CN116730620A - Composite microcrystalline glass and preparation method and application thereof - Google Patents
Composite microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN116730620A CN116730620A CN202310787073.9A CN202310787073A CN116730620A CN 116730620 A CN116730620 A CN 116730620A CN 202310787073 A CN202310787073 A CN 202310787073A CN 116730620 A CN116730620 A CN 116730620A
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- 239000011521 glass Substances 0.000 title claims abstract description 203
- 239000002131 composite material Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 111
- 239000006059 cover glass Substances 0.000 claims abstract description 71
- 239000010410 layer Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000012792 core layer Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims description 44
- 230000008025 crystallization Effects 0.000 claims description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 32
- 238000010899 nucleation Methods 0.000 claims description 28
- 230000006911 nucleation Effects 0.000 claims description 28
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 22
- 239000005340 laminated glass Substances 0.000 claims description 20
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 14
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 239000008395 clarifying agent Substances 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000012545 processing Methods 0.000 abstract description 8
- 230000001681 protective effect Effects 0.000 abstract description 6
- 238000003426 chemical strengthening reaction Methods 0.000 abstract description 5
- 238000000748 compression moulding Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002667 nucleating agent Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000003280 down draw process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000006125 LAS system Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
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- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003286 fusion draw glass process Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- -1 lithium aluminum silicon Chemical compound 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003283 slot draw process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000500 β-quartz 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
- C03C10/0018—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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The application discloses composite microcrystalline glass and a preparation method and application thereof, and the composite microcrystalline glass comprises the following steps: preparing core layer glass liquid and cover layer glass liquid respectively; arranging a core glass liquid and a forming device thereof above the cover glass liquid overflow device, and enabling the core glass to pass through the middle of the cover glass overflow device and cover the cover glass on two surfaces; under the high temperature state, the cover glass is fused on the surface of the core glass, and n cover glass liquid overflow devices are arranged, so that 2n+1 layers of glass can be prepared and thinned to form a composite microcrystalline glass precursor; and cooling, nucleating, crystallizing and annealing the composite microcrystalline glass precursor to form the composite microcrystalline glass. The composite glass ceramics can be reinforced and toughened by chemical strengthening. The composite microcrystalline glass has low cost of raw materials and low processing cost, can be well applied to the protective cover plate of the display device through compression molding, can also be cut and processed by laser, and has wide market prospect.
Description
Technical Field
The application belongs to the technical field of cover glass, and particularly relates to composite microcrystalline glass and a preparation method thereof.
Background
The cover plate glass has the advantages of good light transmittance, contribution to 5G signal transmission and wireless charging, capability of improving strength performance through chemical strengthening, and the like, and becomes a preferred protective material for display terminals such as mobile phones and the like. However, the continuous improvement of the strength of the cover glass is a target pursued by users, and the lithium aluminum silicon cover glass has excellent performance, but the strength improvement space is limited.
Microcrystalline glass is also known as ceramic glass, and has the dual characteristics of glass and ceramic. The crystalline phase in the glass ceramics ensures the intrinsic strength of the glass ceramics, and the residual glass phase of the glass ceramics can be chemically strengthened, so that the glass ceramics has high strength, high hardness and high scratch resistance. Part of microcrystalline glass has high light transmittance and can be used as protective glass for display panels of mobile phones and the like. Meanwhile, the microcrystalline glass has natural and soft texture, and can obtain colorful colors through component and process control, so that the trend of the microcrystalline glass applied to the mobile phone backboard market is initially shown.
At present, many LAS transparent glass ceramics have good light transmittance, high strength and chemical strengthening property, but the cost of raw materials is high. The microcrystalline cover plate glass is produced by a multi-purpose casting method in the market, the processing difficulty of the microcrystalline glass is high, and particularly, the cover plate for the mobile phone is in a 3D form, and the processing cost is higher. Currently, glass-ceramic cover plates are limited to high-end product applications, limiting use in mobile electronic devices.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides composite glass ceramic as well as a preparation method and application thereof.
In order to achieve the purpose, the application is realized by adopting the following technical scheme:
the preparation method of the composite glass ceramic comprises the following steps:
preparing core layer glass liquid and cover layer glass liquid respectively;
cooling the core glass liquid to a forming temperature, and preforming the core glass;
the core glass passes through the middle of the cover glass devices, and the cover glass liquid is fused to the surface of the core glass;
drawing the fused glass to be thin at a high temperature to form a composite microcrystalline glass precursor;
and cooling the composite microcrystalline glass precursor, and performing nucleation, crystallization and annealing treatment to form the composite microcrystalline glass.
Further, the preparation process of the core layer glass liquid comprises the following steps: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 5 to 15mol% of Al 2 O 3 0 to 5mol% of B 2 O 3 2 to 20mol% of alkali metal oxide R 2 O and 0.1-0.2 mol% of clarifying agent are uniformly mixed, melted at 1200-1700 ℃, and clarified to form core layer glass liquid.
