CA2664990A1 - Composition and methods of producing glass and glass-ceramic materials from manganese tailings - Google Patents
Composition and methods of producing glass and glass-ceramic materials from manganese tailings Download PDFInfo
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- CA2664990A1 CA2664990A1 CA 2664990 CA2664990A CA2664990A1 CA 2664990 A1 CA2664990 A1 CA 2664990A1 CA 2664990 CA2664990 CA 2664990 CA 2664990 A CA2664990 A CA 2664990A CA 2664990 A1 CA2664990 A1 CA 2664990A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
A glass-ceramic is comprised of, between 14 and 40% by weight SiO2, between 30 and 47% by weight MnO2, between 10 and 40% by weight B2O3, between 1 and 22% by weight Al2O3, between 1 and 5% by weight Fe2O3, between 2 and 26% by weight Na2O, between 0.1 and 2.5% by weight K2O, between 0.3 and 0.5% by weight TiO2, and between 1 and 7% by weight others. The main sources of raw materials are manganese crust, nodules and stratified manganese ore tailings and silica sand, while borax, boric acid, lithium tetraborate and borosilicate waste glass are useful fluxes. The glasses are suitable for glass fiber, glass wool, various porous glass applications and precursors for preparing glass-ceramics. Glass-ceramic materials are suitable as wall and floor tiles, general construction materials, ornaments and various porous glass-ceramic applications. The glass-ceramic has been trade marked as Manceram.
Description
Composition and Methods of Producing Glass and Glass-Ceramic Materials From Manganese Tailings The present invention relates to novel glasses and glass-ceramics made from manganese nodules, crust and stratified ore tailings with added silica and fluxing agents by producing glasses that are also precursors of resultant glass-ceramics. In addition, the invention relates to novel glass-ceramics and methods of heat treating the precursor glasses to produced the glass-ceramics and relates to potential commercial applications of said resultant glasses and glass-ceramics.
Background Of The Invention Manganese crust and nodule deposits have been extensively studied as potential mineral sources, especially for the very valuable minerals cobalt and palladium, while manganese ore has been mined from stratified deposits for many years. Tailings waste resulting from processing of manganese crust and nodules ore in a commercial or dressing plant will require treatment to decrease volume and potential toxicity. The nearest potential land-based processing plants for these ore deposits mined in the South Pacific would be on small, environmentally-sensitive islands. It is extremely unlikely that the main existing method of tailings treatment (i.e.
tailings impoundment) would be an acceptable approach on these islands, where geographic space is very limited, aesthetics are crucial to commerce and the indigenous people hold nature in high regard.
Impoundment also does nothing to diminish tailings volume. Recycling and reuse would be the optimal approach based largely upon economic feasibility. Even if tailings impoundment was acceptable under intense scrutiny, this method poses serious risks from possible groundwater pollution due to leachates, and potential for catastrophic dam failure.
Vitrification has been proven to be an effective method of converting waste materials into useful products and treating; hazardous radioactive wastes, industrial wastes such as fly ash and other industrial wastes. In addition, vitrification has been shown to be a useful method for treating hazardous mineral ore tailings and thus, a possible alternative approach to tailings impoundment, which would be especially applicable to regions where land surface area is at a premium and the environmental and natural aesthetics are considered very important to the local population.
Commercial glass is primarily made of, (a) a glass former like silica, (b) alkalis like soda and potash to change the state from solid to liquid, (c) stabilizers like CaO, MgO and A1203 to reduce weathering, (d) refining agents like Na2O, K2O and CaSO4 to remove bubbles, and small quantities of other additives to give different characteristics to the glass.
Development of a glass formulation for waste materials represents a challenge with respect to optimizing; (a) waste acceptability, (b) melt processability, (c) glass product durability, and (d) overall economics. The acceptability criterion is essential for the product to function as a barrier against the release of heavy metals or other hazardous wastes into the environment.
McMillan suggested that silica is not always the major former, since boric oxide has partially or completely replaced silica oxide to produce glasses that exhibit flow characteristics, which make them suitable for special applications. Pelino et al. reported the higher the silica content in the raw materials, the higher the melting temperature. Barbieri et al.
suggested that suitable glasses can only be obtained if a satisfactory ratio between glassy network formers and modifiers exists. In addition, the authors described how transition oxides acted as nucleants in a calcium aluminosilcate glass. Common fluxes (e.g. Na2O, K2O, Li02 and B203) can reduce the melting temperature of silicate melts, where the melting point of silica is usually (>2000C), although adding large amounts of alkali fluxes can degrade chemical durability. Fortunately, this may be offset by adding modifiers such as A1203 or transition element oxides such as Fe2O3 or Mn02.
The viscosity of a glass melt, as a function of temperature, is the most important variable affecting the melting rate and pourability of the glass. The viscosity determines the rate of melting of the raw feed, the rate of gas bubble release (foaming and fining), the rate of homogenization, and thus the quality of the final glass product. Barbieri et al reported that melts containing higher alumina content (>15wt%) have displayed higher viscosity values. Volatility of the melt (foaming) relates to the rate and amount of bubble release, the degree of homogenization and thus the quality of the final glass product.
The slowest cooling rate that produces a glass is deemed the critical cooling rate. Glass stability is often characterized by the difference between the onset of the glass transition region (Tg) and the first occurrence of a crystallization peak (Tp). Lack of distinct exothermic peaks may be taken as lack of crystallization. Acosta et al. reported that power plant derived glass was considered stable due to lack of clear exothermic peaks in the DTA curve. Shelby reported that in glasses with (Tds - Tg) <50K, phase separation often occurs. Also that, slow cooling of glass melts tends to diminish the occurrence of thermal shock and weakening of the glass.
The Vickers microhardness of known oxide glasses ranges from 2 to 8 GPa, while a theoretical strength (Kc) of 32GPa is typical for silicate glasses. Due to flaws in glass surfaces, actual strengths are much lower. Alumina ions replacing modifier ions in silicate glass reduce the number of non-bridging oxygen ions, which increases the connectivity of the network and subsequently increases the elastic modulus. Since (E) is related to bond strength, it follows that glasses with high glass transformation temperatures usually have high (E) values. The optimal thermal shock resistance is found in low expansion (low a) and low modulus (low E) glasses.
