CN108821598B - Microcrystalline glass and preparation method thereof - Google Patents
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Abstract
The invention provides amber microcrystalline glass with high hardness and high temperature resistance. The microcrystalline glass comprises the following components in percentage by weight: SiO 22 50‑70％；Al2O3 10.0‑25％；TiO23 to 10 percent; 0.2 to 0.7 percent of CuO; 0-22% of MgO; 0-20% of ZnO; and at least one of MgO and ZnO. The Mohs hardness of the microcrystalline glass is 7.5-8H, and the microcrystalline glass can be applied to decorative materials and ornaments, and overcomes the scratch problem of common amber glass. The microcrystalline glass does not soften at a high temperature of 1150 ℃, is high-temperature resistant, and can be further processed under the high-temperature condition. The microcrystalline glass has high mechanical strength, hardness, thermal stability, chemical stability, wear resistance and electrical insulation performance, and can be used for high-grade decoration projects such as decorative materials, building internal and external walls, floors, pillars and the like.
Description
The present application is a divisional application of an invention patent application having an application number of 201510875782.8, and an application date of 2015, 12, 3, and entitled "glass ceramics and a method for producing the same".
Technical Field
The invention relates to microcrystalline glass and a preparation method thereof, in particular to amber microcrystalline glass and a preparation method thereof.
Technical Field
The microcrystalline glass has the advantages of glass, ceramics and natural stone, has the characteristics of excellent thermodynamic property, good chemical stability, high strength, high wear resistance, uniform and glittering and translucent surface gloss, convenience in cleaning and the like, and the characteristics determine that the microcrystalline glass plays an important role in the field of materials, and can be used in high-grade decoration projects such as inner and outer walls, floors, pillars and the like of buildings.
The traditional amber glass is colored by adding selenium and cadmium into the glass, the cadmium is toxic and is not suitable for being used in the existing environment, the Mohs hardness of the common amber glass is 5H, the Mohs hardness of a commonly used cutter is 5.5-6H, the Mohs hardness of silicon dioxide in grit or dust is 7H, the common amber glass can scratch or wear the surface of the existing amber decorative glass to influence the decorative effect and the service life of the existing amber decorative glass, and the common amber glass cannot resist high temperature, starts to soften at 800 ℃ of 700-.
Disclosure of Invention
The invention aims to provide amber microcrystalline glass with higher hardness and high temperature resistance.
The invention also provides a preparation method of the microcrystalline glass.
The technical scheme adopted by the invention for solving the technical problem is as follows: the microcrystalline glass comprises the following components in percentage by weight: SiO 22 50-70％；Al2O3 10.0-25％；TiO23 to 10 percent; 0.2 to 0.7 percent of CuO; 0-22% of MgO; 0-20% of ZnO; and at least one of MgO and ZnO.
Further, the method also comprises the following steps: ZrO (ZrO)2 0-6％；P2O5 0-1.5％；Sb2O3 0-1.5％；Na2O 0-2％；K2O 0-2％；Y2O3 0-2％；La2O3 0-1％。
Further, Na2O and K2The total content of O is less than 2 percent and/or TiO2、ZrO2And P2O5Is not less than 7%.
Further, the total content of ZnO and MgO is 5-22% and/or TiO25-8% and/or CuO 0.4-0.6% and/or SiO2、Al2O3The total content of (A) is 70-80%.
Further, the total content of ZnO and MgO is 8-15%.
Further, the microcrystalline glass is amber microcrystalline glass, and the Mohs hardness of the microcrystalline glass is 7.5-8H.
The preparation method of the microcrystalline glass comprises the following steps:
(a) ingredients
Weighing the raw materials according to the weight ratio, pouring the raw materials into a mixer, and uniformly mixing the raw materials to obtain a precursor glass raw material;
(b) melting
Putting the precursor glass raw material into a smelting furnace, melting and clarifying at high temperature, dissolving the precursor glass raw material into high-temperature glass stock solution, and removing bubbles and foreign matters in the high-temperature glass stock solution;
(c) shaping and annealing
Molding the molten high-temperature glass stock solution at a certain tapping temperature, and then carrying out rough annealing;
(d) thermal treatment
And (3) putting the glass subjected to the rough annealing into a high-temperature furnace for heat treatment, and generating microcrystalline of spinel crystals in the glass after the heat treatment is finished to obtain the microcrystalline glass.
