CN115304259A - Low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass and preparation method thereof - Google Patents
Low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass and preparation method thereof Download PDFInfo
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- CN115304259A CN115304259A CN202210901520.4A CN202210901520A CN115304259A CN 115304259 A CN115304259 A CN 115304259A CN 202210901520 A CN202210901520 A CN 202210901520A CN 115304259 A CN115304259 A CN 115304259A
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- 239000011521 glass Substances 0.000 title claims abstract description 113
- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 42
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- -1 magnesium-aluminum-silicon Chemical compound 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 105
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 239000002667 nucleating agent Substances 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000010899 nucleation Methods 0.000 claims abstract description 11
- 230000006911 nucleation Effects 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 235000012245 magnesium oxide Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 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 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910000174 eucryptite Inorganic materials 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000006060 molten glass Substances 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000011044 quartzite Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052642 spodumene Inorganic materials 0.000 claims description 3
- 230000008646 thermal stress Effects 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000013081 microcrystal Substances 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 239000002241 glass-ceramic Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 239000006121 base glass Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000005347 annealed glass Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910001753 sapphirine Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 241000218176 Corydalis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 102000002027 Tuberin Human genes 0.000 description 1
- 108050009309 Tuberin Proteins 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical group [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- SZCZSKMCTGEJKI-UHFFFAOYSA-N tuberin Natural products COC1=CC=C(C=CNC=O)C=C1 SZCZSKMCTGEJKI-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C03C10/0036—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 a divalent metal oxide as main constituents
- C03C10/0045—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 a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention belongs to the technical field of glass manufacturing, and particularly discloses low-expansion magnesium-aluminum-silicon cordierite glass ceramic and a preparation method thereof, wherein the preparation method comprises the following steps: crystallizing the glass plate: the crystallization is carried out in two stages, in the first stage, the glass plate after annealing and cutting is heated again to the nucleation temperature T Nucleus And preserving heat; the second stage is heated again to the crystal growth temperature T Crystal grain So that the glass plate is converted into the low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass; the glass plate is prepared from the following components: mgO raw material and Al 2 O 3 Raw material, siO 2 Raw materials and oxide nucleating agents; mgO raw material accounts for 6-35 wt%, al 2 O 3 The raw material accounts for 8-38 wt% and SiO 2 45-72 wt% of raw materials and the balance of oxide nucleating agent. Hair brushBy optimizing the material structure, adding a nucleating agent with a specific proportion, carrying out heat treatment at a certain temperature, carrying out crystallization treatment on glass, controlling the change of basic glass components and controlling the type of precipitated crystal phase and the size of a microcrystalline phase, and then the glass becomes a functional material with uniformly distributed microcrystals and glass phases.
Description
Technical Field
The invention belongs to the technical field of glass manufacturing, and particularly relates to low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass and a preparation method thereof.
Background
The microcrystalline glass is a polycrystalline material obtained by purposefully controlling the generation and growth of crystals by carrying out heat treatment on glass according to a certain process system, and has the basic properties of glass and the characteristics of ceramic polycrystal. After the base glass added with the specific components of the nucleating agent is subjected to heat treatment at a certain temperature, the change of the components of the base glass is controlled, and the type of precipitated crystal phase and the size of a microcrystal phase are controlled, so that the glass becomes a functional material with uniformly distributed microcrystals and glass phases.
The existing microcrystalline glass industry has the defects that the capacity is too small, the market share is less than 10%, the yield of a production line is low, most of the glass is below 30% or even lower, and the main glass defect is that the gas impurities are more and are difficult to solve; the crystallization process is not well mastered, and the yield is too low. The fundamental reasons of the method are that related industrial chains are incomplete, and the material side structure is unreasonable.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass and the preparation method thereof, so as to solve the problems of incomplete control of a crystallization process and unreasonable material prescription structure in the existing microcrystalline glass manufacturing process.
In order to achieve the purpose, the invention adopts the following technical scheme:
on the one hand, the invention provides a preparation method of low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass,
the method comprises the following steps:
carrying out crystallization treatment on the cut glass plate: the crystallization is carried out in two stages, the first stage is to cut the annealed materialThe glass plate is then heated again to the nucleation temperature T Core And preserving heat; the second stage is to increase the temperature to the crystal growth temperature T Crystal So that the glass plate is converted into the low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass;
the glass plate is prepared from the following components: mgO raw material and Al 2 O 3 Raw material, siO 2 Raw materials and an oxide nucleating agent; the components account for the total mass of the raw materials:
the proportion of MgO raw material is 6-35 wt%, al 2 O 3 8 to 38 percent of raw material and SiO 2 45-72 wt% of raw materials and the balance of oxide nucleating agent;
the oxide nucleating agent is TiO 2 Starting Material, zrO 2 Raw Material, P 2 O 5 Raw material, caO raw material, li 2 One or more of O raw materials.
