CN110894137B - Tempered glass, 3D microcrystalline glass and preparation method thereof - Google Patents
Tempered glass, 3D microcrystalline glass and preparation method thereof Download PDFInfo
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- CN110894137B CN110894137B CN201811065146.9A CN201811065146A CN110894137B CN 110894137 B CN110894137 B CN 110894137B CN 201811065146 A CN201811065146 A CN 201811065146A CN 110894137 B CN110894137 B CN 110894137B
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- 239000011521 glass Substances 0.000 title claims abstract description 201
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000005341 toughened glass Substances 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 137
- 238000000034 method Methods 0.000 claims abstract description 108
- 238000001816 cooling Methods 0.000 claims abstract description 104
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 83
- 238000000137 annealing Methods 0.000 claims abstract description 73
- 238000013003 hot bending Methods 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 16
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 14
- 238000001228 spectrum Methods 0.000 claims description 12
- 238000002834 transmittance Methods 0.000 claims description 12
- 229910000500 β-quartz Inorganic materials 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 8
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052863 mullite Inorganic materials 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 238000005498 polishing Methods 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 10
- 238000000227 grinding Methods 0.000 abstract description 6
- 239000000395 magnesium oxide Substances 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 17
- 229910001413 alkali metal ion Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052634 enstatite Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910001753 sapphirine Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011160 research Methods 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
-
- 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
- C03B27/00—Tempering or quenching glass products
- C03B27/02—Tempering or quenching glass products using liquid
- C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
-
- 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
- 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
Abstract
The invention discloses toughened glass, 3D glass ceramics and a preparation method thereof, in the preparation method of the 3D glass ceramics, a glass substrate is accommodated in a forming die and then sequentially subjected to a preheating process, a hot bending forming process, an annealing process and a cooling process to obtain the 3D curved glass, and the key is that the glass substrate selected in the technical scheme has the viscosity of 5 multiplied by 10 at the temperature of 750-850 DEG C7～5×109Pa s, the property of the glass substrate processed by the preheating process can be simultaneously subjected to hot bending and crystallization in the hot bending forming process, so that the 3D curved glass can be obtained after the substrate glass processed by the hot bending forming process is subjected to the annealing process and the cooling process. The method is not the 3D curved glass obtained by preparing the microcrystalline glass and polishing the microcrystalline glass in the prior art, so that the steps of high processing difficulty, long processing time, high cost and low yield of polishing and grinding the microcrystalline glass are eliminated, and the 3D curved glass is produced efficiently and at low cost.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to tempered glass, 3D glass ceramics and a preparation method thereof.
Background
In recent years, with the development of display materials from LCDs to OLEDs, the flexible characteristics of OLEDs enable display screens to be developed towards curved surfaces, which enables cover glass plates to be developed from flat surfaces to 3D curved surfaces. The application of 3D glass board makes the appearance characteristic of product more go up the first floor, and for matching the curved surface display screen, the backplate material of product also tends to curved surface 3D ization for more accord with the outward appearance aesthetic feeling, improve the touch of product and feel.
At present, along with the improvement of mechanical strength requirements of consumers on products such as falling crack resistance, scratch resistance and the like, the strength of a protected cover plate material needs to be further improved to meet the requirements, and along with the application of technologies such as 5G communication, wireless charging and the like, a back plate material is developed from a metal material and a high polymer material to an inorganic non-metal material, the original metal back plate material is not suitable for the product requirements due to the electromagnetic shielding effect, and the poor hand feeling of the high polymer material is eliminated by the market due to the lower hardness and strength of the high polymer material.
The glass is easy to prepare into a transparent product, has strong plasticity and is easy to prepare into a 3D character at high temperature, but has large brittleness; although the ceramic has high strength, high hardness and good wear resistance, the transparency of the ceramic is poor, and the transparent product is difficult to prepare. The microcrystalline glass is a combination of the two, has excellent mechanical strength, thermodynamic property, chemical stability, excellent insulativity and the like, and can control parameters of the type, the grain size and the number of crystals in the microcrystalline glass to a certain extent by changing basic components and adjusting a heat treatment process, so that the thermal expansion coefficient and the transparency of the microcrystalline glass can be adjusted in a large range, and the characteristics determine that the microcrystalline glass plays an important role in the field of inorganic non-material science and have extremely high development, research and application prospects.
At present, because the microcrystalline glass has a certain content of crystal structures, the high-temperature softening effect is greatly reduced compared with that of glass, and the microcrystalline glass has the brittleness of partial ceramics, the 3D hot bending process cannot be carried out. The problems of complex process, low yield and high forming cost exist in the preparation of the 3D curved-surface glass ceramics by the polishing and grinding process, and the application of the glass ceramics in the field of 3D cover plate materials is greatly hindered.
Disclosure of Invention
The invention aims to solve the technical problems that aiming at the defects of the prior art, the invention provides a brand-new preparation method of the 3D curved-surface glass ceramics, the glass ceramics are processed into the 3D curved-surface glass without a complex polishing and grinding process, and the problems of high processing difficulty, long processing time and low yield in the production process of the 3D curved-surface glass ceramics are fundamentally solved.
