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wastes S.E. Saratov Federation November 25 Decembe influence posites produced with PVB. The characterization involved: elongation under rupture, water absorption, tensile strength and elastic provides a means to decrease environmental contamina- tion. Flat glass processing involves the generation of the lack of technological processes oriented towards its glass processing, usually produce both types of the aforementioned wastes or are located close by, it was applications. The best scheme is that for plants produc- ing both wastes, for example in the manufacturing of dierent profiled rods, characterized with high mechan- ical properties stable in conditions of humid atmosphere and temperature changes. However, the presence of * Corresponding author. Tel.: +52 844 438 9600; fax: +52 844 438 9610. E-mail address: alexandesaltillo.cinvestav.mx (A.V. Gorokhovsky). Waste Management 25 0956-053X/$ - see front matter C211 2004 Elsevier Ltd. All rights reserved. wastes, like scrap of glass mirrors as well as strips of poly (vinyl) butiral film (PVB), from the manufacture of automobile windscreens (Garner, 1996) and safety architectural glass (Lievens, 1995). Clean PVB waste can be recycled on the basis of well-known technological processes; however, about 520% of this waste contains contamination, which precludes its recycling. Moreover, in developing countries there is little eorts or possibility for the recycling of this type of waste. Additionally, waste from glass mirror production (scrap or mirrors not meeting standards) has to be disposed because of of interest to investigate the possibility of producing glass-polymer composites based on the complex utiliza- tion of such wastes that are inapplicable for recycling. The production of composites based on PVB wastes is especially attractive in developing countries, where their collection as well as transportation into the plants spe- cialized in PVB recycling is economically unprofitable. The high adhesion properties of the PBV to the soda- lime-silicate glass surface (Garner, 1996; Gopal et al., 1997) make the composite, based on PVB waste and milled glass, a promising material useful for dierent modulus tests. The results showed that the composite containing 10 wt% of filler powder had the best properties among the com- positions studied. The influence of the time of exposure in humid atmosphere on the composite properties was investigated. It was found that the admixture of PVB iso-propanol solution to the scrap of glass mirrors during milling provided stabilization of the properties of the composites produced. C211 2004 Elsevier Ltd. All rights reserved. 1. Introduction The use of industrial wastes to produce composite materials is one of the current problems of industry; this utilization (Foss, 1997). The amounts of such waste can reach 1015% of commercial production in dierent plants. Taking into account that the plants oriented to flat Composite materials based on A.V. Gorokhovsky a, * , J.I. Escalante-Garcia L.P. Nikulina b , a Department of Engineering Ceramics, CINVESTAV Unidad Saltillo, Carr. b Department of Chemical Technology, Technological Institute of Russian Accepted 3 Available online Abstract Glass mirrors scrap and poly (vinyl) butiral waste (PVB) obtained rials to produce composites. The emphasis was on studying the doi:10.1016/j.wasman.2004.11.007 of flat glass processing a , G.Yu. Gashnikova b , Artemenko b Saltillo-Monterrey km13, AP 663, Saltillo, CP25000 Coahuila, Mexico State Technical University, Pl. Svobody 17, Engels 413100, 2004 r 2004 from flat glass processing plants were investigated as raw mate- of milled glass mirror waste contents on properties of com- (2005) 733736 metal particles on the glass surface of milled glass mirror scrap as well as the use of PVB waste could negatively influence the exploitation properties and thus must be investigated. 