CN112047634A - Transparent lithium-aluminum silicate glass ceramic and preparation method thereof - Google Patents
Transparent lithium-aluminum silicate glass ceramic and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 title description 5
- 239000006017 silicate glass-ceramic Substances 0.000 title description 5
- 239000005398 lithium aluminium silicate glass-ceramic Substances 0.000 claims abstract description 36
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008395 clarifying agent Substances 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 15
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 25
- 238000010899 nucleation Methods 0.000 claims description 23
- 230000006911 nucleation Effects 0.000 claims description 23
- 238000005352 clarification Methods 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 22
- 239000006066 glass batch Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 12
- -1 sulfate compound Chemical class 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 239000006060 molten glass Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000005347 annealed glass Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 abstract description 28
- 239000007832 Na2SO4 Substances 0.000 abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 13
- 229910000500 β-quartz Inorganic materials 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 7
- 230000007704 transition Effects 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 239000002131 composite material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000006125 LAS system Substances 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- C03C10/0018—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 SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—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 SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C1/004—Refining agents
Abstract
The invention relates to a transparent lithium aluminosilicate glass ceramic, which comprises the following components in percentage by mol: SiO 22 69～77％，Li2O 4～9％，Al2O3 11～13％，Na2O 0～2.5％，K2O 0～2.0％，TiO2 0.3～2.0％，ZrO2 0.2～1.5％，B2O3 0～2％，SrO 0～0.2％，ZnO 0.5～1.5％，CaO 0～0.1％，MgO 0～1％，P2O50 to 0.3 percent of the total weight of the mixture, 0.4 to 1.0 percent of the clarifying agent, and the clarifying agent is composed of 0.1 percent0.4% of CeO20.0 to 0.3% of Sb2O3And 0.0 to 0.2% of Na2SO4And (3) mixing. The main crystal phase of the transparent lithium aluminosilicate glass ceramic is a beta-quartz solid solution, has the advantages of high transparency, high light transmittance, good thermal shock resistance, high transition temperature and the like, and can be widely applied to parts such as a high-temperature observation window and the like. Meanwhile, the preparation method of the transparent lithium aluminosilicate glass ceramic is also disclosed.
Description
Technical Field
The invention relates to the technical field of Lithium Aluminum Silicon (LAS) microcrystalline glass, in particular to a transparent lithium aluminum silicate glass ceramic and a preparation method thereof.
Background
The glass ceramic is a solid material which is formed by compounding precipitated crystals and residual glass phase after nucleation and crystallization treatment, wherein lithium aluminum silicon (Li)2O-Al2O3-SiO2LAS) series glass ceramics is one of the important. Since the glass ceramic of the LAS system has a high quartz solid solution (mainly β -quartz solid solution) as a main crystal phase, it has advantages of high transparency, high light transmittance, good thermal shock resistance, high transition temperature, and the like, and is widely used for manufacturing products such as optical lenses, substrates for microelectronics, high-temperature windows, heating appliances for laboratory use, kitchenware, fireplace windows, and the like.
Characteristically, the lithium aluminosilicate glass ceramic has: A. the appearance and the light transmission performance of the lithium aluminum silicon glass ceramic with visible light transmission performance are various, and the content, the components, the distribution and the like of the beta-quartz solid solution can influence the light transmission performance of the glass ceramic. B. The lithium-aluminum-silicon glass ceramic with thermal shock resistance is Li2O，Al2O3，SiO2The material which is the main component adopts a structure of compounding precipitated crystals and residual glass formed after heat treatment as a polycrystalline composite material, and the thermal expansion coefficient of the composite material conforms to the addition of the components, so that the lithium aluminum silicon glass ceramic has a very low thermal expansion coefficient and excellent thermal shock resistance. C. The main crystal phase of the lithium aluminum silicon glass ceramic with higher transition temperature is beta-quartz crystal, and the existence of the crystal ensures that the transition temperature of the lithium aluminum silicon glass ceramic is more commonThe soda-lime-silicate glass is greatly improved, so that the lithium-aluminum-silicon glass ceramic can be used in a higher temperature environment. D. Chemical stability is a key characteristic of the main phase beta-quartz solid solution of lithium aluminosilicate glass ceramics, plus R in lithium aluminosilicate glass ceramics2O(Li2O，Na2O，K2O, etc.) and XO (SiO)2And Al2O3) The content is high, so that the high-temperature-resistant high-performance polyurethane resin still has excellent acid and alkali resistance at high temperature.
