WO2022241891A1 - 一种三维微晶玻璃及其制备方法 - Google Patents
一种三维微晶玻璃及其制备方法 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 91
- 230000008569 process Effects 0.000 claims abstract description 86
- 239000013078 crystal Substances 0.000 claims abstract description 30
- 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 abstract description 19
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052670 petalite Inorganic materials 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002241 glass-ceramic Substances 0.000 claims description 51
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000006064 precursor glass Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims 1
- 238000013003 hot bending Methods 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical class [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000012467 final product Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000006058 strengthened glass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
- C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- 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
- C03C4/00—Compositions for glass with special properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Definitions
- the invention relates to the field of glass manufacturing, in particular to a three-dimensional glass-ceramic and a preparation method thereof.
- Cover glass has gone through a development process from 2D to 2.5D to 3D. Compared with traditional 2.5D glass, ceramic cover and metal backplane, 3D glass has superior performance. 3D glass is expected to be widely used in 3C products such as smartphones, smart watches, tablet computers, dashboards and other wearable product screen covers and backplanes in the future. 3D glass is thin, transparent and clean, anti-fingerprint, anti-glare, and weather resistance It can not only enhance the novelty of the appearance of smart terminal products, but also bring excellent touch feel. Since smartphones have become a new generation of mobile terminal equipment, cover glass has become the standard configuration of most smartphones. In fact, the design concept and processing mode of cover glass are mainly based on the experience of the watch glass lens deep processing industry.
- 3D curved glass has a better appearance mode and better protection effect than 2D flat glass.
- the double-curvature 3D curved glass performs particularly well, and is obviously better than 2D flat glass in anti-drop, anti-scratch, and static pressure tests.
- OLED Organic Light Emitting Diode
- 3D glass covers with curved designs and matching curved screens will also shine.
- NFC near field communication technology
- WiFi wireless fidelity
- LIFI visible light wireless communication
- a smartphone with a 3D glass display and a 3D glass back could solve this problem very well.
- 3D glass also has the advantages of smooth feel, light and thin texture, transparent and clean, and prevents glare.
- Glass-ceramic also known as micro-crystalline jade or ceramic glass, is composed of a crystalline phase and a part of a glass phase, so it has dual characteristics of glass and ceramics.
- the crystal phase in the glass-ceramic guarantees the intrinsic strengthening mechanism of the classic glass-ceramic, and at the same time, the remaining glass phase of the glass-ceramic can also be chemically strengthened, thus endowing the glass-ceramic with high strength, high hardness, and high scratch resistance.
- glass-ceramic has a natural and soft texture, and can be controlled by composition and process to obtain rich and colorful colors. Therefore, the trend of glass-ceramic cover plates entering the market is beginning to appear.
- glass-ceramics has a considerable amount of crystal structure, compared with glass, its high-temperature softening effect is greatly reduced, and it has the brittleness of some ceramics, so it cannot be used for 3D hot bending process.
- the preparation of 3D curved glass-ceramic by polishing process has complicated process, low yield and high molding cost, which greatly hinders the application of glass-ceramic in the field of 3D cover material.
- the invention provides a low-cost and high-efficiency three-dimensional glass-ceramic preparation method and its products.
- the specific technical scheme of the present invention is: a preparation method of three-dimensional glass-ceramics, comprising the following steps:
- Step 1 raw material preparation, by weight percentage, weigh SiO 2 : 63-75%; Al 2 O 3 : 4-10%; TiO 2 : 0-4%; CaO: 0-1%; MgO: 0- 1%; Li 2 O:8-11%; Na 2 O:0.1-3%; K 2 O:0.1-1%; P 2 O 5 :1-5%; ZrO 2 :1-6%; BaO: 0-1%; Sb 2 O 3 : 0-2%; Y 2 O 3 : 0-0.5%, mix well;
- Step 2 Transfer the raw materials obtained in Step 1 to a platinum crucible, place the platinum crucible in a high-temperature furnace, gradually raise the temperature to 1500°C-1600°C, keep it warm for 2-24 hours, and undergo bubbling and homogenization treatment (bubbling The purpose is to bring out the small bubbles in the glass and eliminate the bubbles in the molten glass), after melting, pour the molten liquid into a preheated mold for molding, and then place it at 300-550°C for 2-12 hours of annealing treatment to obtain the precursor glass block;
- Step 3 CNC machining the precursor glass block obtained in Step 2 to obtain a precursor glass sheet;
- Step 4 Pre-crystallize the precursor glass flakes obtained in Step 3. Specifically, firstly at 540-590°C for 0.5-5h, then at 600-800°C for 0.5-2h to control glass pre-crystallization
- the crystallinity of the crystal is 10-46%
- the formed crystal is lithium disilicate, lithium silicate and/or lithium petalite, specifically lithium disilicate: 5-20wt%, lithium silicate 5-20wt%, transparent Lithium feldspar 0-6wt%.
