CN110937816A - Purple microcrystalline glass and preparation method thereof - Google Patents
Purple microcrystalline glass and preparation method thereof Download PDFInfo
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- CN110937816A CN110937816A CN201911281548.7A CN201911281548A CN110937816A CN 110937816 A CN110937816 A CN 110937816A CN 201911281548 A CN201911281548 A CN 201911281548A CN 110937816 A CN110937816 A CN 110937816A
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
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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
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Abstract
The invention belongs to the field of glass, and discloses purple glass ceramics and a preparation method thereof. The purple microcrystalline glass comprises a colorant and basic microcrystalline glass, wherein the colorant is a purple colorant, and the basic microcrystalline glass comprises silicon dioxide, strontium oxide, cordierite, spodumene, bismuth oxide, aluminum oxide, calcium oxide, fluorine, lithium oxide, sodium oxide, potassium oxide and zinc oxide. The purple microcrystalline glass has stable coloring performance, fine color, purple and light blue color under different light rays, no pores on the surface, high impact toughness, high bending strength and high compression strength, and is strong in processing and forming performance.
Description
Technical Field
The invention relates to the field of glass, in particular to purple glass ceramics and a preparation method thereof.
Background
The microcrystal glass is also called glass ceramic, is a new material developed by integrating glass and ceramic technology, and is actually microcrystal ceramic, namely a certain amount of crystal nucleus agent is added into a glass formula with certain composition, and melting is carried out under the melting condition, so that basic glass is formed, and the glass is almost completely amorphous due to extremely high cooling speed. The microcrystalline glass has excellent thermal stability, chemical stability, mechanical property and the like, and is widely applied to the fields of electronics, chemical industry, military, aerospace, nuclear industry, building and the like.
However, the microcrystalline glass with excellent quality has strict requirements on the formulation components and the addition amount, and no obvious rule can be followed. Such as Song snow, Wenzun, etc. studied ZrO2The influence on the crystallization and fracture toughness of the tailing microcrystalline glass is found, and the density, the acid resistance, the elastic modulus and the shear modulus of the microcrystalline glass are all dependent on ZrO2The increase in the content shows a tendency to increase first and then decrease, and the vickers hardness and the crack growth length decrease first and then increase. Also like zang and Li YuTing, etc. research on SrO content to Li2O-ZnO-SrO-SiO2Influence of System glass Structure and Properties, it was found that SiO was substituted with SrO2The transition temperature and the softening temperature are increased and then decreased, the weight loss rate of the glass is decreased and then increased, and when the mass fraction of SrO reaches 22.5 percent, the minimum surface weight loss rate is 0.98mg/cm2The chemical properties are most stable. CaO/SiO was studied by Wang Yawen, Gui Yongling, etc2Mass ratio CaO-MgO-SiO2-Al2O3The influence of the crystallization behavior of the microcrystalline glass was found to be CaO/SiO2When the mass ratio of (A) to (B) is 0.30, the main crystal phase is diopside, the crystal is granular, more glass phase residues are left, and CaO/SiO2When the mass ratio of (A) to (B) is 0.44, the main crystal phase is diopside, the particles are uniform and compact, only a small amount of glass phase is dispersed in the crystal phase, and CaO/SiO2When the mass ratio of the CaO/SiO to the anorthite is 0.63, the content of the anorthite is obviously increased, crystals are in a snowflake shape, particles are large, glass phases are increased, and the DSC curve, the XRD pattern and the microstructure of the glass are comprehensively considered to obtain a conclusion that the CaO/SiO is2The mass ratio of (A) to (B) is most reasonable at 0.44. In addition, the surface layer and the inner layer of the microcrystalline glass produced by the traditional method often have a large number of process air holes, and the properties such as breaking strength, water resistance and the like are not strong, and the coloring performance is unstable, so that the popularization and the application of the microcrystalline glass are limited.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide the purple glass ceramics and the preparation method thereof, and the purple glass ceramics has stable coloring performance and fine color and can not change color in the secondary color development process.
In order to achieve the purpose of the invention, the purple microcrystalline glass comprises a colorant and a base microcrystalline glass, wherein the colorant is a purple colorant, and the base microcrystalline glass comprises silicon dioxide, strontium oxide, cordierite, spodumene, bismuth oxide, aluminum oxide, calcium oxide, fluorine, lithium oxide, sodium oxide, potassium oxide and zinc oxide.