As for lithium aluminosilicate glass ceramics, a plurality of patents such as publication nos. CN100352782C, CN105948516A, CN104169232B, CN108069611A, and US7981823B2 disclose lithium aluminosilicate glass ceramics and a method for producing the same. From the above patent documents and the prior art, it is known that the mass production of glass ceramics is mainly divided into the following large steps. Firstly, grinding and mixing mineral raw materials and chemical raw materials to be added to prepare glass ceramic batch before melting, and melting and clarifying the glass ceramic batch at the temperature of 1500-1700 ℃. After melt-refining, the material is rapidly thermoformed, usually by cast forming, calendering or, more recently, the float process proposed, to produce the sheet obtained. The initial glass is then stress-relieved annealed to control crystallization within the initial glass such that the initial glass is converted into a glass-ceramic article.
In the above patent documents and the prior art, arsenic oxide, antimony oxide, and the like are generally used as fining agents for the melt. Although arsenic oxide and antimony oxide have obvious advantages in the system in consideration of technical difficulty and economy of a clarification process, due to safety risks in use and recovery processes, development of substitutes is urgently needed to solve the safety problem of the clarifier. Meanwhile, the clarification effect of the traditional clarification process is also deficient.
Disclosure of Invention
Aiming at the defects in the prior art, the invention improves the prior high-transparency lithium-aluminum silicate glass ceramic by selecting and proportioning raw materials, and simultaneously provides a preparation method of the high-transparency lithium-aluminum silicate glass ceramic.
Transparent lithium aluminosilicate glass ceramic according to mole percentageThe glass ceramic contains the following components: SiO 22 69～77％，Li2O 4～9％，Al2O3 11～13％，Na2O 0～2.5％，K2O 0～2.0％，TiO2 0.3～2.0％，ZrO2 0.2～1.5％，B2O3 0～2％，SrO 0～0.2％，ZnO 0.5～1.5％，CaO 0～0.1％，MgO 0～1％，P2O50-0.3% of a clarifying agent, and 0.4-1.0% of a clarifying agent; the clarifying agent is formed by CeO2、Sb2O3And a sulfate compound.
Further, the Li2O，Na2O，K2The total molar content of O is sigma R2O, said SiO2And Al2O3Has a total molar content of sigma XO, wherein sigma R2O is 8.0-11.0%, sigma R2The O +. Sigma XO is 92-97%.
The main crystal phase of the transparent lithium aluminosilicate glass ceramic is a beta-quartz solid solution, has the advantages of high transparency, high light transmittance, good thermal shock resistance, high transition temperature and the like, and can be widely applied to parts such as a high-temperature observation window and the like.
The crystal grain size of the ceramic crystal reaches the nanometer level, the transmittance in the visible wavelength range is higher than 80%, visible bubbles in the glass ceramic disappear, the thermal shock resistance is strong, the delta T is more than or equal to 700 ℃, the mechanical strength is high, and the ceramic crystal can be used for a long time at a higher temperature.