- the hardness of the glass after pre-crystallization is controlled as: 5000-6500Kg/cm 2 , because a certain pressure needs to be applied in order to make the final product have a good molding effect in the subsequent hot bending process. If the hardness of the pre-crystallization glass is not controlled Hardness, easy to cause damage to the forming mold, so that the hardness value of the pre-crystallized glass is within this range, and the damage to the hot bending mold is minimal;
- Step 5 heat bending forming, the pre-crystallized glass sheet obtained in step 4 is preheated first, then shaped, and finally cooled. After cooling to room temperature, three-dimensional glass-ceramic can be obtained.
- the preheating treatment in the step 5 is divided into 6 process sections, the temperature of the first process section is 350-500°C; the temperature of the second process section is 440-580°C; the temperature of the third process section is 530-660°C °C; the temperature of the fourth process section is 590-670°C; the temperature of the fifth process section is 590-680°C; the temperature of the sixth process section is 620-650°C; the time of each process section is 90-150s.
- the forming stage in the step 5 is divided into 3 process sections, wherein the forming stage is divided into 3 process sections, wherein the temperature of the first process section is 690-780°C, and the pressure applied by the mold is 3-6Kg/cm 2 ;
- the temperature of the second process section is 740-800°C, the pressure applied by the mold is 5-7Kg/cm 2 ;
- the temperature of the third process section is 730-810°C, and the pressure applied by the mold is 8-9Kg/cm 2 ; each The time of the process section is 90-150s.
- applying pressure to the glass through the mold physically hinders the movement and expansion of the glass within the mold, thereby reducing the deformation of the glass during the crystallization process, and applying this pressure can allow the glass to be heated rapidly to the crystallization temperature.
- applying pressure to the glass via the mold may also allow crystallization to take place over a shorter duration.
- the pressurization is completed through one or more process sections, the residence time of each process section is 90-150s, and the mold pressure in the hot bending forming process is 3-9Kg/cm 2 . If the pressure is too low, the bending effect will not be enough. If the pressure is too high, graphite marks will remain on the surface of the glass after hot pressing.
- the hot bending forming temperature is 30°C-60°C above the temperature of the glass expansion and softening point; hot bending is completed through one or more process sections, each process section
- the residence time is 90-150s, and the bending temperature is preferably controlled at 720°C-820°C. If crystallization is performed at a higher temperature, a slight auxiliary pressure is applied to help prevent deformation of the glass during crystallization.
- the cooling stage in the step 5 is divided into 4 process sections, the temperature of the first process section is 720-800°C; the temperature of the second process section is 670-730°C; the temperature of the third process section is 550-630°C ; The temperature of the fourth process section is 550°C; the time of each process section is 90-150s. Finally, slowly cool back to room temperature at a rate of 0.1 °C/s-8 °C/s.
- the glass can be passively cooled from the crystallization temperature to room temperature by exposing the glass to an environment at room temperature.
- step 6 is also included: performing ion exchange strengthening treatment on the three-dimensional glass-ceramics obtained in step five.
- a salt bath of molten NaNO 3 at a temperature of 420° C. to 460° C. Ion exchange was performed for 12 hours; then the three-dimensional glass-ceramics was immersed in a salt bath of molten KNO 3 at a temperature of 400° C. to 460° C. for about 2 to 10 hours to perform ion exchange.
