CN114790085A - 3D glass ceramic and preparation method and application thereof - Google Patents
3D glass ceramic and preparation method and application thereof Download PDFInfo
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- CN114790085A CN114790085A CN202110099277.4A CN202110099277A CN114790085A CN 114790085 A CN114790085 A CN 114790085A CN 202110099277 A CN202110099277 A CN 202110099277A CN 114790085 A CN114790085 A CN 114790085A
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 263
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000011521 glass Substances 0.000 claims abstract description 506
- 238000013003 hot bending Methods 0.000 claims abstract description 190
- 238000002425 crystallisation Methods 0.000 claims abstract description 127
- 230000008025 crystallization Effects 0.000 claims abstract description 127
- 239000013078 crystal Substances 0.000 claims abstract description 116
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 174
- 230000008569 process Effects 0.000 claims description 144
- 238000000137 annealing Methods 0.000 claims description 121
- 239000002994 raw material Substances 0.000 claims description 121
- 238000001816 cooling Methods 0.000 claims description 104
- 238000002834 transmittance Methods 0.000 claims description 104
- 238000010899 nucleation Methods 0.000 claims description 98
- 230000006911 nucleation Effects 0.000 claims description 98
- 238000007731 hot pressing Methods 0.000 claims description 97
- 239000002667 nucleating agent Substances 0.000 claims description 93
- 238000002844 melting Methods 0.000 claims description 73
- 230000008018 melting Effects 0.000 claims description 73
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 70
- 238000005498 polishing Methods 0.000 claims description 52
- 238000000227 grinding Methods 0.000 claims description 46
- 238000004519 manufacturing process Methods 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 40
- 238000009966 trimming Methods 0.000 claims description 40
- 238000005520 cutting process Methods 0.000 claims description 37
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 35
- 239000011780 sodium chloride Substances 0.000 claims description 35
- 229910000500 β-quartz Inorganic materials 0.000 claims description 26
- 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 claims description 21
- 238000003426 chemical strengthening reaction Methods 0.000 claims description 21
- 229910052670 petalite Inorganic materials 0.000 claims description 21
- 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 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 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
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052586 apatite Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- 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 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001676 gahnite Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 229910052664 nepheline Inorganic materials 0.000 claims description 4
- 239000010434 nepheline Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- -1 magnesium aluminate Chemical class 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000006025 fining agent Substances 0.000 claims 2
- 239000011449 brick Substances 0.000 description 179
- 230000005540 biological transmission Effects 0.000 description 46
- 238000002441 X-ray diffraction Methods 0.000 description 45
- 230000005855 radiation Effects 0.000 description 38
- 229910001220 stainless steel Inorganic materials 0.000 description 31
- 239000010935 stainless steel Substances 0.000 description 31
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 28
- 238000005303 weighing Methods 0.000 description 22
- 238000000465 moulding Methods 0.000 description 20
- 238000005452 bending Methods 0.000 description 19
- 239000008395 clarifying agent Substances 0.000 description 19
- 229910018068 Li 2 O Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000008859 change Effects 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000005345 chemically strengthened glass Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000004579 marble Substances 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
- 239000006058 strengthened glass Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005728 strengthening Methods 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/0066—Re-forming shaped glass by bending
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
The invention provides 3D glass ceramics which are characterized in that the crystallinity of the 3D glass ceramics is 14-100 wt%; the average grain diameter of the crystals of the 3D glass ceramics is 10-100 nm; the thickness of the 3D glass ceramics is 0.02-5 mm. The preparation method of the 3D microcrystalline glass has small processing difficulty and low processing cost, and the 3D hot bending crystallization time is far shorter than the conventional crystallization time; 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 3D glass ceramics 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 the microcrystalline glass is internally provided with a large number of nano-scale crystals, the microcrystalline glass has a more stable structure, and a cover plate product with higher strength can be obtained after chemical strengthening.
The 3D hot bending process of the mobile phone cover plate comprises the following steps of through required equipment and raw materials: 3D hot bending machine, 3D hot bending mould (generally graphite mold) and glass log etc.. The processing technology of the 3D hot bending mobile phone cover plate glass is generally carried out by the following steps: the method comprises the steps of firstly forming a glass plate by methods such as a floating method, a rolling method, an overflowing method and the like, then cutting and thinning, and then carrying out CNC processing, polishing, 3D hot bending, 3D polishing, chemical strengthening and the like. 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 mold, and then the mold is placed in a 3D hot bending machine to carry out 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 glass plate after polishing 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 3D hot bending microcrystalline glass is formed by hot bending completely crystallized microcrystalline glass, the processing procedures of the glass plate forming, the glass plate nucleating and crystallizing, the crystallized glass plate thinning, the crystallized glass plate cutting, the CNC and the polishing are carried out, and the operations of 3D hot bending, 3D polishing, chemical strengthening and the like are carried out after the crystallized glass plate is completely crystallized. The existing fully-crystallized glass ceramics have higher mechanical strength and hardness, so that the existing fully-crystallized glass ceramics have low yield of mechanical processing before hot bending and high production cost.
The conventional fully-crystallized glass-ceramics generally have a softening and molding temperature of 700 ℃ or higher, and therefore the 3D hot-bending molding temperature must be higher than 700 ℃. In the hot bending process, the completely crystallized glass ceramics are heated, and the original kinds of crystalline phases, crystal sizes, refractive indexes, Lab (color intensity) values, haze, transmittance and the like of the glass ceramics are greatly changed. When the microcrystalline glass is applied to a display scene, the chromaticity and the transmittance of the microcrystalline glass 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 optical systems for photographing and videoing, such as refractive index, haze and transmittance of microcrystalline glass, particularly ultraviolet and near ultraviolet transmittance, and can directly influence the imaging quality when the ultraviolet and near ultraviolet transmittances are low.
