CN116903253A - Compression-resistant deep-sea transparent microcrystalline glass and preparation method thereof - Google Patents
Compression-resistant deep-sea transparent microcrystalline glass and preparation method thereof Download PDFInfo
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- CN116903253A CN116903253A CN202310865798.5A CN202310865798A CN116903253A CN 116903253 A CN116903253 A CN 116903253A CN 202310865798 A CN202310865798 A CN 202310865798A CN 116903253 A CN116903253 A CN 116903253A
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- 239000011521 glass Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000006835 compression Effects 0.000 title claims abstract description 15
- 238000007906 compression Methods 0.000 title claims abstract description 15
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 39
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 23
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000004321 preservation Methods 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 13
- 230000006911 nucleation Effects 0.000 claims description 13
- 238000010899 nucleation Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000265 homogenisation Methods 0.000 claims description 11
- 239000004111 Potassium silicate Substances 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 10
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000005728 strengthening Methods 0.000 abstract description 12
- 238000009472 formulation Methods 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006123 lithium glass Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal 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
- 238000013001 point bending Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- C03C10/0009—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 silica as main constituent
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The application provides a preparation method of compression-resistant deep-sea transparent glass ceramics, which controls the crystallization degree of aluminum from a glass phase to a microcrystalline phase by adjusting the formula of the glass so as to control an ion exchange channel, and greatly increases the ion exchange depth of the glass ceramics by improving the ion exchange formula and utilizing a large channel provided by an aluminum oxide tetrahedron. The stress relaxation and thermal fatigue problems caused by the common secondary strengthening formulation can be well avoided by improving the formulation of the microcrystalline glass and the ion exchange formulation. The application also provides the compression-resistant deep-sea transparent microcrystalline glass.
Description
The application claims priority of China patent application filed by China patent office at 2023 and 06/year with application number 2023106623113 and the application name of 'compression-resistant deep sea transparent glass ceramics and preparation method thereof', and the whole content of the application is incorporated by reference.
Technical Field
The application belongs to the technical field of ocean exploration, and particularly relates to compression-resistant deep-sea transparent glass ceramic and a preparation method thereof.
Background
Today, pressure-resistant deep-sea transparent glass windows for deep-sea manned detection are very high in pressure resistance, bending resistance, corrosion resistance, light transmittance and the like, and particularly, the pressure resistance is much higher than that of a common glass window, the window needs to bear 1000Pa pressure change of seawater increase every one meter from sea level, and when the manned submersible descends to the pressure born by the deep sea, the pressure can reach tens of megapascals or even hundreds of megapascals, and the window needs to resist the pressure and maintain clear vision.
The glass ceramics are modern novel materials, the performance of the glass ceramics is superior to that of common glass, the conventional ion exchange method of the glass ceramics in China is mainly applied to small electronic devices such as mobile phones and the like, the application of the glass ceramics in places with large-area ion reinforcement such as windows and the like is very small, especially the glass manufactured by the conventional small-area ion reinforcement process at present faces to the deep sea of ten thousand meters and more, the performance of the glass manufactured by the conventional small-area ion reinforcement process can not meet the use requirements of the deep sea environment, and the high protection effect on the personal safety of a manned detector can not be provided.
Disclosure of Invention
The application aims to provide compression-resistant deep-sea transparent microcrystalline glass and a preparation method thereof, wherein the preparation method has better strengthening effect on high-aluminum low-lithium microcrystalline glass, and the prepared microcrystalline glass meets the use requirements of deep-sea environment.
