CN114790081A - Crystallized glass raw material and preparation method and application thereof - Google Patents
Crystallized glass raw material and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 564
- 239000002994 raw material Substances 0.000 title claims abstract description 251
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 238000013003 hot bending Methods 0.000 claims description 182
- 238000002834 transmittance Methods 0.000 claims description 156
- 239000013078 crystal Substances 0.000 claims description 152
- 239000002241 glass-ceramic Substances 0.000 claims description 148
- 238000000034 method Methods 0.000 claims description 127
- 238000000137 annealing Methods 0.000 claims description 121
- 238000002425 crystallisation Methods 0.000 claims description 120
- 230000008025 crystallization Effects 0.000 claims description 120
- 238000010899 nucleation Methods 0.000 claims description 96
- 230000006911 nucleation Effects 0.000 claims description 96
- 238000001816 cooling Methods 0.000 claims description 88
- 239000002667 nucleating agent Substances 0.000 claims description 84
- 238000002844 melting Methods 0.000 claims description 82
- 230000008018 melting Effects 0.000 claims description 82
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 56
- 238000005520 cutting process Methods 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 42
- 239000011780 sodium chloride Substances 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 35
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000006025 fining agent Substances 0.000 claims 2
- 238000012545 processing Methods 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000011449 brick Substances 0.000 description 170
- 230000008569 process Effects 0.000 description 113
- 230000005540 biological transmission Effects 0.000 description 106
- 238000007731 hot pressing Methods 0.000 description 80
- 238000005498 polishing Methods 0.000 description 48
- 238000002441 X-ray diffraction Methods 0.000 description 45
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- 230000005855 radiation Effects 0.000 description 39
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- 239000000203 mixture Substances 0.000 description 31
- 238000005303 weighing Methods 0.000 description 25
- 229910000500 β-quartz Inorganic materials 0.000 description 23
- 238000005452 bending Methods 0.000 description 19
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 18
- 229910052670 petalite Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000003426 chemical strengthening reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008395 clarifying agent Substances 0.000 description 13
- 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 13
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 12
- 229910052644 β-spodumene Inorganic materials 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000005345 chemically strengthened glass Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- -1 lithium-aluminum-silicon Chemical compound 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000006058 strengthened glass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
Images
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
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a crystallized glass raw material, which is characterized in that the thickness of the crystallized glass raw material is 0.02-5 mm; the crystallinity of the crystallized glass raw material is 5-90 wt%. The preparation method of the crystallized glass raw material has small processing difficulty and low processing cost; the time cost is saved, and the energy of heat treatment is saved.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to a crystallized glass raw material and a preparation method and application thereof.
Background
The microcrystalline glass as a new generation high-strength glass has higher performance than the traditional lithium-aluminum-silicon glass. Because a large number of nano-scale crystals are arranged in the microcrystalline glass, the microcrystalline glass has a more stable structure, and a cover plate product with higher strength can be obtained after chemical strengthening.
The manufacturer of the cover plate for a mobile phone may start with a glass raw material and obtain it by forming the glass plate by conventional methods, such as float, rolling and overflow, cutting, thinning, CNC processing, polishing, 3D hot bending, 3D polishing and chemical strengthening. Or some manufacturers purchase crystallized glass raw materials directly and then obtain the 3D microcrystalline glass meeting the requirements through processing such as 3D hot bending, 3D polishing, chemical strengthening and the like.
The 3D hot bending process for crystallized glass materials is generally performed by the following steps: 3D hot bending is carried out with hot bender, and hot bender is including preheating, shaping and cooling work station, preheats the work station and including preheating mould and glass piece, and its effect promotes the inside and outside temperature homogenization of glass, and the cooling work station is through the cooling water for the mould cooling fast, makes the glass temperature progressively reduce to the demolding temperature from forming temperature. The 3D hot bending mold is a graphite mold and is divided into an upper part and a lower part, and the whole 3D hot bending process flow is completed through preheating, molding and cooling stations after glass sheets are placed into the mold. In order to ensure the output efficiency of the 3D hot bending process, the time length of each work station has requirements. During specific operation, the processed and cleaned glass sheet is placed in a 3D mould, and then the mould is placed in a 3D hot bending machine for 3D hot bending according to a preset process.
The principle utilized by the 3D hot bending process is: after being heated to the temperature near the softening point, the glass or the glass ceramic can change the shape under the action of external force, and the shape is quickly cooled down after being changed, so that the shape obtained after hot pressing can be kept. The preheating step in the 3D hot bending process flow can avoid the glass from being heated and broken at high temperature during forming, the forming temperature is higher than a softening point, the glass is quickly softened, the upper surface and the lower surface of the mold are pressed through the pressing rod to enable the glass plate to be bent and formed, the pressure is kept before cooling to maintain the shape of the glass plate, and then the mold is quickly cooled through cooling water. In addition, the whole process of the 3D hot bending process is protected by nitrogen so as to avoid the oxidation of the die.
The defects of edge cracks and the like of the glass plate are reduced through CNC after the glass plate is formed, cut and thinned, and the upper surface and the lower surface of the glass plate are polished. CNC and the polished glass plate are subjected to 3D hot bending, so that the breakage rate of the glass plate in the hot bending process can be reduced.
Disclosure of Invention
The existing crystallized glass raw material is generally in a complete crystallization state, and when the completely crystallized glass raw material is used for carrying out hot bending forming to obtain the microcrystalline glass, the processing procedure flow comprises the following steps of carrying out 3D hot bending, 3D polishing, chemical strengthening and the like on the completely crystallized glass raw material. The existing crystallized glass raw material with complete crystallization has higher mechanical strength and hardness, so that the existing crystallized glass raw material with complete crystallization has low yield rate of mechanical processing before hot bending and high production cost.
The conventional completely crystallized glass material is generally softened to a molding temperature of 700 ℃ or higher, and thus the 3D hot-bending molding temperature must be higher than 700 ℃. In the thermal bending process, the original crystal phase type, crystal size, refractive index, Lab (color scale) value, haze, transmittance and the like of the completely crystallized glass raw material can be greatly changed due to heating. When the method is applied to a display scene, the chromaticity and transmittance of the microcrystalline glass obtained by processing the crystallized glass raw material directly influence the display effects such as the resolution, the color gamut and the saturation of a display screen; the microcrystalline glass has important influences on the refractive index, haze and transmittance of microcrystalline glass obtained by processing crystallized glass raw materials, particularly on the transmittance of ultraviolet and near ultraviolet on an optical system for photographing and shooting, wherein when the transmittance of the ultraviolet and near ultraviolet is low, the imaging quality can be directly influenced.
In addition, the 3D hot bending of the existing completely crystallized glass raw material is only for achieving the purpose of hot bending forming, and repeated crystallization exists, so that energy and time are wasted. Therefore, 3D hot bending of conventional crystallized glass materials with complete crystallization has extremely high technical difficulty, and it is difficult to achieve a yield required for industrial production by processing the material into a 3D form by 3D hot bending.
However, if the 3D hot bending molding is not performed on the fully crystallized glass raw material, but the 3D hot bending molding is performed on the nucleated glass raw material, because the volume shrinkage caused by the crystals grown on the interface between the crystal nucleus and the glass is very obvious in the initial stage of the hot bending crystallization of the nucleated glass raw material, the larger the proportion of the grown crystals is, the larger the volume change of the product is, and the difficulty in size control is high, the larger the volume change of the nucleated glass raw material occurs in the hot bending crystallization process, and the size precision of the molded 3D hot bending glass ceramics is affected.
Therefore, the invention discovers that the 3D hot bending is carried out by adopting a partially crystallized glass raw material, the glass is heated and continuously crystallized to reach the target crystallinity while the glass is subjected to hot bending deformation, the crystallization process during the 3D hot bending is reduced, and the size precision of the 3D microcrystalline glass after the hot bending is higher.
In addition, in the prior art, the short hot pressing time can be controlled during hot bending, and the hot pressing time is long, so that mold marks appear on the surface of the microcrystalline glass product, the surface quality is reduced, and the yield is influenced. The method of the invention adopts partial crystallized glass raw materials to carry out 3D hot bending treatment, and the initial crystallinity of the partial crystallized glass raw materials is relatively high, so that the mold print is not easy to generate. And because the initial crystallinity of the partially crystallized glass raw material is relatively high, the size deformation amount in unit time is small in the hot pressing process, so that the method can adapt to longer hot pressing time, can more accurately control the deformation amount after 3D, and ensures that the tolerance fluctuation of the profile tolerance is small and the size is more stable.
In order to solve the technical problems, the invention aims to provide a crystallized glass raw material which is characterized in that the thickness of the crystallized glass raw material is 0.02-5 mm; the crystallinity of the crystallized glass raw material is 5-90 wt%.
Preferably, the thickness is 0.35-1.2mm, and the crystallinity of the crystallized glass raw material is 30-75 wt% or 75-90 wt%.
Preferably, the average transmittance of the raw material of the crystallized glass at the wavelength of 380-780nm is 83-93 percent, preferably 85-92 percent; alternatively, the average transmittance of the crystallized glass raw material at the wavelength of 360-400nm is 80-91%, preferably 83-90%.
Preferably, the absolute value of the b value (yellow-blue value) when the thickness of the crystallized glass raw material is 0.7mm is 0.2-3, preferably 0.6-2; the haze of the crystallized glass raw material is 0.05-1.0%, preferably 0.2-0.8%.
Preferably, the crystallized glass raw material contains oxides in the following proportions in mol%:
wherein the rare earth oxide is selected from La 2 O 3 ，Eu 2 O 3 ，Pr 6 O 11 ，Nd 2 O 3 ，Er 2 O 3 And Dy 2 O 3 One or more than two of them.
Preferably, the crystallized glass material contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60%; preferably 68-80%; or, contain Na 2 O+Li 2 O is 7 to 30% by mol, preferably 10 to 26%.
Preferably, the crystallized glass raw material comprises a nucleating agent, and the nucleating agent comprises P in terms of oxide, fluoride or simple substance 2 O 5 ，TiO 2 ，ZrO 2 ，Cr 2 O 3 ，CaF 2 ，LiF，NaF，KF，Y 2 O 3 One or more of Au, Ag and Cu; preferably P 2 O 5 ，TiO 2 And ZrO 2 One or more than two of them.
Preferably, the crystallized glass raw material comprises a clarifying agent, and the clarifying agent comprises NaCl and Na 2 SO 4 ，SnO 2 ，As 2 O 3 ，Sb 2 O 3 ，NaNO 3 ，KNO 3 ，CeO 2 And (NH) 4 ) 2 SO 4 One or more than two of (a); preferably NaCl, SnO 2 ，NaNO 3 And CeO 2 One or more than two of them.
Preferably, the crystallized glass raw material has crystals with the average grain diameter of 5-50nm after nucleation and crystallization treatment.
Preferably, the Vickers hardness of the crystallized glass material is greater than 500 under a 300N force load of 10s, and preferably, the Vickers hardness is greater than 560.
The invention also provides a preparation method of the crystallized glass raw material, wherein the preparation method comprises the following steps:
step 1: mixing the preparation raw materials of the 3D glass ceramics, melting, cooling, and annealing to obtain a glass substrate;
and 2, step: carrying out nucleation treatment on the glass substrate obtained in the step 1; wherein cutting can be carried out according to the requirements before and after the nucleation treatment;
and 3, step 3: crystallizing the nucleated glass substrate obtained in the step 2;
and 4, step 4: and cutting the crystallized glass substrate as required to obtain a crystallized glass raw material.