Further, before the glass plate is prepared, the particle size uniformity and the water content of the raw materials are detected; removing metal impurities in the raw materials.
Further, the TiO is 2 Starting Material, zrO 2 Raw Material, P 2 O 5 Raw material, caO raw material, li 2 The O raw material accounts for the total mass of the raw materials as follows:
TiO 2 the raw material accounts for 5 to 20 weight percent, and ZrO 2 2 to 15 percent of raw material and P 2 O 5 0.2-4 wt% of raw material, 0.1-3 wt% of CaO raw material, and Li 2 The proportion of the O raw material is 0.5wt% -1.5 wt%.
Further, after removing metal impurities in the raw materials, uniformly mixing the raw materials by using a paddle type mixer to form a mixture, conveying the mixture to a melting furnace for melting, and melting the uniformly mixed mixture to form molten glass; and (3) diffusing and permeating the glass liquid at high temperature to form a whole, and calendering to form a glass plate with a set size.
Further, after the glass plate is rolled and formed into a glass plate with a set size, the rolled and formed glass plate is annealed to eliminate the thermal stress of the glass plate, and the annealed glass plate is cut into a required size.
Further, the SiO 2 The raw materials are one or more of quartz sand, sandstone, quartzite and gangue quartz; the MgO raw material is magnesium carbonate; the Al is 2 O 3 The raw material is one or more of feldspar, kaolin, pyrophyllite, industrial alumina and aluminum hydroxide.
Further, the MgO and Al 2 O 3 Is less than 1.
Further, the TiO is 2 The raw material is titanium dioxide; the ZrO 2 The raw material is one or more of zircon and baddeleyite; the P is 2 O 5 The raw material is phosphoric anhydride; the CaO raw material is calcium carbonate; the Li 2 The O raw material is one or more of eucryptite, spodumene, lithium carbonate and lithium hydroxide.
Further, the nucleation temperature T Core At 550 ℃; the crystal growth temperature T Crystal grain Ratio T Core The temperature is 150-250 ℃; the crystallization treatment is carried out in a crystallization furnace; the heat preservation time in the first stage is 1-2 hours; the temperature rise rate of the first stage is 8-10 ℃/hr, and the temperature rise rate of the second stage is 3-5 ℃/hr.
In another aspect, the invention provides a low-expansion magnesium aluminosilicate cordierite microcrystalline glass, which is prepared according to any one of the preparation methods of the low-expansion magnesium aluminosilicate cordierite microcrystalline glass.
The invention has at least the following beneficial effects:
1. the invention optimizes the material structure, adds crystal nucleus agent to heat treat at certain temperature, to crystallize the glass, to control the change of basic glass component and the crystal phase type and micro crystal phase size, to change the glass into micro crystal and glass phase evenly distributed functional material.