Further, the content ratio of silicon dioxide to strontium oxide in the basic glass ceramics is 6-10: 1.
further, the content ratio of silicon dioxide to calcium oxide in the basic glass ceramics is 3-5.5: 1.
further, the basic glass ceramics comprise, by mass, 55-65 parts of silicon dioxide, 7-9 parts of strontium oxide, 6-8 parts of cordierite, 5-7 parts of spodumene, 4-5 parts of bismuth oxide, 2-4 parts of alumina, 12-18 parts of calcium oxide, 4-5 parts of fluorine, 4-6 parts of lithium oxide, 6-10 parts of sodium oxide, 7-13 parts of potassium oxide and 1-2 parts of zinc oxide.
Further, the colorant contains neodymium, zinc oxide and a sky blue colorant.
Furthermore, the mass ratio of neodymium to zinc oxide to sky blue in the colorant is 2-3: 0.3-0.8: 0.1-0.3.
The silicon dioxide in the glass ceramics can endow the glass ceramics with good chemical stability and thermal stability, can improve the strength of the glass ceramics and reduce the expansion coefficient of the glass ceramics, and the glass ceramics is used as a glass forming body, the content is more, the glass structure is more stable, so the acid and alkali resistance is strong, the weight loss rate is small, but the viscosity of glass liquid is increased along with the increase of the content, and the melting temperature of the glass ceramics is increased.
The chemical composition of spodumene is LiAl [ Si ]2O6]It is an important component for ensuring the formation of low thermal expansion crystals, and the addition of a small amount of spodumene to the basic glass-ceramic of the present invention is unexpected for improving the impact toughness and strength of the glass-ceramicThe effect of (1). Cordierite is a silicate mineral, generally has light blue or light purple color, glass luster, transparency to translucency, good fire resistance and low thermal expansion rate, and a small amount of cordierite is added into the basic glass ceramics provided by the invention, which also contributes to improving the toughness, strength and hardness of the finished glass ceramics.
The potassium oxide is a good fluxing agent, can improve the glossiness of the microcrystalline glass, promote the melting and clarification of the glass liquid, and can also reduce the viscosity of the glass liquid, and the viscosity of the glass liquid can be improved by adding a certain amount of potassium oxide. In addition, calcium oxide and sodium oxide can also reduce the high-temperature viscosity of the glass liquid, promote the melting and clarification of the glass liquid and increase the chemical stability, mechanical strength and hardness of the microcrystalline glass.
Fluorine is an excellent opacifier, and when the fluorine content is too high, the production stability of the microcrystalline glass is low, the brittleness is high, and the microcrystalline glass is easy to devitrify, so that the fluorine content is not suitable to be too high.
The alumina can reduce the crystallization tendency of the microcrystalline glass, improve the chemical stability, the mechanical strength and the hardness, improve the thermal stability and reduce the electrical insulation, but with the increase of the content of the alumina, the surface of the microcrystalline glass can generate stripes, the viscosity of the glass liquid can be increased, the melting and clarification are difficult, and the crystallization tendency is increased, so the content of the alumina is not suitable to be too high.
The zinc oxide can improve the chemical stability of the glass ceramics and reduce the thermal expansion coefficient of the glass ceramics, but the content of the zinc oxide is not suitable to be too high because the crystallization tendency of the glass ceramics is increased along with the increase of the content of the zinc oxide.
Bismuth oxide can be used for preparing bismuth salt, is used as an electronic ceramic powder material, an electrolyte material, a photoelectric material, a high-temperature superconducting material, a catalyst and the like, is an important additive in the electronic ceramic powder material, and has a melting-assisting effect when bismuth oxide is added into the basic microcrystalline glass.
In another aspect, the invention also provides a method for preparing the purple microcrystalline glass, which comprises the following steps:
(1) using HF solution to pretreat cordierite and spodumene;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to obtain a glass plate;
(5) and carrying out gradient heat preservation treatment on the obtained glass plate to obtain the purple microcrystalline glass.
Further, the pretreatment in the step (1) is to pretreat cordierite and spodumene for 2 to 3 hours by using an HF solution with the mass concentration of 10 to 13 percent.
Further, the thickness of the glass plate in the step (4) is 10mm-15 mm.
Further, the gradient heat preservation treatment in the step (5) is to preserve the temperature of the obtained glass plate for 1-2h at the temperature of 610-.
Preferably, the gradient heat preservation treatment in the step (5) is to preserve heat of the obtained glass plate for 1-2h at 620 ℃, then uniformly heat the glass plate to 690 ℃, preserve heat for 2h, and then heat the glass plate to 820 ℃ and preserve heat for 1 h.