The application provides a preparation method of compression-resistant deep-sea transparent microcrystalline glass, which comprises the following steps:
a) Uniformly mixing the raw materials, and carrying out melting homogenization to obtain glass liquid;
the raw materials comprise the following components in percentage by mass:
b) Pouring the glass liquid into a mould for molding, and annealing the molded glass to obtain common glass;
c) Carrying out nucleation heat treatment and crystallization heat treatment on common glass in sequence to obtain microcrystalline glass;
d) Placing the glass ceramics in first molten salt after first preheating, and carrying out first chemical strengthening;
the first molten salt comprises 28 to 30 weight percent of sodium nitrate, 59 to 61 weight percent of potassium nitrate, 0.02 to 0.03 weight percent of potassium silicate, 0.02 to 0.03 weight percent of sodium silicate, 0.2 to 0.3 weight percent of aluminum oxide, 9 to 12 weight percent of copper chloride and 0.01 to 0.1 weight percent of cerium oxide;
e) Preheating the microcrystalline glass subjected to the first chemical strengthening for the second time, and then placing the microcrystalline glass in second molten salt for the second chemical strengthening to obtain the compression-resistant deep-sea transparent microcrystalline glass;
the second molten salt comprises 93-96 wt% of potassium nitrate, 0.3-0.6 wt% of potassium hydroxide, 0.02-0.03 wt% of potassium silicate, 2-5 wt% of diatomite, 0.02-0.03 wt% of lanthanum oxide and 1.4-1.5 wt% of potassium carbonate.
Preferably, the temperature of the melt homogenization is 1580-1650 ℃, and the heat preservation time of the melt homogenization is 3-4 hours.
Preferably, the annealing temperature is 600-750 ℃; the heat preservation time of the annealing is 1-2 hours.
Preferably, the temperature of the nucleation heat treatment is 680-720 ℃, and the heat preservation time of the nucleation heat treatment is 2-4 hours;
the temperature of the crystallization heat treatment is 780-850 ℃, and the heat preservation time of the crystallization heat treatment is 2-4 hours.
Preferably, the temperature of the first preheating is 300-400 ℃; the heat preservation time of the first preheating is 30-40 min.
Preferably, the temperature of the first chemical strengthening is 450-550 ℃, and the heat preservation time of the first chemical strengthening is 1-5 hours.
Preferably, the temperature of the second preheating is 500-530 ℃; the heat preservation time of the second preheating is 2-4 hours.
Preferably, the temperature of the second chemical strengthening is 400-500 ℃, and the heat preservation time of the second chemical strengthening is 1-5 hours.
Preferably, an ion sieve is added during the first chemical strengthening to absorb Li in the molten salt + 。
The application provides the compressive deep-sea transparent microcrystalline glass prepared by the preparation method.
The application provides a preparation method of compression-resistant deep-sea transparent microcrystalline glass, which comprises the following steps: a) Uniformly mixing the raw materials, and carrying out melting homogenization to obtain glass liquid; the raw materials comprise the following components in percentage by mass: 50-60 wt% of silicon oxide, 24-30 wt% of aluminum oxide, 2-5 wt% of sodium oxide, 2-6 wt% of lithium oxide, 2-8 wt% of zinc oxide, 4-6 wt% of titanium oxide, 0.5-4 wt% of zirconium oxide, 0.5-4 wt% of germanium oxide, 0-3 wt% of yttrium oxide, 0-3 wt% of phosphorus pentoxide and 0-3 wt% of boron trioxide; b) Pouring the glass liquid into a mould for molding, and annealing the molded glass to obtain common glass; c) Carrying out nucleation heat treatment and crystallization heat treatment on common glass in sequence to obtain microcrystalline glass; d) Placing the glass ceramics in first molten salt after first preheating, and carrying out first chemical strengthening; the first molten salt comprises 28 to 30 weight percent of sodium nitrate, 59 to 61 weight percent of potassium nitrate, 0.02 to 0.03 weight percent of potassium silicate, 0.02 to 0.03 weight percent of sodium silicate, 0.2 to 0.3 weight percent of aluminum oxide, 9 to 12 weight percent of copper chloride and 0.01 to 0.1 weight percent of cerium oxide; e) After the microcrystalline glass subjected to the first chemical strengthening is preheated for the second time, the microcrystalline glass is placed in a second molten salt for the second chemical strengthening, and the compressive deep-sea transparent microcrystalline glass is obtained, wherein the second molten salt comprises 93-96 wt% of potassium nitrate, 0.3-0.6 wt% of potassium hydroxide, 0.02-0.03 wt% of potassium silicate, 2-5 wt% of diatomite, 0.02-0.03 wt% of lanthanum oxide and 1.4-1.5 wt% of potassium carbonate. The application needs to be reinforced, namely the novel high-aluminum low-lithium microcrystalline glass has zinc aluminum spinel and zirconium dioxide microcrystalline glass, because the formula of the microcrystalline glass contains high aluminum content (Al is more than 24 wt%) and aluminum is used for replacing silicon to form aluminum oxide tetrahedron, the exchange channel is enlarged, and although a larger channel can be provided for ion exchange, the novel high-aluminum low-lithium microcrystalline glass cannot be optimally reinforced by using the conventional two-step ion reinforcement process, and the conventional secondary ion exchange method for reinforcing the high-aluminum microcrystalline glass can cause the problems of stress relaxation and thermal fatigue of the high-aluminum microcrystalline glass. The high-alumina low-lithium microcrystalline glass takes zinc aluminum spinel and zirconia as main crystalline phases, the application controls the crystallization degree of aluminum from the glass phase to the microcrystalline phase by adjusting the formula of the glass so as to control an ion exchange channel, and the ion exchange depth of the microcrystalline glass can be greatly increased by improving the ion exchange formula and utilizing a large channel provided by an aluminum oxide tetrahedron. The stress relaxation and thermal fatigue problems caused by the common secondary strengthening formulation can be well avoided by improving the formulation of the microcrystalline glass and the ion exchange formulation.