2. The expansion coefficient of the low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass can be from negative expansion to zero expansion of 100 multiplied by 10 -7 An expansion coefficient of greater than/° c, so that it can be well matched to the expansion characteristics of many materials, can be madeThe mechanical strength of the glass ceramics is more than 6 times that of the common glass, the glass ceramics has good thermal stability, can be heated to 900 ℃ and quickly put into 5 ℃ cold water without cracking, has electrical insulation performance close to that of high-voltage electric porcelain, has chemical stability far superior to that of the common glass, and resists acid and alkali corrosion. The cover plate is widely applied to a plurality of aspects such as a computer hard disk substrate, a front cover plate and a rear cover plate of a mobile phone, a computer display screen cover plate, a vehicle-mounted multimedia video display screen cover plate and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
In the drawings:
FIG. 1 shows MgO-Al 2 O 3 —SiO 2 A schematic diagram of a ternary system phase diagram of the cordierite microcrystalline glass;
FIG. 2 shows MgO and Al 2 O 3 A schematic diagram of the microstructure of the microcrystalline glass when the molar ratio is more than 1;
FIG. 3 shows MgO and Al 2 O 3 A schematic diagram of the micro-structure of the microcrystalline glass when the molar ratio is equal to 1;
FIG. 4 shows MgO and Al 2 O 3 And when the molar ratio is less than 1, the microstructure of the microcrystalline glass is shown schematically.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The following detailed description is exemplary in nature and is intended to provide further details of the invention. Unless otherwise defined, all technical 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 is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
A preparation method of low-expansion magnesium aluminum silicon cordierite microcrystalline glass comprises the following steps:
s1: detecting the particle size uniformity, the water content and the like of the raw materials; removing metal impurities such as iron and the like in the raw materials;
s2: the powder is strictly weighed according to the proportion of the powder in the material prescription, and the precision is required to be one in a thousand;
the glass plate is prepared from the following components: mgO raw material and Al 2 O 3 Raw material, siO 2 Raw materials and an oxide nucleating agent; the components account for the total mass of the raw materials as follows:
6-35 wt% of magnesium oxide (MgO) raw material and aluminum oxide (Al) 2 O 3 ) 8 to 38 percent of raw material and silicon dioxide (SiO) 2 ) 45-72 wt% of raw materials, and the balance of oxide nucleating agent;
the oxide nucleating agent is titanium dioxide (TiO) 2 ) Raw material, zirconium dioxide (ZrO) 2 ) Raw material, phosphorus pentoxide (P) 2 O 5 ) Raw material, calcium oxide (CaO) raw material, lithium oxide (Li) 2 O) one or more of the raw materials; tiO 2 2 Starting Material, zrO 2 Raw Material, P 2 O 5 Raw material, caO raw material, li 2 The O raw material accounts for the total mass of the raw materials as follows:
TiO 2 the raw material accounts for 5-20 wt%, zrO 2 2 to 15 percent of raw material and P 2 O 5 0.2-4 wt% of raw material, 0.1-3 wt% of CaO raw material, and Li 2 The proportion of the O raw material is 0.5wt% -1.5 wt%.
S3: uniformly mixing various raw materials by using a paddle type mixer to form a mixture, conveying the mixture to a smelting furnace for melting, and melting the uniformly mixed mixture at a certain temperature to form molten glass; and diffusing the glass liquid at high temperature to achieve uniform penetration, and rolling and forming to obtain the glass plate with the set size.
S4: annealing the rolled and formed glass plate, eliminating the thermal stress of the glass plate, and cutting the annealed glass plate into required sizes;
s5: in the crystallizationCrystallizing the cut glass plate in a furnace to obtain a microcrystalline glass plate: the crystallization is carried out in two stages, the first stage is that the glass plate after annealing and cutting is heated again to the nucleation temperature T Core (at this time T Core 550 ℃ and holding for a certain time (generally 1 to 2 hours for sufficient nucleation) at which a large number of stable nuclei appear in the glass plate; the second stage is to raise the temperature to the crystal growth temperature T Crystal grain (general ratio T) Core The temperature is 150-250 ℃, at this time T Crystal grain 780 ℃) to convert the glass plate into a low-expansion magnesium aluminum silicon cordierite microcrystalline glass with stable submicron or nanometer grain size.
The temperature rising rate of the first stage is 8-10 ℃/hr, and the temperature rising rate of the second stage is 3-5 ℃/hr; the temperature is accurately controlled, the heating rate is reduced, the nucleation and crystallization temperatures are reduced, and the heat preservation time is prolonged, so that the prepared microcrystalline glass has finer crystal grains and a crystal phase with a uniform structure, and the mechanical property of the microcrystalline glass is improved.
And packaging the manufactured microcrystalline glass, and transporting to a downstream manufacturer.
SiO 2 The raw material is one or more of quartz sand, sandstone, quartzite, vein quartz and the like.
The MgO raw material mainly comprises magnesium carbonate and the like.
Al 2 O 3 The raw materials mainly comprise one or more of feldspar, kaolin, pyrophyllite, industrial alumina, aluminum hydroxide and the like.
TiO 2 The raw materials mainly comprise titanium dioxide and the like.
ZrO 2 The raw materials mainly comprise one or more of zircon, baddeleyite and the like.
P 2 O 5 The raw materials mainly comprise phosphoric anhydride and the like.
The CaO raw material is mainly calcium carbonate.
Li 2 The O raw material is one or more of eucryptite, spodumene, lithium carbonate, lithium hydroxide and the like.
