WO2023279819A1 - 化学强化微晶玻璃及其制备方法与应用 - Google Patents
化学强化微晶玻璃及其制备方法与应用 Download PDFInfo
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- WO2023279819A1 WO2023279819A1 PCT/CN2022/090015 CN2022090015W WO2023279819A1 WO 2023279819 A1 WO2023279819 A1 WO 2023279819A1 CN 2022090015 W CN2022090015 W CN 2022090015W WO 2023279819 A1 WO2023279819 A1 WO 2023279819A1
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- Prior art keywords
- chemically strengthened
- strengthened glass
- glass
- ceramic
- ceramics
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 365
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005728 strengthening Methods 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims description 74
- 239000010410 layer Substances 0.000 claims description 71
- 239000011521 glass Substances 0.000 claims description 64
- 239000013078 crystal Substances 0.000 claims description 59
- 150000003839 salts Chemical class 0.000 claims description 44
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- 238000005452 bending Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 17
- 238000002834 transmittance Methods 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 239000002344 surface layer Substances 0.000 claims description 16
- 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 claims description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 239000002667 nucleating agent Substances 0.000 claims description 12
- 229910000500 β-quartz Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- -1 B 2 O 3 Inorganic materials 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 238000013003 hot bending Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 238000003490 calendering Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000000877 morphologic effect Effects 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000005345 chemically strengthened glass Substances 0.000 description 34
- 230000003287 optical effect Effects 0.000 description 29
- 230000005540 biological transmission Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 230000006872 improvement Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000005354 aluminosilicate glass Substances 0.000 description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000006059 cover glass Substances 0.000 description 5
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- OUFSPJHSJZZGCE-UHFFFAOYSA-N aluminum lithium silicate Chemical compound [Li+].[Al+3].[O-][Si]([O-])([O-])[O-] OUFSPJHSJZZGCE-UHFFFAOYSA-N 0.000 description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052670 petalite Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000006017 silicate glass-ceramic Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000006018 Li-aluminosilicate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000009662 stress testing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- 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
- 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
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
- C03B23/035—Re-forming glass sheets by bending using a gas cushion or by changing gas pressure, e.g. by applying vacuum or blowing for supporting the glass while 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
-
- 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
-
- 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 application belongs to the technical field of glass products, and in particular relates to a chemically strengthened glass-ceramic and its preparation method and application.
- Glass is widely used in daily life due to its own characteristics of transparency and high temperature resistance. For example, glass is widely used in protective devices, decoration and other fields. However, glass also has certain deficiencies, such as weak impact resistance and brittleness, which limit the application of glass in some fields.
- the cover glass materials in the industry are developing from aluminum-silicon first-strength glass to lithium-aluminum-silicon second-strength glass.
- the puncture resistance of the cover plate against rough ground is effectively improved.
- the second-strongest glass in the industry is developing towards the direction of increasing deep stress, and has achieved a generation-by-generation improvement in sandpaper drop.
- the main body of the second-strength glass is lithium-aluminosilicate glass.
- the Young's modulus of lithium-aluminosilicate glass is generally ⁇ 80GPa, and the further improvement of its stress strength is limited by the compressive stress storage capacity of the matrix; excessive compressive stress introduces high internal tension. Stress, such as too high tensile stress, will cause the glass failure fragments to be too small ( ⁇ 3mm) or the cover glass to self-explode. Therefore, the improvement of the strength of the second-strength glass is limited by the strength of the body, and the improvement of the drop resistance performance is relatively limited.
- the cover industry will introduce glass-ceramic as a new development direction of cover glass.
- the nanocrystals inside the glass-ceramic can resist crack penetration, and the compressive stress introduced by ion exchange can resist crack propagation, which improves the drop resistance of the cover glass through dual effects (see Figure 1 for the mechanism). Therefore, the anti-drop performance on rough ground is qualitatively improved compared with the second-strength glass.
- the main crystal phases are lithium petalite and lithium disilicate; the strengthening furnace water needs to actively introduce Li 2 O to control the concentration of Na salt on the surface to reduce the temperature at 85° The degree of sodium salt precipitation at 85° humidity.
- This kind of crystal phase design uses K/Na and Na/Li secondary exchange to achieve strength improvement.
- the characteristic of the glass-ceramic is that the crystallinity should be relatively high ( ⁇ 85wt%) in order to ensure the excellent optical properties of the original material (transmittance ⁇ 89.5%, absolute value of color difference b ⁇ 0.5, fog degree ⁇ 0.15%).
- the purpose of this application is to overcome the above-mentioned deficiencies in the prior art, to provide a chemically strengthened glass-ceramic and its preparation method and its application, so as to solve the problem that the compressive stress of the existing aluminosilicate glass and chemically strengthened glass-ceramic is difficult to be further improved, Unsatisfactory technical problems such as anti-drop performance.
- an aspect of the embodiment of the present application provides a chemically strengthened glass-ceramic.
- the chemically strengthened glass-ceramic in the embodiment of the present application has a Na/Li exchange layer, and the depth Doc of the compressive stress layer of the chemically strengthened glass-ceramic is 0.15t-0.22t; the compressive stress intensity CS50 at the strengthening depth of the surface layer of the chemically strengthened glass-ceramic is 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa; and CS50 and Doc meet: CS50/(Doc-50) is 1.4 ⁇ 6, the unit is MPa/ ⁇ m; where, t is chemical strengthening The total thickness of the glass-ceramic.
- the chemically strengthened glass-ceramics in the embodiment of the present application has a specific compressive stress layer depth, compressive stress intensity, and the relationship between the compressive stress layer depth and the compressive stress intensity, which endows the chemically strengthened glass-ceramic with relatively high compressive stress and stress intensity.
- the anti-puncture ability of the chemically strengthened glass-ceramic in the embodiment of the present application is significantly improved on rough ground, and the drop height on rough ground is higher than that of the existing aluminosilicate glass and glass-ceramic.
- the chemically strengthened glass-ceramic is extruded by a metal pressing rod with a round head of 10 mm in diameter until the average size of the longest side of the fragments is greater than or equal to 5 mm when broken.
- the drop height of sandpaper for chemically strengthened glass-ceramic is ⁇ 1.5m.
- no sodium salt precipitation occurs on the outer surface of the chemically strengthened glass-ceramic when stored at a temperature of 85° C./humidity of 85% for 72 hours.
- the thickness of the chemically strengthened glass-ceramic is ⁇ 0.8mm
- the average light transmittance of 400-940nm wavelength is ⁇ 89.5%
- the single-point transmittance difference between 550nm and 400nm wavelength is less than 1%
- chemically strengthened glass-ceramics has the above-mentioned relationship between compressive stress layer depth, compressive stress intensity and compressive stress layer depth and compressive stress intensity
- chemically strengthened glass-ceramics has excellent resistance to rough ground puncture ability, and has High drop resistance, good heat and humidity stability, and good optical properties such as light transmission.