Detailed Description
The application provides a preparation method of compression-resistant deep-sea transparent microcrystalline glass, which comprises the following steps:
a) Uniformly mixing the raw materials, and carrying out melting homogenization to obtain glass liquid;
the raw materials comprise the following components in percentage by mass:
b) Pouring the glass liquid into a mould for molding, and annealing the molded glass to obtain common glass;
c) Carrying out nucleation heat treatment and crystallization heat treatment on common glass in sequence to obtain microcrystalline glass;
d) Placing the glass ceramics in first molten salt after first preheating, and carrying out first chemical strengthening;
the first molten salt comprises 28 to 30 weight percent of sodium nitrate, 59 to 61 weight percent of potassium nitrate, 0.02 to 0.03 weight percent of potassium silicate, 0.02 to 0.03 weight percent of sodium silicate, 0.2 to 0.3 weight percent of aluminum oxide, 9 to 12 weight percent of copper chloride and 0.01 to 0.1 weight percent of cerium oxide;
e) Preheating the glass ceramics subjected to the first chemical strengthening for the second time, and placing the glass ceramics in second molten salt for the second chemical strengthening to obtain the compression-resistant deep-sea transparent glass ceramics
The second molten salt comprises 93-96 wt% of potassium nitrate, 0.3-0.6 wt% of potassium hydroxide, 0.02-0.03 wt% of potassium silicate, 2-5 wt% of diatomite, 0.02-0.03 wt% of lanthanum oxide and 1.4-1.5 wt% of potassium carbonate.
In the present application, in the production raw material, the mass fraction of the silicon oxide is preferably 50 to 60wt%, more preferably 52 to 58wt%, such as 50wt%,51wt%,52wt%,53wt%,54wt%,55wt%,56wt%,57wt%,58wt%,59wt%,60wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of alumina is preferably 24 to 30wt%, more preferably 25 to 28wt%, such as 24wt%,25wt%,26wt%,27wt%,28wt%,29wt%,30wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of sodium oxide is preferably 2 to 5wt%, preferably 3 to 4wt%, such as 2wt%,3wt%,4wt%,5wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of lithium oxide is preferably 2 to 6wt%, preferably 3 to 5wt%, such as 2wt%,3wt%,4wt%,5wt%,6wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of zinc oxide is preferably 2 to 8wt%, preferably 3 to 7wt%, such as 2wt%,3wt%,4wt%,5wt%,6wt%,7wt%,8wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of titanium oxide is preferably 4 to 6wt%, such as 4wt%,5wt%,6wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of zirconia is preferably 0.5 to 4wt%, more preferably 1 to 3wt%, such as 0.5wt%,1wt%,2wt%,3wt%,4wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of germanium oxide is preferably 0.5 to 4wt%, more preferably 1 to 3wt%, such as 0.5wt%,1wt%,2wt%,3wt%,4wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of yttrium oxide is preferably 0 to 3wt%, such as 0wt%,1wt%,2wt%,3wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of phosphorus pentoxide is preferably 0 to 3wt%, such as 0wt%,1wt%,2wt%,3wt%, preferably a range value having any of the above values as an upper limit or a lower limit; the mass fraction of the diboron trioxide is preferably 0 to 3% by weight, such as 0% by weight, 1% by weight, 2% by weight, 3% by weight, preferably in a range having any of the above values as an upper limit or a lower limit.