Commercial glasses must be resistant to the environment in which they are used. The main factors controlling the rate and mechanism of attack on silicate glasses by aqueous solutions are;
glass composition, pH of the solution, and the temperature. Chemical resistance of waste glasses is directly related to the extent these glasses resist chemical reactions with water and associated chemicals. Waste glasses undergo a variety of complex changes in aqueous environments, which is referred to as glass corrosion or glass dissolution. As industrial materials, glasses should have acceptable durability, which is often linked to high mechanical strength.
Sheng et al reported that using minimum additives, lowering process temperature, decreasing waste volume and producing marketable products are major factors affecting overall economics of turning waste into glass.
Glass-ceramics are fine-grained polycrystalline materials formed when glasses of suitable composition are heated and undergo controlled crystallization. Not all glasses can be crystallized into acceptable glass, since some are too stable and difficult to crystallize, while others crystallize too readily and form unacceptable crystal structures. Glass-ceramics are normally only 50 to 98%
crystallized, while the composition of the crystalline phase (or phases) is normally different from the parent glass. The advantage of glass-ceramics over glasses, are their ease of fabrication and superior properties.
To achieve an optimal glass-ceramic, the crystalline process must be controlled to produce the desired microstructure, usually through a two-step (thermal molten process or TMP) heating process. This approach transforms the parent glass into a composite material in which the crystalline phase is bonded by the residual phase. The first step in the TMP approach at lower temperatures, involves the formation of heterogeneous nuclei (small crystallites of size range 10 to 100nm to promote the growth of the major crystal phase. The greater the number of nuclei formed, the finer the structure of the glass-ceramic and the more acceptable the properties of the material. Thus, the presence of an efficient nucleating agent in the correct concentration and the determination of the temperature and time of nucleation and growth, assume specific importance in glass-ceramic formation.
Background Of The Invention Manganese crust and nodule deposits have been extensively studied as potential mineral sources, especially for the very valuable minerals cobalt and palladium, while manganese ore has been mined from stratified deposits for many years. Tailings waste resulting from processing of manganese crust and nodules ore in a commercial or dressing plant will require treatment to decrease volume and potential toxicity. The nearest potential land-based processing plants for these ore deposits mined in the South Pacific would be on small, environmentally-sensitive islands. It is extremely unlikely that the main existing method of tailings treatment (i.e.
tailings impoundment) would be an acceptable approach on these islands, where geographic space is very limited, aesthetics are crucial to commerce and the indigenous people hold nature in high regard.
Impoundment also does nothing to diminish tailings volume. Recycling and reuse would be the optimal approach based largely upon economic feasibility. Even if tailings impoundment was acceptable under intense scrutiny, this method poses serious risks from possible groundwater pollution due to leachates, and potential for catastrophic dam failure.
Vitrification has been proven to be an effective method of converting waste materials into useful products and treating; hazardous radioactive wastes, industrial wastes such as fly ash and other industrial wastes. In addition, vitrification has been shown to be a useful method for treating hazardous mineral ore tailings and thus, a possible alternative approach to tailings impoundment, which would be especially applicable to regions where land surface area is at a premium and the environmental and natural aesthetics are considered very important to the local population.
Commercial glass is primarily made of, (a) a glass former like silica, (b) alkalis like soda and potash to change the state from solid to liquid, (c) stabilizers like CaO, MgO and A1203 to reduce weathering, (d) refining agents like Na2O, K2O and CaSO4 to remove bubbles, and small quantities of other additives to give different characteristics to the glass.
Development of a glass formulation for waste materials represents a challenge with respect to optimizing; (a) waste acceptability, (b) melt processability, (c) glass product durability, and (d) overall economics. The acceptability criterion is essential for the product to function as a barrier against the release of heavy metals or other hazardous wastes into the environment.
McMillan suggested that silica is not always the major former, since boric oxide has partially or completely replaced silica oxide to produce glasses that exhibit flow characteristics, which make them suitable for special applications. Pelino et al. reported the higher the silica content in the raw materials, the higher the melting temperature. Barbieri et al.
suggested that suitable glasses can only be obtained if a satisfactory ratio between glassy network formers and modifiers exists. In addition, the authors described how transition oxides acted as nucleants in a calcium aluminosilcate glass. Common fluxes (e.g. Na2O, K2O, Li02 and B203) can reduce the melting temperature of silicate melts, where the melting point of silica is usually (>2000C), although adding large amounts of alkali fluxes can degrade chemical durability. Fortunately, this may be offset by adding modifiers such as A1203 or transition element oxides such as Fe2O3 or Mn02.
The viscosity of a glass melt, as a function of temperature, is the most important variable affecting the melting rate and pourability of the glass. The viscosity determines the rate of melting of the raw feed, the rate of gas bubble release (foaming and fining), the rate of homogenization, and thus the quality of the final glass product. Barbieri et al reported that melts containing higher alumina content (>15wt%) have displayed higher viscosity values. Volatility of the melt (foaming) relates to the rate and amount of bubble release, the degree of homogenization and thus the quality of the final glass product.
The slowest cooling rate that produces a glass is deemed the critical cooling rate. Glass stability is often characterized by the difference between the onset of the glass transition region (Tg) and the first occurrence of a crystallization peak (Tp). Lack of distinct exothermic peaks may be taken as lack of crystallization. Acosta et al. reported that power plant derived glass was considered stable due to lack of clear exothermic peaks in the DTA curve. Shelby reported that in glasses with (Tds - Tg) <50K, phase separation often occurs. Also that, slow cooling of glass melts tends to diminish the occurrence of thermal shock and weakening of the glass.
The Vickers microhardness of known oxide glasses ranges from 2 to 8 GPa, while a theoretical strength (Kc) of 32GPa is typical for silicate glasses. Due to flaws in glass surfaces, actual strengths are much lower. Alumina ions replacing modifier ions in silicate glass reduce the number of non-bridging oxygen ions, which increases the connectivity of the network and subsequently increases the elastic modulus. Since (E) is related to bond strength, it follows that glasses with high glass transformation temperatures usually have high (E) values. The optimal thermal shock resistance is found in low expansion (low a) and low modulus (low E) glasses.