- the main crystal phase of the plain glass-ceramics used to form chemically strengthened glass-ceramics is any one of lithium silicate or ⁇ -quartz solid solution, and the mass fraction of the total crystal phase contained is 35-75%, wherein The total content of secondary crystal phase is ⁇ 5%.
- the Na/Li exchange layer contained in the chemically strengthened glass-ceramics can be effectively prevented from being adversely affected by Li, and the control of the CS50 range can be effectively realized, thereby Further improve the anti-puncture ability of chemically strengthened glass-ceramics on rough ground. At the same time, it can also improve the impact resistance of chemically strengthened glass-ceramics, and has high optical properties such as light transmission.
- the plain glass-ceramics includes main components and nucleating agents; wherein, the main components include SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfy: SiO 2
- the main components include SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfy: SiO 2
- the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , And satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
- plain glass-ceramics endow plain glass-ceramics and chemically strengthened glass-ceramics with the above-mentioned main crystal phase types and crystal phase content, thereby improving the anti-puncture ability of chemically strengthened glass-ceramics on rough ground and improving the chemical strength of glass-ceramics. Strengthens the optical properties of glass-ceramics such as light transmission.
- the plain glass-ceramic is prepared by melting casting method or calendering method.
- the plain glass-ceramic undergoes the following two-step heat treatment:
- the first step of heat treatment the temperature is 500-600°C, and the treatment time is 0.1-10h;
- the second step of heat treatment the temperature is 640-800°C, and the treatment time is 0.1-10h.
- the main crystal phase and its content of the crystallinity required for the formed glass-ceramic can be obtained, and the main crystal phase and the content of the crystal phase can be adjusted, thereby Achieve improved resistance to rough ground puncture and optical properties of chemically strengthened glass-ceramics.
- the Young's modulus of the chemically strengthened glass-ceramic is ⁇ 95GPa. Based on the chemically strengthened glass-ceramic, the main crystal phase type and crystal phase content of the plain glass-ceramic endow the chemically strengthened glass-ceramic with a high Young's modulus, thereby endowing the chemically strengthened glass-ceramic with a capacity to accommodate greater compressive stress storage The space provides conditions for increasing the compressive stress of chemically strengthened glass-ceramics.
- the surface layer of the chemically strengthened glass ceramics further has a K/Na exchange layer.
- the introduction of the K/Na exchange layer (potassium layer) further improves the impact resistance of the chemically strengthened glass-ceramic, and at the same time helps to maintain the drop resistance of the chemically strengthened glass-ceramic on rough ground.
- the thickness of the K/Na exchange layer is ⁇ 3 ⁇ m.
- the thickness of the K/Na exchange layer (potassium layer)
- the impact resistance and drop resistance of the chemically strengthened glass-ceramics can be further improved.
- the thickness requirement of the K/Na exchange layer can be effectively reduced.
- the chemically strengthened glass-ceramics is any one of 2D morphologically strengthened glass-ceramics, 2.5D morphologically strengthened glass-ceramics, and 3D morphologically strengthened glass-ceramics. Since the chemically strengthened glass-ceramic has the above-mentioned excellent anti-puncture ability on rough ground and optical properties, it can be any of 2D morphologically chemically strengthened glass-ceramic, 2.5D morphologically strengthened glass-ceramic, and 3D morphologically strengthened glass-ceramic , expanding the application range of chemically strengthened glass-ceramics, and improving the quality and performance stability of the corresponding products.
- the color coordinates of the 2D morphologically strengthened glass-ceramics or/and 2.5D morphologically strengthened glass-ceramics b absolute value ⁇ 0.3, haze ⁇ 0.14.
- the chemically strengthened glass-ceramic is chemically strengthened glass-ceramic in 3D form, and the bending angle of the long side thereof is 15-89°.
- the absolute value of color coordinate b of the 3D morphologically strengthened glass-ceramics is ⁇ 0.4, and the haze is ⁇ 0.15.
- chemically strengthened glass-ceramic When chemically strengthened glass-ceramic is used as a 3D form of chemically strengthened glass-ceramic, it still has excellent resistance to rough ground puncture and light transmission.
- Another aspect of the embodiments of the present application provides a method for preparing chemically strengthened glass-ceramics in the above embodiments of the present application.
- the preparation method of chemically strengthened glass-ceramics in the embodiment of the present application comprises the following steps:
- the plain glass-ceramic to be chemically strengthened is chemically strengthened once in a sodium-containing salt bath to form a Na/Li exchange layer.
- the preparation method of the chemically strengthened glass-ceramics of the present application carries out a chemical strengthening treatment to the plain glass-ceramics in a sodium-containing salt bath, so that a Na/Li exchange layer is formed in the surface layer of the plain glass-ceramics, and can pass through a chemical strengthening treatment.
- Control can make the chemically strengthened glass-ceramics formed by chemical strengthening have the compressive stress layer depth and compressive stress intensity CS50 range and the relationship between the two, which endow the chemically strengthened glass-ceramics of the above application.
- Strengthened glass-ceramic has relatively high compressive stress, the stress intensity has been greatly improved, it can resist crack propagation, and has excellent resistance to puncture on rough ground.
- the chemical strengthening conditions of the preparation method of the chemically strengthened glass-ceramics of the present application are easy to control, so that the performance of the prepared chemically strengthened glass-ceramics is stable, the efficiency is high, and the production cost is reduced.
- the sodium-containing salt bath includes NaNO 3 or a mixed salt of NaNO 3 and KNO 3 , and in the mixed salt of NaNO 3 and KNO 3 , the content of NaNO 3 is ⁇ 50wt%.
- the temperature of the first chemical strengthening treatment is 380-450° C.
- the strengthening time is 0.5-6 hours.
- the effect of chemical strengthening treatment on plain glass-ceramics is improved, and the depth of compressive stress layer and compressive stress intensity of chemically strengthened glass-ceramics formed are optimized CS50 range, thereby increasing the compressive stress of chemically strengthened glass-ceramic, improving its anti-puncture ability and light transmission performance on rough ground.
- the first chemical strengthening treatment after the first chemical strengthening treatment, it also includes performing a second chemical strengthening treatment on the chemically strengthened glass-ceramics formed with the Na/Li exchange layer in a salt bath containing potassium to form a K/Na exchange layer.