In order to solve the technical problem, the invention provides a preparation method of 3D glass ceramics, which comprises the following steps: the method comprises the following steps of (1) accommodating a glass substrate in a forming die and then sequentially carrying out a preheating process, a hot bending forming process, an annealing process and a cooling process; wherein the content of the first and second substances,
the preheating process comprises the steps of placing the glass substrate in at least two preheating temperature areas with different temperatures in sequence and staying for a certain time, wherein the temperature of the preheating temperature areas is 300-750 ℃, the temperature of the former preheating temperature area is lower than that of the latter preheating temperature area, and the glass substrate stays in the last preheating temperature area for 1-60 beats;
the hot bending forming process is to place the glass substrate subjected to the preheating process in at least two forming temperature zones with different temperatures in sequence for a certain time, wherein the temperature of the forming temperature zone is 700-950 ℃, the temperature of the former forming temperature zone is lower than that of the latter forming temperature zone, and the glass substrate stays in the last forming temperature zone for 5-100 beats;
the annealing procedure is to place the glass substrate in a plurality of annealing temperature zones with different temperatures in sequence and stay for a certain time, wherein the temperature of the annealing temperature zone is 500-700 ℃, and the glass substrate stays for 5-20 beats in the foremost annealing temperature zone;
the cooling procedure is that the glass substrate after the annealing procedure is sequentially placed in a plurality of cooling temperature areas with different temperatures for a certain time, and the residence time of the glass substrate in each cooling temperature area is 2-15 min;
the time length of each beat is 0.5-5 min;
the viscosity of the glass substrate is 5 multiplied by 10 at 750 ℃ to 850 DEG C7～5×109Pa·s。
In the above technical solution, the 3D curved glass can be obtained by accommodating the glass substrate in the forming mold and then sequentially performing the preheating process, the hot bending process, the annealing process and the cooling process, and the key point is that the glass substrate selected in the above technical solution has a viscosity of 5 × 10 at 750-850 ℃7～5×109The property of Pa s is that the glass base material after the preheating procedure can simultaneously complete the hot bending and the hot bending in the hot bending forming procedureAnd (4) microcrystallizing, and then annealing and cooling the base material glass after the hot bending forming process to obtain the 3D curved glass. The method is not the 3D curved glass obtained by preparing the microcrystalline glass and polishing the microcrystalline glass in the prior art, and the steps of high processing difficulty, long processing time, high cost and low yield of polishing and grinding the microcrystalline glass are eliminated, so that the 3D curved glass is produced efficiently and at low cost.
As a preferable aspect of the production method of the present invention, the glass substrate comprises the following components in mole percent: SiO 22：60％～75％；Al2O3：10％～17％；P2O5：0％～5％；MgO：3％～10％；ZrO2：0％～6％；TiO2：0％～6％；Na2O：3％～12％；Li2O: 0 to 10 percent. Further, SiO2With Al2O3The sum of the contents of (A) is more than or equal to 75 percent; TiO 22And ZrO2The sum of the contents of (A) is more than or equal to 3% and less than or equal to 10%; na (Na)2O and Li2The sum of the contents of O is not less than 7% and not more than 14%.
SiO2Is a main part of a glass network structure and has high content of SiO2Ensures that the glass has excellent performances of high strength, thermal expansion resistance, chemical stability and the like, and SiO2Is a main component of a plurality of microcrystals, such as beta-quartz solid solution, beta-spodumene, enstatite, mullite, etc., preferably, SiO2The content is more than 70 percent to ensure that the glass has proper viscosity in a higher temperature range of 750-850 ℃.
Al2O3Can form [ AlO ] in glass4 +]Tetrahedrally linked [ SiO ]4 +]Non-bridging oxygen of network architecture, tamping network architecture, further improving glass strength and stability, preferably, Al2O3The content is more than 12 percent. As a network constituent, SiO2+Al2O3In an amount of 75% or more, preferably 80% or more, and a high content of the network component in order to make the glass in the range of 800 to 9Has proper hot bending high temperature viscosity in the 50 ℃ interval.
The nucleating agent is preferably TiO2And/or ZrO2，TiO2+ZrO2The content of (B) is not less than 5% and not more than 10%. TiO 22And ZrO2As nucleating agents, the two nucleating agents can improve the crystallization capacity of the microcrystalline glass, so that a large amount of uniform and fine crystals are produced in the microcrystallization treatment in a shorter time.
MgO is preferably 3-10%, magnesium oxide is used as a component of some crystals, the microcrystallization capacity of the crystals can be improved by adding the magnesium oxide to a certain extent, and the magnesium oxide has the effects of reducing the smelting difficulty and improving the glass hardness.
Na2O+Li2The content of O is more than or equal to 7 percent and less than or equal to 14 percent, and a certain amount of alkali metal is helpful for reducing the smelting difficulty, adjusting the high-temperature viscosity and ensuring that the microcrystalline glass has certain chemical strengthening capability.
In a preferred embodiment of the production method of the present invention, the melting temperature of the glass substrate is 1500 to 1650 ℃.
In a preferred embodiment of the production method of the present invention, the thickness of the glass substrate is 0.3mm to 2 mm.
As a preferable scheme of the preparation method of the present invention, the preheating process is to place the glass substrate in four preheating temperature zones with different temperatures in sequence and to stay for a certain time, the four preheating temperature zones with different temperatures include a first preheating temperature zone, a second preheating temperature zone, a third preheating temperature zone and a fourth preheating temperature zone, the temperature of the first preheating temperature zone is 300 ℃ to 400 ℃, the temperature of the second preheating temperature zone is 400 ℃ to 500 ℃, the temperature of the third preheating temperature zone is 500 ℃ to 600 ℃, and the temperature of the fourth preheating temperature zone is 600 ℃ to 750 ℃. Further, the glass substrate stays in the fourth preheating temperature zone for 10-20 beats to ensure that the glass substrate has enough time to complete the nucleation process in the hot bending forming procedure. Furthermore, when the forming mold carries the glass substrate and is arranged in the first preheating temperature zone, the second preheating temperature zone, the third preheating temperature zone and the fourth preheating temperature zone, the forming mold is applied with pressure of 0.01-0.05 Mpa.
As a preferable scheme of the preparation method of the present invention, in the hot bending forming process, the glass substrate after the preheating process is sequentially placed in two forming temperature zones with different temperatures and stays for a certain time, the two forming temperature zones with different temperatures include a first forming temperature zone and a second forming temperature zone, the temperature of the first forming temperature zone is 750 ℃ to 850 ℃, the temperature of the second forming temperature zone is 800 ℃ to 950 ℃, when the forming mold carries the glass substrate and is placed in the first forming temperature zone, a pressure of 0.1 to 1.5Mpa is applied to the forming mold, and when the forming mold carries the glass substrate and is placed in the second forming temperature zone, a pressure of 0.1 to 0.5Mpa is applied to the forming mold. Further, the glass substrate stays in the second forming temperature zone for 30-60 beats. And ensuring that the glass substrate has enough time to complete the crystallization process in the hot bending forming procedure.