The application is characterized in that the raw materials are weighed according to the proportion and then mixed, the mixture is put into a corundum crucible, and molten homogenization is carried out in a high-temperature electric furnace to obtain glass liquid.
In the present application, the temperature of the melt homogenization is preferably 1580 to 1650 ℃, more preferably 1590 to 1630 ℃, such as 1580 ℃,1590 ℃,1600 ℃,1610 ℃,1620 ℃,1630 ℃,1640 ℃,1650 ℃, preferably in a range of any of the above values as an upper limit or a lower limit; the holding time of the melt homogenization is preferably 3 to 4 hours, and the heating rate of the melt homogenization is preferably 1 to 5 ℃/min, more preferably 3 to 4 ℃/min.
After molten glass is obtained, the molten glass is poured into a cast iron mold for standing molding, then the cooled and molded glass is put into a muffle furnace with preset temperature for annealing, and the glass is taken out after cooling to obtain common glass.
In the present application, the annealing temperature is preferably 600 to 750 ℃, more preferably 650 to 700 ℃, such as 600 ℃,610 ℃,620 ℃,630 ℃,640 ℃,650 ℃,660 ℃,670 ℃,680 ℃,690 ℃,700 ℃,710 ℃,720 ℃,730 ℃,740 ℃,750 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the holding time for the annealing is preferably 1 to 2 hours.
And cleaning and polishing the annealed common glass, and then placing the common glass into a box-type silicon carbide rod resistance furnace for two-step heat treatment, wherein the two-step heat treatment sequentially comprises nucleation heat treatment and crystallization heat treatment.
In the present application, the temperature of the nucleation heat treatment is preferably 680 to 720 ℃, more preferably 690 to 710 ℃, such as 680 ℃,690 ℃,700 ℃,710 ℃,720 ℃, preferably a range value having any of the above values as an upper limit or a lower limit; the holding time of the nucleation heat treatment is preferably 2 to 4 hours, more preferably 2 to 3 hours; the heating rate of the nucleation heat treatment is preferably 3 to 10 ℃/min, more preferably 5 to 6 ℃/min.
In the present application, the crystallization heat treatment temperature is preferably 780 to 850 ℃, more preferably 800 to 820 ℃, such as 780 ℃,790 ℃,800 ℃,810 ℃,820 ℃,830 ℃,840 ℃,850 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the heat-preserving time of the crystallization heat treatment is preferably 2 to 4 hours, more preferably 2 to 3 hours; the heating rate of the crystallization heat treatment is preferably 3 to 10 ℃/min, more preferably 5 to 6 ℃/min.
And after the crystallization heat treatment is finished, cooling to room temperature, taking out, cleaning and drying to obtain the microcrystalline glass.
And (3) placing the obtained glass ceramics into a preheating furnace, heating to perform first preheating, and then placing the glass after the first preheating into first molten salt to perform first chemical strengthening.
In the present application, the temperature of the first preheating is preferably 300 to 400 ℃, more preferably 320 to 380 ℃, such as 300 ℃,310 ℃,320 ℃,330 ℃,340 ℃,350 ℃,360 ℃,370 ℃,380 ℃,390 ℃,400 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the heat preservation time of the first preheating is preferably 30-40 min; the heating rate of the first preheating is preferably 8 to 12 ℃/min, more preferably 9 to 10 ℃/min.
In the present application, the first molten salt preferably includes 28 to 30wt% of sodium nitrate, 59 to 61wt% of potassium nitrate, 0.02 to 0.03wt% of potassium silicate, 0.02 to 0.03wt% of sodium silicate, 0.2 to 0.3wt% of aluminum oxide, 9.65 to 11.65wt% of copper chloride, and 0.01 to 0.1wt% of cerium oxide.
In the present application, the temperature of the first chemical strengthening is preferably 450 to 550 ℃, more preferably 180 to 530 ℃, such as 450 ℃,460 ℃,470 ℃,480 ℃,490 ℃,500 ℃,510 ℃,520 ℃,530 ℃,540 ℃,550 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the holding time for the first chemical strengthening is preferably 1 to 5 hours, more preferably 3 to 4 hours.