The chemical formula of the cordierite is 2 MgO.2Al 2 O 3 ·5SiO 2 Root of corydalis TuberIn view of the stoichiometric composition of the stone, the ideal formula of the cordierite microcrystalline glass is as follows (mass fraction): 13.8wt% of MgO and Al 2 O 3 34.9wt% SiO 2 It was 51.3% by weight. In general, magnesium-aluminum-silicon MgO-Al with cordierite as main crystal phase 2 O 3 —SiO 2 The basic composition of the system microcrystalline glass is selected from MgO-Al 2 O 3 —SiO 2 In the region of the cordierite of the ternary system phase diagram.
As shown in FIG. 1, it is a magnesium-aluminum-silicon MgO-Al 2 O 3 —SiO 2 A ternary system phase diagram schematic diagram of the Cordierite microcrystalline glass, wherein Cristabolite is Cristobalite, tridymite is Tridymite, protoenstatite is enstatite, cordierite is Cordierite, sapphirine is Sapphirine, spinel is Spinel, forsterite is Forsterite, periclase is Periclase, mullite is Mullite, and Corundum is Corundum.
Based on magnesium, aluminum, silicon, mgO-Al 2 O 3 —SiO 2 And (3) researching and designing a three-element system phase diagram of the cordierite microcrystalline glass. By studying MgO-A constituting cordierite l2 O 3 —SiO 2 The transition kinetics and the microscopic particle structure of the system microcrystalline glass, it was found that the system is mainly determined by the most primitive glass composition. The composition is rich in MgO and SiO 2 And not according to the stoichiometric composition of cordierite. The laboratory microstructure showed for Al enrichment 2 O 3 In the glass, trivalent aluminum ions Al 3 + Is in a four-coordinate state with a silicon-oxygen tetrahedron (SiO) 4 ) A uniform network structure is formed so that the stability of the network is enhanced, and Al 2 O 3 The higher the content of (b), the more stable the network of the glass. At the same time, with Al 2 O 3 The content is increased, so that the viscosity of the glass is increased, and the crystallization activation energy is increased, so that the heat treatment system of the microcrystalline glass becomes easy to control. By accurately controlling the temperature, reducing the heating rate, reducing the nucleation and crystallization temperatures and increasing the heat preservation time, the prepared microcrystalline glass has finer crystal grains and a crystal phase with a uniform structure, thereby improving the mechanical property of the microcrystalline glass.
Through repeated experiments, mgO-Al 2 O 3 —SiO 2 The basic material prescription of the system microcrystalline glass is biased to be rich in MgO and Al 2 O 3 The main consideration of the components is to optimize the viscosity and the preparation process of the base glass and simultaneously improve various properties of the microcrystalline glass. In the presence of rich MgO and Al 2 O 3 On the basis of the method, other oxides and nucleating agents are added to adjust the microstructure and crystallization of the microcrystalline glass.
One of the oxide nucleating agents used is TiO 2 The experimental analysis result shows that when TiO is used 2 When the mass fraction of the glass is within the range of 5-20 wt%, the glass has a promoting effect on crystallization of the magnesium-aluminum-silicon cordierite microcrystalline glass. During annealing or reheating of the glass, large amounts of submicroscopic particles precipitate in the glass, which particles help to precipitate crystals from the glass. But using TiO alone 2 As a crystal nucleating agent, the optimal nucleation temperature and the optimal crystallization temperature of a glass melt are difficult to determine, and the microcrystalline glass is easy to generate a semitransparent phenomenon during heating, so that the transparency of the microcrystalline glass is poor.
The second oxide nucleating agent used is zirconium dioxide ZrO 2 The experimental results show that when ZrO is introduced 2 When the glass is used as a crystal nucleating agent, the optimal nucleation temperature and the optimal crystallization temperature of the glass melt can be determined, and the visible light transmittance of the microcrystalline glass can be greatly improved.
As shown in FIG. 2, when MgO and Al are mixed 2 O 3 When the molar ratio is more than 1, a large amount of columnar cordierite crystals are precipitated in the microstructure of the crystallized sample, and a small amount of granular spinel crystals are precipitated. At this time, the crystal growth was relatively complete, but the enrichment of the columnar cordierite crystals occurred in a partial region of the sample.
As shown in FIG. 3, when MgO and Al are mixed 2 O 3 When the molar ratio is 1, dense and massive cordierite crystals are precipitated in the microstructure of the crystallized sample, and a small amount of fine and granular spinel crystals are precipitated, but the distribution of the crystals is disordered and very uneven.