As a preferred scheme of the preparation method, in the annealing process, the glass substrate is sequentially placed in two annealing temperature zones with different temperatures and stays for a certain time, the two annealing temperature zones with different temperatures comprise a first annealing temperature zone and a second annealing temperature zone, the temperature of the first annealing temperature zone is 600-700 ℃, and the temperature of the second annealing temperature zone is 500-600 ℃; the annealing process can eliminate internal stress generated by the hot bending forming process in the glass substrate, and prevent the glass substrate from self-breaking. The glass substrate stays in the first annealing temperature zone for 5-20 beats, and the temperature of the second annealing temperature zone is set to be 500-600 ℃ so as to reduce the temperature to the highest temperature suitable for a circulating cooling water jacket cooling mode or a circulating cold air cooling mode. And when the forming die carries the glass substrate and is arranged in the first annealing temperature zone and the second annealing temperature zone, applying pressure of 0.01-0.1 Mpa to the forming die.
In a preferred embodiment of the manufacturing method of the present invention, the cooling step is to place the glass substrate after the annealing step in six cooling temperature regions with different temperatures in sequence and to stay for a certain time, the six cooling temperature zones with different temperatures comprise a first cooling temperature zone, a second cooling temperature zone, a third cooling temperature zone, a fourth cooling temperature zone, a fifth cooling temperature zone and a sixth cooling temperature zone, the temperature of the first cooling temperature zone is 500-600 ℃, the temperature of the second cooling temperature zone is 400-550 ℃, the temperature of the third cooling temperature zone is 300-450 ℃, the temperature of the fourth cooling temperature zone is 200-350 ℃, the temperature of the fifth cooling temperature zone is 100-250 ℃, the temperature of the sixth cooling temperature zone is 50-150 ℃, and when the forming die carries the glass substrate and is arranged in the sixth cooling temperature zone, applying pressure of 0.01-0.05 Mpa to the forming die. The temperature difference of each cooling temperature area is not large, the glass substrate is quickly and uniformly cooled to the room temperature, and a circulating cooling water jacket cooling mode or a circulating cold air cooling mode is adopted for cooling in the whole process.
As a preferable scheme of the preparation method, the duration of each beat is 1-2 min.
The invention also provides 3D glass ceramics, and the 3D glass ceramics is prepared by the preparation method.
In a preferred embodiment of the 3D glass ceramic of the present invention, the thickness of the 3D glass ceramic is 0.3 to 2mm, the full spectrum average transmittance of the 3D glass ceramic is 20 to 90%, the 3D glass ceramic contains 15 to 50 wt% of a crystal phase, the average grain size of the crystal phase in the 3D glass ceramic is not more than 250mm, and the crystal phase of the 3D glass ceramic includes a β -quartz solid solution, β -spodumene, mullite, spinel, rutile, sapphirine, and a phosphate phase.
The invention also provides tempered glass prepared by ion exchange of the 3D glass ceramics as claimed in any one of claims 15 to 16 in a nitrate salt bath.
In a preferable aspect of the tempered glass of the present invention, the tempered glass has a surface compressive stress of 400Mpa or more and a compressive stress depth of 25 μm or more.
Compared with the prior art, the preparation method of the 3D microcrystalline glass provided by the inventionThe preparation method has the following beneficial effects: in the preparation method of the 3D glass ceramics, the glass substrate is accommodated in a forming die and then sequentially subjected to a preheating process, a hot bending forming process, an annealing process and a cooling process to obtain the 3D curved glass, and the key is that the glass substrate selected in the technical scheme has the viscosity of 5 multiplied by 10 at the temperature of 750-850 DEG C7～5×109Pa s, the property of the glass substrate processed by the preheating process can be simultaneously subjected to hot bending and microcrystallization in the hot bending forming process, so that the 3D curved glass can be obtained after the substrate glass processed by the hot bending forming process is subjected to the annealing process and the cooling process. The method is not the 3D curved glass obtained by preparing the microcrystalline glass and polishing the microcrystalline glass in the prior art, and the steps of high processing difficulty, long processing time, high cost and low yield of polishing and grinding the microcrystalline glass are eliminated, so that the 3D curved glass is produced efficiently and at low cost.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the 3D glass ceramics provided by the invention comprises the step of accommodating a glass substrate in a forming die and then sequentially carrying out a preheating process, a hot bending forming process, an annealing process and a cooling process to obtain the 3D glass ceramics.
The forming die can be a graphite die or a silicon carbide die which is commonly used in the existing hot bending forming process.
The viscosity of the glass substrate is 5 multiplied by 10 at 750 ℃ to 850 DEG C7～5×109Pa·s。
The preheating process is to place the glass substrate in at least two preheating temperature areas with different temperatures in sequence and stay for a certain time, wherein the temperature of the preheating temperature area is 300-750 ℃, the temperature of the former preheating temperature area is lower than that of the latter preheating temperature area, and the glass substrate stays in the last preheating temperature area for 1-60 beats. Preferably, the preheating process is to place the glass substrate in four preheating temperature zones with different temperatures in sequence for a certain time, wherein the four preheating temperature zones with different temperatures comprise a first preheating temperature zone, a second preheating temperature zone, a third preheating temperature zone and a fourth preheating temperature zone, the temperature of the first preheating temperature zone is 300-400 ℃, the temperature of the second preheating temperature zone is 400-500 ℃, the temperature of the third preheating temperature zone is 500-600 ℃, and the temperature of the fourth preheating temperature zone is 600-750 ℃. Further, the glass substrate stays in the fourth preheating temperature zone for 10-20 beats. Furthermore, when the forming mold carries the glass substrate and is placed in the fourth preheating temperature zone, 0.01-0.05 Mpa of pressure is applied to the forming mold.