Further, the preparation process of the cover layer glass liquid comprises the following steps: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 2 to 25mol% of alkali metal oxide R 2 O, 3-10 mol% of Al 2 O 3 0 to 2mol% of P 2 O 5 ZrO 0-2 mol% 2 0 to 2mol% of TiO 2 Uniformly mixing with 0-0.1 SnO, melting at 1200-1650 ℃, and clarifying to form a cover glass liquid;
alternatively, 60 to 75 mole% of SiO, expressed as mole percent based on oxide 2 15 to 22mol percent of Al 2 O 3 Na of 2-5 mol% 2 O, 10-15 mol% of Li 2 O, 2-5 mol% of P 2 O 5 Or B is a 2 O 3 ZrO 1-3 mol% 2 And 0 to 0.5mol percent of clarifying agent are evenly mixed, melted at 1200 to 1650 ℃ and clarified to form the glass liquid of the cover layer.
Further, alkaline earth metal oxide RO is added in the preparation process of the core layer glass liquid and the cover layer glass liquid, wherein R in the alkaline earth metal oxide is at least one of alkaline earth metal Mg, ca, ba and Sr;
the mole percentage of the alkaline earth metal oxide RO is 0 to 5 mole percent, expressed as mole percent on oxide basis.
Further, the alkali metal oxide R 2 R in O is at least one of group I metals;
the clarifying agent is SnO 2 And SnO.
Further, in the preparation process of the cover layer glass liquid, al 2 O 3 (mol%) and (R) 2 O (mol%) and RO (mol%) are less than 1, (SiO) 2 +Al 2 O 3 +Li 2 O+K 2 O+Na 2 O) (mol%) and (TiO) 2 +P 2 O 5 +ZrO 2 ) The ratio (mol%) is greater than 27.
Further, the high temperature state is 950-1380 ℃, the nucleation treatment temperature is 700-750 ℃, the nucleation time is 1-4 h, the crystallization treatment temperature is 750-900 ℃, and the crystallization time is 2-24 h.
The composite microcrystalline glass prepared by the preparation method is of a sandwich structure formed by high-temperature fusion, the sandwich structure comprises core glass and a plurality of cover glass layers, the plurality of cover glass layers are symmetrically covered on two opposite surfaces of the core glass, and the cover glass of the outermost layer of the composite microcrystalline glass is microcrystalline glass.
Further, the core glass has a thermal expansion coefficient greater than that of the cover glass, and the difference between the thermal expansion coefficients is greater than 20x10 -7 The thermal expansion coefficient of the cover layer glass is gradually decreased from inside to outside;
the concentration of large-radius alkali metal ions in the core layer glass is larger than that of the cover layer glass, and the concentration of small-radius alkali metal ions in the cover layer glass is larger than that of the core layer glass, so that ion exchange is generated between the core layer glass and the cover layer glass in a high-temperature state.
The application of the composite glass ceramics in laminated glass products.
Compared with the prior art, the application has the following beneficial effects:
the application provides a preparation method of composite glass ceramics, which comprises the steps of preforming prepared core glass liquid into core glass; and (3) under the condition that the temperature of the prepared glass liquid for the covering layer is higher than that of the traditional overflow molding, the glass liquid for the covering layer flows through the brick tip to be attached and fused to the surface of the glass for the core layer, so that the crystallization of the glass for the covering layer is avoided. Precisely controlling the temperature of the formed glass, further thinning the glass by a down-drawing and transverse-drawing mode to form a composite microcrystalline glass precursor, and cooling, nucleating, crystallizing and annealing the glass precursor to form the composite microcrystalline glass. The application avoids the crystallization problem generated by an overflow method for preparing microcrystalline glass, and has the advantages of simple preparation method, easy operation of the preparation process, small processing difficulty and low processing cost. The composite glass ceramics prepared by the application has low cost, and can prepare the protective cover plate suitable for the display device by chemical strengthening and compression molding; the composite microcrystalline glass plate can also be manufactured, and the protective component is manufactured through laser cutting and processing, so that the method has a wide application prospect.
The application also provides the composite microcrystalline glass, the core layer glass is glass with a high expansion coefficient, and the surface of the glass core layer is covered with the cover layer glass with a low expansion coefficient at a high temperature state, and the glass core layer glass and the cover layer glass are fused to form a sandwich structure. The concentration of large radius alkali metal ions in the core layer glass is larger than that of the cover layer glass, and the concentration of small radius alkali metal ions in the cover layer glass is larger than that of the core layer glass.
Furthermore, compression molding, nucleation and crystallization of the composite glass-ceramic precursor can be completed in the cooling and annealing processes after molding, so that the preparation efficiency of the composite glass-ceramic is improved, the energy consumption in the preparation process is reduced, the warpage of the prepared composite glass-ceramic is greatly reduced, and the product quality is improved.
