CN111943513A - Lithium-aluminum-silicon ceramic white microcrystalline glass and manufacturing method thereof - Google Patents
Lithium-aluminum-silicon ceramic white microcrystalline glass and manufacturing method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 55
- -1 Lithium-aluminum-silicon Chemical compound 0.000 title claims abstract description 17
- 239000000919 ceramic Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000003490 calendering Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims 2
- 238000003825 pressing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000008395 clarifying agent Substances 0.000 description 5
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011797 cavity material Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007688 edging Methods 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000006089 photosensitive glass Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910000500 β-quartz Inorganic materials 0.000 description 1
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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
- C03C10/0018—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
- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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Abstract
The invention relates to a lithium-aluminum-silicon ceramic white microcrystalline glass and a manufacturing method thereof, in particular to a matching application of a microcrystalline glass plate for a microwave oven. The material mainly comprises the following raw materials in percentage by weight: SiO 2267.0~70.0%；Al2O317.0~20.0%；Li2O 2.7~3.5%；MgO 0.4~1.4%；ZnO 0.4~1.5%；BaO 0.1~2.0%；TiO21.5~3.0%；ZrO21.2~2.0%；P2O50.5~2.0%；MgF20.1~0.5%；K2O 0.2~0.8%；Na2O 0.2~0.8%；Sb2O30.1~0.25%；SnO20.1-1.0%; 0.1-0.8% of NaCl0. The raw materials are weighed, mixed and stirred uniformly, the mixture is melted, clarified, homogenized, cooled and rolled into a plate in a tank furnace, the plate is annealed and nucleated and crystallized to obtain the lithium-aluminum-silicon ceramic white microcrystalline glass plate, and the plate is cut, edged, printed and inspected to obtain the special plate for the microwave oven, is small in microwave absorption, free of focusing in no-load, free of corrosion and environment-friendly.
Description
Technical Field
The invention relates to a lithium-aluminum-silicon ceramic white microcrystalline glass and a manufacturing method thereof, in particular to a matching application of a microcrystalline glass plate for a microwave oven.
Background
Li2O-Al2O3-SiO2The invention was discovered in 1957 by Corning of America in the production of photosensitive glass, firstly, the lithium-aluminum-silicon glass ceramics, mainly TiO2As a crystal nucleus agent, with As2O3The sodium silicate clarifier is a clarifier and is used for manufacturing high-temperature resistant cookware vessels, is popular with American people due to high temperature resistance, high strength, no pollution and direct firing and is developed into amber transparent microcrystalline glass cookware. Due to the diversification of the crystal nucleus agent, the performance of the microcrystalline glass is diversified, such as the adjustability of linear expansion coefficient, the adjustability of multiple components from negative expansion to zero expansion to low expansion and high expansion, and the application range is greatly improved, such as adjustable zero-expansion transparent microcrystalline glass astronomical telescope lens blanks, the resonant cavity material for a standard timing cesium atomic clock cavity, a matching panel of household appliances, a liquid crystal display touch screen, a mobile phone back panel and the like.
The development of the lithium-aluminum-silicon ceramic white microcrystalline glass is also from single TiO2Nucleation of agents to TiO2、ZrO2、P2O5Isocomplex nucleating agents, the appearance of spodumene (Li)2O:Al2O3:SiO21:1: 4) to form a solid solution of β -quartz, a microcrystalline glass composed of various crystals of eucryptite and spodumene, and a transparent microcrystalline glass. Due to Li2O-Al2O3-SiO2The microcrystalline glass needs to be melted at high temperature, and because the viscosity is large and the forming viscosity range is small, certain difficulty is brought to clarifying the glass liquid,a large amount of As has been used2O3、Sb2O3To eliminate bubbles due to As2O3Has extremely toxic gas emission, brings harm to glass melting furnaces, production workers and the environment, and remains As in glass2O3It also presents a hazard to the user. Although As2O3And Sb2O3As a clarifying agent for producing microcrystalline glass panels, the REACH regulation No. 1907/2006 of European Union limits the content of arsenic and antimony in glass products, so that the clarifying agent which can replace arsenic trioxide and antimony trioxide is researched and developed at home and abroad. Patents such as publication nos. CN107667076A, CN109594674A, CN104609733A and CN109020191A disclose arsenic-free and antimony-free lithium aluminum silicon glass ceramics and a method for producing the same. In the above patent publication, tin dioxide is mainly used as a clarifier for lithium-aluminum-silicon glass ceramics or other glass systems, and cerium oxide, sodium sulfate, barium sulfate and sodium nitrate are added singly or in combination.
Disclosure of Invention
The invention mainly solves the technical problem of providing the lithium aluminum silicon ceramic white microcrystalline glass for the microwave oven and the manufacturing method thereof, and the lithium aluminum silicon ceramic white microcrystalline glass consists of the improved main component and the improved composite clarifying agent, and has the advantages of easy melting, small forming viscosity, good clarifying effect, low cost, short crystallization time, wide crystallization range, no toxicity, no harm and environmental protection.