The hot bending forming process is to place the glass substrate subjected to the preheating process in at least two forming temperature zones with different temperatures in sequence for a certain time, wherein the temperature of the forming temperature zone is 700-950 ℃, the temperature of the former forming temperature zone is lower than that of the latter forming temperature zone, and the glass substrate stays in the last forming temperature zone for 5-100 beats. Preferably, in the hot bending forming process, the glass substrate after the preheating process is sequentially placed in two forming temperature zones with different temperatures and stays for a certain time, the two forming temperature zones with different temperatures comprise a first forming temperature zone and a second forming temperature zone, the temperature of the first forming temperature zone is 750-850 ℃, the temperature of the second forming temperature zone is 800-950 ℃, when the forming mold carries the glass substrate and is placed in the first forming temperature zone, the pressure of 0.1-1.5 Mpa is applied to the forming mold, and when the forming mold carries the glass substrate and is placed in the second forming temperature zone, the pressure of 0.1-0.5 Mpa is applied to the forming mold. Preferably, the glass substrate stays in the second forming temperature zone for 30-60 beats, so that the glass substrate has enough time to complete the crystallization process in the hot bending forming process.
The annealing process is that the glass substrate is sequentially placed in a plurality of annealing temperature zones with different temperatures and stays for a certain time, the temperature of the annealing temperature zone is 500-700 ℃, and the glass substrate stays for 5-20 beats in the foremost annealing temperature zone. Preferably, in the annealing process, the glass substrate is sequentially placed in two annealing temperature zones with different temperatures and stays for a certain time, the two annealing temperature zones with different temperatures comprise a first annealing temperature zone and a second annealing temperature zone, the temperature of the first annealing temperature zone is 600-700 ℃, and the temperature of the second annealing temperature zone is 500-600 ℃; and when the forming die carries the glass substrate and is arranged in the first annealing temperature zone and the second annealing temperature zone, applying pressure of 0.01-0.1 Mpa to the forming die. The annealing process can eliminate internal stress generated by the hot bending forming process in the glass substrate, and prevent the glass substrate from self-breaking. The glass substrate stays in the first annealing temperature zone for 5-20 beats, and the temperature of the second annealing temperature zone is set to be 500-600 ℃ so as to reduce the temperature to the highest temperature suitable for a circulating cooling water jacket cooling mode or a circulating cold air cooling mode.
The cooling procedure is to place the glass substrate subjected to the annealing procedure in a plurality of cooling temperature zones with different temperatures in sequence for a certain time, and the residence time of the glass substrate in each cooling temperature zone is 2-15 min. Preferably, the cooling procedure is to place the glass substrate after the annealing procedure in six cooling temperature zones with different temperatures in sequence for a certain time, the six cooling temperature zones with different temperatures comprise a first cooling temperature zone, a second cooling temperature zone, a third cooling temperature zone, a fourth cooling temperature zone, a fifth cooling temperature zone and a sixth cooling temperature zone, the temperature of the first cooling temperature zone is 500-600 ℃, the temperature of the second cooling temperature zone is 400-550 ℃, the temperature of the third cooling temperature zone is 300-450 ℃, the temperature of the fourth cooling temperature zone is 200-350 ℃, the temperature of the fifth cooling temperature zone is 100-250 ℃, the temperature of the sixth cooling temperature zone is 50-150 ℃, and when the forming die carries the glass substrate and is arranged in the sixth cooling temperature zone, applying pressure of 0.01-0.05 Mpa to the forming die. The temperature difference of each cooling temperature area is not large, the glass substrate is quickly and uniformly cooled to the room temperature, and a circulating cooling water jacket cooling mode or a circulating cold air cooling mode is adopted for cooling in the whole process.
It should be noted that, in the present invention, the time duration of each beat is 0.5 to 5min (preferably 1 to 2 min).
The glass substrate adopted by the invention comprises the following components in percentage by mole: SiO 22：60％～75％；Al2O3：10％～17％；P2O5：0％～5％；MgO：3％～10％；ZrO2：0％～6％；TiO2：0％～6％；Na2O：3％～12％；Li2O: 0 to 10 percent. Further, SiO2With Al2O3The sum of the contents of (A) is more than or equal to 75 percent; TiO 22And ZrO2The sum of the contents of (A) is more than or equal to 3% and less than or equal to 10%; na (Na)2O and Li2The sum of the contents of O is not less than 7% and not more than 14%. Wherein, SiO2Is a main part of a glass network framework and has high content of SiO2Ensures that the glass has excellent performances of high strength, thermal expansion resistance, chemical stability and the like, and SiO2Is a main component of a plurality of microcrystals, such as beta-quartz solid solution, beta-spodumene, enstatite, mullite, etc., preferably, SiO2The content is more than 70 percent to ensure that the glass has proper viscosity in a higher temperature range of 750-850 ℃. Al (Al)2O3Can form [ AlO ] in glass4 +]Tetrahedrally linked [ SiO ]4 +]Non-bridging oxygen of network architecture, tamping network architecture, further improving glass strength and stability, preferably, Al2O3The content is more than 12 percent. As a network constituent, SiO2+Al2O3In an amount of greater than or equal to 75%, preferably greater than or equal to 80%, the high content of network constituents being such that the glass has a suitable hot-bending high-temperature viscosity in the interval 800 ℃ to 950 ℃. The nucleating agent is preferably TiO2And/or ZrO2，TiO2+ZrO2The content of (B) is not less than 5% and not more than 10%. TiO 22And ZrO2As nucleating agents, the two nucleating agents can improve the crystallization capacity of the microcrystalline glass, so that a large amount of uniform and fine crystals are produced in the microcrystallization treatment in a shorter time. MgO is preferably 3-10%, magnesium oxide is used as a component of some crystals, the microcrystallization capacity of the crystals can be improved by adding the magnesium oxide to a certain extent, and the magnesium oxide has the effects of reducing the smelting difficulty and improving the glass hardness. Na (Na)2O+Li2The content of O is more than or equal to 7 percent and less than or equal to 14 percent, and a certain amount of alkali metal is helpful for reducing the smelting difficulty, adjusting the high-temperature viscosity and ensuring that the microcrystalline glass has certain chemical strengthening capability.