In addition, the 3D hot bending of the existing fully-crystallized microcrystalline glass only aims at achieving the purpose of hot bending forming, and repeated crystallization exists, so that energy and time are wasted. Therefore, 3D hot bending of conventional fully-crystallized glass ceramics has extremely high technical difficulty, and it is difficult to achieve a yield required for industrial production by processing the glass into a 3D form by 3D hot bending.
However, if the 3D hot bending forming is not performed on the fully crystallized glass ceramic, but the 3D hot bending forming is performed on the nucleated glass, 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, the larger the volume change of the product is, the greater the size control difficulty is, the larger the volume change of the nucleated glass occurs in the hot bending crystallization process, and the size precision of the formed 3D hot bending glass ceramic is affected.
Therefore, the invention discovers that the 3D hot bending is carried out by adopting the partially crystallized microcrystalline glass, the glass is heated and continuously crystallized while the glass is subjected to the hot bending deformation to reach the target crystallinity, the crystallization process during the 3D hot bending is reduced, and the size precision of the hot bent 3D microcrystalline glass is higher.
In addition, in the prior art, the short hot-pressing time can be controlled during hot bending, and because the hot-pressing time is long, the surface of the microcrystalline glass product has mold marks, so that the surface quality is reduced, and the yield is influenced. The method of the invention adopts the partial crystallized glass original sheet to carry out the 3D hot bending treatment, and the partial crystallized glass original sheet has high initial crystallinity and is not easy to generate the mold print. And because the initial crystallinity of the partially crystallized glass original sheet is 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 3D glass ceramics, which is characterized in that the crystallinity of the 3D glass ceramics is 14-100 wt%; the average grain diameter of the crystals of the 3D glass ceramics is 10-100 nm.
Preferably, the crystallinity of the 3D glass ceramics is 14-30 wt%, or the crystallinity of the 3D glass ceramics is 50-100 wt%; or the crystallinity of the 3D glass ceramics is 31-49 wt%;
or the average grain diameter of the crystals of the 3D glass ceramics is 15-30 nm;
or the thickness of the 3D glass ceramics is 0.02-5mm, and preferably, the thickness of the 3D glass ceramics is 0.35-1.2 mm.
Preferably, the average transmittance of the 3D glass ceramics with the wavelength of 380-780nm is 88-93%, preferably 90-91.5%;
or the average transmittance of the 3D glass ceramics at the wavelength of 360-400nm is 65-91.5%, preferably 79-91%, and more preferably 85-91%.
Preferably, the absolute value of the b value (yellow-blue value) of the 3D glass ceramics with the thickness of 0.7mm is 0.1-3.5, preferably 0.3-1.5;
alternatively, the haze of the 3D glass ceramics is 0.07-1.0%, preferably 0.07-0.5%.
Preferably, the crystalline phase of the 3D glass ceramics is one or more of lithium silicate, lithium disilicate, β -quartz solid solution, petalite, β -spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesia-alumina spinel and rutile.
Preferably, the 3D glass ceramics contain 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.
Preferably, wherein the 3D glass ceramics contain SiO in mol% 2 And Al 2 O 3 The total amount is more than 60 percent; preferably 68-80%;
or alternatively, contains Na 2 O+Li 2 The content of O in mol% is 7-30%, preferably 10-26%.
Preferably, the 3D glass ceramics comprise nucleating agents, and the nucleating agents comprise P in terms of oxide, fluoride or elementary 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 3D glass ceramics comprise 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 original sheet of the 3D glass ceramic is a glass sheet which is subjected to nucleation and crystallization and has crystals with an average grain diameter of 5-50 nm.
Preferably, the crystallized glass original sheet of the 3D glass ceramic is a glass sheet having a crystallinity of 5 to 90 wt% after nucleation and crystallization.
Preferably, the drop height of the 3D glass ceramics after chemical strengthening is more than 1.5m, and preferably, the Vickers hardness of 300N force load 10s is more than 650.
The invention also provides a preparation method of the 3D glass ceramics, 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: cutting the crystallized glass substrate according to the requirement to obtain a crystallized glass raw material;
and 5: 3D hot bending treatment is carried out on the crystallized glass raw material to obtain a 3D microcrystalline glass sample;
wherein the 3D hot bending treatment process in the step 5 is also accompanied by a crystallization treatment process.
Preferably, the method further comprises the step of subjecting the 3D glass ceramic sample to chemical strengthening treatment to obtain a 3D glass ceramic finished product.
Preferably, wherein, 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 melting time is 1 to 5 hours; preferably, the crystallization treatment is carried out after the temperature is preserved for 5-300min at the temperature of 500-900 ℃ in the step 3; preferably, in the step 3, one or more of trimming, CNC machine processing, rough grinding and/or polishing treatment is performed to obtain the crystallized glass raw material.
Preferably, the amount of the nucleating agent added in the step 1 is 1 to 9 mol% of the total amount of the nucleating agent and the microcrystalline glass oxide, and the amount of the nucleating agent is 2 to 5 mol%.
Preferably, the amount of the added refining agent in the step 1 is 0-4 wt%, preferably 0.1-2 wt% of the total mass of the nucleating agent and the microcrystalline glass oxide.
Preferably, in the step 2, the temperature of the nucleation treatment is 450-800 ℃, and the time of the nucleation treatment is 30-360 min; more preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is 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.
Preferably, the hot-bending process in step 5 includes a preheating station, a hot-pressing station and a cooling station.
Preferably, the number of the preheating work stations is 1-30, preferably 2-4; 1-30 hot pressing stations, preferably 1-3 hot pressing stations; the number of the cooling stations is 1-30, preferably 2-4.
Preferably, wherein the temperature of the preheating station is 300-850 ℃; the temperature of the hot pressing station is 600-920 ℃, and the pressure is 0-6 MPa; the temperature of the cooling station is 200-650 ℃.
Preferably, the working time of the preheating work station is 20-800 seconds; the working time of the hot-pressing work station is 20-800 seconds, and the working time of the cooling work station is 20-800 seconds;
preferably, the working time of the preheating work station is 60-600 seconds; the working time of the hot-pressing work station is 60-480 seconds, and the working time of the cooling work station is 60-600 seconds.