Drawings
For a clearer description of the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a composite glass-ceramic of the present application.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present application, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the application in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Various raw materials are used in the following examples, unless otherwise indicated, to the specifications conventional in the art. In the description of the present application and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
The application is described in further detail below with reference to the attached drawing figures:
the application provides a preparation method of composite glass ceramics, which comprises the following steps:
s1, respectively preparing core layer glass liquid and cover layer glass liquid;
s2, arranging a core glass forming device above the cover glass preparation device, respectively adding core glass liquid and cover glass liquid into the device, cooling the core glass liquid to a forming temperature, and preforming to form core glass; the glass plates prepared by the two devices are parallel, and the core glass passes through the middle of the cover glass overflow device and is attached to the two surfaces of the cover glass overflow device, so that the cover glass liquid is attached to the two surfaces of the cover glass overflow device;
s3, in a high-temperature state, the cover glass is fused and attached to the surface of the core glass, the formed glass temperature is precisely regulated, and the glass is thinned in a transverse drawing and downward drawing mode, so that a composite microcrystalline glass precursor is formed;
s4, cooling the composite microcrystalline glass precursor, and performing nucleation, crystallization and annealing treatment to form the composite microcrystalline glass.
Further, in S1, the preparation process of the core glass liquid is as follows: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 5 to 15mol% of Al 2 O 3 0 to 5mol% of B 2 O 3 2 to 20mol% of alkali metal oxide R 2 O and 0.1 to 0.2mol percent of clarifying agent are uniformly mixed, melted at 1200 to 1700 ℃, and clarified to form core layer glass liquid;
the preparation process of the glass liquid of the cover layer comprises the following steps: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 2 to 25mol% of alkali metal oxide R 2 O, 3-10 mol% of Al 2 O 3 、
0 to 2mol% of P 2 O 5 ZrO 0-2 mol% 2 0 to 2mol% of TiO 2 Uniformly mixing with 0-0.1 SnO, melting at 1200-1650 ℃, and clarifying to form a cover glass liquid;
alternatively, 60 to 75 mole% of SiO, expressed as mole percent based on oxide 2 15 to 22mol percent of Al 2 O 3 Na of 2-5 mol% 2 O, 10-15 mol% of Li 2 O, 2-5 mol% of P 2 O 5 Or B is a 2 O 3 ZrO 1-3 mol% 2 And 0 to 0.5mol percent of clarifying agent are evenly mixed, melted at 1200 to 1650 ℃ and clarified to form the glass liquid of the cover layer.
Further, in S2, the preparation method of the core glass includes a slit method and an overflow method; the preparation method of the cover glass is an overflow method. The preparation process of the composite glass ceramics comprises, but is not limited to, a slot draw method, an overflow down draw method and a fusion lamination method, wherein the first molten glass and the second molten composite glass ceramics are enabled to flow, and the first molten glass contacts and fuses the second molten composite glass ceramics together at a temperature higher than any glass transition temperature.
The core layer glass forming device is arranged above the cover layer glass liquid overflow device, the core layer glass liquid is drawn downwards through a slit or overflow to form a glass plate, the core layer glass plate passes through the middle of the cover layer glass overflow device, and the cover layer glass liquid overflows and is attached to the surface of the core layer glass at the brick tip in a fusion bonding manner; and the two surfaces of the core glass are fused with the cover glass liquid, so that the overflow temperature of the cover glass liquid can be increased, and crystallization in the overflow process of the cover glass liquid is avoided.
In the step S3, the core glass is heated by the glass liquid of the cover layer and auxiliary electric heating, the temperature is precisely controlled to be 950-1380 ℃, and the fused glass can be thinned by a down-drawing and transverse-drawing mode to form the composite microcrystalline glass precursor.
The liquidus viscosity of the composite glass-ceramic of the present application is suitable for fusion forming by, for example, fusion down-draw and/or fusion lamination. Specifically, the molding temperature of the composite glass ceramic is 950-1380 ℃.
In S4, the nucleation temperature is 700-750 ℃, the nucleation time is 1-2 h, the crystallization temperature is 750-880 ℃, and the crystallization time is 2-24 h. The composite microcrystalline glass component can be molded in the crystallization process, and the composite microcrystalline glass component can also be prepared by preparing a plate and then cutting and processing the plate by laser.