In addition, the melting temperature of the glass substrate is 1500-1650 ℃, and the thickness of the glass substrate is 0.3-2 mm. This makes the glass substrate more suitable for the method provided by the invention, and 3D glass ceramics meeting the market demand can be prepared by the method.
In the preparation method provided by the invention, the 3D curved glass can be obtained by accommodating the glass substrate in the forming die and then sequentially carrying out the preheating process, the hot bending forming process, the annealing process and the cooling process, and the key point is that the glass substrate selected in the technical scheme has the viscosity of 5 multiplied by 10 at the temperature of 800-950 DEG C7～5×109Pa s, the property of the glass substrate processed by the preheating process can be simultaneously subjected to hot bending and crystallization in the hot bending forming process, so that the 3D curved glass can be obtained after the substrate glass processed by the hot bending forming process is subjected to the annealing process and the cooling process. The method is not the 3D curved glass obtained by preparing the microcrystalline glass and polishing the microcrystalline glass in the prior art, and the steps of high processing difficulty, long processing time, high cost and low yield of polishing and grinding the microcrystalline glass are eliminated, so that the 3D curved glass is produced efficiently and at low cost.
The 3D glass ceramics prepared by the preparation method provided by the invention has the following properties: the thickness of the 3D glass ceramics is 0.3-2 mm, the full spectrum average transmittance of the 3D glass ceramics is 20-90%, the 3D glass ceramics contains 15-50 wt% of crystal phase, the average grain size of the crystal phase in the 3D glass ceramics is less than or equal to 250mm, and the crystal phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene, mullite, spinel, rutile, sapphirine and phosphate phase.
It is further noted that the 3D glass ceramics provided by the present invention can also be ion exchanged, thereby obtaining tempered glass with higher strength. Specifically, the 3D glass ceramics can be coated with NaNO3Or KNO3And (2) carrying out ion exchange in the salt bath, replacing the small-diameter alkali metal ions of the glass with the large-diameter alkali metal ions in the salt bath, and enabling the 3D glass ceramics to generate composite compressive stress through a 'plug squeezing effect'. In the ion exchange process, potassium-sodium or sodium-lithium unitary ion exchange can be carried out, and potassium-sodium and sodium-lithium mixed binary ion exchange can be carried out, wherein the major diameter alkali metal ions are potassium ions and sodium ions, and the minor diameter alkali metal ions are sodium ions and lithium ions. The temperature of ion exchange can be set between 370 ℃ and 450 ℃, and the ion exchange time can be set between 30min and 12 h.
The tempered glass obtained by ion exchange of the above-mentioned 3D curved glass ceramics generally has the following characteristics:
the invention also provides tempered glass prepared by ion exchange of the 3D glass ceramics as claimed in any one of claims 15 to 16 in a nitrate salt bath.
In a preferable aspect of the tempered glass of the present invention, the tempered glass has a surface compressive stress of 400Mpa or more and a compressive stress depth of 25 μm or more.
The following examples are set forth to illustrate the invention in more detail, but are not intended to limit the scope of the invention in any way.
The first embodiment is as follows: preparation of 3D glass ceramics I
In this embodiment, a specific process for preparing the 3D glass ceramic i is as follows:
1) accommodating the glass substrate in a forming mold;
2) the forming die with the glass substrate inside is sequentially placed in a first preheating temperature zone, a second preheating temperature zone, a third preheating temperature zone and a fourth preheating temperature zone which are different in temperature, the temperature of the first preheating temperature zone is 200 ℃, the temperature of the second preheating temperature zone is 400 ℃, the temperature of the third preheating temperature zone is 550 ℃, the temperature of the fourth preheating temperature zone is 680 ℃, the glass substrate respectively stays in the first preheating temperature zone, the second preheating temperature zone and the third preheating temperature zone for 1 beat, and the glass substrate stays in the fourth preheating temperature zone for 15 beats. When the forming die carries the glass substrate and is arranged in the first preheating temperature zone, the second preheating temperature zone and the third preheating temperature zone, the forming die is applied with pressure of 0.01 Mpa.
3) And sequentially placing the forming die with the glass substrate inside in a first forming temperature zone and a second forming temperature zone with different temperatures, wherein the temperature of the first forming temperature zone is 780 ℃ and the temperature of the second forming temperature zone is 850 ℃, and applying 0.5Mpa pressure to the forming die when the forming die carries the glass substrate and is placed in the first forming temperature zone, and applying 0.1Mpa pressure to the forming die when the forming die carries the glass substrate and is placed in the second forming temperature zone. The glass substrate stays at the first forming temperature zone for 1 beat, and stays at the second forming temperature zone for 40 beats;
4) placing the forming die with the glass substrate inside in a first annealing temperature zone and a second annealing temperature zone which are different in temperature in sequence, wherein the temperature of the first annealing temperature zone is 650 ℃, and the temperature of the second annealing temperature zone is 500 ℃; when the forming die carries the glass substrate and is arranged in the first annealing temperature zone and the second annealing temperature zone, the forming die is applied with pressure of 0.1 Mpa. The glass substrate stays in the first annealing temperature zone and the second annealing temperature zone for 5 beats and 1 beat respectively;
5) the forming die with the glass substrate is sequentially placed in a first cooling temperature zone, a second cooling temperature zone, a third cooling temperature zone, a fourth cooling temperature zone, a fifth cooling temperature zone and a sixth cooling temperature zone which are different in temperature, wherein the temperature of the first cooling temperature zone is 500 ℃, the temperature of the second cooling temperature zone is 400 ℃, the temperature of the third cooling temperature zone is 300 ℃, the temperature of the fourth cooling temperature zone is 200 ℃, the temperature of the fifth cooling temperature zone is 100 ℃, the temperature of the sixth cooling temperature zone is 50 ℃, and when the forming die is carried with the glass substrate and placed in the first cooling temperature zone, the second cooling temperature zone, the third cooling temperature zone, the fourth cooling temperature zone, the fifth cooling temperature zone and the sixth cooling temperature zone, the pressure of 0.05Mpa is applied to the forming die. The glass substrate stays in the first cooling temperature zone, the second cooling temperature zone, the third cooling temperature zone, the fourth cooling temperature zone, the fifth cooling temperature zone and the sixth cooling temperature zone respectively for one beat.