- a K/Na exchange layer is formed on the surface of the chemically strengthened glass-ceramics, thereby further improving the impact resistance and performance of the chemically strengthened glass-ceramics. Anti-drop performance on rough ground.
- the potassium-containing salt bath includes KNO 3 or a mixed salt of NaNO 3 and KNO 3 ; in the mixed salt of NaNO 3 and KNO 3 , the content of KNO 3 is ⁇ 80wt%.
- the temperature of the secondary chemical strengthening treatment is 380-450°C, and the strengthening time is 0.2-1h.
- the effect of the secondary chemical strengthening treatment is improved, and the impact resistance and drop resistance of the chemically strengthened glass-ceramics are further improved.
- the step of performing the following heat bending treatment on the plain glass-ceramics is also included:
- the plain glass-ceramic is subjected to a single-stage heat bending treatment at 650-750° C. for 30-120 seconds to form a 3D plain glass-ceramic, wherein the pressure of the single-stage heat bending treatment is 0.1-0.9 MPa.
- 3D plain glass-ceramics is formed by heat-bending the plain glass-ceramic, so that after the above-mentioned primary chemical strengthening treatment or further secondary chemical strengthening treatment, a 3D form of chemically strengthened glass-ceramic can be formed, and the 3D form of chemical strengthening can be guaranteed.
- Glass-ceramic has high compressive stress and has excellent anti-puncture ability and light transmission performance on rough ground.
- the electronic device in the embodiment of the present application includes a glass part, and the glass part is the chemically strengthened glass-ceramic in the above-mentioned application example or the chemically strengthened glass-ceramic prepared according to the preparation method of the chemically strengthened glass-ceramic in the above-mentioned application example.
- the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned excellent resistance to rough ground puncture ability and optical performance or further has excellent impact resistance performance, therefore, the glass parts are endowed with excellent drop resistance and drop resistance, and high strength, thereby The electronic equipment of the embodiment of the present application is endowed with excellent drop resistance, drop resistance and impact resistance, and the quality and stability of the electronic equipment are high.
- the glass component includes at least one of a display cover, a protection cover, and a protection screen.
- the glass part has good light transmittance and strong protection, and is drop-resistant and drop-resistant, has high strength, and has good display or protection performance and is stable.
- Figure 1 is a schematic diagram of the mechanism of glass-ceramic resistance to puncture
- Fig. 2 is the stress curve diagram of existing aluminum-silicon one-strength glass, lithium-aluminum-silicate two-strength glass and chemically strengthened glass-ceramic of the present application embodiment;
- Fig. 3 is a schematic flow chart of a method for preparing chemically strengthened glass-ceramics according to an embodiment of the present application.
- At least one means one or more, and “multiple” means two or more.
- At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
- at least one item (unit) of a, b, or c or “at least one item (unit) of a, b, and c” can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
- the term "and/or” describes the relationship between related objects, indicating that there may be three relationships, for example, A and/or B, which may mean: A exists alone, A and B exist simultaneously, and A and B exist independently. There is a case of B. Among them, A and B can be singular or plural.
- the character "/" generally indicates that the contextual objects are an "or" relationship.
- sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.
- the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
- the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
- the mass described in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
- first and second are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
- first XX can also be called the second XX
- second XX can also be called the first XX.
- a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
- Plain glass-ceramic glass-ceramic that has not been strengthened.
- Chemically strengthened glass-ceramic It is chemically tempered glass-ceramic after high temperature ion exchange process. Large alkali metal ions replace small alkali metal ions in glass in high-temperature molten salt, resulting in a volume difference of exchanged ions, and a high-to-low compressive stress in the surface layer of plain glass, which hinders and delays the expansion of glass microcracks, and achieves an improvement.
- the purpose of glass mechanical strength is used.
- Depth of compressive stress layer Depth of compressive stress layer of chemically strengthened glass-ceramics.
- Compressive stress value at a depth of 50 ⁇ m in the surface layer of chemically strengthened glass indicates the value of compressive stress at a depth of 50 ⁇ m in the surface layer of chemically strengthened glass-ceramics.
- Na/Li exchange layer refers to the sodium-containing layer in which sodium ions of chemically strengthened glass-ceramics replace part of lithium ions.
- K/Na exchange layer refers to the potassium-containing layer in which the potassium ions of the chemically strengthened glass-ceramics replace part of the sodium ions.
- Sodium-lithium ion exchange During chemical strengthening, sodium ions in a salt bath replace lithium ions in the glass.
- Potassium-sodium ion exchange During chemical strengthening, potassium ions in a salt bath replace sodium ions in the glass.
- the embodiment of the present application provides a chemically strengthened glass-ceramic.
- the chemically strengthened glass-ceramic in the embodiment of the present application has a Na/Li exchange layer and a compressive stress layer. It has been measured that the stress curve of the chemically strengthened glass-ceramic in the embodiment of the present application is shown in Figure 2, and its compressive stress layer depth and compressive stress intensity have at least the following 1 to 3 characteristics:
- t in Formula 1-1 and Formula 1-2 is the total thickness of the chemically strengthened glass-ceramic, therefore, t is a positive number greater than 0, and the unit may be mm.
- t is the total thickness of the chemically strengthened glass-ceramic in the embodiment of the present application, which is 0.3-0.8 mm.
- the surface layer strengthening depth of 50 ⁇ m related to formula 1-2 refers to the direction from the surface of the chemically strengthened glass-ceramics to the inside, and the area with an internal depth of 50 ⁇ m.
- the CS50 of the chemically strengthened glass-ceramics of the embodiment of the present application is too small, can cause the reduction such as the puncture ability of anti-rough ground of the chemically strengthened glass-ceramics, reliability is affected;
- CS50 is too high, the chemical The broken fragments of strengthened glass-ceramics are too small.
- the strengthening process generally adopts two strong processes: strengthening one uses pure NaNO 3 or NaNO 3 /KNO 3 mixed salt, the strengthening temperature is 380-450 °C, strengthening two uses pure KNO 3 or NaNO 3 /KNO 3 mixed salt), the strengthening Post-CS ⁇ 700MPa, strengthening depth of potassium layer Dol ⁇ 5 ⁇ m, CS50 ⁇ 130+(20t-13) ⁇ 15MPa, strengthening depth of compressive stress layer Doc ⁇ 0.18t.
- the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned specific compressive stress layer depth, compressive stress intensity, and the relationship between the compressive stress layer depth and compressive stress intensity.
- the chemically strengthened glass-ceramics in the embodiment of the present application has a relatively high compressive stress, and the stress intensity is greatly improved compared with the current aluminosilicate glass and glass-ceramic, and can resist Crack propagation.