Preferably, in the step 1, the melting temperature is 1350-; preferably, the melting temperature is 1400-1650 ℃; more preferably, the melt is cooled to 500-1000 ℃.
Preferably, in the step 1, the amount of the nucleating agent added is 1 to 9 mol%, preferably 2 to 5 mol%, of the total amount of the nucleating agent and the oxide of the crystallized glass raw material.
Preferably, in the step 1, the amount of the refining agent added is 0 to 4 wt%, preferably 0.1 to 2 wt% of the total mass of the nucleating agent and the crystallized glass raw material oxide.
Preferably, in the step 2, the temperature of the nucleation treatment is 450-800 ℃; preferably, the time of the nucleation treatment is 30-360 min;
further preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is preferably 120-300 min.
Preferably, in the step 3, the temperature of the crystallization treatment is 550-;
preferably, the temperature of the crystallization treatment is 600-850 ℃, the time of the crystallization treatment is 10-240min,
further preferably, the temperature of the crystallization treatment is 600-750 ℃, and the time of the crystallization treatment is 10-150 min.
The invention also provides a crystallized glass raw material prepared by the preparation method.
Preferably, the crystallized glass raw material is characterized in that the crystallized glass raw material is transparent or opaque; preferably, the crystallized glass raw material is curved or planar.
The invention also provides the crystallized glass raw material for 3D hot bending to prepare the 3D glass ceramics.
The invention also provides application of the 3D glass ceramics prepared by the crystallized glass raw material in mobile phone display screens, tablet personal computer display screens, handheld game machines, electronic terminals, portable digital devices, vehicle-mounted central control screens, electronic white board glass, intelligent household touch screens, vehicle windshield glass, aircraft windshield glass or aircraft windshield glass.
The invention has the beneficial effects that:
1. according to the invention, 3D hot bending is carried out on part of the crystallized glass raw material, the glass raw material is heated and continuously crystallized to reach the target crystallinity while the glass raw material is subjected to hot bending deformation, the crystallization process in the 3D hot bending process is reduced, and the 3D microcrystalline glass obtained by hot bending the crystallized glass raw material has higher dimensional accuracy. The preparation method of the crystallized glass raw material has the advantages of low processing difficulty, low processing cost, time cost saving and energy saving for heat treatment. The 3D hot bending is carried out by adopting a part of crystallized glass raw material, and the problem of repeated crystallization during the 3D hot bending of the existing crystallized glass raw material with high crystallinity or complete crystallization is avoided.
And 2.2, flat grinding and polishing in the preparation process of the 3D glass ceramics are carried out before 3D hot bending according to requirements. The flat grinding and polishing speed of the 3D glass ceramics is related to hardness, and the greater the hardness, the greater the difficulty of flat grinding and polishing, and the longer the time is needed. The invention uses partial crystallized glass raw material to carry out flat grinding and polishing, the hardness is lower than that of the completely crystallized glass raw material, the flat grinding and polishing processing difficulty of the glass sheet is reduced, and the required time is reduced.
3. The optical performance of the crystallized glass raw material is improved, and because the softening and forming temperature of the conventional completely crystallized glass raw material is generally over 700 ℃, crystals in the crystallized glass raw material continue to grow and the residual glass body is crystallized again in the hot bending process at the temperature higher than 700 ℃, so that the problem of excessive crystallization exists, and the optical performance of the crystallized glass raw material after hot bending is greatly reduced. The optical performance of the crystallized glass raw material is that the average transmittance of 380-780nm wavelength light is 83-93%, the average transmittance of 360-400nm wavelength light is 80-91%, and the absolute value of the b value (yellow-blue value) of the 3D glass ceramics with the thickness of 0.7mm is 0.2-3.0.
4. The control rate of the dimensional accuracy of the crystallized glass raw material is improved. The method adopts partial crystallized glass raw material to carry out 3D hot bending, the glass is heated to be continuously crystallized to reach the target crystallinity, although the glass can generate deformation while being crystallized by hot bending in the process, the deformation is reduced because the crystallization process when the 3D hot bending is reduced, and the size precision of the crystallized glass raw material after the hot bending is favorably controlled.
5. The yield of the crystallized glass raw material is improved. If the nucleated glass or the glass with low initial crystallinity is adopted as the raw material for 3D hot bending forming, the raw material needs a large amount of crystallization in the short time of the hot bending forming, and the raw material among different batches is influenced by too many variable factors in the 3D hot bending process, so that the crystal size, the crystal type and the crystal proportion stability among different batches are poor. The 3D hot bending is carried out by adopting a part of crystallized glass raw material, the crystallinity is relatively high, the growth amount of crystals in the hot bending process is less, and the influence of variable factors is reduced, so that the stability of the 3D microcrystalline glass prepared from the crystallized glass raw material in different batches is easier to control, and the yield is improved.
Drawings
FIG. 1 is an XRD pattern of a glass block obtained before nucleation after annealing in step 2 of example 25;
FIG. 2 is an XRD pattern of a partially crystallized glass original sheet obtained in step 4 of example 25;
FIG. 3 is an XRD pattern of a partially crystallized glass original sheet obtained in step 4 of example 26;
FIG. 4 is an XRD pattern of a partially crystallized glass original piece obtained in step 4 of example 30.
Detailed Description
The invention aims to provide a crystallized glass raw material, which is characterized in that the thickness of the crystallized glass raw material is 0.02-5 mm; the crystallinity of the crystallized glass raw material is 5-90 wt%.
Preferably, the thickness is 0.35-1.2mm, and the crystallinity of the crystallized glass raw material is 30-75 wt%, 75-90 wt%, 6-10 wt%, 11-15 wt%, 16-20 wt%, 21-25 wt%, 26-30 wt%, 31-35 wt%, 36-40 wt%, 41-45 wt%, 46-50 wt%, 51-55 wt%, 56-60 wt%, 61-65 wt%, 66-70 wt%, 71-75 wt%, 76-80 wt%, 81-85 wt%, 86-90 wt%, 10-20 wt%; 21-30 wt%; 31-40 wt%; 41-50 wt%; 51-60 wt%; 61-70 wt%; 71-80 wt%; or 81 to 90 wt%.
Preferably, the average transmittance of the raw material of the crystallized glass at the wavelength of 380-780nm is 83-93 percent, preferably 85-92 percent; or the average transmittance of the raw material of the crystallized glass for 360-400nm wavelength light is 80-91 percent, preferably 83-90 percent.
Preferably, the absolute value of the b value (yellow-blue value) when the thickness of the crystallized glass raw material is 0.7mm is 0.2-3, preferably 0.6-2; the haze of the crystallized glass raw material is 0.05-1.0%, and preferably 0.2-0.8%.
Preferably, the crystallized glass raw material contains oxides in the following proportions in mol%:
wherein the rare earth oxide is selected from La 2 O 3 ，Eu 2 O 3 ，Pr 6 O 11 ，Nd 2 O 3 ，Er 2 O 3 And Dy 2 O 3 One or more than two of them.
Preferably, the crystallized glass material contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60%; preferably 68-80%; or, contain Na 2 O+Li 2 O is 7 to 30%, preferably 10 to 26%, in mol%.
Preferably, the crystallized glass raw material comprises a nucleating agent, and the nucleating agent comprises P in terms of oxide, fluoride or simple substance 2 O 5 ，TiO 2 ，ZrO 2 ，Cr 2 O 3 ，CaF 2 ，LiF，NaF，KF，Y 2 O 3 One or more of Au, Ag and Cu; preferably P 2 O 5 ，TiO 2 And ZrO 2 One or more than two of them.
Preferably, the crystallized glass raw material comprises a clarifying agent, and the clarifying agent comprises NaCl and Na 2 SO 4 ，SnO 2 ，As 2 O 3 ，Sb 2 O 3 ，NaNO 3 ，KNO 3 ，CeO 2 And (NH) 4 ) 2 SO 4 One or more than two of the above; preferably NaCl, SnO 2 ，NaNO 3 And CeO 2 One or more than two of them.
Preferably, the crystallized glass raw material has crystals with an average grain diameter of 5-50nm after nucleation and crystallization.
Preferably, the Vickers hardness of the crystallized glass raw material is more than 500 under the 300N force load of 10s, and preferably, the Vickers hardness is more than 560.
The invention also provides a preparation method of the crystallized glass raw material, wherein the preparation method comprises the following steps:
step 1: mixing the preparation raw materials of the 3D glass ceramics, melting, cooling, and annealing to obtain a glass substrate;
and 2, step: carrying out nucleation treatment on the glass substrate obtained in the step 1; wherein the cutting can be carried out according to the requirement before and after the nucleation treatment;
and step 3: crystallizing the nucleated glass substrate obtained in the step 2;
and 4, step 4: and cutting the crystallized glass substrate according to the requirement to obtain a crystallized glass raw material.
Preferably, in the step 1, the melting temperature is 1350-; preferably, the melting temperature is 1400-1650 ℃; more preferably, the melt is cooled to 500-.
Preferably, in the step 1, the amount of the nucleating agent added is 1 to 9 mol%, preferably 2 to 5 mol%, of the total amount of the nucleating agent and the crystallized glass raw material oxide.
Preferably, in the step 1, the amount of the refining agent added is 0 to 4 wt%, preferably 0.1 to 2 wt%, of the total mass of the nucleating agent and the crystallized glass raw material oxide.
Preferably, in the step 2, the temperature of the nucleation treatment is 450-800 ℃; preferably, the time of the nucleation treatment is 30-360 min;
further preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is preferably 120-300 min.
Preferably, in the step 3, the temperature of the crystallization treatment is 550-;
preferably, the temperature of the crystallization treatment is 600-,
further preferably, the temperature of the crystallization treatment is 600-750 ℃, and the time of the crystallization treatment is 10-150 min.
The invention also provides a crystallized glass raw material prepared by the preparation method.
Preferably, the crystallized glass raw material is characterized in that the crystallized glass raw material is transparent or opaque; preferably, the crystallized glass raw material is curved or planar.
The invention also provides the crystallized glass raw material for 3D hot bending to prepare the 3D glass ceramics.
The invention also provides application of the 3D glass ceramics prepared by the crystallized glass raw material in mobile phone display screens, tablet personal computer display screens, handheld game machines, electronic terminals, portable digital devices, vehicle-mounted central control screens, electronic white board glass, intelligent household touch screens, vehicle windshield glass, aircraft windshield glass or aircraft windshield glass.
