CN111453995A - Microcrystalline glass mainly containing spinel and preparation method thereof - Google Patents
Microcrystalline glass mainly containing spinel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a microcrystalline glass mainly comprising spinel, which comprises the following components in percentage by weight: SiO 2247.5‑70.0％；Al2O310.0 to 20.0 percent; 0-22.0% of MgO; 0 to 12.5 percent of ZnO, and the total content of MgO and ZnO is more than 6 percent, and the crystallized glass contains microcrystal of spinel crystal. The invention adopts proper precursor glass for heat treatment, and the microcrystalline glass is crystallized and separated from the glass matrix to prepare the microcrystalline glass mainly containing spinel, the Mohs hardness of the glass is 7.5-8, the glass can have different colors, the scratch problem of the building microcrystalline glass mainly containing wollastonite is solved, and the service life is prolonged. The microcrystalline glass mainly containing spinel has the characteristics of high mechanical strength, high hardness, good wear resistance, good electrical insulation and the like, and can be used as building decoration materials, chemical and anticorrosive materials, mine wear-resistant materials and the like.
Description
The application is a divisional application of Chinese patent application with the application date of 2014, 11 and 19, the application number of 201410665147.2 and the invention name of microcrystalline glass mainly comprising spinel and a preparation method thereof.
Technical Field
The invention relates to microcrystalline glass mainly containing spinel and a preparation method thereof, belonging to the technical field of glass ceramics.
Background
The microcrystalline glass integrates the advantages of glass, ceramics and natural stone, has the characteristics of excellent thermodynamic property, high chemical stability, large-range adjustable thermal expansion coefficient, excellent insulativity, high wear resistance, high softening point temperature and the like, and can be used for building curtain walls, indoor high-grade decoration, chemical and anticorrosive materials, mine wear-resistant materials and other fields, and the microcrystalline glass plays an important role in the field of materials science.
Spinel is an oxide with cubic structure and has a chemical formula of AB2O4Wherein A is a divalent metal ion of Zn, Fe or Mg having tetrahedral coordination, and B is a metal ion of A1, Cr or Fe having octahedral coordination. Common magnesium aluminum spinel (MgAl)2O4) Because A1-O, Mg-O forms stronger ionic bonds, the structure is firm, the hardness is high (Mohs hardness is 8), the melting point is high (2135 ℃), the chemical property is stable, and the corrosion resistance, the heat resistance, the pressure resistance and the mechanical strength are excellent.
At present, the microcrystalline glass for buildings mainly adopts CaO-Al2O3-SiO2The system takes wollastonite, anorthite, gehlenite, diopside and the like as main crystal phases, and the main crystal phase of the architectural microcrystalline glass with the appearance characteristic of natural marble is wollastonite (CaO-SiO)2). The Mohs hardness of wollastonite, anorthite, gehlenite and diopside crystals is 6H, the Mohs hardness of a commonly used cutter is 5.5-6H, and the Mohs hardness of silicon dioxide contained in gravel or dust is 7H, so that the wollastonite, the anorthite, the gehlenite and the diopside can scratch or abrade the surface of the existing architectural glass ceramics, and the decorative effect and the service life of the glass ceramics are influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing microcrystalline glass mainly comprising spinel.
The invention also provides a preparation method of the spinel-based microcrystalline glass.
The technical scheme adopted by the invention for solving the technical problem is as follows: the microcrystalline glass mainly comprises the following components in percentage by weight:SiO247.5-70.0％；Al2O310.0 to 20.0 percent; 0-22.0% of MgO; 0 to 12.5 percent of ZnO, and the total content of MgO and ZnO is more than 6 percent, and the crystallized glass contains microcrystal of spinel crystal.
Further, the method also comprises the following steps: b is2O30-3.0％；ZrO20-6.0％；P2O50-0.5％；TiO20-5.0％；Sb2O30-0.5％；CeO20-2.0％；Na2O 0-2.0％；K2O 0-2.0％；Cr2O30-1.0％；Mn2O30-1.0％；Fe2O30-1.0％；Y2O30-4.0％；La2O30-1.0％。
Further, wherein, the cosolvent Na2O and K2The total content of O is less than 2 percent.
Further, wherein, the nucleating agent TiO2、ZrO2And P2O5The total content of (A) is more than 6%.
Further, among them, a clarifier Sb2O3And CeO2The total content of (A) does not exceed 2%.
Further, SiO2And Al2O3The total content of (A) is 65-80%.