- the anti-puncture ability of the chemically strengthened glass-ceramic in the embodiment of the present application is significantly improved. Lifting, drop height on rough ground is higher than existing aluminosilicate glass and glass-ceramic.
- the aluminum-silicon-strong glass curve (K/Na exchange) in Figure 2 is tested by the industry's general surface stress testing equipment FSM-6000LEUV, and the lithium-aluminum-silicon two-intensity curve (with K/Na and Na/Li exchange) is the industry's Surface stress testing equipment FSM-6000LEUV and Scattered Photoelastic Stress Instrument SLP2000 fitting test synthesis; the chemically strengthened glass-ceramic curve of this application is tested by SLP2000.
- the chemically strengthened glass-ceramic when the chemically strengthened glass-ceramic is extruded by a 10 mm diameter round-headed metal pressure rod until it is broken, the average size of the longest side of the fragments is ⁇ 5 mm. Therefore, the internal tensile stress of the chemically strengthened glass-ceramics is appropriate, and the resistance to rough ground is strong, avoiding the risk of self-explosion.
- the drop height of the sandpaper of the chemically strengthened glass-ceramic is ⁇ 1.5m. Reflects the excellent drop resistance of chemically strengthened glass-ceramics.
- the sandpaper drop height data is tested under the scene of 180# sandpaper/200g load. Specifically, the chemically strengthened glass-ceramics of the application to be tested is faced down, and a standard 200g load is loaded on the other surface, with a fall of 0.5m , check the appearance every time it falls; if there is no problem, raise it by 0.1m, test directly until the glass breaks, and record the failure height.
- the thickness of the chemically strengthened glass-ceramics is such that when the thickness is ⁇ 0.8mm, the average light transmittance at a wavelength of 400-940nm is ⁇ 89.5%, and the difference between the single point transmittance at a wavelength of 550nm and 400nm is ⁇ 1% , Absolute value of color coordinate b ⁇ 0.4, haze ⁇ 0.15. It embodies the optical properties such as the excellent light transmission of chemically strengthened glass-ceramics.
- the chemically strengthened glass-ceramic has excellent compressive stress in addition to high compressive stress. It is resistant to puncture on rough ground and has high drop resistance, as shown in Table 1 below; it also has excellent heat and humidity stability, and good optical properties such as light transmission.
- the main crystal phase of the plain glass-ceramics used to form the above-mentioned chemically strengthened glass-ceramics is any one of lithium silicate or ⁇ -quartz solid solution, and the mass fraction of the total crystal phase contained is 35-75%. Among them, the total content of secondary crystal phase is less than 5%.
- the above-mentioned plain glass-ceramic includes a main composition and a nucleating agent; wherein, the main composition includes SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfies :
- the content of SiO 2 +Al 2 O 3 +B 2 O 3 is 58-85mol%; the content of Li 2 O+Na 2 O+K 2 O is 10-32mol%;
- the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , and satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
- plain glass-ceramics endow plain glass-ceramics and chemically strengthened glass-ceramics with the above-mentioned main crystal phase types and crystal phase content, thereby improving the anti-puncture ability of chemically strengthened glass-ceramics on rough ground and improving the chemical strength of glass-ceramics. Strengthens the optical properties of glass-ceramics such as light transmission.
- the above-mentioned plain glass-ceramic can be prepared by a melting casting method or a calendering method. In some embodiments, the above-mentioned plain glass-ceramics undergoes the following two-step heat treatment:
- the first step of heat treatment the temperature is 500-600°C, and the treatment time is 0.1-10h;
- the second step of heat treatment the temperature is 640-800°C, and the treatment time is 0.1-10h.
- the main crystal phase and its content of the crystallinity required for the formed glass-ceramic can be obtained, and the main crystal phase and the content of the crystal phase can be adjusted, thereby Achieve improved resistance to rough ground puncture and optical properties of chemically strengthened glass-ceramics.
- plain glass-ceramics Due to the main crystal phase type and crystal phase content of plain glass-ceramics, it has been tested that plain glass-ceramics also has excellent mechanical properties such as Young's modulus and optical properties such as light transmission properties.
- the plain glass-ceramics when the thickness of the plain glass-ceramic is ⁇ 0.8mm, the average light transmittance at 400-940nm wavelength is ⁇ 89.5%, and the single-point transmittance difference between 550nm and 400nm wavelength is less than 1%, and the color coordinates b absolute value ⁇ 0.3, haze ⁇ 0.14.
- the plain glass-ceramics By controlling the main crystal phase type and crystal phase content of the plain glass-ceramics, the plain glass-ceramics has good optical properties such as light transmission and stable optical properties.
- the Young's modulus of the plain glass-ceramic is ⁇ 95GPa. Based on the main crystal phase type and crystal phase content of plain glass-ceramics, high Young's modulus is given to plain glass-ceramics, so as to give high Young's modulus to chemically strengthened glass-ceramics, such as chemically strengthened glass-ceramics with high Young's modulus
- the Young's modulus of the chemically strengthened glass-ceramics is greater than or equal to 95GPa, thereby endowing the chemically strengthened glass-ceramics with a larger compressive stress storage space, which provides conditions for the improvement of the compressive stress of the chemically strengthened glass-ceramics.
- plain glass-ceramics and chemically strengthened glass-ceramics are endowed with high impact resistance. If tested, chemically strengthened glass-ceramics is about 25-30GPa higher than the existing aluminosilicate glass, which effectively reduces the impact of chemically strengthened glass-ceramics on K /Na Exchange layer requirements and dependencies.
- the surface layer of the chemically strengthened glass-ceramic in the above embodiments further has a K/Na exchange layer.
- the K/Na exchange layer is further formed on the surface of the chemically strengthened glass-ceramic, that is, the potassium layer is added to the surface of the chemically strengthened glass-ceramic.
- the chemically strengthened glass-ceramic having high resistance to rough ground it is further optimized. Improve the drop resistance of chemically strengthened glass-ceramics on rough ground, and further improve the impact resistance of chemically strengthened glass-ceramics.
- the chemically strengthened glass-ceramics has a high Young's modulus, such as Young's modulus ⁇ 95GPa, the high Young's modulus supports better impact strength, effectively reducing the K/Na exchange layer rely.
- Young's modulus ⁇ 95GPa the high Young's modulus supports better impact strength, effectively reducing the K/Na exchange layer rely.
- the chemically strengthened glass-ceramic in the embodiment of the present application does not require a larger K/Na exchange layer.
- the thickness of the K/Na exchange layer contained in the chemically strengthened glass-ceramics in the above embodiments is ⁇ 3 ⁇ m.