The invention also provides a preparation method of the transparent lithium aluminosilicate glass ceramic, which comprises the following steps:
(1) mixing raw materials: the preparation method comprises the following steps of (1) mixing the components of the glass ceramic according to the corresponding molar percentage, grinding and uniformly mixing the components to prepare a glass batch, and putting the glass batch into a tiltable crucible which is arranged in a vacuum high-temperature metal smelting furnace and used for containing the glass batch;
(2) melting and clarifying: heating a metal smelting furnace to 1620-1670 ℃ for smelting clarification, wherein the air pressure in the furnace is kept at 0.1-0.02 standard atmospheric pressure during clarification, and the clarification time is controlled at 60-240 min;
(3) and (3) quick cooling and forming: rotating the tiltable crucible, pouring molten glass liquid onto a casting mold positioned below the crucible for rapid cooling and forming;
(4) stress relief annealing: annealing the formed glass at 550-630 ℃ for 1-3 h, and cooling to room temperature along with the furnace;
(5) nucleation and crystallization: heating the annealed glass to 580-730 ℃ for nucleation treatment for 1-2 h, then heating the glass subjected to nucleation treatment to 750-850 ℃ for crystallization treatment for 1-3 h, and cooling to obtain the transparent lithium aluminosilicate glass ceramic.
Further, the furnace body is closed before the glass batch is melted, the gas in the furnace is replaced, and the gas atmosphere in the vacuum high-temperature metal melting furnace is controlled to be an inert gas environment.
Further, after the gas in the furnace is replaced, the gas pressure is kept at 0.5-0.9 standard atmospheric pressure, the temperature of the glass batch is increased to 1620-1670 ℃ at the temperature increasing speed of 10 ℃/min, and the temperature is kept for 5-20 min after the temperature increasing process is finished.
Further, after heat preservation is carried out for 5-20 min, the air pressure in the furnace is reduced to 0.1-0.02 standard atmospheric pressure.
Further, before the tiltable crucible is rotated, the pressure of the inert gas in the furnace is restored to 0.9-1.0 standard atmospheric pressure.
The invention carries out bold innovation on the basis of the traditional clarifying agent and introduces CeO2、Sb2O3And Na2SO4And the composite clarifying agent is formed by multiple phases together, and the addition proportion of the composite clarifying agent is reasonably prepared, so that the economy and the safety of the clarifying agent are optimized.
The conventional fining mode in fusion fining is to reduce bubbles in the molten glass by fining agent in the fining temperature range to release gas to facilitate the escape of residual seeds in the molten glass. According to the invention, when the novel clarifying agent is adopted to clarify glass liquid, a process of accelerating bubble overflow is introduced by vacuum in the clarification process, and the clarification effect of glass can be further optimized by the composite clarification process. In the case of a combination of high-temperature refining and vacuum refining, the glass ceramic has less than 1 bubble per kilogram of glass ceramic, the bubble having a diameter greater than 0.2 mm.
The glass ceramic of the invention adopts TiO2、ZrO2、P2O5The composite crystal nucleus agent with the same composition accelerates the nucleation process of the glass by utilizing the 'synergistic effect' of the crystal nucleus agent, and is matched with a high-precision temperature control process to ensure that the glass rapidly nucleates in a nucleation temperature interval and inhibit the growth of crystal nuclei, thereby finally realizing the rapid and uniform formation of the crystal nuclei. The subsequent crystallization treatment leads the crystal grains to be controlled to grow, realizes the crystal grain size to reach the nanometer level, and has low thermal expansion coefficient and high mechanical strength.
The preparation method of the invention can be used for quickly and efficiently manufacturing the transparent lithium aluminosilicate glass ceramic without visible bubbles.
The transparent lithium aluminosilicate glass ceramic prepared by the invention has the advantages of nanoscale crystal grain size, strong thermal shock resistance and high mechanical strength, and can be used for a long time at higher temperature.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, the present invention is described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a transparent lithium aluminosilicate glass ceramic, which comprises the following components in percentage by mol: SiO 22 69～77％，Li2O 4～9％，Al2O3 11～13％，Na2O 0～2.5％，K2O 0～2.0％，TiO2 0.3～2.0％，ZrO2 0.2～1.5％，B2O3 0～2％，SrO 0～0.2％，ZnO 0.5～1.5％，CaO 0～0.1％，MgO 0～1％，P2O50-0.3% of a clarifying agent, and 0.4-1.0% of a clarifying agent; the clarifying agent is formed by CeO2、Sb2O3And a sulfate compound.