In order to solve the technical problems, the invention provides a formula of lithium aluminum silicon ceramic white microcrystalline glass suitable for a microwave oven, which mainly comprises the following raw materials in percentage by weight: SiO 2267.0-70.0% of (silicon dioxide), and Al2O317.0-20.0% of (aluminum oxide), and Li22.7-3.5% of O (lithium oxide); 0.4-1.4% of MgO (magnesium oxide), 0.4-1.5% of ZnO (zinc oxide) and 0.1-2.0% of BaO (barium oxide); TiO 22(titanium dioxide) 1.5 to 3.0%, ZrO2(zirconium dioxide) 1.2-2.0%，P2O50.5-2.0% of (phosphorus pentoxide), MgF2(magnesium fluoride) 0.1-0.5%; k20.2-0.8% of O (potassium oxide) and Na20.2-0.8% of O (sodium oxide); sb2O30.1-0.25% of (antimony trioxide), SnO20.1-1.0% of (tin dioxide) and 0.1-0.8% of NaCl (sodium chloride).
Preferably, the lithium aluminum silicon ceramic white microcrystalline glass provided by the invention comprises the following raw materials in parts by weight: SiO 2268.0%，Al2O3 18%，Li2O 3.0%；MgO 0.6%，ZnO 0.8%，BaO 2.0%；TiO2 2.8%，ZrO2 1.75%，P2O50.6%，MgF2 0.3%；K2O 0.35%，Na2O 0.6%；Sb2O3 0.22%，SnO2 0.38%，NaCl 0.6%。
The invention relates to a method for manufacturing lithium aluminum silicon ceramic white microcrystalline glass, which comprises the following steps:
1) weighing the raw materials, mixing and stirring uniformly for later use;
2) melting the mixed batch in a pool furnace at 1630-1650 ℃, clarifying, homogenizing and cooling to obtain bubble-free, pockmark-free, stripe-free and stone-free high-quality molten glass, and feeding the molten glass into a feeding channel;
3) sending the glass liquid entering the feeding channel into a calender for calendering and molding to prepare required plate-shaped glass, and sending the plate-shaped glass into a continuous annealing furnace, wherein the annealing temperature is 650 ℃;
4) nucleating the plate-shaped glass in a continuous crystallization furnace at 720 ℃ for 1 hour, crystallizing the plate-shaped glass in a crystallization area at 980-1020 ℃ for 40-60 minutes, cooling and cutting the plate-shaped glass into the required plate.
5) And (3) after cutting, edging, polishing, printing, inspecting and packaging the glass to obtain the lithium aluminum silicon ceramic white microcrystalline glass plate.
The technical advantages of the invention are as follows:
1) the main component of the invention is SiO2If the content of (silicon dioxide) is increased to more than 70%, Al2O3(aluminum oxide) less than 16%, Li2O (lithium oxide) less than 2.7%, it is difficult to obtainMaterials are used in the microwave oven, the microwave transmission in the microwave oven is poor, no-load test is easy to focus on ablation, and even a microcrystalline plate is burnt through;
2) sb for clarifying agent of the invention2O3、SnO2NaCl and trace MgF2The composite clarifying agent has three main functions: firstly, reducing the high-temperature viscosity of the glass; ② the clarification effect is obtained by reducing the gas partial pressure; the function of crystal nucleus agent;
3） Sb2O3、SnO2has the function of clarifying at medium and high temperature, and uses the low-temperature oxygen release of potassium nitrate and sodium to ensure that Sb is2O3、SnO2Absorption of O2The aim of high-temperature reduction and oxygen release is achieved, and the clarification effect is achieved; a certain amount of NaCl releases gas at the high temperature of 1450 ℃ to reduce the partial pressure of other gases to achieve the clarification effect.
The main component of the Li-Al-Si series ceramic white microcrystalline glass can reach a better component range for a microwave oven, the clarifier is nontoxic, harmless and environment-friendly, the main crystal phase of the Li-Al-Si series ceramic white microcrystalline glass is beta-spodumene, the grain size is about 2 mu m, and the thermal expansion coefficient is 0.5-1.65 multiplied by 10-6The bending strength exceeds 100MPa, the temperature of the plate surface does not exceed 150 ℃ on average after the microwave oven is unloaded for 15min, various technical indexes meet the requirement of QB/T4831-2015, and the content of arsenic and antimony meet the requirement of REACH regulation of European Union No. 1907/2006.
In conclusion, the microcrystalline glass of the invention meets the index requirements of microwave oven panels.