Further, the raw material of step (a), wherein MgO, Na2O、K2O is introduced in the form of a carbonate, nitrate or sulfate, and the other components are introduced in the form of oxides.
Further, the melting in step (b) is: the temperature is 1550-; the clarification is as follows: the temperature is 1600 ℃ and 1650 ℃, and the time is 4-10 h.
Further, the tapping temperature in the step (c) is 1500-; the molding is as follows: the molding is carried out by cooling in a hot mold, or by a float method or a press method.
Further, the hot mold is: the temperature of the mould is ensured to be 100-450 ℃ in the forming process; the cooling is as follows: after the high-temperature molten glass is poured into the hot mold, the hot mold is cooled by blowing air.
Further, the heat treatment in the step (d) comprises two stages of crystal nucleus precipitation and microcrystal growth; the temperature required by the crystal nucleus precipitation stage is 750-; the temperature required by the microcrystal growth stage is 800-1000 ℃, and the duration time is 0.5-4 h.
The invention has the beneficial effects that: the invention adopts the method of carrying out heat treatment on the precursor glass and crystallizing and separating out the microcrystal from the glass matrix to prepare the amber microcrystalline glass. The amber microcrystalline glass prepared by the invention has the Mohs hardness of 7.5-8H, can be effectively applied to decorative materials and ornaments, overcomes the scratch problem of common amber glass and prolongs the service life. The amber microcrystalline glass prepared by the invention has extremely high softening temperature, does not soften at 1150 ℃ and is high temperature resistant, and can be further processed at high temperature. The amber microcrystalline glass prepared by the invention has high mechanical strength, hardness, thermal stability, chemical stability, wear resistance and electrical insulation performance, and can be used for high-grade decoration projects such as decorative materials, building interior and exterior walls, floors and pillars.
Detailed Description
The present invention uses ZnO (MgO) -Al2O3-SiO2-TiO2And (4) preparing precursor glass by using CuO as a system through a melting process, and annealing and thermally treating the precursor glass to prepare amber glass ceramics. The contents in weight percent and the effects thereof will be described below.
SiO2、Al2O3MgO or ZnO is a main component constituting the glass ceramics of the present invention, and MgO (or ZnO) -Al is used as the main component2O3-SiO2Phase diagram, in the present invention, SiO2The content of (A) is 50-70%; al (Al)2O3The content of (A) is 10-25%; the content of MgO is 0-22%, the content of ZnO is 0-20%, in the invention, at least one of MgO and ZnO is contained, further, the total content of MgO and ZnO is 5-22%, preferably 8-15%. When the contents of MgO and ZnO are outside the above ranges, other crystals appear in the glass, failing to meet the requirements of the present invention. SiO 22And Al2O3The total content of (A) is 70-80%. When SiO is present2And Al2O3When the total content of (A) is less than 70%, the hardness of the glass does not meet the requirement, and when SiO is contained2And Al2O3When the total content of (B) exceeds 80%, melting is difficult. The content ranges of the components can form magnesium aluminate spinel or/and zinc aluminate spinel crystallites in the glass, thereby improving the hardness of the glass.
TiO2There are two roles in the present invention: 1) due to TiO2The glass can be colored in a glass system, and the precursor glass is light yellow without other coloring agents, the content cannot be too small, and the coloring effect cannot be caused if the content is too small; 2) is the main nucleating agent of the microcrystalline glass. TiO 22The content of (B) is 3 to 10%, preferably 5 to 8%. If the content is too low, the nucleation quantity of the glass is low, and the crystallization of the glass is influenced; if the content exceeds 10%, the nucleating agent is too much, and the molding tends to be creamy, and glass cannot be formed.
The main function of CuO is as a colorant, and in the absence of other colorants, the precursor glass appears blue when the CuO content is 0.2 to 0.7%. When the content of CuO is less than 0.2%, the glass is light blue and cannot achieve the effect; whereas when the content is more than 0.7%, the glass is too dark blue, and in the present invention, the content of CuO is 0.2 to 0.7%, preferably 0.4 to 0.6%.