The core glass comprises 60 to 75mol% of SiO in terms of mole percentage based on oxide 2 5 to 15mol% of Al 2 O 3 0 to 5mol% of B 2 O 3 2 to 20mol% of alkali metal oxide R 2 O, alkali metal oxide R 2 O includes Na 2 O and K 2 O;0-5mol% of alkaline earth metal oxide RO comprising MgO and CaO;0.1 to 0.2mol% of SnO 2 . The difference between the thermal expansion coefficients of the core glass and the cover glass is 30x10 -7 /℃～80x10 -7 /℃。
The cover glass is expressed in mole percent on an oxide basis and comprises the following composition: 60 to 75mol% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 5 to 10mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2 to 25mol% of alkali metal oxide R 2 O，R 2 O includes Li 2 O and Na 2 O;0 to 5mol% of alkaline earth oxide RO, the alkaline earth oxide RO comprising MgO; al (Al) 2 O 3 (mol%) and (R) 2 The ratio of the sum of O (mol%) and RO (mol%) may be less than 1;0 to 2mol% of P 2 O 5 ZrO 0-2 mol% 2 The method comprises the steps of carrying out a first treatment on the surface of the 0 to 2mol% of TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 0 to 0.1mol% of SnO. Nucleating agent: tiO (titanium dioxide) 2 、ZrO 2 、P 2 O 5 And combinations thereof; wherein the proportion (SiO) 2 +Al 2 O 3 +Li 2 O+K 2 O+Na 2 O) mole percent sum of (TiO) 2 +P 2 O 5 +ZrO 2 ) The ratio of the sum of the mole percentages is greater than 26. The thermal expansion coefficient of the cover glass precursor was 65x10 -7 /℃～110x10 -7 a/DEG C; after crystallization, the thermal expansion coefficient is 5x10 -7 /℃～70x10 -7 /℃。
According to one embodiment, the cover glass is expressed in mole percent on an oxide basis and comprises: 60 to 75mol% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the 15 to 22mol% of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 2 to 5mol% of Na 2 O, 10-15 mol% of Li 2 O;2 to 5mol% of P 2 O 5 And/or 2 to 5mol% of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the ZrO 1-3 mol% 2 The method comprises the steps of carrying out a first treatment on the surface of the 0 to 0.5mol% of SnO.
The concentration of alkali metal ions with larger radius in the core layer glass is larger than that of the covering layer, and the concentration of alkali metal ions with smaller radius in the covering layer glass is larger than that of the core layer glass. Ion exchange is generated between the core glass and the cover glass at a high temperature state, and surface compressive stress is generated.
SiO 2 Is the main component of glass network formed by composite glass ceramics, pure SiO 2 Has lower thermal expansionCoefficient of expansion CTE. But pure SiO 2 Has an extremely high melting point. Thus, if SiO 2 When the content of the composite glass ceramics is too high, the formability of the composite glass ceramics is reduced, and the composite glass ceramics is higher in SiO 2 The concentration increases the difficulty of melting the glass, thereby negatively affecting the formability of the glass.
The composite microcrystalline glass generally comprises 60 to 75mol percent of SiO 2 Thereby promoting the fusion forming of the composite glass-ceramic. In some embodiments, siO in the composite glass-ceramic 2 The content is 68-75 mol%.
The composite glass ceramics also comprises Al 2 O 3 ，Al 2 O 3 As glass network former, with SiO 2 Similarly, al 2 O 3 The viscosity of the composite glass-ceramic is increased, and the glass-ceramic is in tetrahedral coordination in a glass melt formed by the composite glass-ceramic. However, when Al 2 O 3 Content of SiO in the composite glass-ceramic 2 At a balance between the content of alkali metal and alkaline earth metal oxides, al 2 O 3 The liquidus temperature of the glass melt can be lowered, thereby enhancing the liquidus viscosity and improving the compatibility of the glass-ceramic with certain shaping processes, such as fusion draw processes.
In the application, in the composite glass ceramics, the coating layer Al 2 O 3 The mole percentage of (2) is 5-12 mol%. Preferably Al 2 O 3 The content of (C) is 7-10 mol%.
The composite glass ceramics also comprises alkali metal oxide R 2 O, wherein R is at least one of group I metals, including but not limited to Li, na, K, rb, cs or combinations thereof. The alkali metal oxide lowers the melting temperature and liquidus temperature of the glass, thereby improving the formability of the composite glass-ceramic. However, the alkali metal oxide increases the CTE of the composite glass-ceramic relative to other oxides contained in the glass, while improving ion exchange properties. By K 2 O replaces Na 2 O generally increases the CTE of the glass, while Li is used 2 O replaces Na 2 O reduces CTE. Thus, the presence of smaller alkali ions in the glass will be reducedLow CTE.
In one embodiment of the application, a composite glass-ceramic is prepared by fusing a lithium ion-free NAS system product with a LAS system glass-ceramic.
Because of alkali metal oxide R 2 O has higher mobility in glass, and alkali metal oxide R is added 2 O also promotes ion exchange strengthening of the composite glass-ceramic. For example, from a cover glass article of composite glass-ceramic, smaller ions, such as Li + And Na (Na) + With larger ions in the molten salt bath, e.g. K + The exchange is performed, thereby creating compressive stress in the surface of the glass article formed from the composite glass-ceramic.
In addition, a specific alkali metal oxide Li 2 O is added to the cover glass to promote initial formation, and then Li is formed in the glass network during crystallization 2 Si 2 O 5 (lithium disilicate). Li (Li) 2 Si 2 O 5 Is the main crystal phase of the composite glass ceramics. Formation of Li in cover glass 2 Si 2 O 5 And the thermal expansion coefficient of the formed composite glass-ceramic is reduced. This allows the Li-containing glass ceramic to be strengthened when the composite glass ceramic is required to be strengthened 2 O is favorable for increasing the depth of chemically strengthened ion exchange.