Commercial glasses must be resistant to the environment in which they are used. The main factors controlling the rate and mechanism of attack on silicate glasses by aqueous solutions are;
glass composition, pH of the solution, and the temperature. Chemical resistance of waste glasses is directly related to the extent these glasses resist chemical reactions with water and associated chemicals. Waste glasses undergo a variety of complex changes in aqueous environments, which is referred to as glass corrosion or glass dissolution. As industrial materials, glasses should have acceptable durability, which is often linked to high mechanical strength.
Sheng et al reported that using minimum additives, lowering process temperature, decreasing waste volume and producing marketable products are major factors affecting overall economics of turning waste into glass.
Glass-ceramics are fine-grained polycrystalline materials formed when glasses of suitable composition are heated and undergo controlled crystallization. Not all glasses can be crystallized into acceptable glass, since some are too stable and difficult to crystallize, while others crystallize too readily and form unacceptable crystal structures. Glass-ceramics are normally only 50 to 98%
crystallized, while the composition of the crystalline phase (or phases) is normally different from the parent glass. The advantage of glass-ceramics over glasses, are their ease of fabrication and superior properties.
To achieve an optimal glass-ceramic, the crystalline process must be controlled to produce the desired microstructure, usually through a two-step (thermal molten process or TMP) heating process. This approach transforms the parent glass into a composite material in which the crystalline phase is bonded by the residual phase. The first step in the TMP approach at lower temperatures, involves the formation of heterogeneous nuclei (small crystallites of size range 10 to 100nm to promote the growth of the major crystal phase. The greater the number of nuclei formed, the finer the structure of the glass-ceramic and the more acceptable the properties of the material. Thus, the presence of an efficient nucleating agent in the correct concentration and the determination of the temperature and time of nucleation and growth, assume specific importance in glass-ceramic formation.
This study considers the control of potential crystalline phases in glass-ceramics derived from manganese ore tailings. The two approaches employed were (a) adjusting the chemical composition of the raw tailings with additives and (b) controlling the crystalline phases by optimizing the heat treatment schedule. The physical and chemical properties of the resulting glass-ceramics were compared to known materials as an indication of achieving suitable conditions for glass-ceramic production.
The invention is directed to glass and glass-ceramic products made from manganese tailings, silica and fluxes; raw batch formulations for making these glass and glass-ceramic products; and methods for making these glass and ceramic products. The invention provides a low-cost method of producing glass and glass-ceramic products from raw waste materials. A wide variety of glass and glass-ceramic products can be manufactured by the invention.
The invention also addresses several current problems: energy usage by the ceramic industry needs to be reduced; new recycled-glass products are needed and a relatively economical and environmentally sensitive method of disposing of manganese ore tailings is required. The ceramic industry consumes large amounts of energy, especially during the firing process. Firing temperatures greater than 1200 C. (2200 F.) are required to sinter typical ceramic raw materials into dense products. Use of fluxes has led to reductions in firing temperatures, in the general ceramic industry, but the improvements are limited because of the types of raw materials used. Most traditional ceramic products, such as tile and brick, consist mainly of clay-based raw materials, which inherently require high firing temperatures. Other ceramic manufacturing steps, such as the drying processes, are also very energy intensive. Energy costs are a major portion of the total manufacturing costs and vitrification is also an expensive process, hence new methods to reduce the amount of energy required will be of a great benefit to the ceramic and waste recycling industries. Thus, reduction in firing temperatures and limiting the length of the manufacturing process are important advancements in waste recycling.
New products utilizing recycled waste materials are needed to further promote waste recycling. Recent research has been conducted and products have been developed using recycled tailings as a glass and ceramic raw material. Past researchers have demonstrated that it was possible to vitrify various ore tailings with or without additives. These previous works have not dealt with the management of manganese tailings as a waste product and whether they can be vitrified into new, glass and glass-ceramic materials, which may have commercial uses that offset disposal costs.
The invention is directed to glass and glass-ceramic products made from manganese tailings, silica and fluxes; raw batch formulations for making these glass and glass-ceramic products; and methods for making these glass and ceramic products. The invention provides a low-cost method of producing glass and glass-ceramic products from raw waste materials. A wide variety of glass and glass-ceramic products can be manufactured by the invention.
The invention also addresses several current problems: energy usage by the ceramic industry needs to be reduced; new recycled-glass products are needed and a relatively economical and environmentally sensitive method of disposing of manganese ore tailings is required. The ceramic industry consumes large amounts of energy, especially during the firing process. Firing temperatures greater than 1200 C. (2200 F.) are required to sinter typical ceramic raw materials into dense products. Use of fluxes has led to reductions in firing temperatures, in the general ceramic industry, but the improvements are limited because of the types of raw materials used. Most traditional ceramic products, such as tile and brick, consist mainly of clay-based raw materials, which inherently require high firing temperatures. Other ceramic manufacturing steps, such as the drying processes, are also very energy intensive. Energy costs are a major portion of the total manufacturing costs and vitrification is also an expensive process, hence new methods to reduce the amount of energy required will be of a great benefit to the ceramic and waste recycling industries. Thus, reduction in firing temperatures and limiting the length of the manufacturing process are important advancements in waste recycling.
New products utilizing recycled waste materials are needed to further promote waste recycling. Recent research has been conducted and products have been developed using recycled tailings as a glass and ceramic raw material. Past researchers have demonstrated that it was possible to vitrify various ore tailings with or without additives. These previous works have not dealt with the management of manganese tailings as a waste product and whether they can be vitrified into new, glass and glass-ceramic materials, which may have commercial uses that offset disposal costs.
Description of Prior Art The use of vitrification to convert various types of waste materials into new materials are outlined in the following Canadian, US and Foreign patents and references.
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Abdrakhimov, V.Z. (1992). Pore structure of ceramic tiles made from beneficiation tailings and wollastonite, Kompleksn. Ispol'z. Miner Syr'ra, (12), pp.70-72.
Beretka, J., Brown, T. (1974). The utilization of mangniferous industrial wastes and by-products in the manufacture of coloured bricks, J. of the Australian Ceramic Society, vol.10, no.1, pp.4-7.
Carter, S., Ponton, C.B., Rawlings, R.D., Rogers, P.S. (1988). Microstructure, chemistry, elastic properties and internal friction of Silceram glass-ceramics, J.Mats. Sci., vol.23, pp.2622-2630.