The above-mentioned TiO content is simultaneously added under the glass system of the invention2And CuO, the precursor glass is yellow-green after being formed, and after heat treatment, the glass has tiny crystals which have a scattering effect on visible light and are mixed with the precursor yellow-green glass to form the amber glass ceramics.
ZrO2And P2O5As a nucleating agent for crystals in glass, various nucleating agents are generally used, which can promote a large number of crystal nuclei and a small and uniform crystal size after crystallization. ZrO (ZrO)2The melting temperature is high, and the content generally does not exceed 6 percent; p2O5Excessive amounts will cause phase separation, generally not exceeding 1.5%.
Preferably, the nucleating agent TiO of the invention2、ZrO2And P2O5Is not less than 7%.
Sb2O3The content of the clarifying agent is not more than 1.5 percent, and the clarifying effect cannot be achieved when the content is too much.
Na2O and K2O is a cosolvent to lower the melting temperature and the refining temperature of the glass, but Na2O、K2The O content should not exceed 2%, and too much will result in a decrease in the hardness of the glass. Preferably, the cosolvent Na of the invention2O and K2Of OThe total content is below 2%.
Y2O3And La2O3Is an additional additive which can slightly lower the melting temperature of the glass without reducing the hardness of the glass, but not too much, Y2O3The content of (A) cannot exceed 2%, La2O3The content of (C) should not exceed 1%.
The amber glass ceramics mainly takes spinel as a main crystal phase and contains a small amount of crystals such as quartz solid solution, cordierite, sapphirine and the like.
The preparation method comprises the following steps:
(a) ingredients
According to the weight content of the precursor glass, wherein MgO and Na2O、K2O is introduced as a carbonate, nitrate or sulfate, and the other components are introduced as oxides. Weighing the raw materials according to the weight ratio, pouring the raw materials into a mixer, and uniformly mixing the raw materials to obtain a precursor glass raw material;
(b) melting
Putting the precursor glass raw material into a smelting furnace, melting and clarifying at high temperature, dissolving the precursor glass raw material into high-temperature glass stock solution, and removing bubbles and foreign matters in the high-temperature glass stock solution;
(c) shaping and annealing
Forming the molten high-temperature glass stock solution in a hot mold under cooling at a certain tapping temperature, or forming the molten high-temperature glass stock solution by a float method and a compression method, and roughly annealing the formed glass in a muffle furnace;
(d) thermal treatment
And (3) putting the rough annealed glass into a high-temperature furnace muffle furnace for heat treatment, and generating a spinel crystal microcrystal in the glass after the heat treatment is finished to obtain the high-hardness microcrystalline glass.
The mixer in the above step (a) may be a V-shaped mixer. The melting in the step (b) is: the temperature is 1550-; the clarification is as follows: the temperature is 1600 ℃ and 1650 ℃, and the time is 4-10 h; the smelting furnace adopts an electric furnace or a crucible furnace. The tapping temperature in the step (c) is 1500-; the hot mold is as follows: the temperature of the mould is ensured to be 100-450 ℃ in the forming process; the cooling means that: after the high-temperature molten glass is poured into the hot mold, the hot mold is cooled by blowing air; the annealing temperature is between 700 ℃ and 800 ℃; the heat treatment process in the step (d) comprises two stages of crystal nucleus precipitation and microcrystal growth, wherein the temperature required by the crystal nucleus precipitation stage is 750-; the temperature required for the microcrystal growth stage is 800-1000 ℃, and the duration time is 0.5-4 h.
The invention adopts precursor glass for heat treatment, and the amber microcrystalline glass is prepared by a method of crystallizing and separating microcrystals from a glass matrix, has the Mohs hardness of 7.5-8H, and can resist the high temperature of 1150 ℃.
Tables 1-2 show examples 1-13 of the present invention, in which the glass raw material was prepared by weighing the components in the compositions of examples 1-13 in tables 1-2, wherein the raw materials may be carbonates, nitrates, oxides, etc., and then mixing the weighed raw materials in a V-shaped mixer. Then the prepared glass raw materials are put into an electric furnace, melting is carried out for 4-10 hours at the temperature of 1550-.