Cover glass alkali metal oxide R 2 O includes Li 2 O and Na 2 At least one of O, in some embodiments, may include K 2 O。Na 2 The O content is generally 1-10 mol%, and the core glass composition material preferably selects an oxide with larger alkali metal ion radius, and the cover glass preferably selects an oxide with smaller alkali metal ion radius.
Li 2 O is present in the cover glass in an amount of 1 to 10mol%, preferably Li 2 The content of O is 3 to 7mol percent or 4 to 6mol percent.
K 2 O is present in the cover glass in an amount of 0 to 10 mole percent. Preferably, K 2 The content of O is 1 to 7mol percent; in some embodiments, the cover glass may be K-free 2 O。
The core glass of the composite glass-ceramic also comprises alkaline earth metal oxide RO, wherein R is alkaline earth metal, including but not limited to one or more of the following: mg, ca, ba and Sr. Alkaline earth oxide RO can improve the melting properties of the composite glass-ceramic, but can also increase the average coefficient of thermal expansion. While alkaline earth metal oxides do not increase the average coefficient of thermal expansion of the composite glass-ceramic as much as alkali metal oxides, they do reduce the mobility of alkali metal ions in the glass, thereby reducing the ion exchange capacity of the composite glass-ceramic. Therefore, in the present application, the addition of the alkaline earth metal oxide RO is limited. In some embodiments, the cover glass is substantially free of alkaline earth oxides, while in other embodiments, the total alkaline earth oxide content is less than or equal to 5 mole percent, i.e., the alkaline earth oxide content in the composite glass-ceramic is from 0 to 5 mole percent.
The alkaline earth oxide MgO has a detrimental effect on the alkali ion diffusivity, which only rarely reduces the ion exchange properties of the composite glass-ceramic. In addition, mgO does not increase the average CTE of composite glass-ceramics as much as other alkaline earth oxides, such as CaO and BaO. Thus, in some embodiments of the composite glass-ceramic comprising an alkaline earth oxide RO, the alkaline earth oxide comprises MgO. In these embodiments, mgO is present in the composite glass ceramic in an amount of 0 to 5 mole percent, preferably, 0 to 3 mole percent.
In some embodiments, the composite glass-ceramic may be substantially free of alkaline earth oxide RO.
The cover glass of the composite microcrystalline glass comprises TiO 2 . Adding TiO 2 Serve as nucleating agents and aid in the formation of Li during crystallization 2 Si 2 O 5 A primary crystalline phase. In addition, tiO 2 The addition to the composite glass-ceramic also leads to nucleation on crystallization and the formation of secondary crystalline phases, in particular rutile (TiO 2 ). In the present application, tiO 2 The content of the composite microcrystalline glass is 0-4mol%. Preferably, tiO 2 The content of (C) is 1-4 mol% or 2-3 mol%.
The cover glass of the composite microcrystalline glass comprises ZrO 2 . With TiO 2 Similarly, add ZrO 2 Serving as a nucleating agent and helping to form Li during crystallization 2 Si 2 O 5 A primary crystalline phase. In the present application, zrO 2 The content of the glass in the cover glass is 0 to 4mol%. Preferably, zrO 2 The content of (C) is 1-3 mol%.
The cover glass of the composite microcrystalline glass can also contain P 2 O 5 With TiO 2 And ZrO(s) 2 Similarly, P 2 O 5 Serving as a nucleating agent and helping to form Li during crystallization 2 Si 2 O 5 A primary crystalline phase. In the composite microcrystalline glass, P 2 O 5 The content of (C) is 0-3 mol%. Preferably, P 2 O 5 The content of (C) is 0.5-1.5 mol%.
The cover glass of the composite glass-ceramic may include a single nucleating agent, i.e., tiO 2 、ZrO 2 And P 2 O 5 One of the above, or a combination of two or more nucleating agents, i.e. TiO 2 、ZrO 2 And P 2 O 5 A combination of two or more of the foregoing.
One or more fining agents may be included in the composite glass-ceramic. Fining agents include SnO 2 And SnO. The content of the clarifying agent in the composite microcrystalline glass is 0-1 mol percent. Preferably, the clarifying agent is present in an amount of 0 to 0.5 mole%.
In the present application, the composite glass-ceramic is substantially free of heavy metals and heavy metal-containing compounds such as Ba, as, sb, cd, and Pb.
In the composite glass ceramic of the present application, al 2 O 3 Content of (2) alkali metal oxide R 2 The ratio of the sum of the O content and the alkaline earth oxide RO content, i.e. Al 2 O 3 (mol％)/(R 2 O (mol%) +RO (mol%)) is less than 1. In some embodiments, the ratio is 0.5 to 0.9. Preferably, the ratio is 0.5 to 0.7. If the content of the constituent components in the composite glass-ceramic is maintained at a ratio of 0.5 to 1, it is useful to maintain the liquidus temperature and liquidus viscosity in a range suitable for fusion forming.
In the composite glass ceramic of the application, siO 2 (mol％)/Al 2 O 3 (mol%) 7-10. Preferably, the ratio is 7.3 to 10.
