CN112645588B - Sodium glass, chemically strengthened glass and preparation method of chemically strengthened glass - Google Patents
Sodium glass, chemically strengthened glass and preparation method of chemically strengthened glass Download PDFInfo
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- CN112645588B CN112645588B CN201911060997.9A CN201911060997A CN112645588B CN 112645588 B CN112645588 B CN 112645588B CN 201911060997 A CN201911060997 A CN 201911060997A CN 112645588 B CN112645588 B CN 112645588B
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- 239000011521 glass Substances 0.000 title claims abstract description 240
- 239000011734 sodium Substances 0.000 title claims abstract description 130
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 88
- 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 title claims abstract description 71
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005342 ion exchange Methods 0.000 claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 238000002834 transmittance Methods 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 114
- 150000003839 salts Chemical class 0.000 claims description 60
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 22
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 nitrate ions Chemical class 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 238000003426 chemical strengthening reaction Methods 0.000 claims 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 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910000500 β-quartz Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 239000006058 strengthened glass Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002500 ions Chemical group 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000005341 toughened glass Substances 0.000 description 6
- 239000006018 Li-aluminosilicate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001066 destructive effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010205 computational analysis Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
Abstract
The invention discloses sodium glass, chemically strengthened glass and a preparation method of the chemically strengthened glass. The sodium glass comprises the following elements in mole percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and 0.01 to 0.25 percent of Cl and S in total; wherein the ratio of the Na content to the Li content is 1-11.5. The sodium glass is particularly suitable for the sodium glass of a windshield of a high-speed moving vehicle, and has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance, uniform-thickness flat plates, large size, large thickness range and low dielectric constant. The sodium glass is taken as a raw material, and the strengthened glass with high strength and high safety can be prepared through one-step ion exchange.
Description
Technical Field
The invention belongs to the technical field of glass and glass manufacturing, and particularly relates to sodium glass, chemically strengthened glass and a preparation method of the chemically strengthened glass.
Background
Ion-exchange strengthened glass is used more and more widely because of its high strength. For example, windshields of high-speed moving vehicles (especially civil aircraft, military aircraft and high-speed trains), protective covers of handheld electronic terminals, and electric automobiles adopting reinforced glass can reduce the thickness, thereby saving energy and prolonging the working mileage of batteries.
The material of the windshield commonly used for aviation, automobiles and high-speed trains at present is generally high-alumina-silica glass, and the high-alumina-silica glass has high melting clarification difficulty, high glass liquid viscosity, difficult bubble discharge and difficult control of the production process due to high aluminum content. Meanwhile, the high-alumina-silica glass has the problems of low overall impact strength, poor safety and auto-explosion risk, and a series of safety accidents caused by the breakage of windshields of civil aircrafts frequently occur in the near term. In order to further improve the impact strength of the glass, most manufacturers form lithium aluminosilicate glass by introducing a large amount of Li as a main alkali metal component into the glass, so that the depth DOL of the compressive stress of the obtained strengthened glass is usually more than 100um, and more internal tensile stress can be accommodated, but the internal tensile stress is increased, and the stability and the safety of the glass are reduced; among all elements capable of being ion exchanged, lithium ions are the smallest, so that the surface compressive stress and the surface hardness generated after ion exchange are too low, irreversible micro scratches and cracks are easy to generate, safety problems are induced, and the problems of instantaneous strength release and complete breakage of glass are solved; li is a rare element and also is the most important component of a lithium battery, the cost of Li is always increased and high with the application of a large amount of new energy and batteries, and in the lithium aluminosilicate glass, the cost of only a lithium raw material accounts for more than 40% of the cost of the glass, so that the production cost of the lithium aluminosilicate glass is high, and meanwhile, because lithium has a very high crystallization tendency, the production process of the lithium aluminosilicate glass is difficult to control due to the high lithium content, and the lithium aluminosilicate glass is not the best choice.