Coa,C., Li,Z., Li, M. (1998). Glass mosaic and tile made from perliye tails, Faming Zhuanli Shenquing Gongkai Shuomingshu CN1182058A, 20 May, patent.
Hirt, W.C., Foot, D.G., Shirts, M.B. (1988). Beneficiation of cobalt-rich manganese crust, Marine Mining, vol.7, n3, pp.165-172.
Jiang, W. (1998). Preparation of glass-ceramic decorative slabs from asbestos tailings, Kuangchan Zonghe Liyong, (4), pp.32-34.
Karamanov, A. Pelino,M., Tagliery, G., Cantalini, C. (1998b). Sintered building glass-ceramics based on jarosite, Proc. Of XVIII ICG, Am. Cer. Soc.
Karamanov, A., Pelino, M.(1999b). Evaluation of the degree of crystallization in glass-ceramics by density measurements, J.Eur. Cer. Soc., vol.19 (5), pp.649-654.
Karamanov, A., Pelino, M. (2001). Crystallization phenomena in iron-rich glasses, J.Non-Crystalline Solids, 81(1-3), pp.139-151.
Khater,G.A.(2002). The use of Saudi slag for the production of glass-ceramic materials, Ceramics Intl., vol.28, pp.59-67.
Kim, H.S., Rawlings, R.D., Rogers, P.S. (1989). Sintering and crystallization phenomena in Silceram glass, J. of Mat. Sci., vol 24, pp.1025-1037.
Lay, G.F.T., Wiltshire, J., Rockwell, M.C., Enomoto, I. (1996). Use of marine tailings in the formulation of specialty glasses, ceramic-glasses and glazes, Oceans Conference Record (IEEE), Proceedings of the 1996 MTS/IEEE Oceans Conference, Part 3 (of 3), Sept. 23-26, Fort Lauderdale, FL, USA, Sponsered by : IEEE, IEEE Piscataway NJ, USA, pp. 1366-1371.
Liao, W. An, F. Zhu, W., Gan, J., Li,H., Zong,J., Luo,X., Liu,J., He,J.
(1996). Manufacture of glass-ceramics from tungsten tailings, Faming Zhuanli Shenquing Gongkai Shuomingshu, patent, 6p.
Liao, Q., Lu, Z., Tan, K. (1997). Study on manufacturing of glass-ceramic decorative slabs from asbestos tailings, Kuangchan Zonghe Liyong, (4), pp.32-34.
Liu, S. Cheng, J. Zhu, Y. (1991). Manufacture of marble from microcrystal glass from phosphorus ore tailings, Faming Zhuanli Shenquing Gonkai Shuomingshu, patent, 5p.
Liu, X., Li,Z., Li,H, Ji,Z., Xiahou,Z. (1996). Manufacture of glass-ceramic products using gold tailings, Faming Zhuanli Shenqing Gongkai Shuomingshu CN 1117029 A, 21 Feb., 8 pp.
Liu, J., Xing, J., Tong, Y., Song, S. (1998). Nucleating agents in glass-ceramics manufacture from metallic tailings, Dongbei Dazue Xuebao, Ziran Kexueban, 19(5), pp.452-455.
Liu, G. Ma, T., Jin, H., Cai, Y., Wang, J. (1999). Study on application of iron ore and perlite tailings in inner-wall tiles, Taoci Xianyang, China, (6), pp.28-3 1.
Liu, J. Song, S. (2000). Effects of nucleation agents TiO2 and Cr2 03 on the crystallization behavior of building glass-ceramics of metallic tailings, J. of Northeastern U., vol.21, no.3, June, pp. 294-297.
Marabini, A.M., Plescia, P., Maccari, D., Burragato, F., Pelino, M. (1998).
New materials from industrial mining wastes: glass-ceramic and glass and rock-wool fibre, Intl.
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Mingulova, F.A., Yunusov, M. (1997). Glass-ceramic materials based on wastes of lead-ore beneficiation, Uzb. Khim. Zh., (6), pp.59-62.
Montanaro, L., Bianchini, N., Rincon, J.Ma., Romero, M.(2001). Sintering behavior of pressed red mud wastes from zinc hydrometallurgy, Ceramics Intl., vol. 27, pp.29-37.
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None of this prior art has addressed the problem of minimizing the volume or stabilizing manganese tailings or producing new marketable products by heat treating these tailings.
Summary Of The Invention It is an object of the invention to provide new glasses and glass-ceramic materials, which exhibit excellent strength, fracture toughness, hardness, relatively low TEC
and acceptable bending strength and chemical resistance compared to known commercial materials. The invention provides a method to transform large quantities of tailings into useful glass and ceramic products by a relatively low-cost, environmentally friendly production process. The major steps of the method involve combining waste materials with a flux; melting the mixture to form a liquid melt; cooling to room temperature or below the melting temperature; then heating to a nucleation temperature and holding for a prescribed time; then heating to a crystallization temperature and holding for a prescribed time, and then cooling to room temperature to form a ceramic product. The method improves strength compared to glasses formed from the same raw materials. In addition, the invention provides a method to sinter silicate parent glasses derived from Mn tailings and flux mixtures to produce useful glass-ceramic products.
Brief Description Of The Drawings Not available.
Detailed Description Of The Invention The major steps of the invention involve combining waste materials, such as manganese tailings, and sometimes silica, with various fluxes, melting the resulting mixtures to form a liquid melt, cooling the melt to room temperature or quenching to form glasses and using the resultant glasses as precursors to produce glass-ceramic materials employing several heat treatment methods.
The invention represents the first attempt to reduce the volume of manganese ore tailings and subsequently produce commercially useful glasses and glass-ceramic products from these waste materials in a relatively economical and environmentally sensitive manner.
Manganese tailings from crust, nodule and stratified ores have been successfully recycled into glass and glass-ceramic materials using vitrification technology. Up to 80% incorporation of the nodules tailings, 70% crust tailings and 60% of stratified ore tailings has been achieved to produce glass and glass-ceramics materials, with the optimal working content being considered closer to 50%. Volume reductions of greater than 27% for slimes tailings, over 38% for nodules tailings and 25% for stratified tailings were determined for a one hour melting duration. It was established by XRD and scanning electron microscope investigations that the parent glasses according to the invention are free from crystals or have minimal crystallites. Different glass phases can be present according to a variance in the quantity of components or application of the heat treatments. These regions or phases are recognizable using the electron microscope as small droplets or phase-in-phase regions.