- the thickness of the K/Na exchange layer (potassium layer)
- the impact resistance and drop resistance of the chemically strengthened glass-ceramics can be further improved.
- the thickness requirement of the K/Na exchange layer can be effectively reduced.
- the chemically strengthened glass-ceramic has excellent anti-puncture ability on rough ground, anti-drop performance and optical properties such as light transmission, or further has high Young's modulus and impact resistance.
- the chemically strengthened glass-ceramic in the embodiment of the present application may be any one of 2D morphologically chemically strengthened glass-ceramic, 2.5D morphologically strengthened glass-ceramic, and 3D morphologically strengthened glass-ceramic.
- the chemically strengthened glass-ceramic has the above-mentioned excellent anti-puncture ability on rough ground and optical performance, which expands its application range and improves the quality and performance stability of corresponding products.
- CS50 and Doc of the chemically strengthened glass-ceramics satisfy: CS50/(Doc- 50) is 1.4-6.
- the average light transmittance at 400-940nm is ⁇ 89.5%
- the single point transmittance difference between 550nm and 400nm wavelength is less than 1%
- the chemically strengthened glass-ceramic when used as a 2D morphological chemically strengthened glass-ceramic or a 2.5D morphologically strengthened glass-ceramic, it has excellent anti-puncture ability and light transmittance on rough ground, which is comparable to the optical performance of plain glass-ceramic. In comparison, its optical properties such as light transmission remain stable.
- the chemically strengthened glass-ceramics in each of the above embodiments is a 3D form of chemically strengthened glass-ceramics
- the bending angle of the long side of the 3D form of chemically strengthened glass-ceramics is 15-89°.
- the CS50, Doc, and the relationship between CS50 and Doc of the chemically strengthened glass-ceramics satisfy the characteristics shown in the above formulas 1-1 to 1-3, and still have excellent anti-puncture ability on rough ground. Has excellent impact resistance.
- the embodiment of the present application provides a method for preparing chemically strengthened glass-ceramics in the above embodiment of the application.
- the process flow of the preparation method of chemically strengthened glass-ceramics in the embodiment of the present application is shown in Figure 3, including the following steps:
- S01 The plain glass-ceramic to be chemically strengthened is subjected to a chemical strengthening treatment in a sodium-containing salt bath to form a Na/Li exchange layer.
- the sodium ions in the sodium-containing salt bath diffuse into the surface layer of the plain glass-ceramics under the action of heat, and exchange with the lithium ions in the surface layer of the plain glass-ceramics, that is, the sodium-lithium ion Exchange, so that Na/Li exchange layer is formed in plain glass-ceramic surface layer, and can pass through the control of chemical strengthening treatment, can make the chemically strengthened glass-ceramic that chemical strengthening forms have above text application embodiment chemically strengthened glass-ceramics as above
- the depth of the compressive stress layer and the CS50 range of the compressive stress intensity shown in the formulas 1-1 to 1-3 and the relationship between the two endow the prepared chemically strengthened glass-ceramic with a relatively high compressive stress, and the stress intensity is obtained Larger lift, able to resist crack propagation, and has excellent resistance to puncture on rough ground.
- the chemical strengthening conditions of the preparation method of the chemically strengthened glass-ceramics of the present application are easy to control, so that the
- the sodium-containing salt bath includes NaNO 3 or a mixed salt of NaNO 3 and KNO 3 .
- the sodium-containing salt bath is a mixed salt comprising NaNO 3 and KNO 3
- the content of NaNO 3 is ⁇ 50 wt%.
- the temperature of one chemical strengthening treatment is 380-450° C., and the strengthening time is 0.5-6 hours.
- the effect of chemical strengthening treatment on plain glass-ceramics is improved, and the depth of compressive stress layer and compressive stress intensity of chemically strengthened glass-ceramics formed are optimized CS50 range, thereby increasing the compressive stress of chemically strengthened glass-ceramic, improving its anti-puncture ability and light transmission performance on rough ground.
- the plain glass-ceramics to be chemically strengthened is the above-mentioned plain glass-ceramics of chemically strengthened glass-ceramics, if the main crystal phase is any one of lithium silicate or ⁇ -quartz solid solution, the total crystal phase contained The mass fraction is 35-75%, wherein the total content of secondary crystal phase is less than 5wt%.
- the plain glass-ceramic in the specific embodiment includes main composition and nucleating agent; main composition includes SiO 2 , Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, and satisfies: SiO 2 + The content of Al 2 O 3 +B 2 O 3 is 58-85mol%; the content of Li 2 O+Na 2 O+K 2 O is 10-32mol%; the nucleating agent includes TiO 2 , P 2 O 5 , ZrO 2 , and Satisfy: the content of TiO 2 +P 2 O 5 +ZrO 2 is 2-8 mol%.
- the chemically strengthened glass-ceramics prepared is a 3D form chemically strengthened glass-ceramic
- the plain glass-ceramics to be chemically strengthened is subjected to a chemical strengthening treatment in a sodium-containing salt bath
- the plain glass-ceramic is also included.
- the glass-ceramic is subjected to the following heat-bending steps:
- the plain glass-ceramic is subjected to a single-stage heat bending treatment at 650-750° C. for 30-120 seconds to form a 3D plain glass-ceramic, wherein the pressure of the single-stage heat bending treatment is 0.1-0.9 MPa.
- 3D plain glass-ceramics is formed by heat-bending the plain glass-ceramic, so that after the above-mentioned primary chemical strengthening treatment or further secondary chemical strengthening treatment, a 3D form of chemically strengthened glass-ceramic can be formed, and the 3D form of chemical strengthening can be guaranteed.
- Glass-ceramic has high compressive stress and has excellent anti-puncture ability and light transmission performance on rough ground.
- the bending angle of the long side of the 3D plain glass-ceramic is 15-89°. In some other specific embodiments, the absolute value of the change difference of the color coordinate b value of the 3D plain glass-ceramic is ⁇ 0.1.
- the existing main crystal phases are microcrystals whose main crystal phases are lithium petalite and lithium disilicate
- the hot bending temperature of the glass is >750°C, and the crystal phase size grows during the hot bending process, resulting in a sharp deterioration of the optical properties after 3D molding (absolute value of color difference b ⁇ 2, haze ⁇ 0.25%); it cannot meet the application of hot bending 3DCG cover plates.
- the above-mentioned main crystal phase of the embodiment of the present application is any kind of plain glass-ceramic in lithium silicate or ⁇ -quartz solid solution.
- the color coordinate b value of the glass changes before and after bending.