In one embodiment, the Li2O，Na2O，K2The total molar content of O is sigma R2O, said SiO2And Al2O3Has a total molar content of sigma XO, wherein sigma R2O is 8.0-11.0%, sigma R2The O +. Sigma XO is 92-97%.
In one embodiment, the transparent lithium aluminosilicate glass ceramic comprises the following components in mole percent: 77-74% SiO24.5 to 5.5% of Li2O, 11.5-13% of Al2O31.9-2.3% of Na2O, 0.5 to 1.5% of K20.5 to 1.5% of TiO20.5 to 1.2% of ZrO20.5 to 1.5% of B2O30 to 0.2 percent of SrO, 0.0 to 0.7 percent of ZnO, 0 to 1 percent of MgO, and 0 to 0.2 percent of P2O5The clarifying agent is 0.1-0.3% of CeO20.0 to 0.3% of Sb2O3And 0.0 to 0.1% of Na2SO4And (3) mixing.
In one embodiment, the transparent lithium aluminosilicate glass ceramic comprises the following components in mole percent: 69-70% SiO27.0 to 9.0% of Li2O, 12.5-13% of Al2O30.2 to 2.5 percent of Na2O, 0.8 to 1.3% of K21.5 to 2.0 percent of TiO21.0 to 1.5% of ZrO21.5 to 2.0 percent of B2O30 to 0.1 percent of CaO, 0.5 to 0.8 percent of ZnO, 0.8 to 1.0 percent of MgO, and a clarifying agent which is 0.1 to 0.3 percent of CeO20.0 to 0.3% of Sb2O3And 0.0 to 0.2% of Na2SO4And (3) mixing.
In one embodiment, the transparent lithium aluminosilicate glass is in mole percentThe ceramic contains the following components: 70-75% of SiO27.0 to 8.0% of Li2O, 11.0-13.0% of Al2O30.5 to 2.5 percent of Na2O, 0.3-2.0% of K21.5 to 2.0 percent of TiO21.0 to 1.5% of ZrO20.5 to 1.5% of B2O30 to 0.1 percent of CaO, 0.5 to 1.5 percent of ZnO, 0.2 to 0.5 percent of MgO, and 0.1 to 0.4 percent of CeO as a clarifying agent20.0 to 0.3% of Sb2O3And 0.0 to 0.2% of Na2SO4And (3) mixing.
In one embodiment, the transparent lithium aluminosilicate glass ceramic comprises the following components in mole percent: 70-74% SiO27.0 to 8.0% of Li2O, 11-12.5% of Al2O30 to 2.5% of Na2O, 0 to 1.5% of K21.3 to 2.0 percent of TiO20.2 to 1.3% of ZrO21.5 to 2.0 percent of B2O30 to 0.2% of SrO, 0.5 to 1.5% of ZnO, 0 to 0.1% of CaO, 0.3 to 0.1% of MgO, and 0 to 0.1% of P2O5The clarifying agent is 0.1-0.4% of CeO20.2 to 0.3% of Sb2O3And 0.0 to 0.2% of Na2SO4And (3) mixing.
The invention also provides a preparation method of the transparent lithium aluminosilicate glass ceramic, which comprises the following steps:
(1) mixing raw materials: the glass ceramic is prepared by grinding and uniformly mixing the components according to the corresponding molar percentage to prepare a glass batch, and putting the glass batch into a tiltable crucible which is arranged in a vacuum high-temperature metal smelting furnace and used for containing the glass batch;
(2) melting and clarifying: heating a metal smelting furnace to 1620-1670 ℃ for smelting clarification, wherein the air pressure in the furnace is kept at 0.1-0.02 standard atmospheric pressure during clarification, and the clarification time is controlled at 60-240 min;
(3) and (3) quick cooling and forming: rotating the tiltable crucible, pouring molten glass liquid onto a casting mold positioned below the crucible for rapid cooling and forming;
(4) stress relief annealing: annealing the formed glass at 550-630 ℃ for 1-3 h, and cooling to room temperature along with the furnace;
(5) nucleation and crystallization: heating the annealed glass to 580-730 ℃ for nucleation treatment for 1-2 h, then heating the glass subjected to nucleation treatment to 750-850 ℃ for crystallization treatment for 1-3 h, and cooling to obtain the transparent lithium aluminosilicate glass ceramic.