Further, the Mohs hardness of the glass is 7.5-8.
The preparation method of the microcrystalline glass mainly containing spinel 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
Forming 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 after the rough annealing into a high-temperature furnace for heat treatment, and generating microcrystal of spinel crystals in the glass after the heat treatment is finished to obtain the microcrystalline glass mainly containing spinel.
Further, the raw material of step (a), wherein MgO, Na2O、K2O is introduced in the form of carbonate or nitrate or sulphate and the other components are introduced in the form of oxides.
Further, the melting in the step (b) is carried out at 1550-; the clarification is carried out at 1600-1650 ℃ for 4-10 h.
Further, the tapping temperature in the step (c) is 1500-; the molding is performed by cooling in a hot mold, or by a float and press molding method.
Further, the hot mold is used for ensuring that the temperature of the mold is 100-450 ℃ in the molding process; and the cooling is to blow air to cool the preheated mould when the high-temperature molten glass is poured into the mould.
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 method is characterized in that proper precursor glass is adopted for heat treatment, and microcrystal is crystallized and precipitated from a glass matrix, so that the microcrystalline glass mainly comprising spinel is prepared. The preparation method has the advantages of simple preparation process, low cost and the like, and is suitable for large-scale production. The spinel-based microcrystalline glass prepared by the method has the Mohs hardness of 7.5-8, can have different colors, can be effectively applied to building microcrystalline glass, overcomes the scratch problem of wollastonite-based building microcrystalline glass, and prolongs the service life. The microcrystalline glass mainly prepared by the method has the characteristics of high mechanical strength, high hardness, high thermal stability, good chemical stability, good wear resistance, good electrical insulation property and the like, and can be used as building decoration materials, chemical and anticorrosive materials, mine wear-resistant materials and the like.
Detailed Description
The invention uses ZnO (MgO, Cr)2O3、Mn2O3、Fe2O3)-Al2O3-SiO2The weight percentage content and the function of the system are as follows:
SiO2and Al2O3And MgO or ZnO is a main component constituting the glass 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 50.0-70.0%; al (Al)2O3The content of (A) is 10.0-20.0%, and when the contents of MgO and ZnO are out of this range, other crystals appear in the glass, which is not satisfactory. The content of MgO is 0-22.0%, the content of ZnO is 0-12.5%, wherein, the total content of MgO and ZnO is more than 6%. The content ranges of the components can form magnesium aluminate spinel or/and zinc aluminate spinel crystallites in the glass.
Preferably, SiO in the present invention2And Al2O3The total content of (A) is 65-80%. When SiO is present2And Al2O3When the total content of the glass is less than 65 percent, the hardness of the glass can not meet the requirement; when SiO is present2And Al2O3When the total content of (B) exceeds 80%, melting is difficult.
ZrO2、P2O5And TiO2As 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 content can cause phase separation, generally not exceeding 5.0%; TiO 22The content of the titanate serving as a main nucleating agent is generally not more than 5.0%, and when the content is excessive, hardness of the titanate formed by nucleation is low, which affects hardness of glass. Preferably, the nucleating agent TiO of the invention2、ZrO2And P2O5The total content of (A) is more than 6%.
Sb2O3And CeO2Sb as clarifying agent, both of which are not used simultaneously2O3The content is not more than 1.5 percent, and the clarification effect cannot be achieved when the content is too high; CeO (CeO)2The content is not more than 2.0%.
Na2O and K2O is a cosolvent, the melting temperature and the clarification temperature are reduced, 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 K2The total content of O is less than 2 percent.
Cr2O3、Mn2O3And Fe2O3The main function is coloring agent, which is different color on glass, Fe ion is blue, Mn ion is purple, and chromium ion is red. Another effect is the formation of small crystals in the glass, such as chromium spinel, manganese spinel and hercynite, which also exhibit different colors, chromium spinel being pink, manganese spinel being black-violet and hercynite being blue. In the present invention, Cr2O3、Mn2O3And Fe2O3Are added in amounts of not more than 1%.
Y2O3And L a2O3Is an additional additive which can slightly lower the glass melting temperature without reducing the glass hardness, but not too much, Y2O3The content of (A) should not exceed 4.0%, L a2O3The content of (A) should not exceed 1.0%.
The present invention relates to a microcrystalline glass mainly composed of spinel, which contains a small amount of crystals such as a quartz solid solution, cordierite, sapphirine, etc.
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.