The purple microcrystalline glass has stable coloring performance, exquisite color, purple and light blue under different light rays, no air holes on the surface, high impact toughness, high bending strength and high compression strength, and has strong processing and forming performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 3 hours by using an HF solution with the mass concentration of 10%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10 mm;
(5) and (3) preserving the temperature of the obtained glass plate for 1h at 610 ℃, uniformly heating to 680 ℃, preserving the temperature for 3h, heating to 810 ℃, and preserving the temperature for 0.5h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 55 parts of silicon dioxide, 7 parts of strontium oxide, 6 parts of cordierite, 5 parts of spodumene, 4 parts of bismuth oxide, 2 parts of aluminum oxide, 12 parts of calcium oxide, 4 parts of fluorine, 4 parts of lithium oxide, 6 parts of sodium oxide, 7 parts of potassium oxide and 1 part of zinc oxide.
The toner comprises the following components in a mass ratio of 2: 0.3: 0.1 neodymium, zinc oxide and sky blue.
Example 2
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2.5h by using an HF solution with the mass concentration of 12%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 15 mm;
(5) and (3) preserving the temperature of the obtained glass plate for 2h at 630 ℃, uniformly heating to 700 ℃, preserving the temperature for 1h, heating to 830 ℃, and preserving the temperature for 0.5h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 65 parts of silicon dioxide, 9 parts of strontium oxide, 8 parts of cordierite, 7 parts of spodumene, 5 parts of bismuth oxide, 4 parts of aluminum oxide, 18 parts of calcium oxide, 5 parts of fluorine, 6 parts of lithium oxide, 10 parts of sodium oxide, 13 parts of potassium oxide and 2 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 3: 0.8: 0.3 neodymium, zinc oxide and sky blue.
Example 3
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 4
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the spodumene pretreated in the step (1), other basic glass ceramic raw materials and the color agent into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic microcrystalline glass comprises, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 5
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite pretreated in the step (1), other basic glass ceramic raw materials and the color agent into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 6
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 12 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 7
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 5 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 8
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 9%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 9
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 15%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 10
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the temperature of the obtained glass plate for 2h at 690 ℃, and then heating to 820 ℃ for 1h to obtain the purple glass ceramics.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 11
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the temperature of the obtained glass plate at 820 ℃ for 1h to prepare the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 12
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, uniformly heating to 820 ℃ and preserving the heat for 1h to obtain the purple glass ceramics.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 13
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 3 parts of alumina, 15 parts of calcium oxide, 4.5 parts of fluorine, 5 parts of lithium oxide, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Example 14
A method of making a violet glass ceramic, the method comprising the steps of:
(1) pretreating cordierite and spodumene for 2 hours by using an HF solution with the mass concentration of 13%;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to prepare a glass plate with the thickness of 10-15 mm;
(5) and (3) preserving the heat of the obtained glass plate for 1.5h at 620 ℃, then uniformly heating to 690 ℃, preserving the heat for 2h, and then heating to 820 ℃ and preserving the heat for 1h to obtain the purple microcrystalline glass.
The basic glass ceramics comprise, by weight, 60 parts of silicon dioxide, 8 parts of strontium oxide, 7 parts of cordierite, 6 parts of spodumene, 4.5 parts of bismuth oxide, 3 parts of aluminum oxide, 15 parts of calcium oxide, 4.5 parts of fluorine, 8 parts of sodium oxide, 10 parts of potassium oxide and 1.5 parts of zinc oxide.
The toner comprises the following components in a mass ratio of 2.5: 0.5: 0.2 neodymium, zinc oxide and sky blue.
Effects of the embodiment
The microcrystalline glass obtained in each example was examined for impact toughness, bulk density, mohs hardness, flexural strength, and compressive strength, and the results are shown in table 1.