In one embodiment, the furnace body is closed before the glass batch is melted and clarified, the gas in the furnace is replaced, and the gas atmosphere in the vacuum high-temperature metal melting furnace is controlled to be an inert gas environment.
In one embodiment, the inert gas may be: n is a radical of2Ar, He or other inert gas simple substance or mixed gas.
In one embodiment, after the gas in the furnace is replaced, the gas pressure is maintained at 0.5-0.9 standard atmospheric pressure, the temperature of the glass batch is increased to 1620-1670 ℃ at a temperature increasing speed of 10 ℃/min, the temperature is maintained for 5-20 min after the temperature increasing process is finished, and then the gas pressure in the furnace is reduced to 0.1-0.02 standard atmospheric pressure.
In one embodiment, the inert gas pressure in the furnace is returned to 0.9 to 1.0 atm before the tiltable crucible is rotated.
In one embodiment, the temperature of the metal smelting furnace is preferably raised to 1640-1660 ℃ for melting clarification, and the temperature of the metal smelting furnace is more preferably raised to 1640-1650 ℃ for melting clarification.
In one embodiment, the pressure in the furnace is preferably maintained at 0.07 to 0.03 atm during the clarification, and more preferably 0.05 to 0.03 atm during the clarification.
In one embodiment, the clarification time is preferably controlled within 100-180 min, and more preferably within 100-140 min.
In one embodiment, the formed glass is annealed at 600-620 ℃ for 2 h.
In one embodiment, the nucleation is carried out at a temperature of between 580 ℃ and 730 ℃, preferably between 650 ℃ and 730 ℃More preferably at a temperature of 700 to 720 ℃ in the presence of a nucleating agent ZrO2/TiO2Forming crystal nucleus under the induction of mixed crystal, adding fluoride and P2O5、SnO2Can also participate in nucleation, and the nucleation process is finished by keeping the temperature for a certain period of time. The nucleation time is 1-2 h, preferably 1.5-2 h.
In one embodiment, the crystallization treatment is to continuously raise the temperature to 750-850 ℃, preferably 770-850 ℃, and more preferably 810-830 ℃ after the nucleation process is completed, so that the glass with the crystal nuclei is transformed into the glass ceramic with the beta-quartz solid solution as the main crystal phase, and the crystallization time is 1-3 hours, preferably 1.8-2.5 hours. In the case of the transformation, crystal growth occurs in the glass ceramic, and the thermal expansion coefficient and the light transmission performance of the glass ceramic are obviously changed.
In one embodiment, after the gas in the furnace is replaced, the gas pressure is maintained at 0.5-0.9 standard atmospheric pressure, the temperature of the glass batch is increased to 1620-1670 ℃ at a temperature increasing speed of 10 ℃/min, the temperature is maintained for 5-20 min after the temperature increasing process is finished, and then the gas pressure in the furnace is reduced to 0.1-0.02 standard atmospheric pressure.
In one embodiment, the inert gas pressure in the furnace is returned to 0.9 to 1.0 atm before the tiltable crucible is rotated.
The invention is further illustrated by the following examples.