The invention also provides the 3D glass ceramics prepared by the preparation method.
Preferably, the 3D glass-ceramic is characterized in that the 3D glass-ceramic is transparent or opaque; preferably, the 3D glass ceramics are curved surfaces or plane surfaces.
The invention also provides application of the 3D glass ceramics or the 3D glass ceramics of claim 24 or claim 25 in mobile phone display screens, tablet computer display screens, handheld game machines, electronic terminals, portable digital devices, vehicle-mounted central control screens, electronic white board glasses, smart home touch screens, vehicle windshield glasses, aircraft windshield glasses or aircraft windshield glasses.
The invention has the beneficial effects that:
1. according to the invention, the 3D hot bending is carried out by adopting the partially crystallized microcrystalline glass, 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 hot-bent 3D microcrystalline glass is higher. The preparation method of the 3D glass ceramics has the advantages of low processing difficulty, low processing cost, time and cost saving and energy saving in heat treatment. The partially crystallized microcrystalline glass is adopted for 3D hot bending, and the problem of repeated crystallization during 3D hot bending of the existing microcrystalline glass with high crystallinity or complete crystallization is solved.
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 the partially crystallized microcrystalline glass for flat grinding and polishing, the hardness is lower than that of the completely crystallized microcrystalline glass, 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 3D microcrystalline glass is improved, and the optical performance of the microcrystalline glass after being thermally bent is greatly reduced due to the fact that the softening and forming temperature of the existing completely-crystallized microcrystalline glass is generally over 700 ℃, the problem of excessive crystallization exists because crystals in the microcrystalline glass continue to grow up and the rest glass body is crystallized again in the thermal bending process of over 700 ℃. The optical performance of the 3D glass ceramics is that the average transmittance of light with the wavelength of 380-780nm is 88-93%, the average transmittance of light with the wavelength of 360-400nm is 65-91.5%, and the absolute value of the b value (yellow-blue value) when the thickness of the 3D glass ceramics is 0.7mm is 0.1-3.5.
4. The control rate of the dimensional accuracy of the 3D glass ceramics is improved. The partially crystallized microcrystalline glass is adopted for 3D hot bending, the glass is heated and continuously crystallized to reach the target crystallinity, although the glass can deform during hot bending crystallization in the process, the deformation is reduced due to the reduction of the crystallization process during 3D hot bending, and the size precision of the 3D microcrystalline glass after hot bending is favorably controlled.
5. The yield of the 3D glass ceramics 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 partially crystallized glass ceramics are adopted for 3D hot bending, the crystallinity is relatively high, the crystal growth amount is less in the hot bending process, and the influence of variable factors is reduced, so that the stability of the 3D glass ceramics of 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 piece 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 provides 3D glass ceramics which are characterized in that the crystallinity of the 3D glass ceramics is 14-100 wt%; the average grain diameter of the crystals of the 3D glass ceramics is 10-100 nm.
Preferably, the crystallinity of the 3D glass ceramics is 14-30 wt%, or the crystallinity of the 3D glass ceramics is 50-100 wt%; or the crystallinity of the 3D glass ceramics is 31-49 wt%; or the crystallinity of the 3D glass ceramics is 10-20 wt%; 21-30 wt%; 31-40 wt%; 41-50 wt%; 51-60 wt%; 61-70 wt%; 71-80 wt%; 81-90 wt%; 91-100 wt%.
Or the average grain diameter of the crystals of the 3D glass ceramics is 15-30 nm;
or the thickness of the 3D glass ceramics is 0.02-5mm, and preferably, the thickness of the 3D glass ceramics is 0.35-1.2 mm.
Preferably, the average transmittance of the 3D glass ceramics for light with wavelength of 380-780nm is 88-93%, preferably 90-91.5%;
or the average transmittance of the 3D glass ceramics at the wavelength of 360-400nm is 65-91.5%, preferably 79-91%, and more preferably 85-91%.
Preferably, the absolute value of the b value (yellow-blue value) of the 3D glass ceramics with the thickness of 0.7mm is 0.1-3.5, preferably 0.3-1.5;
alternatively, the haze of the 3D glass ceramics is 0.07-1.0%, preferably 0.07-0.5%.
Preferably, the crystalline phase of the 3D glass ceramics is one or more of lithium silicate, lithium disilicate, β -quartz solid solution, petalite, β -spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesium aluminate spinel and rutile.
Preferably, the 3D glass ceramics contain 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.
Preferably, wherein, theThe 3D glass ceramics contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60 percent; preferably 68-80%;
or, contain Na 2 O+Li 2 The content of O in mol% is 7-30%, preferably 10-26%.
Preferably, the 3D glass ceramics comprise nucleating agents, and the nucleating agents comprise P in terms of oxides, fluorides or simple substances 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 3D glass ceramics comprise 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 original sheet of the 3D glass ceramic is a glass sheet which is subjected to nucleation and crystallization and has crystals with an average grain diameter of 5-50 nm.
Preferably, the crystallized glass original sheet of the 3D glass ceramics is a glass sheet having a crystallinity of 5 to 90 wt% after nucleation and crystallization, and preferably, the crystallinity is 5 to 10 wt%, 11 to 15 wt%, 16 to 20 wt%, 21 to 25 wt%, 26 to 30 wt%, 31 to 35 wt%, 36 to 40 wt%, 41 to 45 wt%, 46 to 50 wt%, 51 to 55 wt%, 56 to 60 wt%, 61 to 65 wt%, 66 to 70 wt%, 71 to 75 wt%, 76 to 80 wt%, 81 to 85 wt%, 86 to 90 wt%, 91 to 95 wt%, 96 to 100 wt%, 15 to 29 wt%, 30 to 75 wt%, 76 to 90 wt%, and/or 30 to 55 wt%.