The first chemical strengthening is mainly Na + Substitution of Li + Thus, li in molten salt + The content of Li in the molten salt is quickly increased, and the ionic sieve is preferably added into the first molten salt to absorb Li in the molten salt + The mass of the ion sieve added by the molten salt needs to be less than that of the glass ceramic, and is usually 1-10wt%, preferably 3-8wt%, more preferably 5-6wt% of the mass of the molten salt used.
According to the application, molten salt can be added into the microcrystalline glass and the ion sieve respectively in tandem, and the microcrystalline glass is screened in the first chemical strengthening process to ensure the exchange efficiency; alternatively, the ion sieve is placed in the first used molten salt, i.e. the molten salt with a significantly slow ion exchange rate or with no activity, and the Li is sucked out of the molten salt + The sucking time is 15-20 h.
In the application, the main component of the ion sieve comprises 40 to 45mol percent of functional alkali metal oxide sodium oxide, preferably 41 to 44mol percent, more preferably 42 to 43mol percent; silica and alumina constituting the framework of the ion sieve structure, wherein the silica content is 40 to 45mol%, preferably 41 to 44mol%, more preferably 41 to 42mol%, and the alumina content is 10 to 15mol%, preferably 11 to 14mol%, more preferably 12 to 13mol%; and other metal oxides such as magnesium oxide and calcium oxide, wherein the content of the magnesium oxide is 1-3 mol%, preferably 2mol%, and the content of the calcium oxide is 1-3 mol%, preferably 2mol%, so that the ion sieve has certain high-temperature stability.
The ion sieve is made to form a certain porous structure by adding a certain foaming agent, so that the absorption surface area is increased, and the absorption rate is accelerated. The alkali metal ions combine with the chain-ring like network structure to form a steric channel. The ion sieve utilizes the high-temperature environment in the molten salt, and absorbs impurity ions in a solid-phase diffusion mode due to the difference of impurity ion contents at solid-liquid junctions. The three-dimensional ion channel of the ion sieve is easier to select and absorb lithium ions with smaller size.
After the first chemical strengthening is finished, the microcrystalline glass after the first strengthening is placed in a muffle furnace for carrying out the second preheating heat treatment, and then the microcrystalline glass after the heat treatment is placed in second molten salt for carrying out the second chemical strengthening, so that the compressive deep-sea transparent microcrystalline glass is obtained.
In the present application, the temperature of the second preheating is preferably 500 to 530 ℃, more preferably 510 to 520 ℃; the holding time for the second preheating is preferably 2 to 4 hours, more preferably 2 to 3 hours.
In the present application, the second molten salt preferably includes 93 to 96wt% of potassium nitrate, 0.3 to 0.6wt% of potassium hydroxide, 0.02 to 0.03wt% of potassium silicate, 2 to 5wt% of diatomaceous earth, 0.02 to 0.03wt% of lanthanum oxide, and 1.4 to 1.5wt% of potassium carbonate.
In the present application, the temperature of the second chemical strengthening is preferably 400 to 500 ℃, preferably 420 to 480 ℃, such as 400 ℃,410 ℃,420 ℃,430 ℃,440 ℃,450 ℃,460 ℃,470 ℃,480 ℃,490 ℃,500 ℃, preferably a range value with any of the above values as an upper limit or a lower limit; the heat-preserving time of the second chemical strengthening is 1 to 5 hours, preferably 2 to 3 hours.
The application also provides the compressive deep-sea transparent microcrystalline glass which is prepared according to the preparation method.
The application can produce high-aluminum low-lithium glass ceramics with zinc aluminum spinel and zirconium dioxide as main crystal phases by improving the formula of the glass ceramics, but the strengthening effect of the glass ceramics cannot be optimized by using a conventional two-step ion strengthening process, the ion exchange depth of the glass ceramics can be greatly increased by controlling the ion exchange channels from the glass phase to the microcrystal phase to participate in crystallization and controlling the ion exchange channels by adjusting the formula of the high-aluminum low-lithium glass ceramics and utilizing the large channels provided by aluminum oxide tetrahedra by improving the formula of the ion exchange. The stress relaxation and thermal fatigue problems caused by the common secondary strengthening formulation can be well avoided by improving the formulation of the microcrystalline glass and the ion exchange formulation. And, moreover, the method comprises the steps of. The ion exchange quantity and the ion exchange depth in the novel glass ceramics are improved by improving the formulas of the glass ceramics and the ion exchange. Compared with the common secondary strengthening method, the method saves more production cost and time, and controls crystallization and improves the molten salt formula. The performance of the high-aluminum low-lithium glass ceramic is improved, the problems of thermal fatigue, stress relaxation and the like caused by common secondary strengthening molten salt strengthening of the high-aluminum glass ceramic are solved, and the product can be applied to deep sea in a complex environment.