As the mixer 7 in the above step (a), a V-shaped mixer can be used. Melting at high temperature in the step (b), wherein the temperature is 1550-; clarifying at high temperature of 1600 ℃ and 1650 ℃ for 4-10 h; the smelting furnace adopts an electric furnace or a crucible furnace. The tapping temperature of the hot die in the step (c) is 1500-; the hot mold means that the temperature of the mold is ensured to be 100-450 ℃ in the molding process; cooling means that the high-temperature molten glass is poured into a mold, and the preheated mold is cooled by blowing air; 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 the method that the precursor glass is subjected to heat treatment again to crystallize and separate out the microcrystal from the glass matrix, and the microcrystalline glass mainly comprising spinel is prepared, the Mohs hardness is 7.5-8, and the microcrystalline glass has different colors. The microcrystalline glass mainly containing spinel prepared by the invention has the characteristics of high hardness, high mechanical strength, high thermal stability, good chemical stability, good wear resistance, good electrical insulation property and the like, and can be used for building interior, wear-resistant and corrosion-resistant materials and the like.
Example 1:
firstly, 60 percent of SiO by weight220% of Al2O38% of MgO and 1% of Na2O, 1% of K2O, 2% ZnO, 5% TiO22% of ZrO20.5% of P2O5And 0.5% of Sb2O3Weighing, and then putting all the materials into a V-shaped mixer to be fully stirred and mixed to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1600 ℃ for 8 hours, clarifying at 1650 ℃ for 10 hours, cooling the molten glass to 1600 ℃, discharging, forming by a die, cooling by blowing air when the die is at 200 ℃, and performing coarse annealing on the prepared glass at 680 ℃ in a muffle furnace.
And (2) putting the prepared 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 a muffle furnace is kept at 800 ℃, crystal nuclei are generated in the glass as much as possible for 2 hours, then the temperature in the muffle furnace is increased to about 1000 ℃, and the temperature enters the microcrystal growth stage for 0.5 hour, so that uniform magnesia-alumina spinel microcrystal can be generated in the glass, white high-hardness microcrystalline glass is obtained, and the Mohs hardness of the microcrystalline glass is 8.
Example 2:
firstly, 60 percent of SiO by weight220% of Al2O38% of ZnO, 1% of Na2O, 1% of K2O, 2% of MgO and 5% of TiO22% of ZrO20.5% of P2O5And 0.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1600 ℃ for 7 hours, clarifying at 1650 ℃ for 10 hours, cooling the molten glass to 1600 ℃, discharging, forming by a die, blowing and cooling when the die is at 300 ℃, and performing coarse annealing on the prepared glass at 680 ℃ in a muffle furnace.
And (2) putting the prepared 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 a muffle furnace is kept at 750 ℃ for 4 hours to generate crystal nuclei in the glass as much as possible, and then the temperature in the muffle furnace is increased to about 950 ℃ to enter the microcrystal growth stage for 1 hour, so that uniform zinc-aluminum spinel crystallites can be generated in the glass, white microcrystalline glass with high hardness of cyan is obtained, and the Mohs hardness of the microcrystalline glass is 8.
Example 3:
firstly, 60 percent of SiO by weight220% of Al2O39% of MgO and 1% of Na2O, 1% of K2O, 1% Mn2O35% of TiO22% of ZrO20.5% of P2O5And 0.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1600 ℃ for 6 hours, clarifying at 1650 ℃ for 10 hours, cooling the molten glass to 1550 ℃, discharging, forming by a mold, blowing and cooling when the mold is at 400 ℃, and roughly annealing the prepared glass in a muffle furnace at 680 ℃.
And (2) putting the prepared 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 a muffle furnace is kept at 750 ℃ for 4 hours to generate crystal nuclei in the glass as much as possible, and then the temperature in the muffle furnace is increased to about 950 ℃ to enter the microcrystal growth stage for 1 hour, so that uniform magnesium aluminate spinel and manganese spinel microcrystals can be generated in the glass, white microcrystalline glass with purple high hardness is obtained, and the Mohs hardness of the microcrystalline glass is 8.
Example 4:
firstly, 60 percent of SiO by weight2、20％Al of (2)2O38% of MgO and 2% of Na2O, 2% Cr2O35% of TiO22% of ZrO20.5% of P2O5And 1.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
other test conditions and procedures were the same as in example 3, and uniform magnesium aluminate spinel and chromium spinel crystallites were formed in the glass to obtain a white medium-pink high-hardness glass ceramic having a mohs hardness of 8.