The invention designs sodium glass with a special formula, which has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance and low dielectric constant, and the sodium glass is subjected to a one-step ion exchange chemical strengthening process to obtain strengthened glass with gradually reduced and gradually changed single compressive stress, so that the strengthened glass obtained in the way not only has higher destructive strength, but also has excellent safety, and the self-explosion risk is far less than that of the strengthened glass in the prior art, and can be widely applied to windshields of various aviation, high-speed trains and automobile products, protective glass of electronic products and the like. In addition, because lithium has a very good viscosity reducing effect, and simultaneously, the elastic modulus of the glass can be properly improved, and a small amount of lithium is added into the sodium glass, the production process is simple and easy to control, the production cost is low, and the network structure matching is more reasonable.
Disclosure of Invention
The technical problem to be solved by the invention is to provide sodium glass which is particularly suitable for windshields of high-speed moving vehicles and has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance, uniform-thickness flat plates, large size, large thickness range and low dielectric constant.
Another technical problem to be solved by the present invention is to provide a chemically strengthened glass, which is obtained by chemically strengthening the soda glass.
The invention also aims to provide a preparation method of chemically strengthened glass, wherein the preparation method refers to a process for preparing the strengthened glass from the soda glass.
The technical scheme adopted by the invention for solving the problem is to provide sodium glass, wherein the sodium glass comprises the following elements in mole percentage: the sodium glass comprises the following elements in mole percent: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O.
As a preferable aspect of the soda glass provided by the invention, the soda glass contains the following elements in mol percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein, the content of S is 0.01-0.22%, the ratio of Na content to Li content is 1-11.5, and the ratio of Na content to Li content is 1-11.5.
As a preference of the soda glass provided by the invention, the soda glass contains the following oxides in mole percentage: 6 to 18% of Na 2 O, siO 60% or more 2 9% or more of Al 2 O 3 1% -6% of Li 2 O, mgO of more than or equal to 1 percent and SO of 0.01 to 0.2 percent 3 。
The soda glass provided by the invention preferably has an elastic modulus of 65-88.2 Gpa and a Vickers hardness of 490-592 kgf/mm 2 And the brittleness is 57.5-72.3. Wherein the content of the first and second substances,
the brittleness formula is defined in the special example, vickers hardness is introduced in the formula to reflect the plastic deformation capability of the glass, and the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range although the plastic deformation capability of the glass is lower, so that the brittleness of the glass can be effectively reduced.
The sodium glass provided by the invention preferably has a dielectric constant of 5.5-7.75 under the condition that the frequency is 1 MHZ-3.5 GHZ.
The soda glass provided by the invention preferably has an expansion coefficient of 57 x 10 under the temperature condition of 20-400 DEG C -7 /℃～101×10 -7 /℃。
The soda glass provided by the invention preferably has a density of 2.38-2.52g/cm at a temperature of 20 DEG C 3 。
Preferably, the soda glass provided by the invention has a temperature of 1250-1493 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)); the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃.
As a preference of the soda glass provided by the invention, the soda glass further comprises the following oxides in mole percentage: 0.5% -2% of ZrO 2 (ii) a Wherein Li 2 High content of O2% or more of SiO 2 The content of (A) is 62 to 75 percent, and Al 2 O 3 9 to 17 percent of Na 2 Content of O and Li 2 The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent.
The soda glass provided by the invention preferably contains more alkali metal oxide than Al 2 O 3 Content of (A), na 2 Content of O and Li 2 The ratio of the content of O is 1 to 9.
Preferably, in the soda glass provided by the invention, the blending index theta of O and Si in the soda glass is 0.35-1.10. Wherein the blending index
Wherein X is the ratio of the content of O to the content of Si in the sodium glass. Further, the blending index theta is 0.61-1.10, and further, the blending index theta is 0.71-1.10.
As a preference of the soda glass provided by the invention, the soda glass further comprises the following oxides in mole percentage: 1% -4% of B 2 O 3 (ii) a Wherein the total content of alkali metal oxide and Al 2 O 3 Difference of contents of (A) and (B) 2 O 3 The absolute value of the ratio of the contents of (b) is 1 or more.