2. Methodology of glass powder: (a) fresh dry milled, (b) dry milled and exposed to a humid atmosphere for a month, (c) milled with PVB alcohol solution and exposed to a hu- mid atmosphere for a month. The average tensile mechanical strength of the com- posite articles was measured by testing 18 specimens of each system using the ER-5046-5 Russian equipment. The Young modulus was measured following the tested properties decreased only during the first two months of exposure and then stabilized. The same eect Table 1 The properties of composites obtained by extrusion of samples made of separa (wt%) 2.7 7.4 734 A.V. Gorokhovsky et al. / Waste Management 25 (2005) 733736 Properties Contents of glass powder 013 Young module (MPa) 2.3 2.5 Tensile strength (MPa) 6.8 5.2 Wastes of Saratovsteklo Inc. (Russia) were used for the experiments. The glass used to produce mirrors had the following chemical composition (wt%): 73.1 SiO 2 ; 1.1 Al 2 O 3 ; 8.6 CaO; 3.6 MgO; 13.6 Na 2 O. The mirror coating was formed by vacuum sputtering of stainless steel. PVB waste was obtained from the poly- mer film B-17 produced by Monsanto. In Series 1 of the experiments, the filler was produced by dry ball milling of glass mirror scrap, in jars of alu- mina with balls of alumina, to reach a surface area of 4000 100 cm 2 /g (controlled by LHM-8MD Russian equipment). The ground glass was then added to PVB waste molten at 115 C176C, the latter was previously ad- mixed with 0.5 wt% of poly (ethyl) silane (PES-5, Volzh- skii, Russia) to promote the blending of components and increase homogeneity of composition. The ratio of glass powder and molten PVB was varied in the range of 130 wt%. The mixtures obtained were used to pro- duce films by quenching, as well as rods by extrusion. It is well known that water vapor adsorption onto the surface of soda-lime-silicate glasses influences their adhesion to polymers (Kawaguchi and Pearson, 2003; Gu et al., 2000; Radhakrishnan and Unde, 1999). It has been shown (Soshko et al., 1989) that the admixtures of some organic polymers into the glass scrap during milling promoted the modification of the glass surface by the products of their thermo-mechanical destruction (Dhaliwal and Hay, 2000). For this reason, an addi- tional batch of Series 2 was prepared using composites made from the resulting material obtained after joint ball milling of glass mirrors scrap admixed with PVB waste dissolved at room temperature in iso-propanol (15% solution); the weight ratio of glass scrap and PVBalcohol solution was 0.05. It was expected that the glass powder thus obtained would have enhanced hydrophobic properties and improved adhesion to PVB. To characterize such surface modification, the ob- tained fillers were investigated by TGA/DTGA (Perkin Elmer/Seiko Instruments, Japan) for the following types Relative elongation under rupture (%) 318 345 288 was displayed by the results presented in Table 2, show- ing the properties of composites obtained with the fresh and old (exposed in air for a month) glass powder. Such reduction in the exploitation properties observed, in agreement with published results (Keller and Mortelmans, 1999), can be attributed to the pro- cesses taking place on the surface of glass filler before the production of composites: adsorption (condensa- tion) of water vapor from the atmosphere, leaching of sodium ions, and crystallization of Na 2 CO 3 and NaH- te dry milling of glass 51015202530 2.9 4.3 3.8 2.7 2.5 2.3 7.9 11.2 8.4 8.5 7.0 5.4 E1875-00e1 ASTM standard using UZIS equipment (LETI, Russia). Taking into account the influence of environmental factors on the properties of materials produced, speci- mens of the two composites, prepared with the fillers of Series 1 and 2, were exposed for three months at 25 C176C in air (40% humidity); and the same mechanical tests, as previously described, were repeated to determine the range of variation in the main characteristics during exploitation. 3. Results and discussion The main characteristics of composites with dierent contents of glass powder for Series 1, measured immedi- ately after their production, are presented in Table 1. The introduction of 110 wt% of glass powder into the matrix of PVB waste increased the mechanical strength of the composite (by 1.6 times) and decreased its relative elongation under the rupture (by 1.3 times). Further in- crease of glass powder contents decreased the exploita- tion properties. The influence of exposure to a humid atmosphere on the exploitation properties of the composite, made from Series 1 with 10 wt% of glass powder (highest mechani- cal properties), is presented in Figs. 1 and 2. All the 271 237 328 295 286 142 CO 3 as a result of the sodium ions interaction with dis- solved CO 2 . The presence of these crystals and adsorbed water onto the surface of glass filler decreased adhesion with PVB. At the same time, modification of the glass powder surface during the milling of glass mirrors scrap with