As shown in FIG. 4, when MgO and Al are mixed 2 O 3 When the molar ratio is less than 1, a large amount of fine granular spinel crystals and compact blocky cordierite crystals are separated out from the microstructure of the crystallized sample, the crystal granularity is small and is uniformly distributed, and simultaneously, a glass phase and a crystal phase are tightly combined together.
A low-expansion magnesium aluminum silicon cordierite microcrystalline glass is prepared according to a preparation method of the low-expansion magnesium aluminum silicon cordierite microcrystalline glass.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. The preparation method of the low-expansion magnesium aluminum silicon cordierite microcrystalline glass is characterized by comprising the following steps of:
and (3) carrying out crystallization treatment on the cut glass plate: the crystallization is carried out in two stages, the first stage is that the glass plate after annealing and cutting is heated again to the nucleation temperature T Core And preserving heat; the second stage is to increase the temperature to the crystal growth temperature T Crystal So that the glass plate is converted into the low-expansion magnesium-aluminum-silicon cordierite microcrystalline glass;
the glass plate is prepared from the following components: mgO raw material and Al 2 O 3 Raw material, siO 2 Raw materials and oxide nucleating agents; the components account for the total mass of the raw materials as follows:
the proportion of MgO raw material is 6-35 wt%, al 2 O 3 8 to 38 percent of raw material and SiO 2 The raw material accounts for 45-72 wt%, and the balance is oxide nucleating agent;
the oxide nucleating agent is TiO 2 Raw material, zrO 2 Raw Material, P 2 O 5 Raw material, caO raw material, li 2 One or more of O raw materialsAnd (4) a plurality of.
2. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass as claimed in claim 1, wherein before the glass plate is prepared, the particle size uniformity and the water content of raw materials are detected; removing metal impurities in the raw materials.
3. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 1, wherein the TiO is 2 Raw material, zrO 2 Raw Material, P 2 O 5 Raw material, caO raw material, li 2 The O raw material accounts for the total mass of the raw materials as follows:
TiO 2 the raw material accounts for 5-20 wt%, zrO 2 2 to 15 percent of raw material and P 2 O 5 0.2-4 wt% of raw material, 0.1-3 wt% of CaO raw material, and Li 2 The proportion of the O raw material is 0.5wt% -1.5 wt%.
4. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 2, wherein metal impurities in the raw materials are removed, the raw materials are uniformly mixed by a paddle type mixer to form a mixed material, the mixed material is conveyed to a smelting furnace to be melted, and the uniformly mixed material is melted to form molten glass; and (3) diffusing and permeating the glass liquid at high temperature to form a whole, and calendering to form a glass plate with a set size.
5. The method according to claim 4, wherein the annealing treatment is performed to the glass plate after the rolling forming to remove the thermal stress of the glass plate, and the glass plate after the annealing treatment is cut into a desired size.
6. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 1, wherein the SiO is prepared by using a method of mixing a silicon dioxide with a silicon dioxide 2 Raw materialsIs one or more of quartz sand, sandstone, quartzite and gangue quartz; the MgO raw material is magnesium carbonate; the Al is 2 O 3 The raw material is one or more of feldspar, kaolin, pyrophyllite, industrial alumina and aluminum hydroxide.
7. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 6, wherein MgO and Al are used 2 O 3 Is less than 1.
8. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 1, wherein the TiO is 2 The raw material is titanium dioxide; the ZrO 2 The raw material is one or more of zircon and baddeleyite; said P is 2 O 5 The raw material is phosphoric anhydride; the CaO raw material is calcium carbonate; the Li 2 The O raw material is one or more of eucryptite, spodumene, lithium carbonate and lithium hydroxide.
9. The method for preparing the low-expansion magnesium aluminum silicon cordierite microcrystalline glass according to claim 1, wherein the nucleation temperature T is Nucleus At 550 ℃; the crystal growth temperature T Crystal Ratio T Nucleus The temperature is 150-250 ℃; the crystallization treatment is carried out in a crystallization furnace; the heat preservation time in the first stage is 1-2 hours; the temperature rise rate of the first stage is 8-10 ℃/hr, and the temperature rise rate of the second stage is 3-5 ℃/hr.
10. A low-expansion magnesium aluminosilicate cordierite microcrystalline glass, which is prepared according to the preparation method of the low-expansion magnesium aluminosilicate cordierite microcrystalline glass in any one of claims 1 to 9.
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