Hardness, strength and chemical durability are the main characteristics that determine the acceptability and usefulness of glasses and glass-ceramics from waste materials. The high manganese content glass-ceramics exhibit values of density, Vickers hardness (H,,), fracture toughness (Kr) and elastic modulus (E) higher than those of several commercial glasses and are similar to ceramics produced in other recycling studies. The chemical resistances of the glass and glass-ceramic products were also within the range of known industrial products and the established literature. The chemical crystalline compound produced from the crust tailings was identified as a manganese iron silicate, while the nodule tailings apparently produced a two-phase crystalline structure containing manganese oxides braunite and hausmannite. The stratified ore based glass was identified as the manganese oxide pyrolusite. All crystallized tailings mixtures appeared to contain a residual amorphase phase, possible derived from the boron content. The moderate to high iron content of these tailings created bloating effects and presented numerous problems for processing on a small scale, but on a larger scale these difficulties may be overcome such that the bloating effect may be useful in producing marketable porous products on a competitive basis.
The glasses and glass-ceramics produced were designed to be the least-cost materials, such that additional processing steps and lowering the tailings content of the product mix would undoubtedly produce higher quality products, although, at a higher cost.
Comparison of study materials characteristics with known similar materials indicates that these manganese silicates could be employed competitively to produce numerous marketable products. Using materials and production costs of $446/tonne as the break-even point, several potential products would return income to a vitrification operation. In particular geographic locales such as the Hawaiian or South Seas islands where the impoundment method is illegal or unacceptable, the vitrification method appears a competitive alternative, particularly if energy costs can be minimized. Other applications of this approach would be analyzed on a site by site basis.
Specifically, the present invention provides parent glasses and glass-ceramics consisting of essentially the same raw components, which can be processed at relatively low temperatures by several methods. In order to replace known materials, such as construction materials, new materials should display improved characteristics such as increased hardness, strength and toughness. Glasses may also be required for specific applications requiring particular porosities. According to the investigations, it is absolutely necessary to add a source of flux (i.e.
borax, boric acid, lithium tetraborate, borosilicate waste glass) to the raw sample chemical composition, whereby the flux and glass forming agents in the various mixtures act to promote glass and glass-ceramic development. In addition, numerous types of glass and glass-ceramics can be produced by heat treating the same chemical compositions, with additions of various fluxes and SiO2 in the form of quartz sand grains.
The chemical composition of raw tailings and fluxes are displayed in Table A.
The waste glass employed was discarded laboratory glass, which is classed as a borosilicate glass.
Table A. Chemical composition of tailings borax boric acid lithium tetraborate and waste glass (wt.%).
Component Nodules Crust Borax Boric acid Lithium tetraborate Waste glass SiO2 15.54 28.1 80.6 A1203 1.36 20.3 2.2 Fe2O3 1.36 5.6 0.002 0.04 Mn02 44.45 36.0 TiO2 0.39 0.48 B203 36.47 36.47 62.10 12.6 Na2O 16.47 16.47 4.2 K2O 1.30 0.34 CaO 1.14 0.04 0.1 MgO 0.05 Cr2O3 Li2O 5.36 H2O est.15% 8.36 46.57 46.57 32.54 C 0.16 ----LOI 15-27% ----Others 5.0 0.40 0.49 0.50 0.1 The manganese tailings may be the result of beneficiating manganese nodules and manganese crust ores or manganese ore mined from an underground stratigraphic sequence.
Tailings are a waste material, hence there is an expected variance in grain size and percentage composition of the raw materials employed in the process of preparing glasses and glass-ceramics.
The parent glass according to the invention is preferably produced by melting suitable starting materials, such as oxides and carbonates at a temperature range from 1100 to 1180C, over a period of 30 minutes to 2 hours, preferably for one hour, with the formation of a homogeneous melt.
The melt may be quenched in water (i.e. fritted), and the obtained glass granulate ground up after drying, or the melt is permitted to cool slowly in air, or the melt is subjected to further heat treatment using a 2-step heat treatment method.
The glass-ceramic according to the invention is produced in particular by subjecting the obtained granulate of the parent glass according to the invention to thermal treatment at a temperature in the range from 600 to 900C for a period of 30 minutes to 4 hours, preferably 30 minutes to 2 hours. Prior to the heat treatment, the parent glass is preferably ground to a powder having a grain size less than 90um when sieved.
The raw materials plus flux (i.e. borax, boric acid, lithium tetraborate, borosilicate waste glass) are heated (ex. Petrurgic method) at a temperatures up to 11 80C and held at the mixture melting temperature for 30 min to 2 hours. The melt is then permitted to cool slowly at a temperature between 1 and 3C per min to room temperature to form a glass or glass-ceramic, dependent upon the materials present.
The raw materials plus flux (i.e. borax, boric acid, lithium tetraborate, and borosilicate waste glass) are subjected to a 2-step heat treatment approach, whereby the raw materials and flux mixture is heated at temperatures up to 1180C and held at the melting temperature for 30 min to 2 hours, then permitted to cool to between 500C and 600C and held for 30 to 60 min to permit nucleation of the glass melt, then the temperature is raised at 2 to l OC per minute to 800C
to 1000C and held for 30 min to 3 hours to permit crystallization of the melt to occur. Following this, the crystallized melt is permitted to cool to room temperature at 2 to l OC per minute.
In addition, the parent glass is first heated to a temperature between 850C
and 1000C at a rate of between 2 and l OC per min, then sintered by holding for 30 min to 3 hours at a temperature between 850C and 1000C to achieve maximum density of at least 2.3g/cm3.
A total of 94 different parent glasses were prepared from the same raw materials and four different fluxes, while a total of 282 different glass-ceramics were prepared from the 94 parent glass materials using three different heat treatment processes (petrurgic, 2-step and sintering) for each parent glass. The results are provided in Tables I through Table VIII.
Furthermore, the range of physical characteristics of the glasses and glass-ceramics, which were determined using pieces from the sample glasses and glass-ceramics and accepted methods, along with the chemical resistance displayed by glass-ceramics and glasses, compared satisfactorily with known commercial products.