Example 5:
firstly, 60 percent of SiO by weight220% of Al2O39% of MgO and 2% of K2O, 1% Fe2O35% of TiO22% of ZrO20.5% of P2O5And 0.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
other test conditions and procedures were the same as in example 3, and uniform magnesium aluminate spinel and hercynite crystallites were formed in the glass to obtain a white, medium blue, high hardness glass-ceramic having a mohs hardness of 8.
Example 6:
firstly, 50.0 percent of SiO by weight ratio220.0% of Al2O322.0 percent of MgO and 4.5 percent of TiO23.0% of ZrO2And 0.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1550 ℃ for 8 hours, clarifying at 1600 ℃ for 10 hours, cooling the molten glass to 1500 ℃, discharging, forming by a mold, cooling the mold at 200 ℃ by blowing during forming, and performing coarse annealing on the prepared glass in a muffle furnace at 680 ℃.
And (2) putting the prepared 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 a muffle furnace is kept at 750 ℃ for 4 hours to generate crystal nuclei in the glass as much as possible, and then the temperature in the muffle furnace is increased to about 900 ℃ to enter the microcrystal growth stage for 4 hours, so that uniform magnesium aluminate spinel crystallites and a small amount of cordierite crystals can be generated in the glass, and the white-cyan high-hardness glass ceramics are obtained, and the Mohs hardness of the glass ceramics is 8.
Example 7:
firstly, 70 percent of SiO by weight210% of Al2O38% of MgO and 1% of Na2O, 1% of K2O, 1.5% ZnO, 5% TiO21% of ZrO22% of P2O5And 0.5% of Sb2O3Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1600 ℃ for 8 hours, clarifying at 1650 ℃ for 10 hours, cooling the molten glass to 1550 ℃ and discharging, and performing rolling forming to obtain the glass, wherein the prepared glass is subjected to coarse annealing at 680 ℃ in a muffle furnace.
And (2) putting the prepared 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 a muffle furnace is kept at 750 ℃ for 2 hours to generate crystal nuclei in the glass as much as possible, and then the temperature in the muffle furnace is increased to about 900 ℃ to enter the microcrystal growth stage for 0.5 hour, so that uniform magnesium aluminate spinel can be generated in the glass, and white high-hardness microcrystalline glass is obtained, and the Mohs hardness of the microcrystalline glass is 7.5.
Example 8:
firstly, 55.5 percent of SiO by weight ratio216% of Al2O312.5 percent of ZnO, 3 percent of B2O34% of Y2O31% L a2O3、6.0% of ZrO2And 2% of CeO2Weighing, then putting all the materials into a mixer, fully stirring and mixing the materials to be used as a precursor glass raw material;
and then putting the prepared precursor glass raw material into an electric furnace, melting at 1550 ℃ for 8 hours, clarifying at 1600 ℃ for 10 hours, cooling the molten glass to 1500 ℃, discharging, forming by a float method, and roughly annealing the prepared glass in a muffle furnace at 680 ℃.
And (2) putting the prepared 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 a muffle furnace is kept at 750 ℃ for 4 hours to generate crystal nuclei in the glass as much as possible, and then the temperature in the muffle furnace is increased to about 900 ℃ to enter the microcrystal growth stage for 4 hours, so that uniform magnesium aluminate spinel can be generated in the glass, and white high-hardness microcrystalline glass is obtained, and the Mohs hardness of the microcrystalline glass is 8.
Claims (13)
1. The microcrystalline glass mainly containing spinel is characterized in that: the weight percentage composition of the material comprises: SiO 2247.5-70.0％；Al2O310.0 to 20.0 percent; 0-22.0% of MgO; 0 to 12.5 percent of ZnO, and the total content of MgO and ZnO is more than 6 percent, and the crystallized glass contains microcrystal of spinel crystal.
2. A spinel-based microcrystalline glass according to claim 1, wherein: further comprising: b is2O30-3.0％；ZrO20-6.0％；P2O50-0.5％；TiO20-5.0％；Sb2O30-0.5％；CeO20-2.0％；Na2O 0-2.0％；K2O 0-2.0％；Cr2O30-1.0％；Mn2O30-1.0％；Fe2O30-1.0％；Y2O30-4.0％；La2O30-1.0％。
3. A spinel as claimed in claim 2A primary glass-ceramic characterized by: wherein, the cosolvent Na2O and K2The total content of O is less than 2 percent.
4. A spinel-based microcrystalline glass according to claim 2, wherein: wherein, nucleating agent TiO2、ZrO2And P2O5The total content of (A) is more than 6%.