- a three-dimensional glass-ceramic the raw materials for which are expressed by mass fraction based on oxides, containing: SiO 2 : 63-75%; Al 2 O 3 : 4-10%; TiO 2 : 0-4%; CaO: 0 -1%; MgO: 0-1%; Li 2 O: 8-11%; Na 2 O: 0.1-3%; K 2 O: 0.1-1%; P 2 O 5 : 1-5%; ZrO 2 : 1-6%; BaO: 0-1%; Sb 2 O 3 : 0-2%; Y 2 O 3 : 0-0.5%, the content of finished glass crystals is: lithium disilicate: 30-45%; Lithium feldspar: 30-45%, can guarantee the transparency of three-dimensional glass-ceramics.
- the hardness of the three-dimensional glass-ceramic is not lower than 8500Kg/cm 2 .
- the Vickers hardness of the three-dimensional glass is preferably 11000Kg/ cm2 or less, more preferably 10500Kg/ cm2 or less, even more preferably 10000Kg/ cm2 or less.
- the average particle size of the crystal phase in the three-dimensional glass-ceramic is less than 100 nm, preferably, the average particle size of the crystal phase in the three-dimensional glass-ceramic is 20 nm to 70 nm.
- the flat glass is pre-crystallized and nucleated so that it has a crystallinity of 20%-40% and a grain size of 2-15nm. Then perform hot-bending forming treatment to obtain three-dimensional glass-ceramics.
- the hot bending forming step is arranged after the precrystallization, that is, the precrystallized glass product is placed in a hot bending mold for hot bending forming. Before the hot bending forming step, the glass-ceramic forms crystal nuclei, but the crystal phase has not yet grown up, the crystallinity is low, and the hardness is low, which is beneficial to hot bending forming.
- the present invention controls the temperature and time in the pre-crystallization process to produce a specific crystal transformation.
- the main crystal phase of the glass changes to Li 2 Si 2 O 5
- Lithium silicate in the final product is completely dissolved or has a small amount of residue, and the main crystal phase is lithium petalite and lithium disilicate.
- the three-dimensional glass-ceramics prepared by the technical solution of the present invention can also be ion-exchanged, so as to obtain toughened glass with higher strength.
- the three-dimensional glass-ceramic is placed in a NaNO 3 or KNO 3 salt bath for ion exchange.
- potassium-sodium or sodium-lithium unitary ion exchange can be performed, and potassium-sodium and sodium-lithium can also be performed.
- Mixed binary ion exchange large-diameter alkali metal ions are potassium and sodium ions, and small-diameter alkali metals are sodium and lithium ions.
- the small-diameter alkali metal ions in the glass are replaced by the large-diameter alkali metal ions in the salt bath, and the three-dimensional glass-ceramic produces composite compressive stress through the "crowding effect".
- the Vickers hardness of the strengthened product can reach 9000-11000Kg/cm 2 , and its haze is less than 0.15.
- the transmittance of the 8mm thick glass product at the wavelength of 400-800nm is over 85%.
- the three-dimensional glass-ceramic has high Vickers hardness and is not easily damaged.
- the crystal type and crystallinity at different stages have different ranges of hardness at different stages, so as to achieve the ideal mechanical strength of the final product and make the product in the production process.
- the resulting damage is kept to a minimum.
- the main crystal phases of the crystals precipitated in the precrystallization stage are lithium disilicate and lithium silicate, and the crystallinity is 20-40%.
- Lithium disilicate and lithium silicate The hardness is lower than that of the petalite feldspar precipitated in the final product, so the mold will not wear faster due to the excessive hardness of the pre-crystallized glass during the hot bending process, and the crystal main crystal precipitated from the hot bent glass
- the phases are petalite and lithium disilicate, and the crystallinity is in the range of 60-90%, so that the final product has ideal mechanical properties, and the control of the crystallinity of the pre-crystallization in the range of 20-40% can ensure that the thermal During the bending process, there will be no forming difficulties due to excessive crystallization, and it can also be guaranteed that the crystallinity of the final product will not reach the ideal range due to the low crystallization of the pre-crystallized glass, resulting in insufficient mechanical properties of the product.