Preferably, the drop height of the 3D glass ceramics after chemical strengthening is more than 1.5m, and the Vickers hardness of 300N force load 10s is more than 650.
When the thickness of the 3D glass ceramics is 0.65mm, after chemical strengthening, the falling height of the complete machine which bears the load of 160g and falls on the bottom plate with the medium made of marble is more than 1.5m, and preferably, the Vickers hardness of the 3D glass ceramics under the load of 300N force of 10s is more than 650.
The invention also provides a preparation method of the 3D glass ceramics, 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;
step 2: 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 step 3: crystallizing the nucleated glass substrate obtained in the step 2;
and 4, step 4: cutting the crystallized glass substrate according to the requirement to obtain a crystallized glass raw material;
and 5: 3D hot bending treatment is carried out on the crystallized glass raw material to obtain a 3D microcrystalline glass sample;
wherein the 3D hot bending treatment process in the step 5 is also accompanied by a crystallization treatment process.
Wherein, in steps 4 and 5, the crystallized glass material may be a partially crystallized glass material.
Preferably, the method further comprises the step of subjecting the 3D glass ceramic sample to chemical strengthening treatment to obtain a 3D glass ceramic finished product.
Preferably, wherein, 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 melting time is 1 to 5 hours; preferably, the crystallization treatment is carried out after the temperature is preserved for 5-300min at the temperature of 500-900 ℃ in the step 3; preferably, in the step 3, one or more of trimming, CNC machine processing, rough grinding and/or polishing treatment is performed to obtain the crystallized glass raw material.
Preferably, the amount of the added nucleating agent in the step 1 is 1 to 9mol percent of the total amount of the nucleating agent and the microcrystalline glass oxide, and the amount of the nucleating agent is 2 to 5mol percent.
Preferably, the amount of the added refining agent in the step 1 is 0-4 wt%, preferably 0.1-2 wt% of the total mass of the nucleating agent and the microcrystalline glass oxide.
Preferably, in the step 2, the temperature of the nucleation treatment is 450-800 ℃, and the time of the nucleation treatment is 30-360 min; more preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is 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.
Preferably, the hot bending process in step 5 includes a preheating station, a hot pressing station and a cooling station.
Preferably, the number of preheating stations is 1-30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30; preferably 2 to 4; the number of the hot pressing stations is 1-30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 and 30; preferably 1 to 3; the cooling stations comprise 1 to 30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30; preferably 2-4.
Preferably, wherein the temperature of the preheating station is 300-850 ℃; the temperature of the hot pressing station is 600-920 ℃, and the pressure is 0-6 MPa; the temperature of the cooling station is 200-650 ℃.
Preferably, the working time of the preheating work station is 20-800 seconds; the working time of the hot-pressing work station is 20-800 seconds, and the working time of the cooling work station is 20-800 seconds;
preferably, the working time of the preheating work station is 60-600 seconds; the working time of the hot-pressing work station is 60-480 seconds, and the working time of the cooling work station is 60-600 seconds.
The invention also provides the 3D glass ceramics prepared by the preparation method.
Preferably, the 3D glass-ceramic is characterized in that the 3D glass-ceramic is transparent or opaque; preferably, the 3D glass ceramics are curved or planar.
The invention also provides application of the 3D glass ceramics or the 3D glass ceramics of claim 24 or claim 25 in mobile phone display screens, tablet computer display screens, handheld game machines, electronic terminals, portable digital devices, vehicle-mounted central control screens, electronic white board glasses, smart home touch screens, vehicle windshield glasses, aircraft windshield glasses or aircraft windshield glasses.
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 both 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: respectively measuring the transmittances of 360nm, 370nm, 380nm, 390nm and 400nm, wherein the number of the measured transmittances of 360 and 400nm is 5, and the sum of the transmittances is divided by 5 to obtain the average transmittance of 360 and 400 nm;
nucleation: the nucleating substances in the glass grow into crystal nuclei with the length of about 5nm through heat treatment;
crystallization: the glass grows a certain crystal on the basis of the crystal nucleus through heat treatment;
average crystal particle diameter: based on the average value of the grain lengths in the 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. The magnification in the measurement in the example of the present invention was 50 ten thousand times.
b value: the yellow-blue value of the material is represented, the b value in the invention is the b value of transmitted light, and the b value is positive, so 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 3D glass ceramics when the thickness is 0.65mm is that the absolute value of the b value under a D65 light source is 0.1-3.5, and the preferred absolute value of the b value under a D65 light source is 0.3-1.5; the light transmittance at a wavelength of 360nm is 80% or more, preferably 85% 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 the partially crystallized microcrystalline glass is crystallized by hot bending, the crystallization speed is controllable, which is beneficial to growing crystals with the grain diameter of less than 100nm, and the average grain diameter of the precipitated crystals can be ensured to be 10-100nm by controlling the process, so that the optical performance of the 3D microcrystalline glass is improved;
in other specific embodiments, the partially crystallized glass ceramic is subjected to crystallization and 3D bending simultaneously in a 3D bending process, the bending time is generally within 30min, and some examples show that the partially crystallized glass ceramic can reach a crystallinity of 80 wt% or more by 10-20min of 3D bending in a suitable process, and the optical properties meet the requirements.
The crystalline phase of the 3D glass ceramics 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, magnesia-alumina spinel, rutile and the like.
In order that the invention may be better understood, reference will now be made to the following examples which illustrate the 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. To cite this.
TABLE 2 Hot bending Process tables in examples and comparative examples
Example 13D method of making microcrystalline glass:
step 1: preparing and weighing raw materials for preparing 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% of P) 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 formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1650 ℃, the melting time is 5h, and the raw materials are poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 620 ℃, then 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 760 ℃, 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 at 790 ℃ for 10min to obtain a partially crystallized glass brick;
and 4, step 4: and (3) trimming the partially crystallized glass brick by using a grinding and polishing machine, cutting the trimmed 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 x 75 x 0.65mm by using a CNC machine tool, and respectively performing coarse grinding and polishing treatment by using a flat grinder and a polishing machine to obtain partially crystallized glass raw pieces, wherein the crystallinity of the partially crystallized glass raw pieces is 10 wt% according to determination.