- step S02 as shown in Figure 3 is also included: the chemically strengthened glass-ceramics formed with the Na/Li exchange layer is subjected to a secondary chemical strengthening treatment in a potassium-containing salt bath to form K/Na exchange layer.
- the potassium ions in the potassium-containing salt bath diffuse into the surface layer of the chemically strengthened glass-ceramics under the action of heat, and exchange with the sodium ions in the Na/Li exchange layer, that is, carry out potassium- Sodium ion exchange forms a K/Na exchange layer in the surface layer of chemically strengthened glass-ceramics, thereby further improving the impact resistance and drop resistance of chemically strengthened glass-ceramics.
- the potassium-containing salt bath includes KNO 3 or a mixed salt of NaNO 3 and KNO 3 ; when the potassium-containing salt bath is a mixed salt comprising NaNO 3 and KNO 3 , in the mixed salt of NaNO 3 and KNO 3 , KNO 3 content ⁇ 80wt%.
- the temperature of the secondary chemical strengthening treatment is 380-450°C, and the strengthening time is 0.2-1h.
- the chemically strengthened glass-ceramics prepared by the chemically strengthened glass-ceramics and its preparation method according to the above-mentioned embodiments of the present application are combined with the existing glass-ceramics, as mentioned in the background technology section, the main crystal phases are lithium petalite and lithium disilicate compared to glass-ceramics.
- the existing glass-ceramic whose main crystal phase is lithium petalite and lithium disilicate (the material contains a variety of main crystal phases, which require high crystallinity to maintain excellent optical properties), ion exchange requires Greater potential energy, so a higher chemical strengthening temperature/longer chemical strengthening time is required; moreover, the glass-ceramic is sensitive to the Li concentration in the chemical strengthening furnace water, and the chemical strengthening process requires precise control of the Li concentration, and is limited by the Li Inhibition of Na/Li exchange during the chemical strengthening process, therefore, the CS50 of the chemically strengthened glass-ceramics formed by the chemical strengthening of the existing glass-ceramic is ⁇ 130+(20t-13) ⁇ 15MPa.
- the chemically strengthened glass-ceramics in the embodiment of the present application especially the chemically strengthened glass-ceramics containing any one of the main crystal phase lithium silicate or ⁇ -quartz solid solution, has relatively low crystallinity, such as crystallinity ⁇ 75wt%;
- the strengthening treatment process is not sensitive to Li; CS50, Doc and the relationship between CS50 and Doc of the chemically strengthened glass-ceramics obtained by chemical strengthening treatment meet the characteristics shown in the above formulas 1-1 to 1-3, especially the CS50 medium At 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa, so as to obtain better anti-puncture ability on rough ground.
- the embodiment of the present application provides an electronic device.
- the electronic device in the embodiment of the present application includes a glass component, which is the chemically strengthened glass-ceramic in the embodiment of the above application.
- the chemically strengthened glass-ceramic in the embodiment of the present application has the above-mentioned excellent rough ground puncture resistance, optical performance and impact resistance, the glass part is endowed with excellent drop resistance and drop resistance, and has high strength.
- the electronic equipment of the embodiment of the present application including the glass part also has excellent drop resistance, drop resistance and impact resistance, and the quality and working performance stability of the electronic equipment are high.
- the glass part has good light transmittance, good display effect, and can also play a good protective role. At the same time, it is also anti-drop and drop-resistant and high-strength, and has good display or protective performance, so that the electronic equipment is stable.
- the glass part can also be any one of 2D morphology chemically strengthened glass-ceramics, 2.5D morphology chemically strengthened glass-ceramics, and 3D morphology chemically strengthened glass-ceramics, which expands and strengthens the application range of chemically strengthened glass-ceramics, and Improve the quality and performance stability of the corresponding electronic equipment.
- the electronic device includes at least one of a communication mobile terminal, an electronic watch, a bracelet, and a computer.
- the glass components contained therein can be used as front and rear covers of the mobile phone. Because these electronic devices contain the glass component, these electronic devices have excellent drop resistance or further have excellent impact resistance and high strength, so that the performance of the electronic devices is stable.
- This embodiment provides a 3D ⁇ -quartz solid solution chemically strengthened glass-ceramics and a chemically strengthened method thereof.
- the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
- the preparation method of chemically strengthened glass-ceramic comprises the following steps:
- the prepared glass substrate is subjected to two-step heat treatment to obtain the desired crystal phase; the first heat treatment is 600°C, the treatment time is 0.1h, the second step heat treatment is 750-900°C, the treatment time is 0.1h, the obtained crystal
- the main crystal phase is ⁇ -quartz solid solution, and the crystallinity obtained by XRD test is 35wt%;
- step S3 After the 3D glass after hot bending in step S2 is polished with a 3D polishing brush (thickness 0.3 mm after polishing), it is chemically strengthened to form a 3D form of ⁇ -quartz solid solution chemically strengthened glass-ceramic; chemically strengthened The conditions are shown in Table 2.
- This embodiment provides a 2.5D lithium silicate chemically strengthened glass-ceramic and its chemically strengthened method.
- the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
- the preparation method of chemically strengthened glass-ceramic comprises the following steps:
- the prepared glass substrate is subjected to two-step heat treatment to obtain the required crystal phase; the first heat treatment is 500°C, the treatment time is 10h, the second step heat treatment is 640°C, the treatment time is 10h, and the main crystal phase of the obtained crystal is Lithium silicate, the crystallinity obtained by XRD test is 75wt%;
- Cutting/grinding/computer numerical control Computer numerical control, CNC processing/polishing the lithium silicate glass-ceramics prepared in step S1 into a 0.65mm2.5D form carrier;
- step S3 Polish the concave-convex surface of the 2.5D plain glass-ceramics in step S2, and then perform chemical strengthening treatment to form 2.5D lithium silicate chemically strengthened glass-ceramics, the thickness of the finished product is 0.6mm, and the chemical strengthening conditions are shown in Table 2 shown.
- This embodiment provides a 3D lithium silicate chemically strengthened glass-ceramic and a chemically strengthened method thereof.
- the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
- the preparation method of chemically strengthened glass-ceramic comprises the following steps:
- the prepared glass matrix is subjected to two-step heat treatment to obtain the required crystal phase; the first heat treatment is 550°C, the treatment time is 6h, the second step heat treatment is 800°C, and the treatment time is 2h, the main crystal phase of the obtained crystal is Lithium silicate, the crystallinity obtained by XRD test is 65wt%;
- the lithium silicate glass-ceramics prepared in step S1 is cut/grinded/polished into a 0.7mm-thick glass original sheet; then it is bent into a 3D shape with a 3D graphite mold, and the highest bending temperature is 750°C.