The noun explains:
3D glass ceramics: the upper surface and the lower surface are non-planar microcrystalline glass;
2D glass ceramics: the upper surface and the lower surface are plane microcrystalline glass;
2.5D glass ceramics: one surface is a plane, and the other surface is non-planar microcrystalline glass;
degree of crystallinity: the microcrystalline glass contains a crystal phase and a glass phase, and the mass of the crystal phase accounts for the percentage of the total mass of the microcrystalline glass and is the crystallinity;
transmittance: the ratio of radiant energy projected through and through the object to total radiant energy projected onto the object during the course of an incident flux exiting from the illuminated or medium incident face to the other;
average transmittance: the transmittance at each wavelength is measured at intervals of 10nm in a predetermined wavelength range, and the sum of the measured transmittances at each wavelength is divided by the number of the measured transmittances at each wavelength. For example, the average transmittance at the wavelength of 360-400nm is calculated as follows: the transmittances of the wavelengths of 360nm, 370nm, 380nm, 390nm and 400nm are respectively measured, the number of the measured transmittances of 360-400nm is 5, and the sum of the transmittances is divided by 5 to obtain the average transmittance of the wavelengths of 360-400 nm;
nucleation: forming nucleation substance in the glass into crystal nucleus of about 5nm by heat treatment;
and (3) crystallization: the glass grows a certain crystal on the basis of the crystal nucleus through heat treatment;
average crystal particle size: based on the average value of the crystal grain lengths in the crystallized glass raw material or the 3D glass ceramics observed at a magnification of 10 ten thousand to 100 ten thousand times. Measured by observation using a transmission electron microscope (model: ThermoFisher Scientific (original FEI) Talos F200S). During measurement, the method is equivalent to taking a magnified picture of the crystal grains at a certain position, limited crystal grains are in the magnified picture area, the sizes of the limited crystal grains are marked according to a scale, and then the average value is calculated. In the examples of the present invention, the magnification was 50 ten thousand times at the time of measurement.
b value: the value of the yellow blue of the material is represented, the value of b in the invention is the value of b of transmitted light, and the value of b is positive and represents that the material is blue; measured using a chromatograph (model CM-3600A).
Haze: the transmitted light intensity above an angle of 2.5 ° from the incident light is a percentage of the total transmitted light intensity. Measured using a chromatograph (model CM-3600A).
The optical performance of the crystallized glass raw material when the thickness is 0.65mm is that the absolute value of the b value under a D65 light source is 0.2-3.0, and the absolute value of the b value under a D65 light source is preferably 0.6-2.0; light transmittance at a wavelength of 360nm is 70% or more, preferably 360nm transmittance is 80% or more.
Nucleating agents include, but are not limited to, P 2 O 5 ，TiO 2 ，ZrO 2 ，Cr 2 O 3 ，CaF 2 ，LiF，NaF，KF，Y 2 O 3 Au, Ag, Cu, etc.
When part of crystallized glass raw materials are crystallized through hot bending, the crystallization speed is controllable, crystals with the grain diameter of less than 100nm can be grown, and the average grain diameter of the precipitated crystals can be ensured to be 10-100nm through process control, so that the optical performance of the 3D glass ceramics is improved;
in other specific embodiments, the crystallization and the 3D bending molding are performed simultaneously in the 3D bending process, the bending time is generally within 30min, some examples show that the partially crystallized glass material can reach a crystallinity of more than 80 wt% after 10-20min of 3D bending in a suitable process, and the optical properties meet the requirements.
The crystalline phase of the 3D microcrystalline glass finally prepared from the crystallized glass raw material comprises lithium silicate, lithium disilicate, beta-quartz, a beta-quartz solid solution, petalite, beta-spodumene, a beta-spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesium aluminate spinel, rutile and the like.
In order to better understand the present invention, the following examples are included to further illustrate the present invention.
The following description will be made of the manufacturers of raw materials and equipment used in this example, and the equipment and analysis method used in the product analysis, wherein the chemical substances are not labeled as being of the chemical purity grade of conventional reagents.
Wherein, the information of the raw materials used in the examples and comparative examples is shown in the following table 1.
TABLE 1 information on materials and instruments used in the present invention
Examples
The hot bending process in the examples is shown in table 2 below, for example, when the process number is 1, the hot bending process includes 4 preheating stations, 3 hot pressing stations, and 2 cooling stations. The temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, and the temperature of the fourth preheating station is 680 ℃. The temperature of the first hot pressing station is 800 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the second hot pressing station is 810 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 20 s.
For example, the hot bending process with serial number 12 is as follows: the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 700 ℃, and the temperature of the fourth preheating station is 850 ℃. The temperature of the first hot pressing station is 780 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. This is to be enumerated.
TABLE 2 Hot bending Process tables in examples and comparative examples
The examples and comparative examples are a method for preparing a crystallized glass raw material and a method for continuously preparing 3D glass ceramics using the crystallized glass raw material.
Example 1
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 62.00％；Al 2 O 3 17.00％；MgO 2.50％；Na 2 O 2.50％；Li 2 O 10.00％；B 2 O 3 2.00% of rare earth oxide La 2 O 3 0.8% of nucleating agent (containing 2.00% ofP 2 O 5 (ii) a 1.20% of ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g), the raw materials are fully mixed and then are melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1650 ℃, the melting time is 5h, and the mixture is poured into a mold of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material (the same mold as that used in example 1 is used in the later examples and comparative examples) to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 620 ℃, then the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 760 ℃, and the time of the nucleation treatment is 120 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the temperature of the crystallization treatment is 790 ℃, and the time of the crystallization treatment is 10min, so as to obtain the partially crystallized glass brick;
and 4, step 4: after the partially crystallized glass brick is trimmed by a polishing machine, cutting the partially crystallized glass brick into pieces by using a multi-wire cutting machine, processing the glass pieces into glass pieces with the length, width and thickness of 158 × 75 × 0.65mm by using a CNC machine tool, respectively performing coarse grinding and polishing treatment by using a flat grinding machine and a polishing machine to obtain partially crystallized glass raw pieces (namely crystallized glass raw materials), and determining that the crystallinity of the partially crystallized glass raw pieces is 10 wt% and the average grain size of crystals is 12 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.61; the light transmittance at the wavelength of 360nm is 80.14 percent, the light average transmittance at the wavelength of 380-780nm is 88.90 percent, the light average transmittance at the wavelength of 360-400nm is 81.74 percent, and the haze is 0.25 percent.
And 5: (namely continuously preparing 3D glass ceramics by using the crystallized glass raw material) carrying out 3D hot bending treatment on part of the crystallized glass raw sheet; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, and the temperature of the fourth preheating station is 680 ℃. The temperature of the first hot pressing station is 800 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the second hot pressing station is 810 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 20 s. (i.e., the thermal bending process with the number 1 in table 2 is adopted), and a 3D glass ceramic sample 1 is obtained.
And (3) detecting the 3D microcrystalline glass sample 1, and analyzing the detected X-ray diffraction data by using a ray diffractometer and setting the instrument setting voltage to be 40mV, the current to be 30mA, the test range to be 10-50 degrees, the scanning speed to be 1 degree/min and the step length to be 0.02 degree/step, wherein the crystallinity of the 3D microcrystalline glass sample 1 is 15 wt%, the precipitated crystalline phase is beta-spodumene and the average grain size of the crystal is 37 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 1 is 2.30; the light transmission rate at the wavelength of 360nm is 76.30%, the light average transmission rate at the wavelength of 380-780nm is 88.20%, the light average transmission rate at the wavelength of 360-400nm is 80.10%, and the haze is 0.40%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% NaNO at the temperature of 430 DEG C 3 And (5) the solution is subjected to 8 hours, and finally the 3D glass ceramic finished product 1 is obtained.
Example 2
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 64.00％；Al 2 O 3 17.00％；Na 2 O 2.50％；Li 2 O 12.5％；B 2 O 3 2.00%, nucleating agent (0.80% P) 2 O 5 ；1.20％ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then are melted and molded in a high-temperature lifting furnace, the melting and molding treatment temperature is 1650 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 and step 3 are the same as in example 1;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 13 wt%, the average grain size of the crystals was 11 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.52; the light transmittance at the wavelength of 360nm is 81.24%, the light average transmittance at the wavelength of 380-780nm is 91.20%, the light average transmittance at the wavelength of 360-400nm is 83.52%, and the haze is 0.19%.
And 5: and (3) carrying out 3D hot bending treatment on the partially crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 2 by adopting a hot bending process (referring to example 1) with the number 1 in the table 2.
The 3D glass ceramics sample 2 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 2 had a crystallinity of 24 wt% after hot bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 27 nm. When the light source is limited to D65, the absolute value of the b value of the 3D microcrystalline glass sample 2 is measured to be 3.10; the light transmittance at the wavelength of 360nm is 76.00%, the light average transmittance at the wavelength of 380-780nm is 88.00%, the light average transmittance at the wavelength of 360-400nm is 78.00%, and the haze is 0.43%.
Step 6: and (5) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the embodiment 1 to finally obtain a 3D glass ceramics finished product 2.
Example 3
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 63.64％；Al 2 O 3 16.03％；Li 2 O 16.03％；B 2 O 3 2.00%, nucleating agent (0.80% P) 2 O 5 ；1.50％ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 610 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 705 ℃, and the time of the nucleation treatment is 120 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 775 ℃, and the crystallization treatment time is 10min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 9 wt%, the average grain size of the crystals was 16 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.3; the light transmittance at the wavelength of 360nm is 83.36%, the light average transmittance at the wavelength of 380-780nm is 91.30%, the light average transmittance at the wavelength of 360-400nm is 85.44%, and the haze is 0.13%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; by using the hot bending process (see example 1) with number 1 in table 2, a 3D glass ceramic sample 3 was obtained.
The 3D glass ceramics sample 3 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 3 had a crystallinity of 18 wt% after thermal bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 3 is measured to be 1.21 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 83.71 percent, the light average transmission rate at the wavelength of 380-780nm is 90.22 percent, the light average transmission rate at the wavelength of 360-400nm is 84.56 percent, and the haze is 0.16 percent.
Example 4
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.63％；Al 2 O 3 15.13％；MgO 4.76％；Na 2 O 1.55％；Li 2 8.65 percent of O; rare earth oxide La 2 O 3 0.81%, nucleating agent (0.67% P) 2 O 5 ；1.30％ZrO 2 ，Y 2 O 3 0.50 percent) and NaCl accounting for 0.8 percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace), the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the raw materials are poured into a mold made of ASTM SA213 material to obtain the glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 610 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 720 ℃, and the time of the nucleation treatment is 120 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 780 ℃, and the crystallization treatment time is 10min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 11 wt%, the average grain size of the crystals was 16 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.33; the light transmission rate at the wavelength of 360nm is 82.65%, the light average transmission rate at the wavelength of 380-780nm is 90.60%, the light average transmission rate at the wavelength of 360-400nm is 84.73%, and the haze is 0.24%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 4 was obtained by the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 4 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 4 had a crystallinity of 23 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 27 nm. The absolute value of the b value of the 3D microcrystalline glass sample 4 is 1.48 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 80.06%, the light average transmission rate at the wavelength of 380-780nm is 89.5%, the light average transmission rate at the wavelength of 360-400nm is 83.50%, and the haze is 0.25%.
And 6: to step 5 to obtainThe hot-bent 3D glass ceramics is subjected to chemical strengthening treatment, and the glass is immersed in molten 100 wt% NaNO at the temperature of 450 DEG C 3 And (5) the solution is immersed for 7 hours, and a 3D glass ceramic finished product 4 is finally obtained.