- Adopting the technical scheme of the present invention avoids the problem that the 3D hot bending process cannot be performed due to the brittleness of some ceramics after the flat glass has undergone a relatively complete and thorough microcrystallization treatment, and avoids the crystallization after the amorphous glass is bent and shaped
- heat treatment is performed after forming, not only is it easy to deform, but also there is a problem that a dimensional change occurs when the amorphous glass is crystallized, making it difficult to obtain a desired shape.
- the technical solution of the present invention first conducts glass microcrystallization treatment on the plane to obtain a flat glass-ceramic, and then uses a polishing process to prepare the flat glass-ceramic into a 3D curved glass-ceramic.
- the above preparation process has the advantages of high yield and low process cost.
- Figure 1 is a schematic diagram of crystal formation principles corresponding to different process segments
- Fig. 2 is the XRD pattern analysis of the precrystallized glass that embodiment 1 makes;
- Fig. 3 is the XRD pattern analysis of the hot-bent glass that embodiment 1 makes;
- Fig. 4 is the transmittance spectrum in the range of 280-800nm of the three-dimensional glass-ceramic prepared in embodiment 1;
- Fig. 5 is a model diagram of the hot bending product of the present invention.
- the inventors of the present invention have repeatedly tested and studied, and for the specific components constituting the glass-ceramic product, by specifying its content and content ratio as a specific value and making it precipitate several specific crystal phases, it has been obtained at a relatively low cost.
- Glass-ceramics or glass products according to the invention Next, the composition range of each component of the glass ceramics of this invention is demonstrated.
- the content of each component is expressed in weight percent relative to the total amount of glass substances converted into oxides.
- the "composition converted into oxides” means that when the oxides, compound salts, etc. used as raw materials for the composition of the crystallized glass of the present invention are all decomposed and converted into oxides during melting, the The total amount of substances of this oxide is taken as 100%.
- the final required precursor glass obtained is firstly kept at 550° C. for 3 hours, and then at 660° C. for 2 hours for pre-crystallization treatment.
- the pre-crystallized glass is subjected to hot-bending processing.
- the preheating stage is first carried out.
- the preheating stage is divided into 6 process sections.
- the temperature of the first process section is 380°C; the second process
- the temperature of the third process section is 440°C; the temperature of the third process section is 530°C; the temperature of the fourth process section is 590°C; the temperature of the fifth process section is 610°C; the temperature of the sixth process section is 630°C;
- the dwell time of the segment is 120s. Then enter the molding stage.
- the molding stage is divided into 3 process sections, wherein the temperature of the first process section is 700°C, and the pressure applied by the mold is 4Kg/cm 2 ; the temperature of the second process section is 750°C, and the mold The applied pressure is 6Kg/cm 2 ; the temperature of the third process section is 740°C, and the pressure applied by the mold is 8Kg/cm 2 ; the residence time of each process section is 120s.
- the cooling stage of this embodiment is divided into 5 process sections, the temperature of the first process section is 730°C; the temperature of the second process section is 680°C; the temperature of the third process section is 640°C; the fourth process section The temperature of the first section is 590°C; the temperature of the fifth process section is 550°C; the residence time of each process section is 120s.
- the shaped glass product was immersed in molten salt of NaNO 3 at 430°C for 7 hours, and then kept in molten salt of KNO 3 at 450°C for 3 hours to perform ion exchange to obtain the final product.
- the main crystal phase of the final product is Lithium feldspar and lithium disilicate, the transmittance of the product is 90%, the hardness after pre-crystallization is 560MPa; the hardness of the hot-bending glass is 870MPa; the hardness of the strengthened glass is 1020MPa, and the CS value of the strengthened glass is 400MPa , DOC is 10 ⁇ m.