In the cover glass of the composite glass-ceramic of the present application, (Li 2 O(mol％)+2*SiO 2 (mol％))/Al 2 O 3 13 to 22mol percent. Preferably, the ratio is 15 to 22. If the content of the constituent components in the composite glass-ceramic is maintained, the composition is obtained (Li 2 O(mol％)+2*SiO 2 (mol％))/Al 2 O 3 (mol%) of 13 to 22 contributes to the formation of a main crystal phase Li 2 Si 2 O 5 . However, if Al 2 O 3 Is too high, i.e. (Li) 2 O(mol％)+2*SiO 2 (mol％))/Al 2 O 3 (mol%) too low, less of the predominant crystalline phase Li will be formed 2 Si 2 O 5 While less desirable phases will form, e.g., eucryptite, filled beta-quartz, and/or LiAlSiO 4 Is a solid solution of (a).
In the cover glass of the composite glass-ceramic of the present application, the content R of the alkali metal oxide 2 O (mol%) and twice SiO 2 Sum of molar contents of (2) and Al 2 O 3 The ratio of the molar contents, i.e. (R 2 O(mol％)+2*SiO 2 (mol％))/Al 2 O 3 (mol%) 8.5-9.5. If the content of the constituent components in the composite glass-ceramic is maintained, the composition is obtained (R 2 O(mol％)+2*SiO 2 (mol％))/Al 2 O 3 (mol%) of 8.5 to 9.5, contributing to the formation of the main crystalline phase Li 2 Si 2 O 5 . However, when Na 2 O and K 2 The content of O relative to Al 2 O 3 When increased, more Li is formed 2 Si 2 O 5 And for a given crystallization regime the coefficient of thermal expansion of the glass decreases.
In the cover glass of the composite glass ceramics of the application, siO 2 Content (mol%) of Al 2 O 3 Content (mol%), li 2 O content (mol%), K 2 O content (mol%) And Na (Na) 2 The ratio of the sum of O (mol%) to the sum of the contents of the nucleating agents is 25 to 28. If the ratio (SiO 2 (mol％)+Al 2 O 3 (mol％)+Li 2 O(mol％)+K 2 O(mol％)+Na 2 O(mol％))/(TiO 2 (mol％)+P 2 O 5 (mol％)+ZrO 2 (mol%) is kept to 25-28, li can be improved 2 Si 2 O 5 Is used for nucleation of (a). I.e. TiO 2 、ZrO 2 And P 2 O 5 Respectively used as nucleating agents. If the nucleating agent content is too high, less desirable phases, such as rutile and zircon, will form in the composite glass-ceramic. However, if the nucleating agent content is too low, the glass does not crystallize.
Referring to fig. 1, the structure of the composite glass ceramics prepared by the application is that at least 3 layers of multi-layer glass are fused at high temperature to form a sandwich structure, the thickness of the composite glass ceramics is less than 1.5mm, and the preferred thickness is less than 0.7mm, so that the composite glass ceramics can be applied to mobile terminal protective glass. The composite glass ceramics comprises core glass and cover glass, wherein the cover glass is symmetrically covered on two opposite surfaces of the core glass, the cover glass is at least one layer of each of two surfaces of the core glass, the outermost cover glass is glass ceramics, and the glass ceramics can be chemically strengthened, so that the surface compressive stress is increased, and the glass strength is improved.
The thermal expansion coefficient of the core layer glass is larger than that of the cover layer glass, and the difference value of the thermal expansion coefficients is larger than 20x10 -7 Preferably, the difference in thermal expansion coefficients is greater than 50x10 -7 and/C. If the multi-layer cover glass is arranged, the thermal expansion coefficient of the inner layer glass is larger than or equal to that of the outer layer glass.
The core glass can exchange ions with the cover glass, and the inner cover glass and the outer cover glass, so that the inner layer larger radius alkali metal ions exchange the outer layer smaller radius alkali metal ions, and a compressive stress layer is formed on the inner surface of the outer layer glass. And a plurality of compressive stress layers are formed together with the compressive stress layer generated by the chemical strengthening of the microcrystalline glass, so that the strength of the glass is improved.
The composite glass-ceramic is a heat-fused laminated glass product, the cross section of fig. 1 schematically shows the laminated glass product, which comprises core glass and cover glass symmetrically covered on two surfaces of the core glass, and the outermost layer is a glass-ceramic precursor before crystallization into glass-ceramic. And covering the cover glass on two surfaces of the core glass in a thermal fusion mode and integrating the cover glass. Flat structures are produced in which the cover glass is symmetrical in terms of material, thickness, etc., and laminated glass articles may also have non-flat configurations.
