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Polymer-Plastics Technology and Engineering, 49: 15, 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
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Physics Department, Science College, King Saud University, Riyadh, KSA

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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 specic properties such as light weight, color stability, electric insulation, low ammability, 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 signicant amounts of 45 alumina trihydrate (ATH) as a ame retardant material. ATH is the most frequently used ame 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 articial 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 reuxed 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-II, 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

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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 signicantly 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 lls, 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

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

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Before preparing PMMA=SiO2=MWG nanocomposites, the moisture adsorbed on the surface of MWG was removed by heating it at 150 C for 24 h. The elected MWG were soaked in a solution of (nano-SiO2=MMA= 0.1% AIBN) for different durations 3, 6, 12, 18, 24 hrs, and left in open air atmosphere to dry at room temperature to prepare different nanocomposite samples. Five sheets of PMMA=SiO2=MWG nanocomposites were produced by adding MWG to PMMA= SiO2 syrup with a concentration ratio 50%. The mixture was poured into a rectangular glass mold of dimensions 50 50 0.6 cm3 and then immersed in a water bath, kept at 65 C for 10 hrs followed by nal curing at 100 C for 6 hrs[8]. The mechanical properties were tested using tensile machine (UNIVERSAL Tester AT 2.5KN 84-02, Messmer instruments, UK) at rate of 1 mm=min. Impact strength measurements have been carried out according to (ASTM D 256) using charpy impact tester (43-02 monitor=impact, Messmer instruments, UK). The hardness of the samples was measured using a shore tester model (Shore1 S1 Portable Digital Durometer, Wolpert Wilson, USA). The abrasion resistance test was performed according to ASTM (D 1034-98) by using (Taber1 Abrasion Tester models 5130, Messmer instruments, UK). Water swelling test of PMMA=SiO2=MWG nanocomposites, was examined according to ASTM (D1037-87, 100). Thermal conductivity of the samples was measured using thermal conductivity apparatus (PASCO TD-8561, USA). FT-IR spectra for all samples were recorded in the wave number range (4000 400 cm1) with an FT-IR spectrophotometer (Genesis Series, USA). The electrical conductivity r is measured for all the nanocomposite samples by (conductivity meter Model 1116 SLD, UK).

FIG. 1. Stress-strain curves of PMMA and PMMA=SiO2=MWG nanocomposites.

RESULTS AND DISCUSSION Figure 1 illustrates the exural stress-strain curves of 115 pure PMMA and PMMA=SiO2=MWG nanocomposites obtained by ASTM (D638, D3039), at a rate 15 mm=min. It is noticed that the stress-strain curve of PMMA changed from hard and brittle to that of hard and strong material[9]. 120 The modulus of elasticity E has been estimated according to Hook s law relation[9], r Ee where r is the exural stress, e is the strain and E is the modulus of elasticity which is clearly a measure of material 125 resistance to deformation. The values of E, yield (maximum) stress rm and maximum strain em are listed in Table 1. 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. In addition the maximum strain, em, for PMMA=SiO2=MWG

nanocomposites is increased by increasing soaking time of MWG to about 162% over pure PMMA. The values of the compliance D, which is the reciprocal of E, has been calculated for pure PMMA and all PMMA=SiO2=MWG nanocomposites and plotted in Figure 2. It is clear that the compliance of PMMA=SiO2=MWG nanocomposites is lower than that of pure PMMA. This can be attributed to the reduction of nanocomposite matrix free volume by increasing soaking time of MWG and subsequently, good adhesion between PMMA=SiO2 and MWG. The impact strength of PMMA and PMMA=SiO2= MWG nanocomposites is plotted in Figure 3. It is noticed that the impact resistance increased from 2.90 kJ=m2 for pure PMMA to 20.74 kJ=m2 for nanocomposites having MWG soaked for 24 hrs. 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, which is the major component of MWG. 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. The hardness of PMMA and PMMA=SiO2=MWG was estimated according to (ASTM D 256) and plotted in Figure 4. It is noticed that the hardness increased from 200 Mpa for PMMA to 400 Mpa for nanocomposites having MWG soaked for 24 hrs. This can be attributed to the increase of the chain stiffness in the polymer due the absorption of polymer chains at the ller surface. So the incorporation of MWG and SiO2 nanoparticles deduced the molecular motion of PMMA. The surface abrasion of PMMA=SiO2=MWG nanocomposites was estimated according to ASTM (D 1034-98). Figure 5 illustrates the percentage sample weight loss for

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USING WASTE MARBLE GRANULES AND SIO2 NANOCOMPOSITES FOR CONSTRUCTION

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) 72.67 74.62 85.29 93.50 111.38 168.00 189.00 em (%) 3.70 4.30 4.50 4.70 5.20 6.00 8.00 K (Cal=s.cm. C) 4.70 104 8.00 104 5.20 104 4.93 104 4.90 104 4.83 104 6.20 103 rdc (X1 cm1) 5 1018 5 1019 2 1019 9 1020 3 1020 1020 1018 q (gm=cm3) 1.17 1.70 1.72 1.76 1.80 1.84 3.00

FIG. 2. The relationship between soaking time of MWG and the compliance, D, of PMMA=SiO2=MWG nanocomposites.