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. 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 transmittance at the wavelength of 360nm is 76.30%, the light average transmittance at the wavelength of 380-780nm is 88.20%, the light average transmittance 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 kept for 8 hours, and finally the 3D glass ceramics finished product 1 is obtained.
Example 23D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing 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 melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1650 ℃, the melting time is 5h, and the melting and forming treatment is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 1;
step 4 trimming, cutting into pieces, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 13 wt% by determination;
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%.
And 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 33D method for making microcrystalline glass:
step 1: preparing raw materials for preparing the 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 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 die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 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 3, 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 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 9 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 3 was obtained by the hot bending process (refer to example 1) with number 1 in table 2.
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 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 43D method for making microcrystalline glass:
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 melting and forming treatment is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 to preserve the temperature for 5 hours at the temperature of 610 ℃, and reduce the temperature 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 720 ℃, 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 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 were carried out in the same manner as in example 1, and then the crystallinity was measured to be 11 wt%.
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%.
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 7 hours, and a 3D glass ceramic finished product 4 is finally obtained.
Example 53D method for making microcrystalline glass:
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%, nucleating agent (1.68% P) 2 O 5 ；1.30％ZrO 2 ) And 0.4 wt% of NaCl and 0.4 wt% of SnO based on the total mass of the nucleating agent and the preparation raw materials 2 1713.6g of total weight of the raw materials serving as a clarifying agent 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 die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 4;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 16% by weight.
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 setup conditions as in example 1, wherein the 3D glass-ceramic sample 5 had a crystallinity of 33 wt% after hot bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle size 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 transmission rate at the wavelength of 360nm is 72.00 percent, the light average transmission rate at the wavelength of 380-780nm is 88.90 percent, the light average transmission rate at the wavelength of 360-400nm is 78.60 percent, and the haze is 0.54 percent.
Example 63D method of making a microcrystalline glass:
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 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 1713.6g 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 temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 12 wt%.
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. The absolute value of the b value is 3.4 when the light source is limited to D65; 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 73D method for producing microcrystalline glass:
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/TP310S austenitic chromium nickel stainless steel 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, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 17% by weight.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 1 in table 2 (refer to example 1) was employed to obtain a 3D glass ceramic 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.
And 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 9 hours, and a 3D glass ceramic finished product 7 is finally obtained.
Example 83D microcrystalline glass manufacturing method:
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 66.95％；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 NaCl which accounts for 0.7 wt% of the total mass of the nucleating agent and the preparation raw material, wherein 1711.9g 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 temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 precise annealing furnace for nucleation; the temperature of the nucleation treatment is 715 ℃, 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 820 ℃, and the time of the crystallization treatment is 10min to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 28 wt%.
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 glass ceramic sample 8 is 2.90; the light transmission rate at the wavelength of 360nm is 76.11 percent, the light average transmission rate at the wavelength of 380-780nm is 88.10 percent, the light average transmission rate at the wavelength of 360-400nm is 78.80 percent, and the haze is 0.63 percent.
Example 93D method for producing microcrystalline glass:
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 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the glass brick;
step 2 and step 3 are the same as in example 8;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was measured to be 19 wt%.
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-ceramic sample 9 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 9 had a crystallinity of 32 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals 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 transmittance at the wavelength of 360nm is 82.10%, the light average transmittance at the wavelength of 380-780nm is 89.40%, the light average transmittance at the wavelength of 360-400nm is 85.20%, and the haze is 0.21%.
Example 103D method for producing microcrystalline glass:
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 placed in a high-temperature lifting furnacePerforming medium melting molding, wherein the temperature of the melting molding treatment is 1630 ℃, the melting time is 5 hours, and pouring the glass brick into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 was the same as in 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 were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 20% by weight.
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 transmission rate at the wavelength of 360nm is 81.13%, the light average transmission rate at the wavelength of 380-780nm is 89.60%, the light average transmission rate at the wavelength of 360-400nm is 82.80%, and the haze is 0.19%.
Example 113D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the 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 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 1630 ℃, the melting time is 5 hours, and the mixture is poured into ASTM SA213/TP310S austenitic chromium nickelObtaining a glass brick in a stainless steel mold;
step 2 and step 3 were the same as in example 10;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 21 wt%.
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. When the light source is defined as D65, the absolute value of the b value is 1.10; 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 123D method of making a microcrystalline glass:
step 1: preparing raw materials for preparing the 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 percent; 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, 1711.9g of the total weight 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 5h, and the mixture is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 25 wt%.
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 ceramics sample 12 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 12 had a crystallinity of 43 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. When the light source is defined as D65, the absolute value of the b value is 1.15; the light transmittance at the wavelength of 360nm is 83.68%, the light average transmittance at the wavelength of 380-780nm is 90.56%, the light average transmittance at the wavelength of 360-400nm is 86.30%, and the haze is 0.17%.
Step 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 133D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 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 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the 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 precise 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, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 18% by weight.
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 ceramics sample 13 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 13 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 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 143D microcrystalline glass manufacturing method:
step 1: preparing raw materials for preparing the 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 The clarifier is prepared by mixing above raw materials 1711.9g, melting in high temperature furnace at 1630 deg.C for 5 hr, and pouring into ASTM SA213/TP310S austenitic chromium-nickel stainless steelObtaining a glass brick in the mould;
step 2 is the same as in example 13;
step 3 is the same as in example 1;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 35 wt%.
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 153D microcrystalline glass production method:
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 ) 1710.2g of the total weight of the raw materials, namely fully mixing, then melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 690 ℃, 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 750 ℃, and the time of the crystallization treatment is 30min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 32% by weight.