Drawings
FIG. 1 is an unloaded (5 min) focusing diagram of the microwave oven;
FIG. 2 is an XRD pattern of an example porcelain white microcrystalline glass;
FIG. 3 is a SEM photograph of a 5000-fold magnified microstructure;
FIG. 4 is an SEM photograph of a magnified 20000 times microstructure;
FIG. 5 is a table of the average coefficient of thermal expansion from 30 ℃ to 500 ℃.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example A lithiumThe aluminum-silicon ceramic white microcrystalline glass comprises the following raw materials in percentage by weight: SiO 2268.0%；Al2O3 18%；Li2O 3.0%；MgO 0.6%；ZnO 0.8%；BaO 2.0%；TiO2 2.8%；ZrO2 1.75%；P2O50.6%；MgF2 0.3%；K2O 0.35%；Na2O 0.6%；Sb2O3 0.22%；SnO2 0.38%；NaCl 0.6%。
The specific preparation method comprises the following steps:
1) mixing the raw materials (the ingredients with the weight content), uniformly stirring, and preparing into a uniform mixture;
2) melting the mixture in a tank furnace at 1630-1650 ℃, clarifying and homogenizing;
3) carrying out hydraulic calendering on the glass entering the feeding channel to obtain plate-shaped glass, wherein the thickness of the plate-shaped glass is 3.8 +/-0.2 mm;
4) feeding the continuous rolling formed glass plate into a continuous roller way annealing furnace, wherein the annealing temperature is 650 ℃, and annealing for 40 minutes;
5) nucleating the annealed plate-shaped glass obtained in the step 4) for 40 minutes at the temperature of 720 ℃, then heating to 1020 ℃, preserving the heat for 40-60 minutes, and cooling to room temperature along with a roller kiln;
6) and cutting, edging and polishing the crystallized glass plate, and then printing, drying, inspecting and packaging.
The detection shows that the appearance has no bubbles, stripes, good uniformity and good porcelain whiteness, the main crystal phase of the porcelain is beta-spodumene, and a microwave oven no-load (5 min) focusing diagram is shown in figure 1; the XRD pattern is shown in figure 2; the SEM photographs are shown in fig. 3 and 4, wherein fig. 3 is a microstructure magnified 5000 times and fig. 4 is a microstructure magnified 20000 times; the expansion coefficient is shown in fig. 5.
Claims (4)
1. The lithium-aluminum-silicon ceramic white microcrystalline glass mainly comprises the following raw materials in parts by weight: SiO 22 67.0~70.0%；Al2O317.0~20.0%；Li2O 2.7~3.5%；MgO 0.4~1.4%；ZnO 0.4~1.5%；BaO 0.1~2.0%；TiO2 1.5~3.0%；ZrO2 1.2~2.0%；P2O5 0.5~2.0%；MgF2 0.1~0.5%；K2O 0.2~0.8%；Na2O 0.2~0.8%；Sb2O3 0.1~0.25%；SnO2 0.1~1.0%；NaCl 0.1~0.8%。
2. The lithium aluminum silicon system porcelain white microcrystalline glass according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: SiO 22 68.0%；Al2O3 18%；Li2O 3.0%；MgO 0.6%；ZnO 0.8%；BaO 2.0%；TiO2 2.8%；ZrO21.75%；P2O5 0.6%；MgF2 0.3%；K2O 0.35%；Na2O 0.6%；Sb2O3 0.22%；SnO2 0.38%；NaCl 0.6%。
3. The method for producing a lithium aluminosilicate porcelain white microcrystalline glass according to claim 1 or 2, comprising the steps of;
weighing the raw materials, mixing and stirring uniformly for later use;
melting the mixed batch in a pool furnace at 1630-1650 ℃, clarifying, homogenizing and cooling to obtain bubble-free, pockmark-free, stripe-free and stone-free high-quality molten glass, and feeding the molten glass into a feeding channel;
sending the glass liquid entering the feeding channel into a calender for calendering and molding to prepare required plate-shaped glass, and sending the plate-shaped glass into a continuous annealing furnace, wherein the annealing temperature is 650 ℃;
nucleating the plate-shaped glass in a continuous crystallization furnace at 720 ℃ for 1 hour, crystallizing the plate-shaped glass in a crystallization area at 980-1020 ℃ for 40-60 minutes, cooling and cutting the plate-shaped glass into the required plate.
4. The method for producing a lithium aluminosilicate porcelain white microcrystalline glass according to claim 3, wherein: wherein the forming treatment in the step 3 is calendering or pressing to form the cooker.
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| CN113024121A (en) * | 2021-04-26 | 2021-06-25 | 赵国祥 | Microcrystalline glass plate production process |
| WO2022228583A1 (en) * | 2021-04-28 | 2022-11-03 | 深圳晶酝科技有限公司 | Glass-ceramic material, preparation method therefor and application thereof in semiconductor devices |
| CN116730623A (en) * | 2023-06-20 | 2023-09-12 | 青岛融合新材料科技有限公司 | Machinable composite phase mica microcrystalline glass and preparation process thereof |
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