Example 5
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.96％；Al 2 O 3 14.20％；MgO 4.79％；Na 2 O 0.56％；Li 2 9.70 percent of O; rare earth oxide Er 2 O 3 0.81% of nucleating agent (1.68% of P) 2 O 5 ；1.30％ZrO 2 ) NaCl accounting for 0.4 wt% of the total mass of the nucleating agent and the preparation raw materials and SnO accounting for 0.4 wt% of the total mass of the nucleating agent and the preparation raw materials 2 The glass brick is prepared by the following steps of (1) fully mixing 1713.6g of the raw materials as a clarifying agent, then melting and molding the mixture in a high-temperature lifting furnace, wherein the melting and molding treatment temperature is 1630 ℃, the melting time is 5 hours, and pouring the mixture into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 and step 3 were the same as in example 4;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity is 16 wt%, the average grain size of the crystal is 18 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.42; the light transmittance at the wavelength of 360nm is 81.35 percent, the light average transmittance at the wavelength of 380-780nm is 91.12 percent, the light average transmittance at the wavelength of 360-400nm is 84.04 percent, and the haze is 0.26 percent.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 5 was obtained by the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 5 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 5 had a crystallinity of 33 wt% after thermal bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle diameter of the crystals was 22 nm. When the light source is limited to D65, the absolute value of the 5b value of the 3D microcrystalline glass sample is 3.24; the light transmittance at the wavelength of 360nm is 72.00 percent, the light average transmittance at the wavelength of 380-780nm is 88.90 percent, the light average transmittance at the wavelength of 360-400nm is 78.60 percent, and the haze is 0.54 percent.
Example 6
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 66.95％；Al 2 O 3 14.20％；MgO 2.29％；Na 2 O 1.56％；ZnO 1.00％，Li 2 9.70 percent of O; rare earth oxide La 2 O 3 0.81%, nucleating agent (1.68% P) 2 O 5 ；1.31％ZrO 2 ；0.5％Y 2 O 3 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 765 ℃, and the crystallization treatment time is 20min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 12 wt%, the average grain size of the crystals was 23 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.73; the light transmittance at the wavelength of 360nm is 78.02%, the light average transmittance at the wavelength of 380-780nm is 88.30%, the light average transmittance at the wavelength of 360-400nm is 80.12%, and the haze is 0.38%.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and a 3D glass ceramic sample 6 was obtained by using the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 6 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 6 had a crystallinity of 23 wt% after hot bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle diameter of the crystals was 30 nm. When the light source is defined as D65, the absolute value of the b value is 3.4; the light transmission rate at the wavelength of 360nm is 66.30%, the light average transmission rate at the wavelength of 380-780nm is 88.30%, the light average transmission rate at the wavelength of 360-400nm is 76.20%, and the haze is 0.96%.
Example 7
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.42％；Al 2 O 3 14.09％；MgO 4.75％；Na 2 O 1.55％；Li 2 O9.62%, nucleating agent (0.67% P) 2 O 5 ；1.3％ZrO 2 ；1.6％TiO 2 ) And NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 750 ℃, and the time of the crystallization treatment is 20min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity is 17 wt%, the average grain size of the crystal is 12 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.22; the light transmittance at the wavelength of 360nm is 84.05%, the light average transmittance at the wavelength of 380-780nm is 92.70%, the light average transmittance at the wavelength of 360-400nm is 85.72%, and the haze is 0.21%.
And 5: the 3D hot bending process is performed on the partially crystallized glass original sheet, and a hot bending process with the number 1 in table 2 (refer to example 1) is employed to obtain a 3D microcrystalline glass sample 7.
The 3D glass ceramics sample 7 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 7 had a crystallinity of 34 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 7 is measured to be 1.20 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 83.10 percent, the light average transmittance at the wavelength of 380-780nm is 90.28 percent, the light average transmittance at the wavelength of 360-400nm is 84.62 percent, and the haze is 0.15 percent.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 430 DEG C 3 And (5) the solution is immersed for 9 hours, and finally the 3D glass ceramic finished product 7 is obtained.
Example 8
Step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mol: SiO 2 2 66.95％；Al 2 O 3 13.20％；CaO 1.0％；MgO3.79％；Na 2 O 1.56％；Li 2 9.70 percent of O; nucleating agent (1.68% P) 2 O 5 ；1.51％ZrO 2 ，0.61％Ti 2 O and a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 715 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 820 ℃, and the time of the crystallization treatment is 10min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 28 wt%, the average grain size of the crystals was 23 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.18; the light transmission rate at the wavelength of 360nm is 85.11%, the light average transmission rate at the wavelength of 380-780nm is 92.90%, the light average transmission rate at the wavelength of 360-400nm is 88.01%, and the haze is 0.12%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating work station is 480 ℃, the temperature of the second preheating work station is 635 ℃, the temperature of the third preheating work station is 685 ℃, and the temperature of the fourth preheating work station is 715 ℃. The temperature of the first hot pressing station is 745 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.6 MPa; the temperature of the second hot-pressing station is 760 ℃, the upper pressure is 0MPa, and the lower pressure is 0. MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 80 s. (i.e., the thermal bending process with serial number 8 in table 2) was used to obtain 3D glass ceramics sample 8.
The 3D glass ceramics sample 8 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 8 had a crystallinity of 45 wt% after thermal bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle diameter of the crystals was 37 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 8 is 2.90; the light transmittance at the wavelength of 360nm is 76.11 percent, the light average transmittance at the wavelength of 380-780nm is 88.10 percent, the light average transmittance at the wavelength of 360-400nm is 78.80 percent, and the haze is 0.63 percent.
Example 9
Step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mole: SiO 2 2 66.96％；Al 2 O 3 13.20％；MgO 5.79％；Na 2 O 1.26％；Li 2 O 8.00％；B 2 O 3 1.00 percent; rare earth oxide Er 2 O 3 0.9% of nucleating agent (1.68% of P) 2 O 5 ；1.21％ZrO 2 ) And nucleating agents and preparations0.7 wt% of clarifier NaCl in the total mass of the raw materials, 1711.9g of the total weight of the raw materials, fully mixing, then melting and molding in a high-temperature lifting furnace, wherein the melting and molding treatment temperature is 1630 ℃, the melting time is 5h, and pouring into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 and step 3 were the same as in example 8;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the pieces to be cut into pieces to be 19 wt%, the average grain diameter of the crystal to be cut into pieces to be 14 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.23; the light transmittance at the wavelength of 360nm is 84.21 percent, the light average transmittance at the wavelength of 380-780nm is 92.40 percent, the light average transmittance at the wavelength of 360-400nm is 85.83 percent, and the haze is 0.16 percent.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 9.
The 3D glass ceramics sample 9 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 9 had a crystallinity of 32 wt% after thermal bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 9 is measured to be 1.30 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 82.10%, the light average transmission rate at the wavelength of 380-780nm is 89.40%, the light average transmission rate at the wavelength of 360-400nm is 85.20%, and the haze is 0.21%.
Example 10
Step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mol: SiO 2 2 71.65％；Al 2 O 3 13.20％；MgO 2.79％；Na 2 O 0.56％；Li 2 O8.00 percent; rare earth oxide Er 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ；1.51％ZrO 2 ) And a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, and the raw materials are fully mixed and then are lifted and lowered at high temperatureMelting and molding in a furnace, wherein the melting and molding treatment temperature is 1630 ℃, the melting time is 5 hours, and pouring into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 is the same as example 8;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 800 ℃ for 10min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity is 20 wt%, the average grain size of the crystals is 16 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.2; the light transmission rate at the wavelength of 360nm is 84.33 percent, the light average transmission rate at the wavelength of 380-780nm is 92.60 percent, the light average transmission rate at the wavelength of 360-400nm is 85.60 percent, and the haze is 0.22 percent.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 10.
The 3D glass-ceramic sample 10 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 10 had a crystallinity of 37 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 27 nm. The absolute value of b is 1.60 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 81.13%, the light average transmittance at the wavelength of 380-780nm is 89.60%, the light average transmittance at the wavelength of 360-400nm is 82.80%, and the haze is 0.19%.
Example 11
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 70.65％；Al 2 O 3 13.20％；MgO 2.79％；Na 2 O 1.56％；Li 2 O8.00 percent; rare earth oxide La 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ；1.51％ZrO 2 ) And the total mass of the nucleating agent and the preparation raw material0.7 wt% of a clarifying agent NaCl, which accounts for 1711.9g of the total weight of the raw materials, fully mixing, then melting and molding in a high-temperature lifting furnace, wherein the melting and molding temperature is 1630 ℃, the melting time is 5h, and pouring into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 and step 3 were the same as in example 10;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 21 wt%, the average grain size of the crystals was 10 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.16; the light transmission rate at the wavelength of 360nm is 85.33 percent, the light average transmission rate at the wavelength of 380-780nm is 92.50 percent, the light average transmission rate at the wavelength of 360-400nm is 88.46 percent, and the haze is 0.10 percent.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 8 in table 2 (refer to example 8) was used to obtain a 3D glass ceramic sample 11.
The 3D glass ceramics sample 11 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 11 had a crystallinity of 41 wt% after thermal bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 22 nm. The absolute value of the b value is 1.10 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 82.40%, the light average transmittance at the wavelength of 380-780nm is 90.60%, the light average transmittance at the wavelength of 360-400nm is 85.30%, and the haze is 0.13%.
Example 12
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 70.65％；Al 2 O 3 12.92％；MgO 2.42％；ZnO 0.80％；Na 2 O 1.05％；Li 2 O8.25%; rare earth oxide La 2 O 3 1.22%, nucleating agent (1.37% P) 2 O 5 ；1.32％Y 2 O 3 ) And NaNO accounting for 0.3 wt% of the total mass of the nucleating agent and the preparation raw materials 3 And 0.4 wt% of As 2 O 3 As a clarifying agent, the above1711.9g of raw materials by weight are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 700 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as example 5;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 25 wt%, the average grain size of the crystals was 16 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 0.92; the light transmission rate at the wavelength of 360nm is 86.03 percent, the light average transmission rate at the wavelength of 380-780nm is 92.80 percent, the light average transmission rate at the wavelength of 360-400nm is 88.22 percent, and the haze is 0.13 percent.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 12.
The 3D glass-ceramic sample 12 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 12 had a crystallinity of 43 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 24 nm. When the light source is defined as D65, the absolute value of the b value is 1.15; the light transmission rate at the wavelength of 360nm is 83.68%, the light average transmission rate at the wavelength of 380-780nm is 90.56%, the light average transmission rate at the wavelength of 360-400nm is 86.30%, and the haze is 0.17%.
And 6: and (4) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5), wherein the chemical strengthening conditions are the same as those in the embodiment 7, and finally obtaining a 3D glass ceramics finished product 12.
Example 13
Step 1: preparing and weighing raw materials for preparing glassThe composition comprises the following components in percentage by mol: SiO 2 2 71.15％；Al 2 O 3 12.70％；MgO 2.79％；Na 2 O 0.56％；Li 2 O 8.00％；B 2 O 3 1.00% of rare earth oxide Nd 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ；1.51％CaF 2 ) And a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 710 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as in example 10;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 18 wt%, the average grain size of the crystals was 25 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.02; the light transmittance at the wavelength of 360nm is 85.53%, the light average transmittance at the wavelength of 380-780nm is 92.60%, the light average transmittance at the wavelength of 360-400nm is 87.13%, and the haze is 0.18%.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 8 in table 2 (refer to example 8) was used to obtain a 3D glass ceramic sample 13.
The 3D glass-ceramic sample 13 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 13 had a crystallinity of 34 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 35 nm. The absolute value of the b value is 1.75 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 81.03 percent, the light average transmittance at the wavelength of 380-780nm is 89.00 percent, the light average transmittance at the wavelength of 360-400nm is 82.30 percent, and the haze is 0.23 percent.