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 setting conditions as in example 1, wherein the 3D glass-ceramic sample 15 had a crystallinity of 53 wt% after being thermally bent, 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 transmittance at the wavelength of 360nm is 85.22%, the light average transmittance at the wavelength of 380-780nm is 91.20%, the light average transmittance at the wavelength of 360-400nm is 87.50%, and the haze is 0.16%.
Example 163D method for producing microcrystalline glass:
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 1710.2g 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 1620 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 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 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 40 wt%.
And 5: 3D hot bending treatment is carried out on a part of crystallized glass sheet, 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 work stations, 3 hot pressing work stations and 2 cooling work 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 setup conditions as in example 1, wherein the 3D glass-ceramic sample 16 had a crystallinity of 60 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. The absolute value of b is 0.62 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 86.02%, 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 88.10%, and the haze is 0.17%.
And 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 kept for 11 hours, and finally the 3D glass ceramics finished product 16 is obtained.
Example 173D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the 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 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 die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 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, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 78 wt%.
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 transmittance at the wavelength of 360nm is 84.32 percent, the light average transmittance at the wavelength of 380-780nm is 90.80 percent, the light average transmittance at the wavelength of 360-400nm is 86.40 percent, and the haze is 0.16 percent.
Example 183D method for producing microcrystalline glass:
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 1708.5g of the total weight of the raw materials are fully mixed, then are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 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 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 120min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 72 wt%.
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 13 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 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.
And (3) detecting the 3D glass-ceramic sample 18, 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 crystallinity of the 3D glass-ceramic sample 18 after being subjected to thermal bending is 92 wt%, the precipitated crystal phase is lithium disilicate and petalite, and the average grain size of the crystal is 18 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 87.17 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 90.30 percent, and the haze is 0.11 percent.
Example 193D method for making a microcrystalline glass:
steps 1-2 are the same as those of example 18;
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 630 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 60 wt% by determination;
and 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 19 was obtained by the hot bending process (see example 18) with number 13 in table 2.
The 3D glass ceramics sample 19 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 19 had a crystallinity of 86 wt% after thermal bending, and the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystal 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 203D method for producing microcrystalline glass:
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 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, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 51 wt% after determination;
and 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process (see example 18) numbered 13 in table 2 was used to obtain a 3D glass ceramic sample 20.
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 setup conditions as in example 1, wherein the 3D glass-ceramic sample 20 had a crystallinity of 73 wt% after hot bending, 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 0.58 when the light source is defined as 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 213D method for producing microcrystalline glass:
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 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 were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 30% by weight,
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-ceramic sample 21 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 21 had a crystallinity of 65 wt% after hot bending, the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 25 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 85.14%, the light average transmittance at the wavelength of 380-780nm is 91.60%, the light average transmittance at the wavelength of 360-400nm is 88.10%, and the haze is 0.15%.
Example 223D method for making microcrystalline glass:
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 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 are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 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 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 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 39 wt%.
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 measured to be 0.42 when the light source is limited to 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 kept for 9 hours, and finally the 3D glass ceramics finished product 22 is obtained.
Example 233D method for producing microcrystalline glass:
step 1: preparation of glass weighing raw materials (molar percentage comprising the following group)Dividing into: SiO 2 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 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.5 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1550 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 545 ℃, 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 at the temperature of 610 ℃ for 200min to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 45 wt%.
And 5: 3D hot bending treatment is carried out on a part of crystallized glass original sheets, and a hot bending process (refer to example 22) with the serial number of 15 in Table 2 is adopted to obtain a 3D microcrystalline glass sample 23;
the 3D glass ceramics sample 23 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 23 had a crystallinity of 92 wt% after thermal 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.
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 example 22 to finally obtain a 3D glass ceramics finished product 23.
Example 243D method for making microcrystalline glass:
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 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.5 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1550 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 43 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts a hot bending process with the serial number of 14 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 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 (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 24.
Example 253D method of making a microcrystalline glass:
step 1: preparing raw materials for preparing the 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 are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 ℃, keeping the temperature for 5 hours, and reducing the temperature to 30 ℃ at 1 ℃/min), and carrying out XRD test on the obtained annealed glass brick to obtain a figure 1, wherein the 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 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 47 wt%. 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 partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 25 was obtained by the hot bending process (see example 24) with reference number 14 in table 2.
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) the solution is subjected to the treatment for 10 hours, and finally a 3D glass ceramic finished product 25 is obtained.
Example 263D microcrystalline glass production method:
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％，ZnO1.68％，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 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 is1708.5g, fully mixing, 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 die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 is the same as in example 25;
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 615 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 55 wt%. 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 partially crystallized glass original piece was subjected to 3D hot bending treatment, and a hot bending process (see example 22) numbered 15 in table 2 was used to obtain a 3D microcrystalline glass 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 measured to be 0.42 when the light source is limited to 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 273D method of making microcrystalline glass:
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 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 480 ℃, and the time of the nucleation treatment is 360 min;
and 3, 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 were carried out in the same manner as in example 1, and then the crystallinity was determined to be 6% by weight.
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 3D glass ceramics sample 27 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 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 the b value of the 3D microcrystalline glass 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 283D method of making microcrystalline glass:
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 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 precise annealing furnace, wherein the temperature of the crystallization treatment is 570 ℃, and the time of the crystallization treatment is 280min, so as to obtain a partially crystallized glass brick;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was measured to be 8 wt%.
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 the b value of the 3D microcrystalline glass sample 28 is 0.25; the light transmission rate at the wavelength of 360nm is 90.10 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 91.20 percent, and the haze is 0.09 percent.
Example 293D microcrystalline glass preparation method:
step 2 was the same as in example 28;
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 560 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 9 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the sequence number of 1 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 28.
The 3D glass ceramics sample 29 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 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 transmission rate at the wavelength of 360nm is 90.50 percent, the light average transmission rate at the wavelength of 380-780nm is 92.70 percent, the light average transmission rate at the wavelength of 360-400nm is 91.50 percent, and the haze is 0.08 percent.