In order to further illustrate the present application, the following examples are provided to describe the compressive deep sea transparent glass ceramics and the preparation method thereof in detail, but the present application is not to be construed as limiting the scope of the present application.
Examples
And (3) batching: after each component of the sample formula is determined (as shown in table 1), the specific raw material amount required by the mass percentages of each component in table 1 is calculated, the calculated raw materials are weighed out by a precise electronic scale, and finally each raw material is uniformly mixed to obtain the batch.
Melt homogenization: and placing the uniformly mixed batch into a corundum crucible, melting and homogenizing in a high-temperature electric furnace, wherein the heating rate is 3 ℃/min, the melting temperature is 1650 ℃, and the heat preservation time is 3 hours.
And (3) forming: pouring the molten glass into a graphite mold for standing molding.
Annealing: and (3) putting the cooled and formed glass into a muffle furnace with preset temperature for annealing, preserving heat for 2 hours at about 600 ℃, and taking out the cooled and formed glass to obtain the common glass.
And (3) heat treatment: placing the polished glass into a box-type silicon carbide rod resistance furnace for two-step heat treatment, wherein the heating rate is set to be 5 ℃/min, and nucleating: the nucleation temperature is 700 ℃, and the heat preservation time is 2 hours. Crystallization: the crystallization temperature is 850 ℃, the heat preservation time is 2 hours, the glass ceramics are taken out after being cooled to the room temperature, and the glass ceramics are cleaned and dried.
Preheating: and placing the microcrystalline glass into a preheating furnace, heating to 350 ℃ at 10 ℃/min, and preserving heat for 35min.
Chemical strengthening: the preheated glass substrate and the ion sieve are added into first molten salt with the temperature of 450 ℃ in sequence, and the component content of the first molten salt is shown in table 2. The heat preservation time is 3 hours.
Preheating: and placing the glass ceramics subjected to primary strengthening in a muffle furnace for heat treatment at 500-530 ℃ for 3 hours.
Chemical strengthening is as follows: and (3) placing the microcrystalline glass after heat treatment into a second molten salt with the temperature of 400-500 ℃ for secondary strengthening, wherein the content of the first molten salt is shown in table 3, and the heat preservation time is 2 hours. And obtaining the microcrystalline glass.
By comparison with high-lithium low-aluminum glass ceramics subjected to primary ion exchange
Comparative example 1
Glass ceramics were prepared according to the preparation process in the examples, except that the glass ceramics formulation in comparative example 1 was referred to in table 1 and only one chemical strengthening was performed, the molten salt composition used was referred to in table 2, and other process parameters were the same as in the examples.
Comparative example 2
Glass ceramics were prepared according to the preparation process in the examples, except that the glass ceramics formulation in comparative example 2 was referred to in table 1 and only one chemical strengthening was performed, the molten salt composition used was referred to in table 2, and other process parameters were the same as in the examples.
Table 1 content of glass-ceramic component (wt%)
Table 2 component content (wt%) of first molten salt in example
Table 3 component content (wt%) of the second molten salt in the example
The glass ceramics prepared in examples 1 to 7 were subjected to performance test, and the results are shown in Table 4, and the performance test
The block glass ceramics obtained by the embodiment of the application are subjected to performance test according to the following method, wherein specific test items and test methods (or test standards) are as follows:
test of modulus of elasticity: the stress-strain of the material in the elastic deformation zone is tested by a static method, wherein the static method refers to applying a constant bending stress on a sample, measuring the elastic bending deflection of the sample, and calculating the elastic modulus according to the stress and the strain.