FIG. 4. The hardness nanocomposites.

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FIG. 3. The impact strength of PMMA and PMMA=SiO2=MWG nanocomposites.

FIG. 5. The surface abrasion of PMMA and PMMA=SiO2=MWG nanocomposites.

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pure PMMA and all the as prepared PMMA=SiO2=MWG nanocomposites. It is noticed that the abrasion loss of PMMA=SiO2=MWG nanocomposites is much lower than pure PMMA. In addition it is noticed that the abrasion resistance increases by increasing the soaking time of MWG. This can be attributed to the increase of matrix rigidity due to the decrease of the porosity of MWG by increasing soaking time. Moreover, marble, SiO2 nanoparticles and ATH are excellent non-corrosive materials so that they provide a large increase in the scratch resistance. Water absorption was measured for PMMA, MWG and PMMA=SiO2=MWG nanocomposites after 24 hrs of soaking according to ASTM (D1037-87, 100), our results are plotted in Figure 6. One notes that the water absorption decreases by increasing the soaking time of MWG. It is also clear that the water absorption in case of the optimum PMMA=SiO2=MWG nanocomposite is equal to 7%, which is very low compared to natural marble 54% for the same period of soaking at the same atmospheric conditions. This can be attributed to the fact that polymer solution lls the pores of MWG and protects them from water penetration after the complete polymerization of nanocomposites. 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. Figure 7 shows FT-IR transmission spectra of PMMA and the optimum PMMA=SiO2=MWG nanocomposite in the wavenumber range (2000500 cm1). The disappearance C=C stretching mode (16501610 cm1) characterizing MMA, pointing to the complete polymerization of monomer for the two samples. This indicates that the polymerization of MMA is not decelerated by introducing the inorganic phase. The comparison between the two spectra shows that the most interesting feature is the shape and

FIG. 7. FT-IR spectra for (a) PMMA and (b) PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs.

position of ester carbonyl groups (C=O stretching mode) 200 expanded in the band (18001500 cm1), as shown in Figure 8. It is observed that although the vibrational peaks of C=O stretching mode have the same position (1728 cm1), the band width (FWHM) is reduced from 50 cm1 for 205 PMMA to 43 cm1 for the PMMA=SiO2=MWG nanocomposite. This band narrowing is accompanied by the weakness of the intensity of the shoulder appearing at 1685 cm1 for pure PMMA and can be attributable to the ester carbonyl groups which are hydrogen-bonded to surface silanol groups 210 (SiOH)[10]. This can be explained by the acidic feature

FIG. 6. The water absorption for PMMA, natural marble and PMMA= SiO2=MWG nanocomposites.

FIG. 8. Expanded FT-IR spectra in the range (18001500 cm1) for (a) PMMA and (b) PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs.

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the products are lightweight when compared with natural marble, making it easy to transport, store and use. 235 Figure 9 shows a photograph of PMMA=SiO2=MWG nanocomposites. 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. 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. In addition the compliance and water absorption are 245 decreased by increasing the treatment time by soaking MWG overnight in MMA=nano SiO2 solution. Moreover, PMMA=SiO2=MWG nanocomposite can be considered as a potential replacement of natural marble, since its hydrophobic nature makes it easy to clean and more resistant to 250 erosion caused from air pollution, specially acidic rains.
FIG. 9. The surface morphology of PMMA=SiO2=MWG nanocomposites having MWG soaked for 24 hrs.

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SiOH group and the strong amphoteric character of C=O group, which acts as a basic site or proton acceptor. The presence of the 1728 cm1 band in the nanocomposite lm, which is largely attributed to the non-bonded C=O groups, conrms that the majority of them are actually free from hydrogen bonding. This proposed molecular interaction is simply an interfacial phenomenon between the organic PMMA and inorganic silica phases; PMMA molecules that are above the bonded layer of the nanocomposite matrix will behave in a fashion similar to those in pure PMMA matrix. Therefore, both the chemical and physical properties of PMMA should be largely retained in PMMA=SiO2=MWG nanocomposites[11,12]. The thermal conductivity, K, and electrical conductivity, rdc, of all the prepared PMMA=SiO2=MWG nanocomposites was evaluated in comparison with natural marble and PMMA and listed in Table 1. The results illustrated excellent thermal and electrical insulation of all the nanocomposites compared to natural marble. The density, q, of PMMA=SiO2=MWG nanocomposites was evaluated in comparison with natural marble and PMMA and listed in Table 1. The results showed that

ACKNOWLEDGMENTS The authors deeply appreciate the funding of this work from Saudi Basic Industries Corporation (SABIC), which is one of the worlds leading manufacturers of chemicals, 255 fertilizers, plastics and metals.

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