Table B also shows that as a rule, a glass-ceramic displays a higher expansion coefficient, and greater hardness, strength and toughness values than a glass of corresponding chemical composition. In addition, the hardness and strength values of sintered glass-ceramics display greater hardness and strength values than the corresponding glasses and glass-ceramics of similar composition that have been subjected to the 2-step heat treatment process. It has been concluded that the increased strength and hardness values of the sintered samples is due to the variance in the heat treatment process.
The invention can be explained in detail below on the basis of Examples. The Examples illustrate how glass and glass-ceramics with different properties can be obtained by altering the type and amount of raw materials, flux and silica and changing the heat treatment methods employed.
The data obtained show that the glasses and glass-ceramics produced according to the invention exhibit very good strength, fracture toughness and hardness, acceptable bending strength, moderate Young's modulus and good chemical durability, all of which properties suggest their use as ceramic wall and floor tiles. Several glasses also exhibit various porosities, which would make them useful for such things as kiln furniture, honeycomb substrates for catalysts and heat exchangers.
EXAMPLES
Examples 1 to 94 Table I -A total of six different manganese crust tailings-based glasses, according to the invention, with the weight percentage compositions of raw materials, silica and flux given in Table I were prepared using the method of melting the raw materials with borax flux at temperatures up to 1180C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Borax Silica Glass-ceramics were prepared from parent glass materials as given in examples 1 to 6 (Table 1).
The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 18 different glass-ceramics.
Table II -A total of nine different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table II were prepared using the method of melting the raw materials with boric acid flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, hold the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Boric acid Silica Glass-ceramics were prepared from parent glass materials as given in examples 7 to 15. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 27 different glass-ceramics.
Table III -A total of thirteen different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table III were prepared using the method of melting the raw materials with lithium tetraborate flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Lithium tetraborate Silica Glass-ceramics were prepared from parent glass materials as given in examples 16 to 28. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics.
Table IV -A total of eight different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table IV were prepared using the method of melting the raw materials with borosilicate waste glass flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Borosilicate waste Silica glass Glass-ceramics were prepared from parent glass materials as given in examples 29 to 36. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 24 different glass-ceramics. Details are provided in Table C, regarding the tested properties of these glass-ceramics.
Table V -A total of sixteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table V were prepared using the method of melting the raw materials with borax flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Borax Silica Glass-ceramics were prepared from parent glass materials as given in examples 37 to 52. The heat treatment approach was varied (i.e. petruric, 2-step and sintering) for each parent glass, thus giving a total of 48 different glass-ceramics.
Table VI -A total of thirteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VI were prepared using the method of melting the raw materials with boric acid flux at temperatures up to 11 50C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Boric acid Silica Glass-ceramics were prepared from parent glass materials as given in examples 53 to 65. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics..
Table VII -A total of sixteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VII were prepared using the method of melting the raw materials with lithium tetraborate flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Lithium tetraborate Silica Glass-ceramics were prepared from parent glass materials as given in examples 66 to 81. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 48 different glass-ceramics.
Table VIII -A total of thirteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VIII were prepared using the method of melting the raw materials with borosilicate waste glass flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Borosilicate waste Silica glass Glass-ceramics were prepared from parent glass materials as given in examples 82 to 94. The heat treatment approach was varied (i. e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics.
A notable use of the invention is to make glass wool and glass-ceramic tiles for use in construction applications.
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None of this prior art has addressed the problem of minimizing the volume or stabilizing manganese tailings or producing new marketable products by heat treating these tailings.
Summary Of The Invention It is an object of the invention to provide new glasses and glass-ceramic materials, which exhibit excellent strength, fracture toughness, hardness, relatively low TEC
and acceptable bending strength and chemical resistance compared to known commercial materials. The invention provides a method to transform large quantities of tailings into useful glass and ceramic products by a relatively low-cost, environmentally friendly production process. The major steps of the method involve combining waste materials with a flux; melting the mixture to form a liquid melt; cooling to room temperature or below the melting temperature; then heating to a nucleation temperature and holding for a prescribed time; then heating to a crystallization temperature and holding for a prescribed time, and then cooling to room temperature to form a ceramic product. The method improves strength compared to glasses formed from the same raw materials. In addition, the invention provides a method to sinter silicate parent glasses derived from Mn tailings and flux mixtures to produce useful glass-ceramic products.
Brief Description Of The Drawings Not available.
Detailed Description Of The Invention The major steps of the invention involve combining waste materials, such as manganese tailings, and sometimes silica, with various fluxes, melting the resulting mixtures to form a liquid melt, cooling the melt to room temperature or quenching to form glasses and using the resultant glasses as precursors to produce glass-ceramic materials employing several heat treatment methods.
The invention represents the first attempt to reduce the volume of manganese ore tailings and subsequently produce commercially useful glasses and glass-ceramic products from these waste materials in a relatively economical and environmentally sensitive manner.
Manganese tailings from crust, nodule and stratified ores have been successfully recycled into glass and glass-ceramic materials using vitrification technology. Up to 80% incorporation of the nodules tailings, 70% crust tailings and 60% of stratified ore tailings has been achieved to produce glass and glass-ceramics materials, with the optimal working content being considered closer to 50%. Volume reductions of greater than 27% for slimes tailings, over 38% for nodules tailings and 25% for stratified tailings were determined for a one hour melting duration. It was established by XRD and scanning electron microscope investigations that the parent glasses according to the invention are free from crystals or have minimal crystallites. Different glass phases can be present according to a variance in the quantity of components or application of the heat treatments. These regions or phases are recognizable using the electron microscope as small droplets or phase-in-phase regions.
Hardness, strength and chemical durability are the main characteristics that determine the acceptability and usefulness of glasses and glass-ceramics from waste materials. The high manganese content glass-ceramics exhibit values of density, Vickers hardness (H,,), fracture toughness (Kr) and elastic modulus (E) higher than those of several commercial glasses and are similar to ceramics produced in other recycling studies. The chemical resistances of the glass and glass-ceramic products were also within the range of known industrial products and the established literature. The chemical crystalline compound produced from the crust tailings was identified as a manganese iron silicate, while the nodule tailings apparently produced a two-phase crystalline structure containing manganese oxides braunite and hausmannite. The stratified ore based glass was identified as the manganese oxide pyrolusite. All crystallized tailings mixtures appeared to contain a residual amorphase phase, possible derived from the boron content. The moderate to high iron content of these tailings created bloating effects and presented numerous problems for processing on a small scale, but on a larger scale these difficulties may be overcome such that the bloating effect may be useful in producing marketable porous products on a competitive basis.