Visible light transmittance of glass: and detecting by adopting a transmittance meter designed by a parallel light path.
Chemical strengthening stress layer depth of glass and surface compressive stress of glass: the SLP-2000 compressive stress tester is used for calculating the surface compressive stress and the thickness of the compressive stress layer through the optical path difference and the polarization characteristic of the polarized light path, which occur due to the delay of the laser beam.
Ball drop impact value: the steel balls with certain mass are lifted to different heights to fall on the surface of the material until the material is destroyed to the required height.
Four-point bending test strength: the strip-shaped sample is horizontally placed in a bending test fixture to form a simply supported beam, the length of the sample is adjustable due to the distance between two lower supporting points for supporting the sample, and two symmetrical loading points are arranged above the sample. By applying force to the sample until the material is deformed to a desired strength
Alkali resistance: detection according to the acid and alkali resistance test method in standard 'low expansion transparent glass ceramic' JC/T2157-2012
Acid resistance: the acid and alkali resistance test method in the standard ' low-expansion transparent glass ceramic ' JC/T2157-2012 ' is adopted for detection.
Vickers hardness: the test was conducted under the condition of an experimental load of 200gf and a holding time of 10S.
Table 4 Performance test of glass ceramics in examples
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (10)
1. A preparation method of compression-resistant deep-sea transparent microcrystalline glass comprises the following steps:
a) Uniformly mixing the raw materials, and carrying out melting homogenization to obtain glass liquid;
the raw materials comprise the following components in percentage by mass:
b) Pouring the glass liquid into a mould for molding, and annealing the molded glass to obtain common glass;
c) Carrying out nucleation heat treatment and crystallization heat treatment on common glass in sequence to obtain microcrystalline glass;
d) Placing the glass ceramics in first molten salt after first preheating, and carrying out first chemical strengthening;
the first molten salt comprises 28 to 30 weight percent of sodium nitrate, 59 to 61 weight percent of potassium nitrate, 0.02 to 0.03 weight percent of potassium silicate, 0.02 to 0.03 weight percent of sodium silicate, 0.2 to 0.3 weight percent of aluminum oxide, 9 to 12 weight percent of copper chloride and 0.01 to 0.1 weight percent of cerium oxide;
e) Preheating the microcrystalline glass subjected to the first chemical strengthening for the second time, and then placing the microcrystalline glass in second molten salt for the second chemical strengthening to obtain the compression-resistant deep-sea transparent microcrystalline glass;
the second molten salt comprises 93-96 wt% of potassium nitrate, 0.3-0.6 wt% of potassium hydroxide, 0.02-0.03 wt% of potassium silicate, 2-5 wt% of diatomite, 0.02-0.03 wt% of lanthanum oxide and 1.4-1.5 wt% of potassium carbonate.
2. The method according to claim 1, wherein the temperature of the melt-homogenizing is 1580 to 1650 ℃, and the heat-preserving time of the melt-homogenizing is 3 to 4 hours.
3. The method of claim 1, wherein the annealing temperature is 600-750 ℃; the heat preservation time of the annealing is 1-2 hours.
4. The method according to claim 1, wherein the temperature of the nucleation heat treatment is 680 to 720 ℃, and the heat preservation time of the nucleation heat treatment is 2 to 4 hours;
the temperature of the crystallization heat treatment is 780-850 ℃, and the heat preservation time of the crystallization heat treatment is 2-4 hours.
5. The method of claim 1, wherein the first preheating is at a temperature of 300 to 400 ℃; the heat preservation time of the first preheating is 30-40 min.
6. The method according to claim 5, wherein the temperature of the first chemical strengthening is 450-550 ℃, and the heat-preserving time of the first chemical strengthening is 1-5 hours.
7. The method according to claim 6, wherein the temperature of the second preheating is 500 to 530 ℃; the heat preservation time of the second preheating is 2-4 hours.
8. The method according to claim 7, wherein the temperature of the second chemical strengthening is 400 to 500 ℃, and the holding time of the second chemical strengthening is 1 to 5 hours.
9. The method of any one of claims 1 to 8, wherein an ion sieve is added during the first chemical strengthening to absorb Li in the molten salt + 。
10. The deep sea transparent glass ceramics with compression resistance prepared by the preparation method according to any one of claims 1 to 9.
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