Example 303D method for producing microcrystalline glass:
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 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 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 37 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the sequence number of 3 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 30. 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.
And (3) detecting the 3D microcrystalline glass sample 30, 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 microcrystalline glass sample 30 after being subjected to hot bending is 75 wt%, the precipitated crystal phase is petalite + beta-quartz solid solution, and the average grain size of the crystal is 18 nm. The absolute value of b is measured to be 0.35 when the light source is limited to 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 313D method for producing a crystallized glass:
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 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 800 ℃, and the time of the nucleation treatment is 30 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 870 ℃, and the time of the crystallization treatment is 15min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were performed in the same manner as in example 1, and then the crystallinity was determined to be 88 wt%.
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 the b value is measured to be 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 323D method for producing microcrystalline glass:
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 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 900 ℃, and the time of the crystallization treatment is 5min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 58 wt%.
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 instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 32 had a crystallinity of 98 wt% after hot bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 81 nm. The absolute value of b is 2.80 when the light source is defined as 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 333D method for producing microcrystalline glass:
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 ) The glass brick is prepared by the following steps of mixing 1713.5g of raw materials, melting and molding in a high-temperature lifting furnace at 1650 ℃ for 5h after fully mixing, and pouring the mixture into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick, wherein NaCl accounts for 0.8 wt% of the total mass of the nucleating agent and the prepared raw materials;
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 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 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 820 ℃, and the time of the crystallization treatment is 30min, so as to obtain the glass brick after partial crystallization treatment;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 90 wt%.
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 33.
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 transmittance at the wavelength of 360nm is 63.10 percent, the light average transmittance at the wavelength of 380-780nm is 88.20 percent, the light average transmittance at the wavelength of 360-400nm is 65.40 percent, and the haze is 0.98 percent.
Example 343D microcrystalline glass production method:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 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 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 4h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel 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 620 ℃, and the time of the nucleation treatment is 240 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 650 ℃, and the time of the crystallization treatment is 40min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 68 wt%.
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 34.
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 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 353D method of producing a crystallized glass:
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 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 4h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 35;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 82 wt%.
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 ceramics sample 35 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 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 crystal was 42 nm. The absolute value of b is measured to be 0.68 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 85.42%, the light average transmittance at the wavelength of 380-780nm is 91.10%, the light average transmittance at the wavelength of 360-400nm is 87.20%, and the haze is 0.19%.
Example 363D method of making microcrystalline glass:
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 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 3h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel 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 were carried out in the same manner as in example 1, and then the degree of crystallinity was measured to be 63 wt%.
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 373D microcrystalline glass production method:
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;
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 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 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 600 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 75 wt%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 37 by adopting a hot bending process with the serial number 6 in the table 2.
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 illuminant 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 383D method of making microcrystalline glass:
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 20 in the table 2; the hot bending treatment comprises 3 preheating work stations, 4 hot pressing work stations and 2 cooling work 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 setup conditions as in example 1, wherein the 3D glass ceramics sample 22F had a crystallinity of 84 wt% after hot bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystal 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 393D microcrystalline glass manufacturing method:
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. 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 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 work station, the hot pressing work station and the cooling work station is the same and is 140s, and the 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 setting conditions as in example 1, wherein the 3D glass ceramics sample 22G had a crystallinity of 90 wt% after thermal bending, and 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 13D method for producing crystallized glass:
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 formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 23D method for producing microcrystalline glass:
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 formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chrome-nickel stainless steel to obtain a glass brick;
step 2: crystals are separated out from the central part of the glass brick obtained in the step 1 in the process of cooling to 800 ℃, and the glass brick is cracked and cannot be machined due to the stress difference inside the glass brick.
Comparative example 33D method for producing microcrystalline glass:
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 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.8 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the 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 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 43D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing 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 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 total weight 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 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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 53D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the 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 total weight 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 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel 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; the uncontrollable crystallization of the glass brick after the nucleation treatment due to the over-high nucleation temperature and the stress difference in the glass brick cause the glass brick to break and the subsequent treatment and processing can not be carried out.
Comparative example 63D method for producing microcrystalline glass:
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 16 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 480 ℃, 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 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 instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 22B had a crystallinity of 100 wt% after hot bending, a precipitated crystal phase of β -spodumene + lithium disilicate, and an average particle diameter of the crystal was 111 nm. The absolute value of b is 7.45 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 64.10%, the light average transmittance at the wavelength of 380-780nm is 86.50%, the light average transmittance 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 73D method for producing microcrystalline glass:
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 process 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 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 transmission rate at the wavelength of 360nm is 62.40 percent, the light average transmission rate at the wavelength of 380-780nm is 87.30 percent, the light average transmission rate 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 bluish, and imaging is affected.
Comparative example 83D method for producing microcrystalline glass:
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 18 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 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 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 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 93D method for producing microcrystalline glass:
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 work stations, 3 hot pressing work stations and 2 cooling work stations. 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 on 3D glass ceramics obtained by chemically strengthening the above-described examples 1,2, 4, 7, 12, 16, 22,23,24 and 25, and the test glass thickness was 0.65, and the results of the tests are shown in table 3.
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 measured by the SLP-2000 stress meter is divided by the thickness of the glass.
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;
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 tested sample under the action of a load of 300N, removing the load after keeping for 10s, measuring the diagonal length d 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, in the embodiment, the surface compressive stress of the chemically strengthened 3D glass ceramic finished product 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 for 10s) of the chemically strengthened 3D glass ceramic finished product 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 (26)
1. The 3D glass ceramics is characterized in that the crystallinity of the 3D glass ceramics is 14-100 wt%; the average grain diameter of the crystals of the 3D glass ceramics is 10-100 nm.
2. The 3D glass ceramic according to claim 1, wherein the 3D glass ceramic has a crystallinity of 14 to 30 wt%, or the 3D glass ceramic has a crystallinity of 50 to 100 wt%; or the crystallinity of the 3D glass ceramics is 31-49 wt%;
or the average grain diameter of the crystals of the 3D glass ceramics is 15-30 nm;
or the thickness of the 3D glass ceramics is 0.02-5mm, and preferably, the thickness of the 3D glass ceramics is 0.35-1.2 mm.