Table 1 partial property test results of the crystallized glass obtained in each example
| Test item | Impact toughness (kj/cm) | Bulk density (g/cm dry) | Mohs hardness | Flexural strength/MPa | Compressive strength/MPa |
| Example 1 | 5.7 | 2.6 | 7.4 | 85 | 710 |
| Example 2 | 5.6 | 2.7 | 7.5 | 83 | 720 |
| Example 3 | 5.8 | 2.6 | 7.6 | 86 | 713 |
| Example 4 | 5.1 | 2.6 | 7.5 | 70 | 672 |
| Example 5 | 5.0 | 2.7 | 6.6 | 67 | 655 |
| Example 6 | 5.3 | 2.6 | 6.7 | 76 | 662 |
| Example 7 | 5.0 | 2.6 | 6.9 | 75 | 669 |
| Example 8 | 5.1 | 2.6 | 7.0 | 73 | 668 |
| Example 9 | 5.2 | 2.7 | 6.7 | 65 | 656 |
| Example 10 | 4.9 | 2.6 | 7.0 | 72 | 653 |
| Example 11 | 4.5 | 2.6 | 6.6 | 65 | 625 |
| Example 12 | 4.7 | 2.6 | 6.8 | 70 | 640 |
| Example 13 | 5.1 | 2.6 | 5.9 | 71 | 645 |
| Example 14 | 5.0 | 2.6 | 6.2 | 73 | 676 |
From the results, the basic glass ceramics disclosed by the invention have the advantages that the basic glass ceramics are all lack of components, a small amount of cordierite and spodumene are added, the toughness, the strength and the hardness of the glass ceramics finished product are favorably improved, various materials are strictly added according to the proportion, particularly the proportion of strontium oxide, calcium oxide and silicon dioxide is required to be controlled, and the performance of the obtained glass ceramics finished product is favorably improved by pretreating the cordierite and the spodumene for 2-3h by using an HF solution with the mass concentration of 10-13% before the glass ceramics is prepared.
It will be understood by those skilled in the art that the foregoing is merely exemplary of the present invention, and is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The purple microcrystalline glass is characterized by comprising a coloring agent and base microcrystalline glass, wherein the coloring agent is a purple coloring agent, and the base microcrystalline glass comprises silicon dioxide, strontium oxide, cordierite, spodumene, bismuth oxide, aluminum oxide, calcium oxide, fluorine, lithium oxide, sodium oxide, potassium oxide and zinc oxide.
2. The purple microcrystalline glass according to claim 1, wherein the content ratio of silicon dioxide to strontium oxide in the base microcrystalline glass is 6-10: 1.
3. the purple microcrystalline glass according to claim 1, wherein the content ratio of silicon dioxide to calcium oxide in the base microcrystalline glass is 3-5.5: 1.
4. the purple microcrystalline glass according to claim 1, wherein the basic microcrystalline glass comprises, by mass, 55-65 parts of silicon dioxide, 7-9 parts of strontium oxide, 6-8 parts of cordierite, 5-7 parts of spodumene, 4-5 parts of bismuth oxide, 2-4 parts of aluminum oxide, 12-18 parts of calcium oxide, 4-5 parts of fluorine, 4-6 parts of lithium oxide, 6-10 parts of sodium oxide, 7-13 parts of potassium oxide, and 1-2 parts of zinc oxide.
5. The purple microcrystalline glass according to claim 1, wherein the colorant comprises neodymium, zinc oxide and a sky blue colorant.
6. The purple microcrystalline glass as claimed in claim 5, wherein the mass ratio of neodymium, zinc oxide and sky-blue pigment in the pigment is 2-3: 0.3-0.8: 0.1-0.3.
7. A method for producing a violet glass ceramic according to any one of claims 1 to 6, characterized in that the method comprises the steps of:
(1) using HF solution to pretreat cordierite and spodumene;
(2) putting the cordierite, spodumene and other basic glass ceramic raw materials and the color agent pretreated in the step (1) into a mixer to be uniformly mixed;
(3) delivering the mixed mixture into an electric melting furnace, melting at 1400 ℃ and 1500 ℃, and clarifying to obtain glass liquid;
(4) the obtained glass liquid is subjected to press-rolling forming at the temperature of 1120-1180 ℃ to obtain a glass plate;
(5) and carrying out gradient heat preservation treatment on the obtained glass plate to obtain the purple microcrystalline glass.
8. The method for preparing the purple microcrystalline glass according to claim 7, wherein the pretreatment in the step (1) is to pretreat cordierite and spodumene with HF solution with a mass concentration of 10-13% for 2-3 h.
9. The method for producing a violet glass ceramic according to claim 7, wherein the glass plate in the step (4) has a thickness of 10mm to 15 mm.
10. The preparation method of the purple microcrystalline glass as claimed in claim 7, wherein the gradient heat preservation treatment in the step (5) is to preserve the temperature of the obtained glass plate at 630 ℃ for 1-2h, then to uniformly heat up to 680-700 ℃ for 1-3h, and then to heat up to 830 ℃ for 0.5-1.5 h; preferably, the gradient heat preservation treatment in the step (5) is to preserve heat of the obtained glass plate for 1-2h at 620 ℃, then uniformly heat the glass plate to 690 ℃, preserve heat for 2h, and then heat the glass plate to 820 ℃ and preserve heat for 1 h.
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