The soda glass provided by the invention preferably has an elastic modulus of 65-77 Gpa, a dielectric constant of 5.59-7.58 under the condition that the frequency is 1 MHZ-3.5 GHZ, and a density at 20 ℃ of 2.387-2.495 g/cm 3 。
Preferably, the soda glass provided by the invention has a corresponding temperature of 1274 to 1493 ℃, a liquid line temperature of 1086 to 1300 ℃, and a softening point temperature of 726 to 876 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)).
As a preference of the soda glass provided by the invention, the soda glass includes an amorphous portion and a plurality of shaped portions; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50nm; the average size of all of the shaped portions is less than 30nm.
Preferably, the sodium glass of the present invention has an average size of all the shaped portions of 10 to 30nm.
As a preference of the sodium glass provided by the invention, the shaped part comprises nepheline and ZrO 2 One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.
As the preference of the soda glass provided by the invention, al in the soda glass 2 O 3 Is 9 to 15.5 percent, and the sodium glass also comprises the following oxides in percentage by mol: 0.5-2% of rare earth oxide and 0.5-4% of K 2 O,0 to 7% of P 2 O 5 (ii) a Wherein the rare earth oxide at least comprises CeO 2 And CeO 2 The content of (A) is more than or equal to 0.5 percent; k 2 O、Na 2 O and Li 2 The sum of the contents of O is 1 to 20 percent.
The soda glass provided by the invention preferably has an elastic modulus of 65.6-75.4 Gpa and a Vickers hardness of 510-592 kgf/mm 2 The sodium glass has an expansion coefficient of 60 multiplied by 10 under the temperature condition of 20-400 DEG C -7 /℃～100.3×10 -7 The density at 20 ℃ is 2.39-2.491 g/cm 3 。
Preferably, the soda glass provided by the invention has a temperature of 1299 to 1493 ℃, a liquidus temperature of 1112 to 1300 ℃, a softening point temperature of 745 to 876 ℃ and a transition point Tg temperature of 515 to 579 ℃ when the viscosity of the soda glass is lg3 (visc./(poison)).
The soda glass provided by the invention preferably has an elastic modulus of 67-75.4 Gpa and a density at 20 ℃ of 2.417-2.48 g/cm 3 。
Preferably, the soda glass provided by the invention has brittleness of 60-69.2.
The soda glass provided by the invention is preferably Na 2 The content of O is 9-15.5%, li 2 The content of O is 2-5%.
As the preferable aspect of the soda glass provided by the invention, the elastic mold of the soda glass67.2 to 75.4GPa, the sodium glass has a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 at a frequency of 1MHZ to 3.5GHZ, and an expansion coefficient of 71 x 10 at a temperature of 20 to 400 DEG C -7 /℃～100.3×10 -7 The density at 20 ℃ is 2.42-2.48 g/cm 3 (ii) a The corresponding temperature is 1330-1450 ℃ when the viscosity of the sodium glass is lg3 (visc./(Poise)), the liquid line temperature is 1130-1255 ℃, and the softening point temperature is 745-850 DEG C
In the soda glass, na is preferably added to the soda glass in a molar percentage 2 The content of O is 11-15.5%, li 2 The content of O is 2 to 5 percent.
The thickness of the soda glass is preferably 0.4-10 mm.
The thickness of the soda glass is preferably 0.4-8 mm.
Preferably, the soda glass provided by the invention further comprises 0.01 to 0.25% of S in mol percentage.
As the sodium glass provided by the invention, the mole percentage content of S in the sodium glass is 0.01-0.22%,
the sodium glass provided by the invention preferably contains 0.01 to 0.15 mol% of S.
Preferably, the soda glass provided by the invention is subjected to ion exchange treatment, and then the size of the soda glass is increased by 0.05-0.1%.
In order to solve the technical problem, the invention also provides chemically strengthened glass, which is formed by placing the sodium glass in a salt bath for ion exchange, wherein the thickness of a compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to one tenth of the thickness of the glass, and the surface compressive stress is more than or equal to 600MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92 percent, and a temperature of 1300 ℃ or less when the viscosity is lg4 (visc./(Poise)).
Preferably, the chemically strengthened glass of the present invention has a surface compressive stress of 650 to 1100MPa.