Example 14
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 68.00％；Al 2 O 3 12.00％；MgO 3.5％；Na 2 O 0.50％；Li 2 O 10.00％；B 2 O 3 3.00%, nucleating agent (2.00% P) 2 O 5 ；1.00％Y 2 O 3 ) NaCl accounting for 0.2 wt% of the total mass of the nucleating agent and the preparation raw materials and SnO accounting for 0.2 wt% of the total mass of the nucleating agent and the preparation raw materials 2 And 0.2 wt% of CeO 2 1711.9g of the raw materials are fully mixed as a clarifying agent, then the mixture is melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 is the same as in example 13;
step 3 is the same as in example 1;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 35 wt%, the average grain size of the crystals was 14 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.52; the light transmittance at the wavelength of 360nm is 81.53%, the light average transmittance at the wavelength of 380-780nm is 91.60%, the light average transmittance at the wavelength of 360-400nm is 84.49%, and the haze is 0.25%.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 14.
The 3D glass-ceramic sample 14 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the crystallinity of the 3D glass-ceramic sample 14 after hot bending was 62 wt%, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 27 nm. When the light source is defined as D65, the absolute value of the b value is 1.11; the light transmission rate at the wavelength of 360nm is 84.20 percent, the light average transmission rate at the wavelength of 380-780nm is 90.90 percent, the light average transmission rate at the wavelength of 360-400nm is 85.80 percent, and the haze is 0.22 percent.
Example 15
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.95％；Al 2 O 3 11.20％；CaO 1.20％；MgO 4.59％；Na 2 O 1.26％；Li 2 O 9.00％；B 2 O 3 2.00% of rare earth oxide Nd 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ；1.51％ZrO 2 ) And a clarifier NaCl accounting for 0.6 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1710.2g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at 550 ℃, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 690 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 750 ℃, and the time of the crystallization treatment is 30min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the crystal to be 32 wt% and the average grain diameter of the crystal to be 18 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.54; the light transmittance at the wavelength of 360nm is 81.13%, the light average transmittance at the wavelength of 380-780nm is 91.20%, the light average transmittance at the wavelength of 360-400nm is 83.43%, and the haze is 0.27%.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 15.
The 3D glass-ceramic sample 15 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 15 had a crystallinity of 53 wt% after hot bending, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 24 nm. The absolute value of b is measured to be 0.70 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 85.22%, the light average transmission rate at the wavelength of 380-780nm is 91.20%, the light average transmission rate at the wavelength of 360-400nm is 87.50%, and the haze is 0.16%.
Example 16
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 65.10％；Al 2 O 3 8.51％；Na 2 O 1.00％；Li 2 O 20.83％；B 2 O 3 1.52%, nucleating agent (0.82% P) 2 O 5 ；1.72％ZrO 2 (ii) a 0.5 percent of NaF), and NaNO accounting for 0.3 percent of the total mass of the nucleating agent and the preparation raw materials by weight 3 And 0.3 wt% of As 2 O 3 As a clarifying agent, 1710.2g of the total weight of the raw materials are fully mixed, then are melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1620 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at 550 ℃, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 670 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 710 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 40 wt%, the average grain size of the crystals was 11 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.24; the light transmission rate at the wavelength of 360nm is 83.13 percent, the light average transmission rate at the wavelength of 380-780nm is 91.80 percent, the light average transmission rate at the wavelength of 360-400nm is 86.41 percent, and the haze is 0.21 percent.
And 5: 3D hot bending treatment is carried out on a part of crystallized glass original sheets, the hot bending process adopts a hot bending process with the sequence number of 6 in the table 2, and the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 710 ℃. The temperature of the first hot pressing station is 730 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.3 MPa; the temperature of the second hot pressing station is 740 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 60 s. A 3D glass ceramic sample 16 was obtained.
The 3D glass ceramic sample 16 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramic sample 16 had a crystallinity of 60 wt% after being thermally bent, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 21 nm. The absolute value of b is measured to be 0.62 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 86.02%, the light average transmittance at the wavelength of 380-780nm is 91.10%, the light average transmittance at the wavelength of 360-400nm is 88.10%, and the haze is 0.17%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 430 DEG C 3 And (5) the solution is subjected to 11 hours, and a 3D glass ceramic finished product 16 is finally obtained.
Example 17
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 68.00％；Al 2 O 3 5.50％；CaO 0.50％；Na 2 O 1.00％；Li 2 O 21.00％；B 2 O 3 1.50%, nucleating agent (0.80% P) 2 O 5 ；1.70％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 500 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 570 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 640 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 78 wt%, the average grain size of the crystals was 25 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.16; the light transmittance at the wavelength of 360nm is 84.16%, the light average transmittance at the wavelength of 380-780nm is 91.30%, the light average transmittance at the wavelength of 360-400nm is 85.94%, and the haze is 0.19%.
And 5: the 3D hot bending process is performed on the partially crystallized glass original sheet, and the hot bending process with serial number 6 in table 2 (refer to example 16) is employed to obtain a 3D microcrystalline glass sample 17.
The 3D glass-ceramic sample 17 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 17 had a crystallinity of 91 wt% after hot bending, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 21 nm. When the light source is defined as D65, the absolute value of the b value is 1.0; the light transmission rate at the wavelength of 360nm is 84.32 percent, the light average transmission rate at the wavelength of 380-780nm is 90.80 percent, the light average transmission rate at the wavelength of 360-400nm is 86.40 percent, and the haze is 0.16 percent.
Example 18
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 69.14％；Al 2 O 3 5.21％；Na 2 O 0.46％；Li 2 O 21.13％；B 2 O 3 1.52%, nucleating agent (0.82% P) 2 O 5 ；1.72％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 490 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 530 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 640 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 72 wt%, the average grain size of the crystals was 19 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.44; the light transmission rate at the wavelength of 360nm is 82.31 percent, the light average transmission rate at the wavelength of 380-780nm is 91.00 percent, the light average transmission rate at the wavelength of 360-400nm is 84.91 percent, and the haze is 0.24 percent.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 13 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 710 ℃. The temperature of the first hot pressing station is 720 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.3 MPa; the temperature of the second hot pressing station is 720 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 18 was obtained.
The 3D glass-ceramic sample 18 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 18 had a crystallinity of 92 wt% after hot bending, the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 18 nm. The absolute value of b is 0.43 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 87.17 percent, the light average transmission rate at the wavelength of 380-780nm is 92.10 percent, the light average transmission rate at the wavelength of 360-400nm is 90.30 percent, and the haze is 0.11 percent.
Example 19
Steps 1-2 are the same as those of example 18;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 630 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the crystal to be 60 wt% and the average grain diameter of the crystal to be 6 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.32; the light transmittance at the wavelength of 360nm is 84.00 percent, the light average transmittance at the wavelength of 380-780nm is 91.40 percent, the light average transmittance at the wavelength of 360-400nm is 85.70 percent, and the haze is 0.36 percent;
and 5: the partially crystallized glass original piece was subjected to 3D hot bending, and a 3D glass ceramic sample 19 was obtained by the hot bending process (see example 18) numbered 13 in table 2.
The 3D glass-ceramic sample 19 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 19 had a crystallinity of 86 wt% after hot bending, the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 19 nm. The absolute value of b is measured to be 0.44 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 87.31 percent, the light average transmission rate at the wavelength of 380-780nm is 92.30 percent, the light average transmission rate at the wavelength of 360-400nm is 89.50 percent, and the haze is 0.11 percent.
Example 20
Steps 1-2 are identical to those of example 18;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 625 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of 51 wt% and the average grain size of the crystal of 13 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.29; the light transmission rate at the wavelength of 360nm is 83.15%, the light average transmission rate at the wavelength of 380-780nm is 90.80%, the light average transmission rate at the wavelength of 360-400nm is 84.15%, and the haze is 0.21%;
and 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 20 was obtained by the hot bending process (see example 18) with number 13 in table 2.
The 3D glass-ceramic sample 20 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 20 had a crystallinity of 73 wt% after being thermally bent, and the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 23 nm. The absolute value of b is measured to be 0.58 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 86.20 percent, the light average transmittance at the wavelength of 380-780nm is 92.10 percent, the light average transmittance at the wavelength of 360-400nm is 87.80 percent, and the haze is 0.10 percent.
Example 21
The preparation method of the crystallized glass raw material and the preparation method for continuously preparing the 3D glass ceramics by using the crystallized glass raw material comprise the following steps:
steps 1-2 are identical to those of example 18;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the crystallization treatment temperature is 620 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the product to be 30 wt% and the average grain diameter of the crystal to be 15 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.24; the light transmission rate at the wavelength of 360nm is 83.02 percent, the light average transmission rate at the wavelength of 380-780nm is 91.80 percent, the light average transmission rate at the wavelength of 360-400nm is 84.82 percent, the haze is 0.33 percent,
and 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 21 was obtained by the hot bending process (see example 18) with number 13 in table 2.
The 3D glass ceramics sample 21 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 21 had a crystallinity of 65 wt% after being thermally bent, and the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystal was 25 nm. The absolute value of b is measured to be 0.62 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 85.14%, the light average transmission rate at the wavelength of 380-780nm is 91.60%, the light average transmission rate at the wavelength of 360-400nm is 88.10%, and the haze is 0.15%.
Example 22
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 69.5％；Al 2 O 3 5.3％；Na 2 O 1.60％；Li 2 O 20.5％；B 2 O 3 0.55% of nucleating agent (0.8% of P) 2 O 5 ；1.75％ZrO 2 ) And a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, fully mixing, then melting and molding in a high-temperature lifting furnace, wherein the temperature of the melting and molding treatment is 1550 ℃, the melting time is 5 hours, and pouring into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, preserving the heat for 5 hours, and reducing the temperature to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 560 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 630 ℃, and the crystallization treatment time is 100min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 39 wt%, the average grain size of the crystals was 14 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.19; the light transmittance at the wavelength of 360nm is 84.92%, the light average transmittance at the wavelength of 380-780nm is 92.80%, the light average transmittance at the wavelength of 360-400nm is 88.32%, and the haze is 0.21%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 15 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 740 ℃. The temperature of the first hot pressing station is 770 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 22 was obtained.
The 3D glass ceramics sample 22 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 22 had a crystallinity of 85 wt% after thermal bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystals was 19 nm. The absolute value of b is 0.42 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.23%, the light average transmittance at the wavelength of 380-780nm is 92.10%, the light average transmittance at the wavelength of 360-400nm is 89.30%, and the haze is 0.15%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 450 DEG C 3 And (5) the solution is subjected to 9 hours, and finally the 3D glass ceramics finished product 22 is obtained.
Example 23
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 71.80％；Al 2 O 3 4.80％；MgO 1.40％；Na 2 O 1.00％；Li 2 18.80 percent of O; ZnO 0.3%, nucleating agent (0.8% P) 2 O 5 ；1.1％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, the temperature is kept for 5 hours, and the temperature is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 545 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 610 ℃, and the crystallization treatment time is 200min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 45 wt%, the average grain size of the crystals was 19 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.25; the light transmission rate at the wavelength of 360nm is 83.36%, the light average transmission rate at the wavelength of 380-780nm is 92.50%, the light average transmission rate at the wavelength of 360-400nm is 87.16%, and the haze is 0.15%.
And 5: 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 15 in the table 2 (refer to example 22) is adopted to obtain a 3D microcrystalline glass sample 23;
the 3D glass-ceramic sample 23 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 23 had a crystallinity of 92 wt% after hot bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystals was 20 nm. The absolute value of b is 0.61 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 85.82 percent, the light average transmittance at the wavelength of 380-780nm is 91.50 percent, the light average transmittance at the wavelength of 360-400nm is 88.00 percent, and the haze is 0.15 percent.
