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Waste Management 25 (2005) 733–736
www.elsevier.com/locate/wasman
Composite materials based on wastes of ?at glass processing
A.V. Gorokhovsky a,*, J.I. Escalante-Garcia a, G.Yu. Gashnikova b, L.P. Nikulina b, S.E. Artemenko b
a Department of Engineering Ceramics, CINVESTAV Unidad Saltillo, Carr. Saltillo-Monterrey km13, AP 663, Saltillo, CP25000 Coahuila, Mexico
b Department of Chemical Technology, Technological Institute of Saratov State Technical University, Pl. Svobody 17, Engels 413100, Russian Federation
Accepted 3 November 2004
Available online 25 December 2004
Abstract
Glass mirrors scrap and poly (vinyl) butiral waste (PVB) obtained from ?at glass processing plants were investigated as raw mate-
rials to produce composites. The emphasis was on studying the in?uence of milled glass mirror waste contents on properties of com- posites produced with PVB. The characterization involved: elongation under rupture, water absorption, tensile strength and elastic modulus tests. The results showed that the composite containing 10 wt% of ?ller powder had the best properties among the com- positions studied. The in?uence 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.
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 provides a means to decrease environmental contamina- tion. Flat glass processing involves the generation of wastes, like scrap of glass mirrors as well as strips of poly (vinyl) butiral ?lm (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 5–20% of this waste contains contamination, which precludes its recycling. Moreover, in developing countries there is little e?orts 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 the lack of technological processes oriented towards its
* Corresponding author. Tel.: +52 844 438 9600; fax: +52 844 438
9610.
E-mail address: alexande@saltillo.cinvestav.mx (A.V. Gorokhovsky).
utilization (Foss, 1997). The amounts of such waste
can reach 10–15% of commercial production in di?erent plants.
Taking into account that the plants oriented to ?at glass processing, usually produce both types of the aforementioned wastes or are located close by, it was 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 unpro?table. 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 di?erent applications. The best scheme is that for plants produc- ing both wastes, for example in the manufacturing of di?erent pro?led rods, characterized with high mechan- ical properties stable in conditions of humid atmosphere and temperature changes. However, the presence of
0956-053X/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2004.11.007
734 A.V. Gorokhovsky et al. / Waste Management 25 (2005) 733–736
metal particles on the glass surface of milled glass mirror
scrap as well as the use of PVB waste could negatively in?uence the exploitation properties and thus must be investigated.
2. Methodology
Wastes of Saratovsteklo Inc. (Russia) were used for the experiments. The glass used to produce mirrors had the following chemical composition (wt%): 73.1
SiO2; 1.1 Al2O3; 8.6 CaO; 3.6 MgO; 13.6 Na2O. The mirror coating was formed by vacuum sputtering of stainless steel. PVB waste was obtained from the poly- mer ?lm B-17 produced by Monsanto.
In Series 1 of the experiments, the ?ller 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 cm2/g (controlled by LHM-8MD Russian
equipment). The ground glass was then added to PVB waste molten at 115 C, 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 1–30 wt%. The mixtures obtained were used to pro- duce ?lms by quenching, as well as rods by extrusion.
It is well known that water vapor adsorption onto the surface of soda-lime-silicate glasses in?uences 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 modi?cation 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 PVB–alcohol 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 modi?cation, the ob- tained ?llers were investigated by TGA/DTGA (Perkin Elmer/Seiko Instruments, Japan) for the following types
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 E1875-00e1 ASTM standard using UZIS equipment
(LETI, Russia).
Taking into account the in?uence of environmental factors on the properties of materials produced, speci- mens of the two composites, prepared with the ?llers of Series 1 and 2, were exposed for three months at 25
C 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 di?erent contents of glass powder for Series 1, measured immedi- ately after their production, are presented in Table 1. The introduction of 1–10 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 in?uence 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 tested properties decreased only during the ?rst two months of exposure and then stabilized. The same e?ect 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 ?ller before the production of composites: adsorption (condensa- tion) of water vapor from the atmosphere, leaching of sodium ions, and crystallization of Na2CO3 and NaH-
Table 1
The properties of composites obtained by extrusion of samples made of separate dry milling of glass
Properties Contents of glass powder (wt%)
0 1 3 5 10 15 20 25 30
Young module (MPa) 2.3 2.5 2.7 2.9 4.3 3.8 2.7 2.5 2.3
Tensile strength (MPa) 6.8 5.2 7.4 7.9 11.2 8.4 8.5 7.0 5.4
Relative elongation under rupture (%) 318 345 288 271 237 328 295 286 142
A.V. Gorokhovsky et al. / Waste Management 25 (2005) 733–736 735
35
30
25 Relative elongation
60
50
40
1
4 5
6
C
20
15
10
under a rupture
Tensile strength
30
20
10
1
1
2
2
3
B
5 Young
A
0
modulus
0 50 100 150
Exposure, days
0
50 100 150 200 250 300 350 400 450 500
Temperature,?C
Fig. 1. In?uence 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 1), tensile strength (MPa), Young modulus (MPa).
CO3 as a result of the sodium ions interaction with dis- solved CO2. The presence of these crystals and adsorbed water onto the surface of glass ?ller decreased adhesion with PVB. At the same time, modi?cation 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- erties of the composite produced in Series 2 can be noted.
3
2.5
2
1.5
1
0.5
0
0 50 100 150
Exposure, days
Fig. 2. In?uence 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).
Fig. 3. DTGA data obtained for di?erent types of ?ller: 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.
The obtained data of DTGA (Fig. 3) indicates that the ‘‘old’’ glass ?ller, in comparison with the ‘‘fresh’’ ?l- ler obtained by dry ball milling, is characterized by the additional intensive peak at 350–420 C, related to the desorption of chemically adsorbed water (Hench, 1978; Gorokhovsky, 1988). At the same time, this peak is ab- sent for the ?ller 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 ?ller are related to the melting and thermal decomposition of PVB (Dhaliwal and Hay, 2000). Thus,
it is possible to propose that the e?ect of stabilization of the mechanical properties, obtained for the composite produced on the base of glass powder with modi?ed sur- face (Series 2), was achieved due to a decreased adsorp- tion of water vapor.
The composite rods of di?erent pro?les, produced by extrusion of the batch based on the PVB wastes and glassy ?ller (10 wt%), obtained by joint ball milling of glass mirrors scrap with PVB waste, dissolved at room temperature in iso-propanol (15% solution), were ap- 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).
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
4. Conclusions
Composite materials with attractive exploitation properties can be produced on the basis of typical wastes of ?at glass processing: poly (vinyl) butiral ribbons and
One month
after milling
‘‘Fresh’’ powder
glass mirror scrap. The contents about of 10 wt% of
glass powder results in composites with high and stable
Young modulus (MPa) 3.8 4.3
Tensile strength (MPa) 8.2 11.2
mechanical properties. The introduction of PVB alco-
hol solution resulted in the stabilization of properties
Relative elongation before
the rupture (%)
281 237
of the composites in the case of exposure to humid
atmospheres.
736 A.V. Gorokhovsky et al. / Waste Management 25 (2005) 733–736
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