Preferably, the chemically strengthened glass provided by the present invention has a surface compressive stress of 700 to 900MPa.
Preferably, the chemically strengthened glass provided by the present invention has a tensile stress linear density of 28000 to 58000Mpa/mm.
As the chemically strengthened glass provided by the invention, the tensile stress linear density of the chemically strengthened glass is preferably 28000-50000 MPa/mm.
Preferably, in the chemically strengthened glass of the present invention, the depth of the ion exchange layer formed on the surface of the chemically strengthened glass by ion exchange is at least 20 μm greater than the depth of the compressive stress layer.
The chemically strengthened glass provided by the present invention preferably has an expansion coefficient of 50X 10 at a temperature of-100 to 100 ℃ -7 /℃～100×10 -7 /℃。
Preferably, in the chemically strengthened glass provided by the present invention, in a static pressure destructive test, an area of a largest fragment formed by breaking the chemically strengthened glass having a length × width × thickness dimension of 50mm × 50mm × 0.7mm is 5% to 45% of a total area of the chemically strengthened glass subjected to the test.
In addition, the invention also provides a preparation method of the chemically strengthened glass, which is to place the sodium glass in the mixed salt bath for ion exchange to prepare the chemically strengthened glass; the mixed salt bath contains at least three metal ions which are respectively K + 、Na + 、Li + Wherein, K is + The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na + The content in the mixed salt bath is not less than 500ppm + In the mixed saltThe content in the bath is 20-1000 ppm.
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, K + Molar amount of (A)>Na + Molar amount of (A)>Li + The molar amount of (c).
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, na + The molar amount of (b) is 30% or less of the total molar amount of alkali metal ions.
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, na + The molar amount of (a) is less than 25% of the total molar amount of alkali metal ions.
Preferably, in the preparation method provided by the present invention, the mixed salt bath further contains non-ionic alumina, and the non-ionic alumina accounts for 2% or less of the mass of the mixed salt bath.
As a preference of the preparation method provided by the present invention, the preparation method is a single ion exchange.
As the optimization of the preparation method provided by the invention, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃.
Preferably, the mixed salt bath contains nitrate ion NO 3 - ，NO 3 - The molar amount of (a) is 95% or more of the total molar amount of the anions.
Preferably, the mixed salt bath contains hydroxide ions OH - ，OH - The molar amount of (a) is 2.5% or less of the total molar amount of anions.
As a preference of the preparation method provided by the present invention, the mixed salt bath further contains other anions: CO 2 3 2- Or/and PO 4 3- 。
Preferably, in the preparation method provided by the invention, li in the mixed salt bath + The content of (B) is 20-600ppm.
Preferably, the mixed salt bath contains hydroxide ions OH - ，OH - In molar amount ofMore than 1.1 percent of the total molar amount of anions.
Drawings
FIG. 1 is a schematic diagram illustrating the comparison of DOI and DOL in a chemically strengthened glass according to the present invention;
FIG. 2 example 75 provides a DOI profile and a DOL profile within a chemically strengthened glass.
Detailed Description
Before describing the soda glass, the preparation method and the chemically strengthened glass, it is necessary to explain some terms and some methods for measuring physicochemical properties.
Method for measuring compressive stress value (CS): the measurements were carried out using an optical guided Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).
The detection method of the depth of layer (DOL) of the compressive stress comprises the following steps: measurements were performed using an optical guided Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).
The detection method of the tensile stress value (CT) comprises the following steps: after the compressive Stress distribution data of the Surface and the interior of the glass are obtained by measuring with an optical guided wave Surface Stress Meter (FSM 6000 LE), the compressive Stress, the maximum tensile Stress, the average tensile Stress and the tensile Stress distribution are obtained by fitting with Orihara Pmc software.
DOI indicates the depth of penetration of alkali metal ions into the glass due to the ion exchange process and can be determined by Electron Probe Microanalysis (EPMA) or glow discharge-optical emission spectroscopy (GD-OES). The DOI of the chemically strengthened glass provided by the present invention is generally much greater than DOL.