- the compressive stress is 0.1MPa, and the single-station bending time is 120s;
- step S3 Use a 3D polishing brush to polish the concave-convex surface of the plain glass-ceramic in step S2, and then perform chemical strengthening treatment to form a 3D lithium silicate chemically strengthened glass-ceramic.
- the thickness of the finished product is 0.65 mm.
- the chemical strengthening conditions are shown in Table 2. .
- This embodiment provides a 2.5D lithium silicate chemically strengthened glass-ceramic and its chemically strengthened method.
- the relevant properties of the chemically strengthened glass-ceramic and the relevant process parameters of the chemical strengthening method are respectively described in Table 2 below.
- the preparation method of chemically strengthened glass-ceramic comprises the following steps:
- the prepared glass substrate is subjected to two-step heat treatment to obtain the desired crystal phase; the first heat treatment is at 550° C. for 6 hours, and the second step is 800° C. for 2 hours.
- the main crystal phase of the obtained crystal is lithium silicate, and the crystallinity obtained by XRD test is 65wt%;
- step S3 Perform chemical strengthening treatment on the 2.5D plain glass-ceramic in step S2, and the strengthening conditions of chemical strengthening are shown in Table 1.
- the depth Doc of the compressive stress layer of the chemically strengthened glass-ceramics in each embodiment is consistent with the thickness of the chemically strengthened glass-ceramics in the range of 0.15t to 0.22t;
- the thickness of CS50 and chemically strengthened glass-ceramics conforms to 130+(20t-13) ⁇ 15MPa ⁇ 230+(20t-13) ⁇ 15MPa;
- CS50 and Doc meet:
- CS50/(Doc-50) is 1 ⁇ 7.5, and It has high resistance to puncture on rough ground, excellent optical properties such as light transmission, and good heat and humidity stability.
- the shape and thickness of the aluminum-silicon one-strength glass, the lithium-aluminum-silicate two-strength glass and the chemically strengthened glass-ceramic in the embodiment of the present application are the same.
- the test results are shown in Table 2:
- the CS50 and sandpaper surface slump height of the chemically strengthened glass-ceramic in the embodiment of the present application are significantly higher than the CS50 and the sandpaper surface slump height of the existing aluminum-silicon first-strength glass and lithium-aluminum-silicate second-strength glass. Therefore, the present application EXAMPLES
- the chemically strengthened glass-ceramic has significantly improved resistance to rough ground puncture. Therefore, the chemically strengthened glass-ceramic provided by the embodiment of the present application is used in electronic products, such as front and rear covers of mobile phones, specifically 2D cover, 2.5D cover, 3D cover, etc.
- the anti-drop performance of the product endows the corresponding electronic products with excellent anti-drop performance, and can also improve the impact resistance of electronic products such as mobile phones, thereby making the performance of electronic products stable.
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Abstract
Description
Claims (17)
- 一种化学强化微晶玻璃,其特征在于:具有Na/Li交换层,所述化学强化微晶玻璃的压应力层深度Doc为0.15t~0.22t;所述化学强化微晶玻璃表层强化深度50μm处的压应力强度CS50为130+(20t-13)×15MPa~230+(20t-13)×15MPa;且所述CS50与所述Doc满足:CS50/(Doc-50)为1.4~6,单位为MPa/μm;其中,t为所述化学强化微晶玻璃的总厚度。
- 根据权利要求1所述的化学强化微晶玻璃,其特征在于:采用10mm直径圆头金属压杆挤压所述化学强化微晶玻璃至破碎时,碎片最长边平均尺寸≥5mm;和/或厚度为0.6mm时,所述化学强化微晶玻璃的砂纸跌落高度≥1.5m;和/或在温度85℃/湿度85%环境保存72h,所述化学强化微晶玻璃的外表面不出现钠盐析出;和/或所述化学强化微晶玻璃在厚度≤0.8mm时,在400-940nm波长的光平均透过率≥89.5%,且550nm与400nm波长时的单点透过率差<1%,色坐标b绝对值≤0.4,雾度≤0.15%。
- 根据权利要求1-2任一项所述的化学强化微晶玻璃,其特征在于:用于形成所述化学强化微晶玻璃的素微晶玻璃的主晶相为硅酸锂或β-石英固溶体中的任一种,所含总晶相质量分数为35~75%,其中次晶相总含量<5%。
- 根据权利要求3所述的化学强化微晶玻璃,其特征在于:所述素微晶玻璃包括主要组成和成核剂;所述主要组成包括SiO 2、Al 2O 3、B 2O 3、Li 2O、Na 2O、K 2O,且满足:SiO 2+Al 2O 3+B 2O 3含量为58~85mol%;Li 2O+Na 2O+K 2O含量为10~32mol%;所述成核剂包括TiO 2、P 2O 5、ZrO 2,且满足:TiO 2+P 2O 5+ZrO 2含量为2~8mol%。
- 根据权利要求3所述的化学强化微晶玻璃,其特征在于:所述素微晶玻璃采用熔融浇筑法或者压延法制备形成;和/或所述素微晶玻璃经过如下两步热处理:第一步热处理:温度为500-600℃,处理时间为0.1-10h;第二步热处理:温度为640-800℃,处理时间为0.1-10h。
- 根据权利要求3所述的化学强化微晶玻璃,其特征在于:所述化学强化微晶玻璃的杨氏模量≥95GPa。