And 6: and (4) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the example 22 to finally obtain a 3D glass ceramics finished product 23.
Example 24
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 69.50％；Al 2 O 3 4.25％；Na 2 O 1.60％；Li 2 O 20.5％；B 2 O 3 1.60%, nucleating agent (0.8% P) 2 O 5 ；1.75％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1708.5g of the total weight of the raw materials are fully mixed, then the mixture is melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1550 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, the temperature is kept for 5 hours, and the temperature is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 538 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 620 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 43 wt%, the average grain size of the crystals was 17 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.17; the light transmission rate at the wavelength of 360nm is 84.21 percent, the light average transmission rate at the wavelength of 380-780nm is 92.20 percent, the light average transmission rate at the wavelength of 360-400nm is 85.98 percent, and the haze is 0.19 percent.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts a hot bending process with the sequence number of 14 in Table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 720 ℃. The temperature of the first hot pressing station is 750 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 24 was obtained.
And b, detecting the 3D glass-ceramic sample 24 by using light with the absolute value of a wavelength of 360nm, and analyzing the detected X-ray diffraction data by using a ray diffractometer under the same instrument setting conditions as in example 1, wherein the crystallinity of the 3D glass-ceramic sample 24 after being subjected to thermal bending is 82 wt%, the precipitated crystal phase is petalite + lithium disilicate, and the average particle size of the crystal is 22 nm. The absolute value of b is measured to be 0.43 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.17%, the light average transmittance at the wavelength of 380-780nm is 92.60%, the light average transmittance at the wavelength of 360-400nm is 89.60%, and the haze is 0.11%.
Step 6: and (3) carrying out chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the embodiment 22 to finally obtain a 3D glass ceramics finished product 24.
Example 25
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 68.76％；Al 2 O 3 4.13％；MgO 0.98％，ZnO 0.98％，Na 2 O 0.45％；Li 2 O 20.71％；B 2 O 3 1.49%, nucleating agent (0.81% P) 2 O 5 ；1.69％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1708.5g of the total weight of the raw materials are fully mixed, then the mixture is melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1550 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), carrying out XRD test on the obtained annealed glass brick to obtain a figure 1, wherein the obtained glass brick is in a glass state, and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 540 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as in example 24;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of 47 wt% and the average grain size of the crystal 15 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.09; the light transmittance at the wavelength of 360nm is 85.01%, the light average transmittance at the wavelength of 380-780nm is 92.40%, the light average transmittance at the wavelength of 360-400nm is 85.81%, and the haze is 0.24%. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 2, which was seen to be in a partially crystallized state.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process (refer to example 24) numbered 14 in table 2 was employed to obtain a 3D glass ceramic sample 25.
And (3) detecting the 3D glass-ceramic sample 25, and analyzing the detected X-ray diffraction data by using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 25 has a crystallinity after being thermally bent, the crystallinity after being thermally bent is 87 wt%, the precipitated crystal phase is a solid solution of lithium disilicate, petalite and beta-quartz, and the average particle size of the crystal is 18 nm. The absolute value of b is 0.39 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 88.80%, the light average transmission rate at the wavelength of 380-780nm is 92.70%, the light average transmission rate at the wavelength of 360-400nm is 89.80%, and the haze is 0.09%.
And 5: carrying out chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 4, and soaking the glass in molten 100 wt% of NaNO at the temperature of 450 DEG C 3 And (5) performing solution treatment for 10 hours to finally obtain a 3D glass ceramic finished product 25.
Example 26
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 68.73％；Al 2 O 3 4.13％；MgO 0.98％，ZnO 1.68％，Na 2 O 0.45％；Li 2 O 20.01％；B 2 O 3 1.49%, nucleating agent (0.81% P) 2 O 5 ；1.72％ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 is the same as in example 25;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 615 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 55 wt%, the average grain size of the crystals was 16 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.34; the light transmittance at the wavelength of 360nm is 83.16%, the light average transmittance at the wavelength of 380-780nm is 92.00%, the light average transmittance at the wavelength of 360-400nm is 84.26%, and the haze is 0.29%. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 3, which was seen to be in a partially crystallized state.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 15 in table 2 (see example 22) was employed to obtain a 3D glass ceramic sample 26.
The 3D glass ceramics sample 26 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 30 had a crystallinity of 91 wt% after thermal bending, the precipitated crystal phase was petalite, and the average particle size of the crystal was 23 nm. The absolute value of b is 0.42 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.13%, the light average transmittance at the wavelength of 380-780nm is 92.80%, the light average transmittance at the wavelength of 360-400nm is 89.90%, and the haze is 0.11%.
Example 27
Step 1: the same as in example 18, except for the temperature of the melt molding treatment; the temperature of the melting and forming treatment in the embodiment is 1610 ℃;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is to keep the temperature at 460 ℃ for 5 hours and reduce the temperature to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 480 ℃, and the time of the nucleation treatment is 360 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 550 ℃ for 300min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 6 wt%, the average grain size of the crystals was 5 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 0.2; the light transmission rate at the wavelength of 360nm is 90.80 percent, the light average transmission rate at the wavelength of 380-780nm is 93.00 percent, the light average transmission rate at the wavelength of 360-400nm is 91 percent, and the haze is 0.05 percent.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process with the number 1 in table 2 (the same as in example 1) was used to obtain a 3D microcrystalline glass sample 27.
The above 3D glass ceramics sample 27 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 27 had a crystallinity of 14 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 10 nm. When the light source is defined as D65, the absolute value of b of the 3D glass ceramics sample 27 is 0.15; the light transmittance at the wavelength of 360nm is 90.60%, the light average transmittance at the wavelength of 380-780nm is 93.00%, the light average transmittance at the wavelength of 360-400nm is 91.40%, and the haze is 0.07%.
Example 28
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is to preserve heat at 460 ℃ for 5 hours and reduce the temperature to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 500 ℃, and the time of the nucleation treatment is 300 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the crystallization treatment temperature is 570 ℃, and the crystallization treatment time is 280min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 8 wt%, the average grain size of the crystals was 7 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 0.23; the light transmission rate at the wavelength of 360nm is 90.50 percent, the light average transmission rate at the wavelength of 380-780nm is 92.80 percent, the light average transmission rate at the wavelength of 360-400nm is 90.80 percent, and the haze is 0.06 percent.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 28 by adopting a hot bending process with the sequence number 1 in the table 2.
The above 3D glass ceramics sample 28 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 28 had a crystallinity of 16 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 15 nm. When the light source is defined as D65, the absolute value of b of the 3D glass ceramic sample 28 is 0.25; the light transmittance at the wavelength of 360nm is 90.10 percent, the light average transmittance at the wavelength of 380-780nm is 92.80 percent, the light average transmittance at the wavelength of 360-400nm is 91.20 percent, and the haze is 0.09 percent.
Example 29
step 2 was the same as in example 28;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 560 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the pieces to 9 wt% and the average grain size of the crystals to 9 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 0.21; the light transmittance at the wavelength of 360nm is 91%, the light average transmittance at the wavelength of 380-780nm is 92.90%, the light average transmittance at the wavelength of 360-400nm is 90.60%, and the haze is 0.08%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 28 by adopting a hot bending process with the sequence number 1 in the table 2.
The above 3D glass ceramics sample 29 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 29 had a crystallinity of 17 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 13 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 29 is 0.23; the light transmittance at the wavelength of 360nm is 90.50 percent, the light average transmittance at the wavelength of 380-780nm is 92.70 percent, the light average transmittance at the wavelength of 360-400nm is 91.50 percent, and the haze is 0.08 percent.
Example 30
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 500 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 600 ℃, and the time of the nucleation treatment is 80 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 610 ℃, and the crystallization treatment time is 180min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 37 wt%, the average grain size of the crystals was 15 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 0.26; the light transmission rate at the wavelength of 360nm is 90.20 percent, the light average transmission rate at the wavelength of 380-780nm is 93.00 percent, the light average transmission rate at the wavelength of 360-400nm is 90.30 percent, and the haze is 0.09 percent.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 30 by adopting a hot bending process with the sequence number 3 in the table 2. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 4, which was seen to be in a partially crystallized state.
The 3D glass-ceramic sample 30 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 30 had a crystallinity of 75 wt% after hot bending, the precipitated crystal phase was petalite + β -quartz solid solution, and the average particle size of the crystal was 18 nm. The absolute value of b is 0.35 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.20 percent, the light average transmittance at the wavelength of 380-780nm is 92.60 percent, the light average transmittance at the wavelength of 360-400nm is 90.00 percent, and the haze is 0.11 percent.
Example 31
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 600 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 800 ℃, and the time of the nucleation treatment is 30 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 870 ℃, and the time of the crystallization treatment is 15min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, and measuring the crystallinity of the crystal to 88 wt% and the average grain diameter of the crystal to 26 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 2.4; the light transmittance at the wavelength of 360nm is 74.50%, the light average transmittance at the wavelength of 380-780nm is 88.10%, the light average transmittance at the wavelength of 360-400nm is 80.50%, and the haze is 0.84%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 4 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 31.
The 3D glass ceramics sample 31 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 31 had a crystallinity of 99 wt% after thermal bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 48 nm. The absolute value of b is 2.60 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 74.10%, the light average transmittance at the wavelength of 380-780nm is 89.30%, the light average transmittance at the wavelength of 360-400nm is 80.50%, and the haze is 0.78%.
Example 32
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept for 5 hours at the temperature of 600 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 780 ℃, and the time of the nucleation treatment is 60 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 900 ℃ for 5min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 58 wt%, the average grain size of the crystals was 50 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 2.5; the light transmittance at the wavelength of 360nm is 73.60%, the light average transmittance at the wavelength of 380-780nm is 88.80%, the light average transmittance at the wavelength of 360-400nm is 80.10%, and the haze is 0.79%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 7 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 32.
The 3D glass ceramics sample 32 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 32 had a crystallinity of 98 wt% after being thermally bent, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 81 nm. The absolute value of b is measured to be 2.80 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 62.00 percent, the light average transmittance at the wavelength of 380-780nm is 88.60 percent, the light average transmittance at the wavelength of 360-400nm is 65.80 percent, and the haze is 0.72 percent.
Example 33
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 67.45％；Al 2 O 3 14.20％；CaO 0.50％；MgO 1.79％；Na 2 O 1.56％；Li 2 9.70 percent of O; nucleating agent (2.18% P) 2 O 5 ；0.81％TiO 2 ；1.31％ZrO 2 ；0.5％Y 2 O 3 ) And a nucleating agent andpreparing a clarifier NaCl with the total mass of 0.8 wt% of the raw materials, wherein the total weight of the raw materials is 1713.5g, fully mixing, then melting and molding in a high-temperature lifting furnace, wherein the melting and molding treatment temperature is 1650 ℃, the melting time is 5h, and pouring into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 500 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 650 ℃, and the time of the nucleation treatment is 160 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 820 ℃, and the time of the crystallization treatment is 30min, so as to obtain the glass brick after partial crystallization treatment;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 90 wt%, the average grain size of the crystals was 47 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 2.8; the light transmittance at the wavelength of 360nm is 72.80 percent, the light average transmittance at the wavelength of 380-780nm is 88.40 percent, the light average transmittance at the wavelength of 360-400nm is 80.10 percent, and the haze is 0.97 percent.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 33 by adopting a hot bending process with the serial number 6 in the table 2.