It should be noted that, in this embodiment, the time corresponding to one beat is 3 min.
The glass substrate used in this example satisfies the following conditions:
comprises the following components in mol percentage: SiO 22：65.55％；Al2O3：12.73％；MgO：3.25％；ZrO2：2.53％；TiO2：3.57％；Na2O：5.02％；Li2O：7.36％；
Viscosity at 750-850 deg.C is 5 × 107～7×108Pa·s；
The melting temperature is 1600 ℃;
the thickness is 0.7 mm.
The 3D glass ceramics I prepared by the preparation method has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 87%;
the color is colorless;
contains 38 wt% of a crystalline phase;
the average grain diameter of the crystal phase is 40-80 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and rutile.
Example two: preparation of 3D glass ceramics II
The 3D glass ceramic ii was prepared according to the same preparation method as in example one, except that:
the glass substrate stays in the fourth preheating temperature zone for 1 beat;
the glass substrate stays in the second forming temperature zone for 60 beats;
the 3D glass ceramics II obtained by the preparation method provided by the embodiment has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 88%;
the color is colorless;
contains 29 wt% of a crystalline phase;
the average grain diameter of the crystal phase is 30-65 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and rutile.
Example three: preparation of 3D glass ceramics III
3D glass ceramics III was prepared by the same preparation method as in example one, except that:
the glass substrate stays in the fourth preheating temperature zone for 30 beats (each beat corresponds to 4 min);
the temperature of the second forming temperature zone is 880 ℃;
the glass substrate stays in the second forming temperature zone for 60 beats (here, each beat corresponds to 4 min);
the glass substrate stays in the first annealing temperature zone for 10 beats (here, the time corresponding to each beat is 3 min);
the 3D glass ceramic iii obtained by the preparation method provided in this example has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 84%;
the color is colorless;
contains 48 wt% of crystalline phase;
the average grain diameter of the crystal phase is 60-110 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene, spinel and rutile.
Example four: preparation of 3D glass ceramics IV
A 3D glass ceramic iv was prepared according to the same preparation method as in example one, except that:
the temperature of the fourth preheating temperature zone is 700 ℃;
the glass substrate stays in the fourth preheating temperature zone for 20 beats;
the temperature of the first forming temperature zone is 760 ℃;
the temperature of the second forming temperature zone is 880 ℃;
the glass substrate in this example satisfies the following conditions:
1) comprises the following components in mol percentage: SiO 22：65.55％；Al2O3：12.73％；MgO：3.25％；ZrO2：3.43％；TiO2：2.03％；Na2O：5.00％；Li2O：8.00％；
2) The viscosity at 750-850 deg.C is 4X 107～5×108Pa·s；
3) The melting temperature is 1600 ℃;
the thickness is 0.7 mm.
The 3D glass ceramic IV obtained by the preparation method provided by the embodiment has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 90%;
the color is colorless;
contains 36 wt% of crystalline phase;
the average grain diameter of the crystal phase is 40-80 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and spinel.
Example five: preparation of 3D glass ceramics V
A 3D glass-ceramic v was produced in the same production method as in example one, except that:
the temperature of the fourth preheating temperature zone is 700 ℃;
the glass substrate stays in the fourth preheating temperature zone for 20 beats;
the temperature of the first forming temperature zone is 760 ℃;
the temperature of the second forming temperature zone is 900 ℃;
the glass substrate stays in the second forming temperature zone for 60 beats (here, the time corresponding to one beat is 4 min);
comprises the following components in mol percentage: SiO 22：65.55％；Al2O3：12.73％；MgO：3.25％；ZrO2：3.43％；TiO2：2.03％；Na2O：5.00％；Li2O：8.00％；
The viscosity at 750-850 deg.C is 4X 107～5×108Pa·s；
The melting temperature is 1600 ℃;
the thickness is 0.7 mm.
The 3D glass-ceramic v obtained by the preparation method provided in this example has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 88%;
the color is colorless;
contains 45 wt% of crystalline phase;
the average grain diameter of the crystal phase is 60-90 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and spinel.
Example six: preparation of 3D glass ceramics VI
A 3D glass ceramic vi was prepared by the same preparation method as in example one, except that:
the temperature of the fourth preheating temperature zone is 700 ℃;
the glass substrate stays in the fourth preheating temperature zone for 1 beat;
the temperature of the first forming temperature zone is 810 ℃;
the temperature of the second forming temperature zone is 920 ℃;
the glass substrate stays in the first annealing temperature zone for 10 beats;
the glass substrate in this example satisfies the following conditions:
comprises the following components in mol percentage: SiO 22：70.5％；Al2O3：11.00％；MgO：3.00％；TiO2：5.15％；Na2O：3.07％；Li2O：7.23％；
Viscosity at 750-850 deg.C is 5 × 108～4×109Pa·s；
The melting temperature is 1650 ℃;
the thickness is 0.7 mm.
The 3D glass-ceramic VI obtained by the preparation method provided by the embodiment has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 83%;
the color is slightly yellowish;
contains 26 wt% of crystalline phase;
the average grain size of the crystal phase is 50-120 m;
the crystalline phase of the 3D glass ceramics comprises beta-spodumene, mullite, spinel and rutile.
Example seven: preparation of 3D glass ceramics VII
The 3D glass ceramics vii was prepared by the same preparation method as in example one, except that:
the glass substrate stays in the fourth preheating temperature zone for 20 beats;
the temperature of the first forming temperature zone is 810 ℃;
the temperature of the second forming temperature zone is 950 ℃;
the glass substrate stays in the second forming temperature zone for 40 beats (here, the time corresponding to one beat is 5 min);
the glass substrate in this example satisfies the following conditions:
comprises the following components in mol percentage: : SiO 22：70.5％；Al2O3：11.00％；MgO：3.00％；TiO2：5.15％；Na2O：3.07％；Li2O：7.23％；
Viscosity at 750-850 deg.C is 5 × 108～4×109Pa·s；
The melting temperature is 1650 ℃;
the thickness is 0.7 mm.