- 根据权利要求3所述的化学强化微晶玻璃,其特征在于:所述化学强化微晶玻璃的表层还具有K/Na交换层。
- 根据权利要求7所述的化学强化微晶玻璃,其特征在于:所述K/Na交换层的厚度≤3μm。
- 根据权利要求1、2、4-8任一项所述的化学强化微晶玻璃,其特征在于:所述化学强化微晶玻璃为2D形态化学强化微晶玻璃、2.5D形态化学强化微晶玻璃、3D形态化学强化微晶玻璃中的任一种。
- 根据权利要求9所述的化学强化微晶玻璃,其特征在于:所述化学强化微晶 玻璃为2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃,所述2D形态化学强化微晶玻璃或/和2.5D形态化学强化微晶玻璃的色坐标b绝对值≤0.3,雾度≤0.14。
- 根据权利要求9所述的化学强化微晶玻璃,其特征在于:所述化学强化微晶玻璃为所述3D形态化学强化微晶玻璃,其长边折弯角度为15~89°;和/或所述3D形态化学强化微晶玻璃的色坐标b绝对值≤0.4,雾度≤0.15。
- 一种化学强化微晶玻璃的制备方法,包括如下步骤:将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理,形成Na/Li交换层。
- 根据权利要求12所述的制备方法,其特征在于:所述含钠盐浴包括NaNO 3或NaNO 3与KNO 3的混合盐,在所述NaNO 3与KNO 3的混合盐混合盐中,所述NaNO 3含量≥50wt%;和/或所述一次化学强化处理的温度380-450℃,强化时间0.5-6h。
- 根据权利要求12或13所述的制备方法,其特征在于:在所述一次化学强化处理之后,还包括对形成有所述Na/Li交换层的化学强化微晶玻璃于含钾盐浴中进行二次化学强化处理,形成K/Na交换层。
- 根据权利要求14所述的制备方法,其特征在于:所述含钾盐浴包括KNO 3或NaNO 3与KNO 3的混合盐;在所述NaNO 3与KNO 3的混合盐中,所述KNO 3含量≥80wt%;和/或所述二次化学强化处理的温度380-450℃,强化时间0.2-1h。
- 根据权利要求12所述的制备方法,其特征在于:在所述将待化学强化处理的素微晶玻璃于含钠盐浴中进行一次化学强化处理之前,还包括将所述素微晶玻璃进行如下热弯处理的步骤:将所述素微晶玻璃于650~750℃下进行单段热弯处理30~120s,形成3D素微晶玻璃,其中,所述单段热弯处理的压力为0.1~0.9MPa。
- 一种电子设备,其特征在于:包括玻璃部件,所述玻璃部件为权利要求1-11任一所述的化学强化微晶玻璃或根据权利要求12-16任一所述的制备方法制备的化学强化微晶玻璃。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110845153A (zh) * | 2019-12-03 | 2020-02-28 | 深圳市东丽华科技有限公司 | 一种具有高压应力层深度的强化微晶玻璃及其制备方法 |
CN110872175A (zh) * | 2018-08-31 | 2020-03-10 | 深圳市东丽华科技有限公司 | 一种微晶玻璃及利用其制成的具有复合压应力的玻璃基板 |
CN111018356A (zh) * | 2019-12-30 | 2020-04-17 | 深圳市东丽华科技有限公司 | 一种高晶体含量的微晶玻璃及其制备方法 |
TW202100482A (zh) * | 2019-06-26 | 2021-01-01 | 日商Agc股份有限公司 | 化學強化玻璃之製造方法及化學強化玻璃 |
US20210024405A1 (en) * | 2018-10-26 | 2021-01-28 | Cdgm Glass Co., Ltd | Microcrystalline Glass, Microcrystalline Glass Product, and Manufacturing Method Therefor |
CN112608033A (zh) * | 2020-09-12 | 2021-04-06 | 重庆鑫景特种玻璃有限公司 | 一种化学强化微晶玻璃及强化方法 |
CN112919812A (zh) * | 2019-12-06 | 2021-06-08 | 华为技术有限公司 | 微晶玻璃、化学强化微晶玻璃、其制备方法及电子设备 |
CN112939472A (zh) * | 2019-12-11 | 2021-06-11 | 四川旭虹光电科技有限公司 | 微晶玻璃及其制备方法和应用 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010032113B9 (de) * | 2010-07-23 | 2017-06-22 | Schott Ag | Transparente oder transparente eingefärbte Lithiumaluminiumsilikat-Glaskeramik mit einstellbarer thermischer Ausdehnung und deren Verwendung |
JP7268673B2 (ja) * | 2018-02-27 | 2023-05-08 | Agc株式会社 | 3次元形状の結晶化ガラス、3次元形状の化学強化ガラスおよびそれらの製造方法 |
CN114988704A (zh) * | 2019-02-08 | 2022-09-02 | Agc株式会社 | 微晶玻璃、化学强化玻璃和半导体支撑基板 |
CN110510879A (zh) * | 2019-08-21 | 2019-11-29 | 成都光明光电股份有限公司 | 微晶玻璃制品、微晶玻璃及其制造方法 |
CN110627365B (zh) * | 2019-09-25 | 2022-12-27 | 重庆鑫景特种玻璃有限公司 | 一种透明的强化玻璃陶瓷及其制备方法 |
CN110734226B (zh) * | 2019-12-03 | 2021-12-17 | 重庆鑫景特种玻璃有限公司 | 一种具有超高分叉阈值的微晶玻璃 |
CN110981206B (zh) * | 2019-12-20 | 2022-04-05 | 重庆鑫景特种玻璃有限公司 | 一种多晶核复合透明玻璃陶瓷及其制备方法 |
CN111320392B (zh) * | 2020-03-05 | 2022-09-06 | 科立视材料科技有限公司 | 微晶玻璃、强化微晶玻璃及其制备方法 |
CN113754286B (zh) * | 2020-12-31 | 2024-03-15 | 成都光明光电股份有限公司 | 微晶玻璃、微晶玻璃制品及其制造方法 |
-
2021
- 2021-07-08 CN CN202110774451.0A patent/CN115594406A/zh active Pending
- 2021-07-08 CN CN202211530153.8A patent/CN115959831A/zh active Pending
-
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- 2022-04-28 EP EP22773381.3A patent/EP4137468A4/en active Pending
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- 2022-04-28 US US17/913,060 patent/US20240217870A1/en active Pending
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110872175A (zh) * | 2018-08-31 | 2020-03-10 | 深圳市东丽华科技有限公司 | 一种微晶玻璃及利用其制成的具有复合压应力的玻璃基板 |
US20210024405A1 (en) * | 2018-10-26 | 2021-01-28 | Cdgm Glass Co., Ltd | Microcrystalline Glass, Microcrystalline Glass Product, and Manufacturing Method Therefor |
TW202100482A (zh) * | 2019-06-26 | 2021-01-01 | 日商Agc股份有限公司 | 化學強化玻璃之製造方法及化學強化玻璃 |
CN110845153A (zh) * | 2019-12-03 | 2020-02-28 | 深圳市东丽华科技有限公司 | 一种具有高压应力层深度的强化微晶玻璃及其制备方法 |
CN112919812A (zh) * | 2019-12-06 | 2021-06-08 | 华为技术有限公司 | 微晶玻璃、化学强化微晶玻璃、其制备方法及电子设备 |
CN112939472A (zh) * | 2019-12-11 | 2021-06-11 | 四川旭虹光电科技有限公司 | 微晶玻璃及其制备方法和应用 |
CN111018356A (zh) * | 2019-12-30 | 2020-04-17 | 深圳市东丽华科技有限公司 | 一种高晶体含量的微晶玻璃及其制备方法 |
CN112608033A (zh) * | 2020-09-12 | 2021-04-06 | 重庆鑫景特种玻璃有限公司 | 一种化学强化微晶玻璃及强化方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4137468A4 |
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