As described above, after the laminated glass is formed, nucleation and growth of the crystal phase of the cover layer can be induced by heat treatment, thereby reducing the coefficient of thermal expansion of the cover layer (glass-ceramic). The process of inducing nucleation and growth of crystalline phases in composite glass-ceramic is divided into two steps, including cooling the laminated glass to nucleation temperature and maintaining for a period of time to promote nucleation of nanocrystalline phases. And further heating the laminated glass to a crystallization temperature and maintaining for a certain time, so that crystal nuclei grow into nanocrystals, and the laminated glass is converted into composite microcrystalline glass. Wherein, the nucleation temperature of the cover glass is 700-750 ℃, the nucleation time is 1-4 h, the crystallization temperature is 750-900 ℃ and the crystallization time is 2-24 h. However, the crystallization has the same number of crystal nuclei, and when the crystallization time is more than 24 hours, the crystal phase content does not increase with the time, but the size of the crystal phase increases, and the thermal expansion coefficient of crystallized glass can be reduced after the crystallization for a longer crystallization time.
After a certain heat treatment, the microcrystalline glass precursor of the cover layer is converted into microcrystalline glass through nucleation and crystallization, the thermal expansion coefficient of the microcrystalline glass is smaller than that of the microcrystalline glass precursor, and the thermal expansion coefficient difference exists between the surface layer and the adjacent layer. The strength of the glass ceramics is obviously higher than that of common glass, thereby improving the strength of the composite glass ceramics.
The application is described in further detail below in connection with specific examples:
examples 1 to 9:
the following examples 1-2 are exemplary material compositions and amounts of core glass, it being understood that other core glass compositions and amounts are contemplated and may be used, as specifically shown in table 1:
TABLE 1 core glass composition
To determine the effect of the heat treatment regimen of the composite glass-ceramic on the CTE of the glass-ceramic precursor and the CTE after crystallization, a series of glass samples were prepared having the compositions shown in table 2 below. Measurement of the coefficient of thermal expansion of the sample, the CTE value of the glass-ceramic precursor of the sample was 66X10 -7 /℃～72x10 -7 and/C. Then, according to the different heat treatment schemes shown in table 2, samples of each glass listed in table 2 were treated (nucleated, crystallized), and CTE values of the samples after crystallization were measured. Specifically, the CTE data of the samples of examples 3-9 in table 2 after crystallization are provided according to the heat treatment protocol experienced by the samples, which is expressed using conventions (a, B) and (C, D), where a is the nucleation temperature, B is the nucleation time, C is the crystallization temperature, and D is the crystallization time. Thus, in the heat treatment (700 ℃,2 h) (750 ℃,24 h) corresponds to a nucleation temperature of 700 ℃ and a nucleation time of 2h, and a crystallization temperature of 750 ℃ and a crystallization time of 24h.
TABLE 2 cover glass composition
As shown in table 2, the heat treatment of the glass-ceramic samples generally reduced the CTE relative to the glass-ceramic precursor, with the glass-ceramic CTE being dependent on the type, amount, and distribution of crystalline phases contained in the composite glass-ceramic. In the composite glass-ceramic samples of examples 1 to 9, the predominant crystal phase present after heat treatment was Li 2 Si 2 O 5 And has rutile (TiO) 2 ) Is a minor phase of (c). The number of the two crystalline phases depends on the time and temperature of the processing conditions and the composite glass-ceramic material. Specifically, the content Na is determined 2 O＞K 2 O causes more Li 2 Si 2 O 5 Nucleation and crystallization of the phase, which in turn provides a more pronounced CTE drop after crystallization.
Furthermore, it was found experimentally that for glass ceramics (precursors) of the same material, two samples with different crystallization times were heat treated at the same nucleation temperature and nucleation time and subsequently at the same crystallization temperature, the samples with longer crystallization times heat treated had fewer, larger crystals than the samples with shorter crystallization times, although both samples had about the same number of nucleating agents in the initial nucleation phase of the heat treatment.
Example 10:
laminating a sodium aluminum silicate glass, a transparent lithium aluminum silicate system and a magnesium aluminum silicate system low-expansion microcrystalline glass precursor sample, namely sandwiching sodium aluminum silicate glass between two microcrystalline glass precursor samples, adding laminated glass between two silicon carbide plates, placing the laminated glass in a high-temperature muffle furnace, heating to 50 ℃ above the higher softening point of the two glass, preserving heat for 30min, cooling to the nucleation temperature of the microcrystalline glass, nucleating and crystallizing according to respective heat treatment systems, and annealing and cooling to room temperature. The state of fusion between the layers of the laminated glass was examined, the state of fusion was good, and the thickness of the laminated glass was reduced to about 60% of the thickness before the furnace entry. And chemically strengthening the laminated glass ceramics and the corresponding non-laminated glass ceramics under the same conditions. The surface compressive stress of the laminated glass and the surface compressive stress of the corresponding glass ceramics (not laminated) were compared, and the surface compressive stress after crystallization of the laminated glass was increased by about 180 to 230MPa. The transmittance of the experimental sample reaches more than 90%, and the transmittance is reduced by about 1%.
The CTE of the crystallized composite glass ceramics prepared by the application is smaller than that of the glass precursor, so that the composite glass ceramics can be well suitable for being used as a glass coating layer of a reinforced laminated glass product.