5. A spinel-based microcrystalline glass according to claim 2, wherein: wherein the clarifying agent Sb2O3And CeO2The total content of (A) does not exceed 2%.
6. A spinel-based microcrystalline glass according to claim 1 or 2, wherein: SiO 22And Al2O3The total content of (A) is 65-80%.
7. A spinel-based microcrystalline glass according to claim 1 or 2, wherein: the Mohs hardness of the glass is 7.5-8.
8. The preparation method of the microcrystalline glass mainly containing spinel is characterized by comprising the following steps of: the method 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
Forming 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 after the rough annealing into a high-temperature furnace for heat treatment, and generating microcrystal of spinel crystals in the glass after the heat treatment is finished to obtain the microcrystalline glass mainly containing spinel.
9. A method for producing a microcrystalline glass having a spinel as a main component according to claim 8, wherein: the raw material of the step (a), wherein MgO and Na2O、K2O is introduced in the form of carbonate or nitrate or sulphate and the other components are introduced in the form of oxides.
10. A method for producing a microcrystalline glass having a spinel as a main component according to claim 8, wherein: the melting in the step (b) is carried out at 1550-; the clarification is carried out at 1600-1650 ℃ for 4-10 h.
11. A method for producing a microcrystalline glass having a spinel as a main component according to claim 8, wherein: the tapping temperature in the step (c) is 1500-; the molding is performed by cooling in a hot mold, or by a float and press molding method.
12. A method for producing a spinel-based microcrystalline glass according to claim 11, wherein: the hot mold is used for ensuring the temperature of the mold to be 100-450 ℃ in the molding process; and the cooling is to blow air to cool the preheated mould when the high-temperature molten glass is poured into the mould.
13. A method for producing a microcrystalline glass having a spinel as a main component according to claim 8, wherein: 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.
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| CN107056067A (en) * | 2016-12-26 | 2017-08-18 | 吴中区穹窿山倪源交通器材经营部 | A kind of High-silicon jade-liked devitrified glass and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250034A (en) * | 1998-09-11 | 2000-04-12 | 株式会社小原 | Glass ceramic chip using for information storage medium and its producing process and information storage medium disc |
| CN1254688A (en) * | 1998-10-27 | 2000-05-31 | 康宁股份有限公司 | Low-expansion glass-ceramics |
| TW506952B (en) * | 1997-03-31 | 2002-10-21 | Corning Inc | Glass-ceramics |
| CN101905952A (en) * | 2009-06-04 | 2010-12-08 | 株式会社小原 | Crystallized glass substrate for information recording medium and method of producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101466534A (en) * | 2006-05-31 | 2009-06-24 | 康宁股份有限公司 | Transparent glass-ceramic armor |
| CN102089252A (en) * | 2008-07-03 | 2011-06-08 | 康宁股份有限公司 | Durable glass-ceramic housings/enclosures for electronic devices |
| EP2450320B1 (en) * | 2010-11-04 | 2014-01-08 | Corning Incorporated | Transparent spinel glass-ceramics free of As2O3 and Sb2O3 |
-
2014
- 2014-11-19 CN CN201410665147.2A patent/CN105601115A/en active Pending
- 2014-11-19 CN CN202010354594.1A patent/CN111453995A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW506952B (en) * | 1997-03-31 | 2002-10-21 | Corning Inc | Glass-ceramics |
| CN1250034A (en) * | 1998-09-11 | 2000-04-12 | 株式会社小原 | Glass ceramic chip using for information storage medium and its producing process and information storage medium disc |
| CN1254688A (en) * | 1998-10-27 | 2000-05-31 | 康宁股份有限公司 | Low-expansion glass-ceramics |
| CN101905952A (en) * | 2009-06-04 | 2010-12-08 | 株式会社小原 | Crystallized glass substrate for information recording medium and method of producing the same |
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| CN115057621A (en) * | 2022-03-29 | 2022-09-16 | 东华大学 | Colorless transparent magnesium-aluminum-silicon microcrystalline glass and preparation method thereof |
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| CN114988863A (en) * | 2022-06-29 | 2022-09-02 | 江苏师范大学 | Method for preparing magnesia-alumina spinel transparent ceramic by amorphous crystallization |
| CN115304279A (en) * | 2022-07-27 | 2022-11-08 | 浙江大学 | Spinel crystal phase and indian stone crystal phase composite microcrystalline glass and preparation method thereof |
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