The glasses and glass-ceramics produced were designed to be the least-cost materials, such that additional processing steps and lowering the tailings content of the product mix would undoubtedly produce higher quality products, although, at a higher cost.
Comparison of study materials characteristics with known similar materials indicates that these manganese silicates could be employed competitively to produce numerous marketable products. Using materials and production costs of $446/tonne as the break-even point, several potential products would return income to a vitrification operation. In particular geographic locales such as the Hawaiian or South Seas islands where the impoundment method is illegal or unacceptable, the vitrification method appears a competitive alternative, particularly if energy costs can be minimized. Other applications of this approach would be analyzed on a site by site basis.
Specifically, the present invention provides parent glasses and glass-ceramics consisting of essentially the same raw components, which can be processed at relatively low temperatures by several methods. In order to replace known materials, such as construction materials, new materials should display improved characteristics such as increased hardness, strength and toughness. Glasses may also be required for specific applications requiring particular porosities. According to the investigations, it is absolutely necessary to add a source of flux (i.e.
borax, boric acid, lithium tetraborate, borosilicate waste glass) to the raw sample chemical composition, whereby the flux and glass forming agents in the various mixtures act to promote glass and glass-ceramic development. In addition, numerous types of glass and glass-ceramics can be produced by heat treating the same chemical compositions, with additions of various fluxes and SiO2 in the form of quartz sand grains.
The chemical composition of raw tailings and fluxes are displayed in Table A.
The waste glass employed was discarded laboratory glass, which is classed as a borosilicate glass.
Table A. Chemical composition of tailings borax boric acid lithium tetraborate and waste glass (wt.%).
Component Nodules Crust Borax Boric acid Lithium tetraborate Waste glass SiO2 15.54 28.1 80.6 A1203 1.36 20.3 2.2 Fe2O3 1.36 5.6 0.002 0.04 Mn02 44.45 36.0 TiO2 0.39 0.48 B203 36.47 36.47 62.10 12.6 Na2O 16.47 16.47 4.2 K2O 1.30 0.34 CaO 1.14 0.04 0.1 MgO 0.05 Cr2O3 Li2O 5.36 H2O est.15% 8.36 46.57 46.57 32.54 C 0.16 ----LOI 15-27% ----Others 5.0 0.40 0.49 0.50 0.1 The manganese tailings may be the result of beneficiating manganese nodules and manganese crust ores or manganese ore mined from an underground stratigraphic sequence.
Tailings are a waste material, hence there is an expected variance in grain size and percentage composition of the raw materials employed in the process of preparing glasses and glass-ceramics.
The parent glass according to the invention is preferably produced by melting suitable starting materials, such as oxides and carbonates at a temperature range from 1100 to 1180C, over a period of 30 minutes to 2 hours, preferably for one hour, with the formation of a homogeneous melt.
The melt may be quenched in water (i.e. fritted), and the obtained glass granulate ground up after drying, or the melt is permitted to cool slowly in air, or the melt is subjected to further heat treatment using a 2-step heat treatment method.
The glass-ceramic according to the invention is produced in particular by subjecting the obtained granulate of the parent glass according to the invention to thermal treatment at a temperature in the range from 600 to 900C for a period of 30 minutes to 4 hours, preferably 30 minutes to 2 hours. Prior to the heat treatment, the parent glass is preferably ground to a powder having a grain size less than 90um when sieved.
The raw materials plus flux (i.e. borax, boric acid, lithium tetraborate, borosilicate waste glass) are heated (ex. Petrurgic method) at a temperatures up to 11 80C and held at the mixture melting temperature for 30 min to 2 hours. The melt is then permitted to cool slowly at a temperature between 1 and 3C per min to room temperature to form a glass or glass-ceramic, dependent upon the materials present.
The raw materials plus flux (i.e. borax, boric acid, lithium tetraborate, and borosilicate waste glass) are subjected to a 2-step heat treatment approach, whereby the raw materials and flux mixture is heated at temperatures up to 1180C and held at the melting temperature for 30 min to 2 hours, then permitted to cool to between 500C and 600C and held for 30 to 60 min to permit nucleation of the glass melt, then the temperature is raised at 2 to l OC per minute to 800C
to 1000C and held for 30 min to 3 hours to permit crystallization of the melt to occur. Following this, the crystallized melt is permitted to cool to room temperature at 2 to l OC per minute.
In addition, the parent glass is first heated to a temperature between 850C
and 1000C at a rate of between 2 and l OC per min, then sintered by holding for 30 min to 3 hours at a temperature between 850C and 1000C to achieve maximum density of at least 2.3g/cm3.
A total of 94 different parent glasses were prepared from the same raw materials and four different fluxes, while a total of 282 different glass-ceramics were prepared from the 94 parent glass materials using three different heat treatment processes (petrurgic, 2-step and sintering) for each parent glass. The results are provided in Tables I through Table VIII.
Furthermore, the range of physical characteristics of the glasses and glass-ceramics, which were determined using pieces from the sample glasses and glass-ceramics and accepted methods, along with the chemical resistance displayed by glass-ceramics and glasses, compared satisfactorily with known commercial products.
Table B also shows that as a rule, a glass-ceramic displays a higher expansion coefficient, and greater hardness, strength and toughness values than a glass of corresponding chemical composition. In addition, the hardness and strength values of sintered glass-ceramics display greater hardness and strength values than the corresponding glasses and glass-ceramics of similar composition that have been subjected to the 2-step heat treatment process. It has been concluded that the increased strength and hardness values of the sintered samples is due to the variance in the heat treatment process.
The invention can be explained in detail below on the basis of Examples. The Examples illustrate how glass and glass-ceramics with different properties can be obtained by altering the type and amount of raw materials, flux and silica and changing the heat treatment methods employed.
The data obtained show that the glasses and glass-ceramics produced according to the invention exhibit very good strength, fracture toughness and hardness, acceptable bending strength, moderate Young's modulus and good chemical durability, all of which properties suggest their use as ceramic wall and floor tiles. Several glasses also exhibit various porosities, which would make them useful for such things as kiln furniture, honeycomb substrates for catalysts and heat exchangers.