When the composite glass-ceramic is used to make a laminated glass article, the laminated glass article can be used in a variety of applications including, for example, cover glass or glass back sheets for consumer or commercial electronic devices, including, for example, LCD, LED, OLED and quantum dot displays, computer display screens, and Automated Teller Machines (ATMs); for touch screens or touch sensors, for portable electronic devices including, for example, mobile phones, personal media players, and tablet computers; for photovoltaic applications; for architectural glass applications; for automotive or vehicular glass applications; for commercial or household appliance applications; for lighting or guidance sign applications, such as static or dynamic guidance signs; or for transportation applications including, for example, rail and aerospace applications.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the composite glass ceramic is characterized by comprising the following steps of:
preparing core layer glass liquid and cover layer glass liquid respectively;
cooling the core glass liquid to a forming temperature, and preforming the core glass;
the core glass passes through the middle of the cover glass devices, and the cover glass liquid is fused to the surface of the core glass;
drawing the fused glass to be thin at a high temperature to form a composite microcrystalline glass precursor;
and cooling the composite microcrystalline glass precursor, and performing nucleation, crystallization and annealing treatment to form the composite microcrystalline glass.
2. The method for preparing composite glass ceramics according to claim 1, wherein the preparation process of the core glass liquid is as follows: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 5 to 15mol% of Al 2 O 3 0 to 5mol% of B 2 O 3 2 to 20mol% of alkali metal oxide R 2 O and 0.1-0.2 mol% of clarifying agent are uniformly mixed, melted at 1200-1700 ℃, and clarified to form core layer glass liquid.
3. The method for preparing composite glass ceramics according to claim 1, wherein the preparation process of the cover glass liquid is as follows: expressed as mole percent based on oxide, 60 to 75 mole percent of SiO 2 2 to 25mol% of alkali metal oxide R 2 O, 3-10 mol% of Al 2 O 3 0 to 2mol% of P 2 O 5 ZrO 0-2 mol% 2 0 to 2mol% of TiO 2 And 0 to 0.1 SnO 2 Uniformly mixing, melting at 1200-1650 ℃, and clarifying to form a cover layer glass liquid;
alternatively, 60 to 75 mole% of SiO, expressed as mole percent based on oxide 2 15 to 22mol percent of Al 2 O 3 Na of 2-5 mol% 2 O, 10-15 mol% of Li 2 O, 2-5 mol% of P 2 O 5 Or B is a 2 O 3 ZrO 1-3 mol% 2 And 0 to 0.5mol percent of clarifying agent are evenly mixed, melted at 1200 to 1650 ℃ and clarified to form the glass liquid of the cover layer.
4. The method for preparing composite glass-ceramic according to claim 1, wherein alkaline earth metal oxide RO is added in the preparation process of the core glass liquid and the cover glass liquid, wherein R in the alkaline earth metal oxide is at least one of alkaline earth metal Mg, ca, ba and Sr;
the mole percentage of the alkaline earth metal oxide RO is 0 to 5 mole percent, expressed as mole percent on oxide basis.
5. A method for producing a composite glass-ceramic according to claim 2 or 3, wherein the alkali metal oxide R 2 R in O is at least one of group I metals;
the clarifying agent is SnO 2 And SnO.
6. The method for producing a composite glass-ceramic according to claim 3, wherein the glass-ceramic liquid is produced byIn the process, al 2 O 3 (mol%) and (R) 2 O (mol%) and RO (mol%) are less than 1, (SiO) 2 +Al 2 O 3 +Li 2 O+K 2 O+Na 2 O) (mol%) and (TiO) 2 +P 2 O 5 +ZrO 2 ) The ratio (mol%) is greater than 26.
7. The method for producing a composite glass-ceramic according to claim 1, wherein the high temperature is 950 to 1380 ℃, the nucleation temperature is 700 to 750 ℃, the nucleation time is 1 to 4 hours, the crystallization temperature is 750 to 900 ℃, and the crystallization time is 2 to 24 hours.
8. The composite glass-ceramic prepared by the preparation method according to any one of claims 1 to 7, wherein the composite glass-ceramic is a sandwich structure formed by high-temperature fusion, the sandwich structure comprises core glass and a plurality of cover glass layers, the plurality of cover glass layers are symmetrically covered on two opposite surfaces of the core glass, and the glass-ceramic outermost layer of the composite glass-ceramic is glass-ceramic.
9. The glass-ceramic composite according to claim 8, wherein the core glass has a higher coefficient of thermal expansion than the cover glass, and the difference in coefficient of thermal expansion is greater than 20x10 -7 The thermal expansion coefficient of the cover layer glass is gradually decreased from inside to outside;
the concentration of large-radius alkali metal ions in the core layer glass is larger than that of the cover layer glass, and the concentration of small-radius alkali metal ions in the cover layer glass is larger than that of the core layer glass, so that ion exchange is generated between the core layer glass and the cover layer glass in a high-temperature state.
10. Use of a composite glass-ceramic according to claim 8 or 9 in a laminated glass article.
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