PVB alcohol solution (Series 2) can increase the hydrophobic properties of the glass powder and stabilize the structure of the composite. A comparison of proper- ties for composites from Series 1 and 2 is shown in Figs. 1 and 2; an improvement and increased stability of prop- glass mirrors scrap with PVB waste, dissolved at room temperature in iso-propanol (15% solution), were ap- Temperature,C 35 30 Characteristics 25 Relative elongation under a rupture 20 15 Tensile strength 10 5 Young modulus 0 0 50 100 150 Exposure, days Fig. 1. Influence of exposure to humid atmosphere on properties of composites produced with powder obtained from Series 1 (continuous lines) and Series 2 (dashed lines): relative elongation under a rupture (%10 C01 ), tensile strength (MPa), Young modulus (MPa). A.V. Gorokhovsky et al. / Waste Management erties of the composite produced in Series 2 can be noted. 3 2.5 Sweling, wt.% 2 1.5 1 0.5 0 Table 2 Properties of composites, made from Series 1 and with 10 wt% of glass powder, produced immediately after the milling and after one month of glass powder storage in air Property Type of glass powder applied One month after milling Fresh powder Young modulus (MPa) 3.8 4.3 Tensile strength (MPa) 8.2 11.2 Relative elongation before the rupture (%) 281 237 0 50 100 150 Exposure, days Fig. 2. Influence of exposure in humid atmosphere (dashed lines) and water (continuous lines) on weight of composite rods produced from Series 1 (d) and Series 2 (s). The obtained data of DTGA (Fig. 3) indicates that the old glass filler, in comparison with the fresh fil- ler obtained by dry ball milling, is characterized by the additional intensive peak at 350420 C176C, related to the desorption of chemically adsorbed water (Hench, 1978; Gorokhovsky, 1988). At the same time, this peak is ab- sent for the filler milled jointly with the PVB solution in iso-propanol; moreover, the quantity of condensed water is much less. The additional peaks in the thermo- gram of this filler are related to the melting and thermal decomposition of PVB (Dhaliwal and Hay, 2000). Thus, it is possible to propose that the eect of stabilization of the mechanical properties, obtained for the composite produced on the base of glass powder with modified sur- face (Series 2), was achieved due to a decreased adsorp- tion of water vapor. The composite rods of dierent profiles, produced by extrusion of the batch based on the PVB wastes and glassy filler (10 wt%), obtained by joint ball milling of Fig. 3. DTGA data obtained for dierent types of filler: A fresh dry milled, B old dry milled, C old milled with PVB alcohol solution. 1, 2 desorption of condensed water, 3 desorption of chemically adsorbed water, 4 melting of PVB; 5, 6 thermal decomposition of PVB and its derivatives formed by milling. 0 10 20 30 40 50 60 50 100 150 200 250 300 350 400 450 500 DTG, microg/min 1 2 3 4 5 6 1 1 2 A B C 25 (2005) 733736 735 plied in Salavatsteklo Co. (Salavat, Russia) to manufac- ture the double glazing blocks, as well as bases for the storage and transportation of glass sheets of high thick- ness (weight). 4. Conclusions Composite materials with attractive exploitation properties can be produced on the basis of typical wastes of flat glass processing: poly (vinyl) butiral ribbons and glass mirror scrap. The contents about of 10 wt% of glass powder results in composites with high and stable mechanical properties. The introduction of PVB alco- hol solution resulted in the stabilization of properties of the composites in the case of exposure to humid atmospheres. References Dhaliwal, A.K., Hay, J.N., 2000. The characterization of polyvinyl butyral by thermal analysis. Thermochimica Acta 391 (12), 245 255. Foss, R.V., 1997. Recycling of architectural and automotive glass in Europe. With emphasis on Germany. In: Proc. of 6th International Conference on Architectural and Automotive Glass, Tampere, pp. 4448. Garner, J., 1996. Automotive glass windscreen design and shaping. Glass Technology 37 (5), 151152. Gopal, S., Ramchandran, R., Agnihotry, R.S.A., 1997. Polyvinyl butyral based solid polymeric electrolytes: preliminary studies. Solar Energy Materials and Solar Cell 45 (1), 1725. Gorokhovsky, A.V., 1988. About the nature of surface acidity of multi-component silicate glass. Fizika I Khimiya Stekla (Glass Physics and Chemistry) 14 (5), 739743. Gu, W., Wu, H.F., Kampe, S.L., Lu, G.-Q., 2000. 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