EXAMPLES
Examples 1 to 94 Table I -A total of six different manganese crust tailings-based glasses, according to the invention, with the weight percentage compositions of raw materials, silica and flux given in Table I were prepared using the method of melting the raw materials with borax flux at temperatures up to 1180C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Borax Silica Glass-ceramics were prepared from parent glass materials as given in examples 1 to 6 (Table 1).
The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 18 different glass-ceramics.
Table II -A total of nine different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table II were prepared using the method of melting the raw materials with boric acid flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, hold the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Boric acid Silica Glass-ceramics were prepared from parent glass materials as given in examples 7 to 15. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 27 different glass-ceramics.
Table III -A total of thirteen different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table III were prepared using the method of melting the raw materials with lithium tetraborate flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Lithium tetraborate Silica Glass-ceramics were prepared from parent glass materials as given in examples 16 to 28. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics.
Table IV -A total of eight different manganese crust tailings-based glasses according to the invention with the weight percentage compositions given in Table IV were prepared using the method of melting the raw materials with borosilicate waste glass flux at temperatures up to 11 80C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Crust tailings Borosilicate waste Silica glass Glass-ceramics were prepared from parent glass materials as given in examples 29 to 36. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 24 different glass-ceramics. Details are provided in Table C, regarding the tested properties of these glass-ceramics.
Table V -A total of sixteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table V were prepared using the method of melting the raw materials with borax flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Borax Silica Glass-ceramics were prepared from parent glass materials as given in examples 37 to 52. The heat treatment approach was varied (i.e. petruric, 2-step and sintering) for each parent glass, thus giving a total of 48 different glass-ceramics.
Table VI -A total of thirteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VI were prepared using the method of melting the raw materials with boric acid flux at temperatures up to 11 50C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Boric acid Silica Glass-ceramics were prepared from parent glass materials as given in examples 53 to 65. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics..
Table VII -A total of sixteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VII were prepared using the method of melting the raw materials with lithium tetraborate flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Lithium tetraborate Silica Glass-ceramics were prepared from parent glass materials as given in examples 66 to 81. The heat treatment approach was varied (i.e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 48 different glass-ceramics.
Table VIII -A total of thirteen different manganese nodules tailings-based glasses according to the invention with the weight percentage compositions given in Table VIII were prepared using the method of melting the raw materials with borosilicate waste glass flux at temperatures up to 1150C, cooling the melt at 2 to 15C per minute to 400 to 600C to anneal the glass, holding the glass at the annealing temperature for 30 to 120 minutes, then permitting the glass to cool at 2 to 15C per min to room temperature.
Glass Nodules tailings Borosilicate waste Silica glass Glass-ceramics were prepared from parent glass materials as given in examples 82 to 94. The heat treatment approach was varied (i. e. petrurgic, 2-step and sintering) for each parent glass, thus giving a total of 39 different glass-ceramics.
A notable use of the invention is to make glass wool and glass-ceramic tiles for use in construction applications.
Claims (10)
1) Glass materials, which comprise the following components; the chemical compositions by weight of raw tailings, silica and fluxes as displayed in Table A.
2) Glass materials according to claim 1, wherein said materials are combined in various percentages by weight as given in Tables I to VIII, providing various compositions of said raw materials, silica and fluxes.
3) Glass materials according to claims 1 and 2, wherein said raw tailings are mixed with said silica and either of several said flux materials, being borax, boric acid, lithium tetraborate or borosilicate waste glass to form said compositions and subjected to one of several possible heat treatment methods resulting in at least 94 new glasses.
4) Glass materials according to claims 1, 2 and 3 wherein said glasses are formed by heating said mixtures, as described in said Tables I to VIII, at a rate less than 15C/min, to form melts at temperatures less than 1180C, and cooling said melts at a rate less than 15C/min to an annealing temperature of approximately 600C, or quenching said melts to form frits.
5) Glass materials according to claims 1, 2, 3 and 4, wherein said glass materials are useful as general construction materials, glass fibers, glass wool, ornaments, water treatment and purification applications, porous glass applications, pre-cursors to glass-ceramics and as insect and rodent control and eradication treatments in powder form.
6) Glass-ceramic materials according to Claims 1, 2, 3 and 4, wherein said glasses acting as precursors or parent glasses to said glass-ceramic materials are subjected to one of several possible heat treatment methods resulting in at least 282 new glass-ceramics.
7) A method of preparing said glass-ceramic materials according to claim 6, wherein said percentage compositions by weight of raw tailings, silica, and fluxes, according to said Tables I
to VIII, are heated to a melting temperature up to 1180C, held for 1 to 2 hours at said melting point, then permitted to cool at a rate of up to 15C/min to said room temperature.
to VIII, are heated to a melting temperature up to 1180C, held for 1 to 2 hours at said melting point, then permitted to cool at a rate of up to 15C/min to said room temperature.
8) A method of preparing said glass-ceramic materials according to claim 6, wherein said percentage compositions by weight of raw tailings, silica, and fluxes, according to said Tables I
to VIII, are heated to a melting temperature up to 1180C, held for 1 to 2 hours at said melting point, permitted to cool at a rate of up to 15C/min to 400C to 600C, nucleated at 400C to 600C
for 30 min to 60 min, then heated at a rate up to 15C/min to a temperature from 800C to 1000C
and held at that crystallization temperature for 1 to 4 hours, then permitted to cool to said room temperature at a rate up to 15C/min.
to VIII, are heated to a melting temperature up to 1180C, held for 1 to 2 hours at said melting point, permitted to cool at a rate of up to 15C/min to 400C to 600C, nucleated at 400C to 600C
for 30 min to 60 min, then heated at a rate up to 15C/min to a temperature from 800C to 1000C
and held at that crystallization temperature for 1 to 4 hours, then permitted to cool to said room temperature at a rate up to 15C/min.
9) A method of preparing glass-ceramic materials according to claim 6, wherein said parent glass materials, in the form of frits, are sintered at a temperature of less than 1100C, held for 1 to 2 hours at the crystallization temperature, then permitted to cool at less than 35C/min to said room temperature.
10) Glass-ceramic materials according to claims 6, 7, 8 and 9, wherein said glass-ceramic materials are useful as general construction materials, floor and wall tiles, ornaments, and porous glass applications.
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