Example 1
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO276.6％，Al2O311.9％，Li2O5.0％，Na2O2.0％，K2O1.0％，TiO20.5％，ZrO20.5％，B2O30.5％，SrO0.1％，ZnO0.5％，MgO1.0％，CeO20.2％，Sb2O30.1％，Na2SO40.1％。
Preparation method
Example 2
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO273.5％，Al2O312.8％，Li2O4.7％，Na2O2.0％，K2O0.5％，TiO21.6％，ZrO21.1％，B2O31.5％，ZnO0.6％，CaO0.1％，MgO0.9％，P2O50.2％，CeO20.2％，Sb2O30.2％，Na2SO40.1％。
Example 3
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO269..7％，Al2O313.0％，Li2O9.0％，Na2O0.2％，K2O0.9％，TiO21.7％，ZrO21.3％，B2O32.0％，SrO0.1％，ZnO0.6％，CaO0.1％，MgO0.8％，CeO20.2％，Sb2O30.3％，Na2SO40.1％。
Example 4
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO270.0％，Al2O312.5％，Li2O7.6％，Na2O2.1％，K2O1.3％，TiO21.5％，ZrO21.1％，B2O31.6％，SrO0.1％，ZnO0.5％，CaO0.1％，MgO0.8％，CeO20.3％，Sb2O30.3％，Na2SO40.2％。
Example 5
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO270.5％，Al2O313.0％，Li2O7.0％，Na2O2.2％，K2O1.6％，TiO21.5％，ZrO21.2％，B2O31.5％，SrO0.1％，ZnO0.4％，CaO0.1％，MgO0.5％，CeO20.1％，Sb2O30.2％，Na2SO40.1％。
Example 6
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO274.9％，Al2O311.0％，Li2O7.5％，Na2O0.7％，K2O0.3％，TiO21.6％，ZrO21.1％，B2O30.5％，SrO0.2％，ZnO1.1％，CaO0.1％，MgO0.4％，CeO20.4％，Sb2O30.1％，Na2SO40.1％。
Example 7
A lithium aluminosilicate glass ceramic comprising, in mole percent, SiO274.0％，Al2O311.0％，Li2O7.0％，Na2O0.5％，K2O0.5％，TiO21.3％，ZrO21.2％，B2O32.0％，SrO0.2％，ZnO1.3％，CaO0.1％，MgO0.3％，P2O50.1％，CeO20.2％，Sb2O30.2％，Na2SO40.1％。
Examples 1-7 were prepared as follows:
mixing raw materials: the glass ceramic comprises the following components in percentage by mol, grinding and mixing the components uniformly to prepare a glass batch, and putting the glass batch into a tiltable crucible arranged in a vacuum high-temperature metal smelting furnace and used for containing the glass batch;
melting and clarifying: sealing the furnace body before melting and clarifying the glass batch, replacing gas in the furnace, controlling the gas atmosphere in the vacuum high-temperature metal melting furnace to be an inert gas environment, wherein the inert gas can be used as follows: n is a radical of2Ar, He or other inert gas simple substances or mixed gas, wherein after gas in the furnace is replaced, the gas pressure is kept at 0.5-0.9 standard atmospheric pressure, the temperature of the glass batch is raised to 1620-1670 ℃ at the temperature raising speed of 10 ℃/min, the temperature is kept for 5-20 min after the temperature raising process is finished, the gas pressure in the furnace is kept at 0.1-0.02 standard atmospheric pressure during clarification, and the clarification time is controlled at 60-240 min;
and (3) quick cooling and forming: restoring the pressure of inert gas in the furnace to 0.9-1.0 standard atmospheric pressure, rotating the tiltable crucible, pouring molten glass liquid onto a casting mold positioned below the crucible for rapid cooling and forming;
stress relief annealing: annealing the formed glass at 550-630 ℃ for 1-3 h, and cooling to room temperature along with the furnace;
nucleation and crystallization: heating the annealed glass to 580-730 ℃ for nucleation treatment for 1-2 h, specifically at a temperature between 580 ℃ and 730 ℃ in the presence of a nucleating agent ZrO2/TiO2Forming crystal nucleus under the induction of mixed crystal, adding fluoride and P2O5、SnO2Can also participate in nucleation, and the nucleation process is finished by heat preservation for 1-2 h; and then heating the nucleated glass to 750-850 ℃ for crystallization for 1-3 h, specifically, after the nucleation process is finished, continuously increasing the temperature to 750-850 ℃ to convert the glass with crystal nuclei into glass ceramic with a beta-quartz solid solution as a main crystal phase, and crystallizing for 1-3 h. In the case of the transformation, crystal growth occurs in the glass ceramic, and the thermal expansion coefficient and the light transmission performance of the glass ceramic are obviously changed. During the nucleation and crystallization processes, the glass ceramic is kept in an oxygen-rich atmosphere, so that the stability of the glass components is ensured;
and after crystallization and cooling are finished, obtaining the transparent lithium aluminosilicate glass ceramic.