And (2) putting the prepared mother glass into a high-temperature furnace for heat treatment, wherein the heat treatment process comprises two stages of crystal nucleus precipitation and microcrystal growth, wherein in the crystal nucleus precipitation stage, the temperature in the muffle furnace is kept at 900 ℃ for 1-4h to generate crystal nuclei as many as possible in the glass, and then the temperature in the muffle furnace is increased to about 800 ℃ and 1000 ℃ to enter the microcrystal growth stage for 0.5-4h, so that the amber glass ceramics is prepared.
The composition, the type of crystal phase and the Mohs hardness of the microcrystalline glass are shown in Table 1-2.
TABLE 1
TABLE 2
Claims (10)
1. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 22 50-70%；Al2O3 10-25%；TiO23 to 10 percent; 0.2 to 0.7 percent of CuO; 9-22% of MgO; 6-20% of ZnO, wherein the microcrystalline glass is amber microcrystalline glass, and the Mohs hardness of the microcrystalline glass is 7.5-8H.
2. The glass-ceramic according to claim 1, further comprising: ZrO (ZrO)2 0-6%；P2O5 0-1.5%；Sb2O30-1.5%；Na2O 0-2%；K2O 0-2%；Y2O3 0-2%；La2O3 0-1%。
3. The microcrystalline glass according to claim 2, characterised in that Na2O and K2The total content of O is less than 2 percent and/or TiO2、ZrO2And P2O5Is not less than 7%.
4. Microcrystalline glass according to claim 1, characterised in that the total content of ZnO and MgO is 15-22% and/or TiO25-8% and/or CuO 0.4-0.6% and/or SiO2、Al2O3The total content of (A) is 70-80%.
5. A method for producing a crystallized glass according to claim 1, which comprises the steps of:
(a) ingredients
Weighing the raw materials according to the weight ratio, pouring the raw materials into a mixer, and uniformly mixing the raw materials to obtain a precursor glass raw material;
(b) melting
Putting the precursor glass raw material into a smelting furnace, melting and clarifying at high temperature, dissolving the precursor glass raw material into high-temperature glass stock solution, and removing bubbles and foreign matters in the high-temperature glass stock solution;
(c) shaping and annealing
Molding the molten high-temperature glass stock solution at a certain tapping temperature, and then carrying out rough annealing;
(d) thermal treatment
And (3) putting the glass subjected to the rough annealing into a high-temperature furnace for heat treatment, and generating microcrystalline of spinel crystals in the glass after the heat treatment is finished to obtain the microcrystalline glass.
6. The method for producing a glass ceramic according to claim 5, wherein the raw material in the step (a), MgO, Na2O、K2O is introduced in the form of a carbonate, nitrate or sulfate, and the other components are introduced in the form of oxides.
7. The method for producing a glass ceramic according to claim 5, wherein the melting in the step (b) is: the temperature is 1550-; the clarification is as follows: the temperature is 1600 ℃ and 1650 ℃, and the time is 4-10 h.
8. The method for preparing glass-ceramic according to claim 5, wherein the tapping temperature in the step (c) is 1500-1600 ℃; the molding is as follows: the molding is carried out by cooling in a hot mold, or by a float method or a press method.
9. The method for producing a crystallized glass according to claim 8, wherein the hot mold is: the temperature of the mould is ensured to be 100-450 ℃ in the forming process; the cooling is as follows: after the high-temperature molten glass is poured into the hot mold, the hot mold is cooled by blowing air.
10. The method for producing a glass-ceramic according to claim 5, wherein the heat treatment in the step (d) includes two stages of crystal nucleus precipitation and crystallite growth; the temperature required by the crystal nucleus precipitation stage is 750-; the temperature required by the microcrystal growth stage is 800-1000 ℃, and the duration time is 0.5-4 h.
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| CN108821598A (en) | 2018-11-16 |
| CN105347685B (en) | 2019-01-04 |
| CN105347685A (en) | 2016-02-24 |
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