The 3D glass ceramics sample 33 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 33 had a crystallinity of 100 wt% after being thermally bent, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 98 nm. When the light source is defined as D65, the absolute value of the b value is 3.8; the light transmission rate at the wavelength of 360nm is 63.10 percent, the light average transmission rate at the wavelength of 380-780nm is 88.20 percent, the light average transmission rate at the wavelength of 360-400nm is 65.40 percent, and the haze is 0.98 percent.
Example 34
Step 1: preparing and weighing raw materials (molar percentage is calculated by package) for preparing glassComprises the following components: SiO 2 2 66.65％；Al 2 O 3 10.87％；MgO 2.44％；ZnO 2.82％；Na 2 O 0.21％；K 2 O 0.21％；Li 2 O 9.88％；B 2 O 3 0.94 percent; nucleating agent (1.85% P) 2 O 5 ；2.00％ZrO 2 ；2.13％CaF 2 ) And a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1640 ℃, the melting time is 4h, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 500 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 620 ℃, and the time of the nucleation treatment is 240 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 650 ℃, and the time of the crystallization treatment is 40min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 68 wt%, the average grain size of the crystals was 42 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.45; the light transmittance at the wavelength of 360nm is 82.90%, the light average transmittance at the wavelength of 380-780nm is 91.70%, the light average transmittance at the wavelength of 360-400nm is 85.60%, and the haze is 0.38%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 34 by adopting a hot bending process with the serial number of 7 in the table 2.
The 3D glass ceramics sample 34 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 34 had a crystallinity of 79 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 65 nm. The absolute value of b is measured to be 0.76 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 84.22 percent, the light average transmission rate at the wavelength of 380-780nm is 91.00 percent, the light average transmission rate at the wavelength of 360-400nm is 87.50 percent, and the haze is 0.16 percent.
Example 35
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 64.55％；Al 2 O 3 10.45％；MgO 2.37％；ZnO 2.73％；Na 2 O 0.21％；K 2 O 0.20％；Li 2 O 9.58％；B 2 O 3 0.91 percent; nucleating agent (1.94% P) 2 O 5 ；2.91％TiO 2 ；2.02％ZrO 2 ；2.13％CaF 2 ) And a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the melting and molding treatment temperature is 1640 ℃, the melting time is 4 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 and step 3 were the same as in example 35;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was determined to be 82 wt%, the average grain size of the crystals was 35 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.32; the light transmission rate at the wavelength of 360nm is 83.40%, the light average transmission rate at the wavelength of 380-780nm is 91.40%, the light average transmission rate at the wavelength of 360-400nm is 86.30%, and the haze is 0.31%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 35 by adopting a hot bending process with the serial number 6 in the table 2.
The 3D glass-ceramic sample 35 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 35 had a crystallinity of 86 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 42 nm. The absolute value of b is 0.68 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 85.42%, the light average transmission rate at the wavelength of 380-780nm is 91.10%, the light average transmission rate at the wavelength of 360-400nm is 87.20%, and the haze is 0.19%.
Example 36
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.13％；Al 2 O 3 11.50％；MgO 2.57％；ZnO 2.97％；Na 2 O 0.22％；K 2 O 0.22％；Li 2 O 10.40％；B 2 O 3 0.99 percent; nucleating agent (0.84% P) 2 O 5 ；0.16％CaF 2 ) And a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1640 ℃, the melting time is 3 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 and step 3 were the same as in example 34;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the crystallinity was found to be 63 wt%, the average grain size of the crystals was 24 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.32; the light transmission rate at the wavelength of 360nm is 84.10%, the light average transmission rate at the wavelength of 380-780nm is 91.60%, the light average transmission rate at the wavelength of 360-400nm is 87.10%, and the haze is 0.33%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 36 by adopting a hot bending process with the serial number 5 in the table 2.
The 3D glass-ceramic sample 36 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 36 had a crystallinity of 70 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 37 nm. It was determined that when the illuminant was defined as D65, the absolute value of b was 0.53; the light transmittance at the wavelength of 360nm is 86.00%, the light average transmittance at the wavelength of 380-780nm is 92.20%, the light average transmittance at the wavelength of 360-400nm is 88.60%, and the haze is 0.10%.
Example 37
The preparation method of the crystallized glass raw material and the preparation method for continuously preparing the 3D glass ceramics by using the crystallized glass raw material comprise the following steps:
step 1: the same as in example 17, except for the temperature and melting time of the melt molding process. The temperature of the melting and forming treatment in the embodiment is 1650 ℃, and the melting time is 2 h;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 500 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 600 ℃, and the time of the nucleation treatment is 80 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 600 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing the same as in example 1, after which the degree of crystallinity was determined to be 75 wt%, the average grain size of the crystals was 29 nm; when the light source is limited to D65, the absolute value of the b value of the partially crystallized glass original sheet is 1.5; the light transmission rate at the wavelength of 360nm is 83.50%, the light average transmission rate at the wavelength of 380-780nm is 91.20%, the light average transmission rate at the wavelength of 360-400nm is 85.80%, and the haze is 0.39%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 6 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 37.
The 3D glass-ceramic sample 37 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 37 had a crystallinity of 88 wt% after hot bending, the precipitated crystal phase was petalite + β -quartz solid solution, and the average particle size of the crystal was 57 nm. It was determined that when the light source was defined as D65, the absolute value of b was 0.38; the light transmission rate at the wavelength of 360nm is 88.40%, the light average transmission rate at the wavelength of 380-780nm is 92.80%, the light average transmission rate at the wavelength of 360-400nm is 90.10%, and the haze is 0.12%.
Example 38
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts a hot bending process with the serial number of 20 in the table 2; the hot bending treatment comprises 3 preheating stations, 4 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, and the temperature of the third preheating station is 650 ℃. The temperature of the first hot-pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 750 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 720 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the fourth hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating work station, the hot pressing work station and the cooling work station is the same and is 140s, and the 3D microcrystalline glass sample 22F is obtained.
The 3D glass ceramics sample 22F was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 22F had a crystallinity of 84 wt% after thermal bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystals was 18 nm. The absolute value of b is 0.43 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.15 percent, the light average transmittance at the wavelength of 380-780nm is 92.77 percent, the light average transmittance at the wavelength of 360-400nm is 89.45 percent, and the haze is 0.11 percent.
Example 39
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 21 in the table 3; the hot bending treatment comprises 5 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, the temperature of the fourth preheating station is 680 ℃, and the temperature of the fifth preheating station is 720 ℃. The temperature of the first hot pressing station is 745 ℃, the upper pressure is 0.5MPa, and the lower pressure is 0.5 MPa; the temperature of the second hot-pressing station is 760 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 140s, and a 3D microcrystalline glass sample 22G is obtained.
The 3D glass ceramics sample 22G was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 22G had a crystallinity of 90 wt% after hot bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystal was 22 nm. The absolute value of b is measured to be 0.55 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 86.12%, the light average transmittance at the wavelength of 380-780nm is 92.40%, the light average transmittance at the wavelength of 360-400nm is 88.40%, and the haze is 0.10%.
Comparative example
Comparative example 1
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 62.40％；Al 2 O 3 13.24％；MgO 4.46％；Na 2 O 1.46％；Li 2 O9.04%, nucleating agent (0.94% P) 2 O 5 ；6.58％ZrO 2 ；1.88％TiO 2 9.40 percent of nucleating agent in total), and NaCl accounting for 0.8 weight percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2 is the same as example 4; it can be seen that the nucleated glass sheet has precipitated crystals and is in a ceramic state, which does not meet the conditions of the subsequent hot bending process.
Comparative example 2
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 60.70％；Al 2 O 3 12.87％；MgO 4.34％；Na 2 O 1.42％；Li 2 O8.79%, nucleating agent (0.91% P) 2 O 5 ；9.14％ZrO 2 ；1.83％TiO 2 11.88 percent of nucleating agent in total), and NaCl accounting for 0.8wt percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 material to obtain a glass brick;
step 2: and (3) crystals are precipitated at the central part of the glass brick obtained in the step (1) in the process of cooling to 800 ℃, and stress difference occurs inside the glass brick, so that the glass brick is broken and cannot be machined.
Comparative example 3
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 67.45％；Al 2 O 3 14.20％；CaO 0.50％；MgO 1.79％；Na 2 O 1.56％；Li 2 9.70 percent of O; nucleating agent (2.18% P) 2 O 5 ；1.31％ZrO 2 ；0.81％TiO 2 And 0.5% Y 2 O 3 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the temperature of the crystallization treatment is 930 ℃, and the time of the crystallization treatment is 30 min; uncontrollable crystallization occurs in the glass brick after crystallization treatment due to overhigh crystallization temperature, and stress difference occurs in the glass brick, so that the glass brick is cracked and cannot be machined.
Comparative example 4
Step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.33％；Al 2 O 3 14.82％；Na 2 O 1.63％；Li 2 10.11 percent of O; 1.34 percent of MgO; ZnO 1.04%, nucleating agent (0.52% P) 2 O 5 ；0.21％ZrO 2 ) And the clarifying agents NaCl and SnO accounting for 0.4 wt% and 0.4 wt% of the total mass of the nucleating agent and the preparation raw materials respectively 2 1708.5g of the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
the conditions of step 2 and step 3 are the same as those of example 33, and XRD test is performed on the glass brick after nucleation, so that it can be seen that no crystal nucleus appears due to too little nucleating agent, uncontrollable crystallization appears during crystallization treatment, and stress difference appears inside the glass, which causes breakage of the hot-bent glass.
Comparative example 5
Step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 70.45％；Al 2 O 3 13.16％；MgO 2.78％；Na 2 O 0.56％；Li 2 O 7.98％；B 2 O 3 1.00 percent; nucleating agent (1.67% P) 2 O 5 ；1.30％ZrO 2 ；0.60％TiO 2 And 0.5% Y 2 O 3 ) And clarifying agents NaCl and CeO accounting for 0.4 wt% and 0.3 wt% of the total mass of the nucleating agent and the preparation raw materials 2 1711.9g of the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213 materials to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 900 ℃, and transferring the glass brick to a precision annealing furnace for nucleation treatment; the temperature of the nucleation treatment is 850 ℃, and the time of the nucleation treatment is 120 min; uncontrollable crystallization occurs in the glass brick after the nucleation treatment due to overhigh nucleation temperature, and stress difference occurs in the glass brick, so that the glass brick is cracked and cannot be subjected to subsequent treatment and processing.
Comparative example 6
and 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts the hot bending process with the serial number of 16 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating work station is 480 ℃, the temperature of the second preheating work station is 600 ℃, the temperature of the third preheating work station is 650 ℃, and the temperature of the fourth preheating work station is 720 ℃. The temperature of the first hot pressing station is 940 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 920 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 90 s. A 3D glass ceramics sample 22B was obtained.
The 3D glass ceramics sample 22B was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 22B had a crystallinity of 100 wt% after thermal bending, a precipitated crystal phase of β -spodumene + lithium disilicate, and an average particle diameter of the crystals was 111 nm. The absolute value of b is 7.45 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 64.10%, the light average transmission rate at the wavelength of 380-780nm is 86.50%, the light average transmission rate at the wavelength of 360-400nm is 69.20%, and the haze is 0.99%. Due to the fact that the hot pressing temperature is too high, the average grain size of crystals of the finally prepared microcrystalline glass is too high, the b value is increased, the light transmittance is reduced, the b value is too high, the microcrystalline glass is bluish, and imaging is affected.