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Abstract
Description
Claims (10)
- 一种三维微晶玻璃,其特征在于其制备原料以氧化物基准的质量分数表示,含有:SiO 2:63-75%;Al 2O 3:4-10%;Li 2O:8-11%;Na 2O:0.1-3%;K 2O:0.1-1%;P 2O 5:1-5%;ZrO 2:1-6%,成品玻璃晶体含量为:二硅酸锂:30-45%;透锂长石:30-45%。
- 如权利要求1所述的三维微晶玻璃,其特征在于制备原料中还包括TiO 2:0-4%;CaO:0-1%;MgO:0-1%;BaO:0-1%;Sb 2O 3:0-2%;Y 2O 3:0-0.5%。
- 如权利要求1所述的三维微晶玻璃,其特征在于0.8mm厚度的三维微晶玻璃,在从400nm到800nm的波长中有着大于或等于85%的透射率。
- 一种如权利要求1-3中任一项权利要求所述的三维微晶玻璃的制备方法,包括以下步骤:步骤一,原料配备,按重量百分比计,称取SiO 2:63-75%;Al 2O 3:4-10%;TiO 2:0-4%;CaO:0-1%;MgO:0-1%;Li 2O:8-11%;Na 2O:0.1-3%;K 2O:0.1-1%;P 2O 5:1-5%;ZrO 2:1-6%;BaO:0-1%;Sb 2O 3:0-2%;Y 2O 3:0-0.5%,混合均匀;步骤二:将步骤一得到的原料转移至铂坩埚中,将铂坩埚置入高温炉内,逐渐升温至1500℃~1600℃,保温2~24小时,经鼓泡和均化处理,在熔融后,将熔融液倒入至预热后的模具中进行成型,然后将其在300-550℃下,进行2-12小时的退火处理得到前驱体玻璃块;步骤三:将步骤二得到的前驱体玻璃块经CNC加工后得到前体玻璃薄片;步骤四:将步骤三得到的前体玻璃薄片进行预晶化处理,具体为首先在540-590℃下,保温0.5-5h,然后在600-800℃下,保温0.5-2h控制玻璃预晶化后的结晶度为10-46%;步骤五:热弯成型,将步骤四得到的预晶化玻璃薄片先进行预热处理,再经成型处理,最后冷却处理,待冷却至室温后,即可制得三维微晶玻璃。
- 根据权利要求4所述的三维微晶玻璃的制备方法,其特征在于步骤四预晶化过程中形成的晶体为二硅酸锂、硅酸锂和/或透锂长石。
- 根据权利要求2所述的三维微晶玻璃的制备方法,其特征在于步骤四预晶化过程中形成的晶体含量为二硅酸锂:5-20wt%,硅酸锂5-20wt%,透锂长石0-6wt%。
- 根据权利要求4所述的三维微晶玻璃的制备方法,其特征在于所述步骤五中的预热处理分为6个工艺段,第一工艺段的温度为350-500℃;第二工艺段的温度为440-580℃;第三工艺段的温度为530-660℃;第四工艺段的温度为590-670℃;第五工艺段的温度为590-680℃;第六工艺段的温度为620-650℃;每个工艺段的时间为90-150s。
- 根据权利要求4所述的三维微晶玻璃的制备方法,其特征在于所述步骤五中的成型阶段分为3个工艺段,其中第一工艺段的温度为690-780℃、模具施加的压力为3-6Kg/cm 2;第二工艺段的温度为740-800℃、模具施加的压力为5-7Kg/cm 2;第三工艺段的温度为730-810℃、模具施加的压力为8-9Kg/cm 2;每个工艺段的时间为90-150s。
- 根据权利要求4所述的三维微晶玻璃的制备方法,其特征在于所述步骤五中的冷却阶段分为4个工艺段,第一工艺段的温度为720-800℃;第二工艺段的温度为670-730℃;第三工艺段的温度为550-630℃;第四工艺段的温度为550℃;每个工艺段的时间为90-150s。
- 根据权利要求4所述的三维微晶玻璃的制备方法,其特征在于还包括步骤六:将步骤五得到的三维微晶玻璃进行离子交换强化处理,首先,将三维微晶玻璃浸没于420℃~460℃的温度的熔融NaNO 3的盐浴中3~12小时来进行离子交换;接着再将三维微晶玻璃浸没于400℃~460℃的温度的熔融KNO 3的盐浴中约2~10小时来进行离子交换。
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