorption decreases by increasing the soaking time of MWG. As well as adding SiO2 nanoparticles and the cross-linking agent decreases the free volume of PMMA and prevents the presence of voids and cracks. The comparison between the two spectra shows that the most interesting feature is the shape and FIG. This can be attributed to the increase of matrix rigidity due to the decrease of the porosity of MWG by increasing soaking time. 7. This can be explained by the acidic feature FIG. This band narrowing is accompanied by the weakness of the intensity of the shoulder appearing at 1685 cmÀ1 for pure PMMA and can be attributable to the ester carbonyl groups which are hydrogen-bonded to surface silanol groups 210 (Si–OH)[10].

G. C. C.C. Chem. Test 2008. Polym.E. F. Vitras. 100. 243. C. J. 10. T.). S. 334.A. 88.. 540. rdc. M. The thermal conductivity. Kim.-A. Sol-Gel Sci. 643. E. S.G.. store and use. This proposed molecular interaction is simply an interfacial phenomenon between the organic PMMA and inorganic silica phases.G.Y. Fire Sciences 2006.. of PMMA=SiO2=MWG nanocomposites was evaluated in comparison with natural marble and PMMA and listed in Table 1.... 793. 260 265 5. C. Phys. Costache. 1963. D. K. 27. 215 220 225 230 Si–OH group and the strong amphoteric character of C=O group. E.12]. Wetter. Non-Cryst. Proceedings of Fifth Asian Symposium on Polymers in Concrete. 27. Kil.. which is one of the world’s leading manufacturers of chemicals.S. Y.. Park. The presence of the 1728 cmÀ1 band in the nanocomposite film. PMMA molecules that are above the bonded layer of the nanocomposite matrix will behave in a fashion similar to those in pure PMMA matrix. 6. PMMA=SiO2=MWG nanocomposite can be considered as a potential replacement of natural marble. Hammam. Eitel. U. N.S.. Moreover. Wilkie.. Ohama.M. Hammam. (Eds. REFERENCES 1.M. Solids 1994. 4. confirms that the majority of them are actually free from hydrogen bonding. which acts as a basic site or proton acceptor. H. T.H.. Shin.. 7. Mechanical Performance of Plastics. S. Kanugh. X.567. 3. 2003. 24... Infrared Spectra of Inorganic and Coordination Compounds. Li. J. J. Vaidyanathan.. Sci. Li. Nakamoto. Iovu. Minghetti. J. 12. El-Shaarawy. Encyclopedia of Polymer Science and Technology.K. The results showed that ACKNOWLEDGMENTS The authors deeply appreciate the funding of this work from Saudi Basic Industries Corporation (SABIC). F. T.F. 433.. A. M. Polym.. 255 fertilizers.. Appl. 235 Figure 9 shows a photograph of PMMA=SiO2=MWG nanocomposites. Vitras. J. Zhu. T. 9.. both the chemical and physical properties of PMMA should be largely retained in PMMA=SiO2=MWG nanocomposites[11. Mansour. J. 2007. M.V. Hwang. Liao. S. The surface morphology of PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs. A. Patent 5. El-Mansy. Technol. M. Ind. 1996. Bulearca. 9. making it easy to transport. Garea. M. 7.. Current Appl. 10. E. X.S. 2006. El-Mansy. Eng. M.. El-Shaarawy. El-Bashir. The results illustrated excellent thermal and electrical insulation of all the nanocomposites compared to natural marble. 203.J. M.. q. A. 7. 8. 12. 216.A. and electrical conductivity. Zhao. J. Chennai. Shi. 323.USING WASTE MARBLE GRANULES AND SIO2 NANOCOMPOSITES FOR CONSTRUCTION 5 the products are lightweight when compared with natural marble.H. since its hydrophobic nature makes it easy to clean and more resistant to 250 erosion caused from air pollution.: New York and London. 270 Q3 275 . Neelamegam. 11.. 2006.K. FIG. Z. John Wiley & Sons Inc. Therefore.A.745 (1996). Yang. Polym. which is largely attributed to the non-bonded C=O groups. 240 CONCLUSIONS The treatment of marbe waste granules (MWG) with MMA=nano SiO2 solution enhances their rigidity and abraision resistance of PMMA=SiO2=MWG nanocomposite. India.S. M.. Hwang.P. A. H. In addition the compliance and water absorption are 245 decreased by increasing the treatment time by soaking MWG overnight in MMA=nano SiO2 solution. 170. specially acidic rains.. S. of all the prepared PMMA=SiO2=MWG nanocomposites was evaluated in comparison with natural marble and PMMA and listed in Table 1. 2. in: Laksmanan. Test 2008. John Wiley & Sons: New York. Kim. plastics and metals.. K. El-Bashir.P. Vol. King.. It is clear that MWG have a uniform distribution and that PMMA coating gives MWG a remarkable ability to restore its normal properties when subjected to scratches or cracks.A. Cai.M. The density. King.... F.

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