Tensile stress linear density: the tempered glass is formed by ion exchange in a salt bath, a tensile Stress layer is formed in the glass in the ion exchange process, the tensile Stress layer is provided with an upper boundary which is at a certain interval with the upper Surface of the tempered glass and a lower boundary which is at a certain interval with the lower Surface of the tempered glass, a curve which is drawn by taking the tensile Stress at a certain point which is perpendicular to the upper boundary and the lower boundary in the tensile Stress layer and has upper and lower end points falling on a line segment on the upper boundary and the lower boundary respectively as a Y axis and the distance from the corresponding point to the upper boundary as an X axis is taken as a tensile Stress curve, and the ratio of the fixed integral of the tensile Stress curve to the thickness of the tempered glass is taken as the tensile Stress line density, namely the ratio of the sum of the tensile stresses of the tempered glass measured by an Orihara Surface Stress Meter, FSM6000LE Stress Meter to the thickness of the tempered glass.
Static pressure destructive test method:
1) The sample size was: length × width × thickness =50mm × 50mm × 0.7mm;
2) The operation method comprises the following steps: refer to ISSN1003-8817 and the fifth stage of 2019, which is published under the unified publication number CN22-1187/U in the United states of America and industry, and describe the obtuse stress release test method in the document of "application prospect of lithium sodium aluminum silicon chemically strengthened glass on automobile glass" published by Hu Wei, mushroom Wen Cheng, shibaoqi et al.
The Vickers hardness, modulus of elasticity, compressive strength, dielectric constant, coefficient of expansion, density, viscosity, liquidus temperature, softening point temperature, transition point Tg temperature, visible light average transmittance, viscosity referred to herein are determined using methods common in the art.
The crystalline form of the shaped portion within the soda glass can be obtained by XRD analysis.
The sodium glass provided by the invention comprises the following elements in percentage by mole: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O. Preferably, the soda glass contains the following elements in mole percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg and 58.52 to 61.52 percent of O; wherein the ratio of the Na content to the Li content is 1-11.5. The content of Si is controlled by controlling the content of O in the sodium glass raw components and a certain functional relation, so that the glass network structure taking Si as a core is controlled, and the glass has a better complete network structure. The sodium glass has certain characteristics of low content of Li and small content of Li, and mainly aims to reduce the high-temperature viscosity of the glass, facilitate melting, optimize the glass structure, improve the elasticity of the glass and construct a good network structure. In a word, the components of the sodium glass designed by the invention can comprehensively improve the network quality of the sodium glass, further realize higher intrinsic strength of the glass and improve the impact resistance and the compressive stress storage capacity of the sodium glass. In addition, the thickness range of the sodium glass easy to form is 0.4-10.0mm, preferably 0.4-8mm, transparent, equal-thickness and large-size glass can be obtained through the float normal line production, the thickness can be applied to the front windshield, and the thickness can be applied to the side window.
In some embodiments, the soda glass comprises the following oxides: 6 to 18 percent of Na 2 O, siO 60% or more 2 9% or more of Al 2 O 3 1 to 6% of Li 2 O, and MgO with the content of more than or equal to 1 percent. The soda glass has a certain amount of Al 2 O 3 The wear resistance of the sodium glass is obviously improved; controlling Al 2 O 3 The content of more than or equal to 9 percent is beneficial to improving the network structure size and the network integrity of the glass, and can improve the storage capacity of the compressive stress formed by ion exchange. Incorporation of MgO and relatively small amounts of Li in glass 2 The O, mg and Li ions have higher field strength, have an aggregation effect at low temperature, can greatly tamp the glass network and increase the elasticity of the glass under the condition that the glass network is relatively complete, so the anti-falling capability of the glass is increased, the two elements have a melting promoting effect at high temperature, the melting difficulty of the glass is reduced, the Li has higher crystallization inclination, and the glass is sodium glass mainly exchanging K-Na ions, so the introduction amount of the Li needs to be controlled.