3. The 3D glass ceramic according to claim 1 or 2, wherein the 3D glass ceramic has an average transmittance of light with wavelength of 380-780nm of 88-93%, preferably 90-91.5%;
or the average transmittance of the 3D glass ceramics at the wavelength of 360-400nm is 65-91.5%, preferably 79-91%, and more preferably 85-91%.
4. The 3D glass ceramic according to any one of claims 1-3, wherein the absolute value of the b-value (yellow-blue value) at a thickness of 0.7mm of the 3D glass ceramic is 0.1-3.5, preferably 0.3-1.5;
alternatively, the haze of the 3D glass ceramics is 0.07-1.0%, preferably 0.07-0.5%.
5. The 3D glass ceramic according to any one of claims 1-4, wherein the crystalline phase of the 3D glass ceramic is one or more of lithium silicate, lithium disilicate, β -quartz solid solution, petalite, β -spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesium aluminate spinel and rutile.
6. The 3D glass ceramic according to any one of claims 1-5, wherein the 3D glass ceramic contains oxides 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.
7. The 3D glass ceramic according to claim 6, wherein the 3D glass ceramic contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60%; preferably 68-80%;
or alternatively, contains Na 2 O+Li 2 The content of O in mol% is 7-30%, preferably 10-26%.
8. The 3D glass ceramic according to any one of claims 1-7, wherein the 3D glass ceramic comprises a nucleating agent, the 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.
9. The 3D glass ceramic according to any one of claims 1-8, wherein the 3D glass ceramic comprises a fining agent, the fining agent comprising 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.
10. The 3D glass ceramic according to any one of claims 1 to 9, wherein the crystallized glass material of the 3D glass ceramic is a glass material having crystals with an average particle size of 5 to 50nm after nucleation and crystallization.
11. The 3D glass ceramic according to any one of claims 1 to 9, wherein the crystallized glass raw material of the 3D glass ceramic is a glass material having a crystallinity of 5 to 90 wt% after nucleation and crystallization.
12. The 3D glass ceramic according to any one of claims 1-11, wherein the 3D glass ceramic has a drop height > 1.5m after chemical strengthening, preferably a Vickers hardness of greater than 650 at 300N force load of 10 s.
13. The method for producing 3D glass-ceramic according to any of claims 1 to 12, wherein the production method 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: cutting the crystallized glass substrate as required to obtain a crystallized glass raw material;
and 5: 3D hot bending the crystallized glass raw material to obtain a 3D microcrystalline glass sample;
wherein the 3D hot bending treatment process in the step 5 is also accompanied by a crystallization treatment process.
14. The method as claimed in claim 13, wherein the melting temperature in step 1 is 1350-; preferably, the melting temperature is 1400-1650 ℃; more preferably, cooling to 500-; further preferably, the method may further include the step of performing chemical strengthening treatment on the 3D glass ceramic sample to obtain a 3D glass ceramic finished product.
15. The method according to claim 13 or 14, wherein in step 1, the melting time is 1-5 hours; preferably, the crystallization treatment is carried out after the temperature is preserved for 5-300min at the temperature of 500-900 ℃ in the step 3; preferably, in the step 3, one or more of trimming, CNC machine processing, rough grinding and/or polishing treatment is performed to obtain the crystallized glass raw material.
16. The method according to any one of claims 13-15, wherein the amount of added nucleating agent in step 1 is 1-9 mol%, further preferred is 2-5 mol% of the total amount of nucleating agent and glass-ceramic oxide.
17. The method according to any of claims 13-16, wherein the amount of added refining agent in step 1 is 0-4 wt%, preferably 0.1-2 wt% of the total mass of nucleating agent and glass-ceramic oxide.
18. The method as claimed in any one of claims 13 to 17, wherein, in the step 2, the temperature of the nucleation treatment is 450-800 ℃, and 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 120-300 min.
19. The method as claimed in any one of claims 13 to 18, 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.
20. The method according to any one of claims 13 to 19, wherein the hot bending process in step 5 comprises a pre-heating station, a hot pressing station and a cooling station.
21. A method as claimed in claim 20, wherein the number of pre-heating stations is 1-30, preferably 2-4; 1-30 hot pressing stations, preferably 1-3 hot pressing stations; the number of the cooling stations is 1-30, preferably 2-4.
22. The method as claimed in claim 20 or 21, wherein the pre-heating station temperature is 300-850 ℃; the temperature of the hot pressing station is 600-920 ℃, and the pressure is 0-6 MPa; the temperature of the cooling station is 200-650 ℃.
23. The method of any of claims 20-22, wherein the pre-heat station is operated for a time of 20-800 seconds; the working time of the hot-pressing work station is 20-800 seconds, and the working time of the cooling work station is 20-800 seconds;
preferably, the working time of the preheating work station is 60-600 seconds; the working time of the hot-pressing work station is 60-480 seconds, and the working time of the cooling work station is 60-600 seconds.
24. 3D glass ceramics prepared by the preparation method of any one of claims 13 to 23.
25. The 3D glass-ceramic according to claim 24, wherein the 3D glass-ceramic is transparent or opaque; preferably, the 3D glass ceramics are curved surfaces or plane surfaces.
26. Use of the 3D glass ceramic according to any one of claims 1 to 12 or the 3D glass ceramic according to claim 24 or 25 in a display screen of a mobile phone, a display screen of a tablet computer, a handheld game console, an electronic terminal, a portable digital device, a vehicle central control screen, an electronic whiteboard glass, a smart home touch screen, a vehicle windshield, an aircraft windshield or an aircraft windshield.
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| CN202110099277.4A CN114790085A (en) | 2021-01-25 | 2021-01-25 | 3D glass ceramic 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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