The 3D microcrystalline glass VII obtained by the preparation method provided by the embodiment has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 80%;
the color is yellow;
contains 50 wt% of crystalline phase;
the average grain size of the crystal phase is 80-150 m;
the crystalline phase of the 3D glass ceramics comprises beta-spodumene, mullite, spinel and rutile.
Example eight: preparation of 3D glass ceramics VIII
The 3D glass ceramic viii was prepared by the same preparation method as in example one, except that:
the temperature of the fourth preheating temperature zone is 700 ℃;
the glass substrate stays in the fourth preheating temperature zone for 30 beats;
the temperature of the second forming temperature zone is 900 ℃;
the glass substrate stays in the second forming temperature zone for 60 beats;
the glass substrate in this example satisfies the following conditions:
comprises the following components in mol percentage: SiO 22：66.00％；Al2O3：12.50％；MgO：6.50％；ZrO2：3.00％；TiO2：1.25％；Na2O：10.75％；
The viscosity at 750-850 deg.C is 6 x 107～9×108Pa·s；
The melting temperature is 1650 ℃;
the thickness is 0.7 mm.
The 3D glass ceramic viii obtained by the preparation method provided in this example has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 88%;
the color is colorless;
contains 27 wt% of crystalline phase;
the average grain diameter of the crystal phase is 30-70 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and spinel.
Example nine: preparation of 3D glass ceramics IX
A3D glass ceramic IX was prepared in the same manner as in example one except that:
the temperature of the fourth preheating temperature zone is 720 ℃;
the glass substrate stays in the fourth preheating temperature zone for 40 beats;
the temperature of the second forming temperature zone is 900 ℃;
the glass substrate stays in the second forming temperature zone for 70 beats (here, the time corresponding to one beat is 5 min);
the glass substrate stays in the first annealing temperature zone for 10 beats;
the glass substrate in this example satisfies the following conditions:
comprises the following components in mol percentage: SiO 22：66.00％；Al2O3：12.50％；MgO：6.50％；ZrO2：3.00％；TiO2：1.25％；Na2O：10.75％；
The viscosity at 750-850 deg.C is 6 x 107～9×108Pa·s；
The melting temperature is 1650 ℃;
the thickness is 0.7 mm.
The 3D glass-ceramic IX obtained by the preparation method provided in this example has the following characteristics:
the thickness is 0.7 mm;
the full spectrum average transmittance is 85%;
the color is colorless;
contains 43 wt% of crystalline phase;
the average grain size of the crystal phase is 60-100 nm;
the crystalline phase of the 3D glass ceramics comprises beta-quartz solid solution, beta-spodumene and spinel.
Example ten
In this embodiment, the 3D glass ceramics prepared in the first to ninth embodiments are chemically tempered to obtain tempered glass with higher strength.
Specifically, the 3D glass ceramics can be placed in NaNO3Or KNO3And (2) carrying out ion exchange in the salt bath, replacing the small-diameter alkali metal ions of the glass with the large-diameter alkali metal ions in the salt bath, and enabling the 3D glass ceramics to generate composite compressive stress through a 'plug squeezing effect'. In the ion exchange process, potassium-sodium or sodium-lithium unitary ion exchange can be carried out, and potassium-sodium and sodium-lithium mixed binary ion exchange can be carried out, wherein the major diameter alkali metal ions are potassium ions and sodium ions, and the minor diameter alkali metal ions are sodium ions and lithium ions. The temperature of ion exchange can be set between 370 ℃ and 450 ℃, and the ion exchange time can be set between 30min and 12 h. The following table lists the conditions under which the 3D glass-ceramics prepared in examples one to nine are ion-exchanged and the characteristics of the corresponding tempered glass.
While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and many modifications may be made by those skilled in the art without departing from the spirit and the scope of the invention as defined by the appended claims.
Claims (13)
1. A preparation method of 3D glass ceramics is characterized by comprising the following steps: the method comprises the following steps of (1) accommodating a glass substrate in a forming die and then sequentially carrying out a preheating process, a hot bending forming process, an annealing process and a cooling process; wherein the content of the first and second substances,
the preheating process comprises the steps of placing the glass substrate in at least two preheating temperature areas with different temperatures in sequence and staying for a certain time, wherein the temperature of the preheating temperature area is 300-750 ℃, the temperature of the former preheating temperature area is lower than that of the latter preheating temperature area, and the glass substrate stays in the last preheating temperature area for 1-60 beats;
the hot bending forming process is to place the glass substrate subjected to the preheating process in at least two forming temperature zones with different temperatures in sequence for a certain time, wherein the temperature of the forming temperature zone is 700-950 ℃, the temperature of the former forming temperature zone is lower than that of the latter forming temperature zone, and the glass substrate stays in the last forming temperature zone for 5-100 beats; the hot bending forming process is to place the glass substrate subjected to the preheating process in two forming temperature regions with different temperatures in sequence for a certain time, wherein the two forming temperature regions with different temperatures comprise a first forming temperature region and a second forming temperature region, the temperature of the first forming temperature region is 750-850 ℃, the temperature of the second forming temperature region is 800-950 ℃, when the forming mold carries the glass substrate and is placed in the first forming temperature region, the pressure of 0.1-1.5 MPa is applied to the forming mold, and when the forming mold carries the glass substrate and is placed in the second forming temperature region, the pressure of 0.1-0.5 MPa is applied to the forming mold; the glass substrate stays in the second forming temperature zone for 30-60 beats, and the glass substrate is ensured to have enough time to complete a crystallization process in the hot bending forming procedure; the hot bending and microcrystallization are simultaneously completed in the hot bending forming procedure;
the annealing process comprises the steps of placing the glass substrate in two annealing temperature zones with different temperatures in sequence and staying for a certain time, wherein the two annealing temperature zones with different temperatures comprise a first annealing temperature zone and a second annealing temperature zone, the temperature of the annealing temperature zone is 500-700 ℃, the temperature of the first annealing temperature zone is 600-700 ℃, the temperature of the second annealing temperature zone is 500-600 ℃, and the glass substrate stays in the foremost annealing temperature zone for 5-20 beats;
the cooling procedure is that the glass substrate after the annealing procedure is sequentially placed in a plurality of cooling temperature areas with different temperatures for a certain time, and the residence time of the glass substrate in each cooling temperature area is 2-15 min;
the time length of each beat is 0.5-5 min;
the viscosity of the glass substrate is 5 multiplied by 10 at 750 ℃ to 850 DEG C7～5×109Pa·s；
The glass substrate comprises the following components in mole percent:
SiO2：60％～75％；
Al2O3：10％～17％；
P2O5：0％～5％；
MgO：3％～10％；
ZrO2：0％～6％；
TiO2：0％～6％；
Na2O：3％～12％；
Li2O：0％～10％；
the contents of all components meet the following relationship:
SiO2with Al2O3The sum of the contents of (A) is more than or equal to 75 percent;
TiO2and ZrO2The sum of the contents of (A) is more than or equal to 3% and less than or equal to 10%;
Na2o and Li2The sum of the contents of O is not less than 7% and not more than 14%.