Comparative example 7
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 17 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 720 ℃. The temperature of the first hot pressing station is 930 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 920 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramics sample 22C was obtained.
The 3D glass ceramics sample 22C was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 22C had a crystallinity of 100 wt% after thermal bending, a precipitated crystal phase of β -spodumene + lithium disilicate, and an average particle diameter of the crystals was 124 nm. The absolute value of b is 7.86 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 62.40 percent, the light average transmittance at the wavelength of 380-780nm is 87.30 percent, the light average transmittance at the wavelength of 360-400nm is 68.20 percent, and the haze is 1.10 percent. Due to the fact that the hot pressing temperature is too high, the average grain size of crystals of the finally prepared microcrystalline glass is too high, the b value is increased, the light transmittance is reduced, the b value is too high, the microcrystalline glass is in bluish color, and imaging is affected.
Comparative example 8
and 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts the hot bending process with the serial number of 18 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 650 ℃. The temperature of the first hot pressing station is 580 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 90 s. A 3D glass ceramics sample 22D was obtained. Due to the excessively low hot pressing temperature, the 3D glass ceramic sample 22D cannot be hot-bent into the target shape.
Comparative example 9
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts a hot bending process with the serial number of 19 in Table 2; the hot bending treatment comprises 3 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 500 ℃, the temperature of the second preheating station is 550 ℃, and the temperature of the third preheating station is 600 ℃. The temperature of the first hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot-pressing station is 580 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 550 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 90s, and the 3D microcrystalline glass sample 22E is obtained. Since the hot pressing temperature was too low, the 3D glass ceramic sample 22E could not be hot-bent into the target shape.
Application example
Mechanical parameters were measured for 3D glass ceramics obtained by chemically strengthening the glass of example 1, example 2, example 4, example 7, example 12, example 16, example 22, example 23, example 24 and example 25, and the thickness of the glass was 0.65, and the results are shown in table 3.
The test is carried out by using an SLP-2000 stress meter, the photoelastic coefficient is set to be 25.5, the refractive index is set to be 1.54, the test result belongs to the conventional test, the test result comprises surface compressive stress, compressive stress depth and average tensile stress, the linear density of the tensile stress is a calculated value, and the sum of the tensile stress and the glass thickness is divided by the SLP-2000 stress meter.
Surface compressive stress (MPa): after the glass is chemically strengthened, the alkali metal ions with smaller radius on the surface are replaced by the alkali metal ions with larger radius, and the surface of the glass generates compressive stress due to the squeezing effect of the alkali metal ions with larger radius, which is called surface compressive stress;
depth of compressive stress (μm): the distance from the surface of the chemically strengthened glass to a position where the compressive stress is zero;
average tensile stress CT-AV (MPa): the ratio of the sum of tensile stress and the thickness of a tensile stress area obtained by testing according to an SLP-2000 stress meter;
and (3) tensile stress linear density CT-LD: according to SLP-2000 stress meter test, the ratio of tensile stress integral and glass thickness of the chemically strengthened glass under the thickness section is obtained;
and (3) complete machine drop test: a method for testing the strength of strengthened glass includes sticking the strengthened glass to the specimen of electronic equipment such as mobile telephone, falling down from high position, recording the broken height of glass, and testing the whole falling test. The testing method is characterized in that a mobile phone with 180g of tempered glass sheet load freely falls on 120-mesh abrasive paper, and the abrasive paper is tightly attached to a marble bottom plate;
vickers hardness (Hv) (300N pressure hold 10 s): pressing a diamond regular pyramid pressure head with an included angle of 136 degrees between opposite surfaces into the surface of the sample to be tested under the action of a load of 300N, removing the load after keeping for 10s, measuring the length d of a diagonal line of the indentation, further calculating the surface area of the indentation, and finally solving the average pressure on the surface area of the indentation, namely the Vickers hardness value of the glass, which is represented by a symbol HV.
TABLE 3 determination of mechanical parameters
As can be seen from the above table, the surface compressive stress of the 3D glass-ceramic finished product after chemical strengthening in the example is 108-514MPa, the depth of the compressive stress is 109-121 μm, the average tensile stress CT-AV is 42-93MPa, the linear density CT-LD of the tensile stress is 30145-43157, the total machine drop test height is 1.51-1.82m, and the Vickers hardness (300N pressure retention 10s) of the 3D glass-ceramic finished product after chemical strengthening is 712-741 Hv.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (20)
1. The crystallized glass raw material is characterized in that the thickness of the crystallized glass raw material is 0.02-5 mm; the crystallinity of the crystallized glass raw material is 5-90 wt%.
2. The crystallized glass raw material of claim 1, wherein the thickness is 0.35 to 1.2mm, and the crystallized glass raw material has a crystallinity of 30 to 75 wt% or 75 to 90 wt%.
3. The crystallized glass material as claimed in claim 1 or 2, wherein the crystallized glass material has an average transmittance of light with a wavelength of 380-780nm of 83-93%, preferably 85-92%; alternatively, the average transmittance of the crystallized glass raw material at the wavelength of 360-400nm is 80-91%, preferably 83-90%.
4. A crystallized glass raw material according to any one of claims 1 to 3, wherein the absolute value of b value (yellow-blue value) at a thickness of 0.7mm is 0.2 to 3, preferably 0.6 to 2; the haze of the crystallized glass raw material is 0.05-1.0%, preferably 0.2-0.8%.
5. The crystallized glass material as set forth in any one of claims 1 to 4, wherein the crystallized glass material contains oxides in mol% in the following proportions:
wherein the rare earth oxide is selected from La 2 O 3 ，Eu 2 O 3 ，Pr 6 O 11 ，Nd 2 O 3 ，Er 2 O 3 And Dy 2 O 3 One or more than two of them.
6. The crystallized glass material as set forth in claim 5, wherein the crystallized glass material contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60%; preferably 68-80%; or, contain Na 2 O+Li 2 O is 7 to 30%, preferably 10 to 26%, in mol%.
7. The crystallized glass material of any one of claims 1 to 6, wherein the crystallized glass material comprises a nucleating agent comprising P on an oxide, fluoride, or elemental basis 2 O 5 ，TiO 2 ，ZrO 2 ，Cr 2 O 3 ，CaF 2 ，LiF，NaF，KF，Y 2 O 3 One or more of Au, Ag and Cu; preferably P 2 O 5 ，TiO 2 And ZrO 2 One or more than two of them.
8. The crystallized glass stock material of any one of claims 1 to 7, wherein the crystallized glass stock material comprises a fining agent, wherein the fining agent comprises NaCl, Na 2 SO 4 ，SnO 2 ，As 2 O 3 ，Sb 2 O 3 ，NaNO 3 ，KNO 3 ，CeO 2 And (NH) 4 ) 2 SO 4 One or more than two of (a); preferably NaCl, SnO 2 ，NaNO 3 And CeO 2 One or more than two of them.
9. The crystallized glass raw material according to any one of claims 1 to 8, wherein the crystallized glass raw material has crystals with an average particle size of 5 to 50nm after the nucleation and crystallization.
10. The crystallized glass raw material of any one of claims 1 to 9, wherein the crystallized glass raw material has a vickers hardness of greater than 500 for a 300N force load of 10s, preferably a vickers hardness of greater than 560.
11. The method for producing a crystallized glass raw material according to any one of claims 1 to 10, wherein the method for producing the crystallized glass raw material comprises the steps of:
step 1: mixing the preparation raw materials of the 3D glass ceramics, melting, cooling and annealing to obtain a glass substrate;
step 2: carrying out nucleation treatment on the glass substrate obtained in the step 1; wherein the cutting can be carried out according to the requirement before and after the nucleation treatment;
and 3, step 3: crystallizing the nucleated glass substrate obtained in the step 2;
and 4, step 4: and cutting the crystallized glass substrate as required to obtain a crystallized glass raw material.
12. The method as claimed in claim 11, wherein the melting temperature is 1350-1700 ℃ in the step 1; preferably, the melting temperature is 1400-1650 ℃; more preferably, the melt is cooled to 500-1000 ℃.
13. The method according to claim 11 or 12, wherein in step 1, the nucleating agent is added in an amount of 1 to 9 mol%, preferably 2 to 5 mol%, based on the total amount of the nucleating agent and the crystallized glass raw material oxide.
14. The method according to any one of claims 11-13, wherein in step 1, the refining agent is added in an amount of 0-4 wt%, preferably 0.1-2 wt%, of the total mass of nucleating agent and crystallized glass raw material oxide.
15. The method according to any one of claims 11-14, wherein, in step 2,
the temperature of the nucleation treatment is 450-800 ℃; preferably, the time of the nucleation treatment is 30-360 min;
further preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is preferably 120-300 min.
16. The method as claimed in any one of claims 11 to 15, wherein, in the step 3, the temperature of the crystallization treatment is 550-900 ℃, and the time of the crystallization treatment is 5-300 min;
preferably, the temperature of the crystallization treatment is 600-850 ℃, the time of the crystallization treatment is 10-240min,
further preferably, the temperature of the crystallization treatment is 600-750 ℃, and the time of the crystallization treatment is 10-150 min.
17. A crystallized glass raw material produced by the production method according to any one of claims 11 to 16.
18. A crystallized glass material according to claim 17, wherein said crystallized glass material is transparent or opaque; preferably, the crystallized glass raw material is curved or planar.
19. Use of a crystallized glass material according to claim 17 or 18 for 3D hot bending to produce 3D glass-ceramic.
20. The use of the 3D glass-ceramic made from the crystallized glass feedstock of claim 19 in a mobile phone display screen, a tablet computer display screen, a handheld game console, an electronic terminal, a portable digital device, a vehicle-mounted central control screen, an electronic whiteboard glass, an intelligent home touch screen, a vehicle windshield, an aircraft windshield, or an aircraft windshield.
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| CN202110099301.4A CN114790081A (en) | 2021-01-25 | 2021-01-25 | Crystallized glass raw material and preparation method and application thereof |
| JP2023544498A JP2024504395A (en) | 2021-01-25 | 2022-01-21 | 3D crystallized glass and its manufacturing method and use |
| KR1020237027189A KR20230132509A (en) | 2021-01-25 | 2022-01-21 | 3D glass-ceramics and their manufacturing methods and applications |
| JP2023544499A JP2024504396A (en) | 2021-01-25 | 2022-01-21 | Crystallized glass material and its manufacturing method and use |
| PCT/CN2022/073214 WO2022156772A1 (en) | 2021-01-25 | 2022-01-21 | Crystallized glass raw material, preparation method therefor and use thereof |
| US18/273,511 US20240317636A1 (en) | 2021-01-25 | 2022-01-21 | Crystallized glass raw material, preparation method therefor and use thereof |
| KR1020237027191A KR20230132510A (en) | 2021-01-25 | 2022-01-21 | Crystallized glass raw materials and their manufacturing methods and applications |
| US18/273,514 US20240076228A1 (en) | 2021-01-25 | 2022-01-21 | 3d glass-ceramic, preparation method therefor and application thereof |
| PCT/CN2022/073213 WO2022156771A1 (en) | 2021-01-25 | 2022-01-21 | 3d glass-ceramic, preparation method therefor and application thereof |
| EP22742251.6A EP4276077A4 (en) | 2021-01-25 | 2022-01-21 | Crystallized glass raw material, preparation method therefor and use thereof |
| EP22742250.8A EP4265573A4 (en) | 2021-01-25 | 2022-01-21 | 3d glass-ceramic, preparation method therefor and application thereof |
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