The lithium aluminosilicate glass ceramics prepared in examples 1-7 were tested to have the properties shown in Table 1.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A transparent lithium aluminosilicate glass ceramic, characterized in that the glass ceramic comprises the following components in mol percent: SiO 22 69～77％，Li2O 4～9％，Al2O3 11～13％，Na2O 0～2.5％，K2O 0～2.0％，TiO2 0.3～2.0％，ZrO2 0.2～1.5％，B2O3 0～2％，SrO 0～0.2％，ZnO 0.5～1.5％，CaO 0～0.1％，MgO 0～1％，P2O50-0.3% of a clarifying agent, and 0.4-1.0% of a clarifying agent; the clarifying agent is formed by CeO2、Sb2O3And a sulfate compound.
2. The transparent lithium aluminosilicate glass-ceramic according to claim 1, wherein the Li is2O，Na2O，K2The total molar content of O is sigma R2O, said SiO2And Al2O3Has a total molar content of sigma XO, wherein sigma R2O is 8.0-11.0%, sigma R2The O +. Sigma XO is 92-97%.
3. The preparation method of the transparent lithium aluminosilicate glass ceramic is characterized by comprising the following steps:
(1) mixing raw materials: the glass ceramic of claim 1 or 2 is prepared by mixing the components in the molar percentages, grinding and mixing the components uniformly, and putting the mixture into a pourable crucible arranged in a vacuum high-temperature metal smelting furnace for containing glass batch;
(2) melting and clarifying: heating a metal smelting furnace to 1620-1670 ℃ for smelting clarification, wherein the air pressure in the furnace is kept at 0.1-0.02 standard atmospheric pressure during clarification, and the clarification time is controlled at 60-240 min;
(3) and (3) quick cooling and forming: rotating the tiltable crucible, pouring molten glass liquid onto a casting mold positioned below the crucible for rapid cooling and forming;
(4) stress relief annealing: annealing the formed glass at 550-630 ℃ for 1-3 h, and cooling to room temperature along with the furnace;
(5) nucleation and crystallization: heating the annealed glass to 580-730 ℃ for nucleation treatment for 1-2 h, then heating the glass subjected to nucleation treatment to 750-850 ℃ for crystallization treatment for 1-3 h, and cooling to obtain the transparent lithium aluminosilicate glass ceramic.
4. The transparent lithium aluminosilicate glass ceramic according to claim 3, wherein the furnace body is closed before the glass batch is melted, the gas in the furnace is replaced, and the gas atmosphere in the vacuum high-temperature metal melting furnace is controlled to be an inert gas environment.
5. The transparent lithium aluminosilicate glass ceramic according to claim 4, wherein after the gas replacement in the furnace, the gas pressure is maintained at 0.5 to 0.9 atm, the glass batch is heated to 1620 to 1670 ℃ at a heating rate of 10 ℃/min, the temperature is maintained for 5 to 20min after the heating process is completed, and then the gas pressure in the furnace is reduced to 0.1 to 0.02 atm.
6. The transparent lithium aluminosilicate glass ceramic according to claim 5, wherein the inert gas pressure in the furnace is returned to 0.9 to 1.0 atm before the rotation of the pourable crucible.
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Application publication date: 20201208 |