2. The method according to claim 1, wherein the glass substrate has a melting temperature of 1500 ℃ to 1650 ℃.
3. The production method according to claim 1, wherein the glass substrate has a thickness of 0.3mm to 2 mm.
4. The method according to claim 1, wherein the preheating step comprises placing the glass substrate in four preheating temperature zones of different temperatures in sequence and staying for a certain time, wherein the four preheating temperature zones of different temperatures comprise a first preheating temperature zone, a second preheating temperature zone, a third preheating temperature zone and a fourth preheating temperature zone, the temperature of the first preheating temperature zone is 300 ℃ to 400 ℃, the temperature of the second preheating temperature zone is 400 ℃ to 500 ℃, the temperature of the third preheating temperature zone is 500 ℃ to 600 ℃, and the temperature of the fourth preheating temperature zone is 600 ℃ to 750 ℃.
5. The manufacturing method according to claim 4, wherein the glass substrate stays in the fourth preheating temperature zone for 10 to 20 beats.
6. The production method according to claim 4, wherein when the forming mold carries the glass substrate and is placed in the first preheating temperature zone, the second preheating temperature zone, the third preheating temperature zone, and the fourth preheating temperature zone, a pressure of 0.01 to 0.05Mpa is applied to the forming mold.
7. The manufacturing method according to claim 1, wherein the annealing process comprises the steps of sequentially placing the glass substrate in two annealing temperature zones with different temperatures for a certain time, and applying a pressure of 0.01-0.1 Mpa to the forming mold when the forming mold carries the glass substrate and is placed in the first annealing temperature zone and the second annealing temperature zone.
8. The preparation method according to claim 1, wherein the cooling step is to place the glass substrate after the annealing step in six cooling temperature zones of different temperatures in sequence for a certain time, the six cooling temperature zones of different temperatures include a first cooling temperature zone, a second cooling temperature zone, a third cooling temperature zone, a fourth cooling temperature zone, a fifth cooling temperature zone and a sixth cooling temperature zone, the temperature of the first cooling temperature zone is 500 ℃ to 600 ℃, the temperature of the second cooling temperature zone is 400 ℃ to 550 ℃, the temperature of the third cooling temperature zone is 300 ℃ to 450 ℃, the temperature of the fourth cooling temperature zone is 200 ℃ to 350 ℃, the temperature of the fifth cooling temperature zone is 100 ℃ to 250 ℃, the temperature of the sixth cooling temperature zone is 50 ℃ to 150 ℃, and when the forming mold carries the glass substrate to be placed in the sixth cooling temperature zone, and applying pressure of 0.01-0.05 Mpa to the forming die.
9. The method according to any one of claims 1 to 8, wherein the duration of each beat is 1 to 2 min.
10. 3D glass-ceramic, characterized in that the 3D glass-ceramic is prepared by the preparation method according to any one of claims 1 to 9.
11. The 3D glass ceramic according to claim 10, wherein the thickness of the 3D glass ceramic is 0.3-2 mm, the full spectrum average transmittance of the 3D glass ceramic is 20-90%, the 3D glass ceramic contains 15-50 wt% of crystal phase, the average grain size of the crystal phase in the 3D glass ceramic is less than or equal to 250mm, and the crystal phase of the 3D glass ceramic comprises beta-quartz solid solution, beta-spodumene, mullite, spinel and rutile.
12. A tempered glass produced by ion-exchanging the 3D glass-ceramic according to any one of claims 10 to 11 in a nitrate salt bath.
13. The tempered glass of claim 12, wherein the tempered glass has a surface compressive stress of 400Mpa or more and a depth of compressive stress of 25 μm or more.
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| CN114436535A (en) * | 2020-10-30 | 2022-05-06 | 程珵 | Nucleated glass raw material and preparation method and application thereof |
| EP4276077A1 (en) * | 2021-01-25 | 2023-11-15 | Chongqing Aureavia Hi-tech Glass Co., Ltd | Crystallized glass raw material, preparation method therefor and use thereof |
| CN114790085A (en) * | 2021-01-25 | 2022-07-26 | 程珵 | 3D glass ceramic and preparation method and application thereof |
| CN114790081A (en) * | 2021-01-25 | 2022-07-26 | 程珵 | Crystallized glass raw material and preparation method and application thereof |
| CN114835400B (en) * | 2021-01-30 | 2023-03-31 | 华为技术有限公司 | Chemically strengthened glass ceramics, preparation method thereof and electronic equipment |
| CN113248152B (en) * | 2021-05-21 | 2022-06-10 | 常熟佳合显示科技有限公司 | Three-dimensional glass ceramics and preparation method thereof |
| CN113771433B (en) * | 2021-09-30 | 2022-08-19 | 福耀玻璃工业集团股份有限公司 | Laminated glass for vehicle |
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