The sodium glass described in the above examples had an elastic modulus of 65 to 88.2GPa and a Vickers hardness of 490 to 592kgf/mm 2 And the brittleness is 57.5-72.3. Wherein the content of the first and second substances,
the common product solves the problem of high strength, which is divided into impact resistance, drop resistance, probe resistance and roller resistance, and the patent is mainly used for solving the problems of high strengthThe brittleness formula is defined in the special example, vickers hardness is introduced in the formula to reflect the plastic deformation capability of the glass, and although the plastic deformation capability of the glass is lower, the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range, so that the brittleness of the glass can be effectively reduced.
The sodium glass described in the above examples has a dielectric constant of 5.5 to 7.75 at a frequency of 1MHz to 3.5 GHz. The sodium glass has low dielectric constant and small electrostatic adsorption, so that the sodium glass does not influence microwave communication in high-speed motion.
The sodium glass described in the above examples has an expansion coefficient of 57X 10 at a temperature of 20 to 400 deg.C -7 /℃～101×10 -7 /. Degree.C.. The lower expansion coefficient does not generate larger deformation, stress and strain in a larger temperature range, thereby obviously improving the safety and the reliability of the glass. Therefore, when the application scene of the product is extremely cold and hot, the safety of the product is ensured by the small expansion size.
The density of the sodium glass in the above embodiment is 2.38-2.52g/cm at 20 DEG C 3 . The invention controls the density range of the sodium glass to be 2.38-2.52g/cm 3 The glass has smaller density and substantially larger atom packing density, thereby having relatively larger plastic deformation capacity, reducing the brittleness of the glass and increasing the toughness of the glass.
The temperature for the soda glass described in the above examples is 1250 to 1493 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)); the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃. In the composition of soda glass, mgO and Li are controlled 2 The content of O is small, so that the viscosity of the glass at high temperature is directly influenced, and the soda-alumina-silica glass has good viscosity and temperature gradient change characteristics and has a great effect on large-size forming; the sodium glass has a lower softening point, is lower than the softening point of common high-alumina sodium glass by more than 50 ℃ on average, and is more suitable for hot-forming required by various complex shapes.
The sodium glass of the above embodiment is subjected to ion exchange treatment and then the size of the sodium glass is increased by 0.05 to 0.1 percent. That is, the dimensional change of the soda glass before and after the chemical strengthening treatment is not large, and the control is easy.
In some embodiments, the soda glass further comprises, in mole percent, the following oxides: 0.5% -2% of ZrO 2 (ii) a Wherein, li 2 O content of 2% or more, siO 2 The content of (A) is 62 to 75 percent, and Al 2 O 3 9 to 17 percent of Na 2 Content of O and Li 2 The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent; and the total content of alkali metal oxides is greater than Al 2 O 3 Content of (A), na 2 Content of O and Li 2 The ratio of the content of O is 1 to 9.
The sodium glass described in the above examples had an elastic modulus of 65 to 77Gpa, a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5GHZ, and a density of 2.387 to 2.495g/cm at 20 ℃ 3 . By adding appropriate amount of ZrO 2 While to Li 2 Content of O, siO 2 Content of (C), al 2 O 3 Further control of the content of (A) and Na 2 Content of O and Li 2 The control of the ratio of the contents of O enables the density of the soda glass to reach a smaller value with the elastic modulus and the dielectric constant of the soda glass kept at good levels.
The soda glass described in the above examples has a viscosity lg3 (visc./(Poise)) corresponding to a temperature of 1274 to 1493 ℃, a liquidus temperature of 1086 to 1300 ℃, and a softening point temperature of 726 to 876 ℃.
In some embodiments, in the soda glass, the blending index θ of O and Si in the soda glass is 0.35 to 1.10; more preferably, the blending index theta is 0.61-1.10; more preferably, the blending index θ is 0.71 to 1.10. Wherein the blending index
Wherein X is the ratio of the content of O to the content of Si in the soda glass.
In some casesIn an embodiment, the soda glass further comprises, in mole percent, the following oxides: 1% -4% of B 2 O 3 (ii) a Wherein the total content of alkali metal oxide and Al 2 O 3 Difference of contents of (A) and (B) 2 O 3 The absolute value of the ratio of the contents of (a) is 1 or more.
In some embodiments, the soda glass includes an amorphous portion and a plurality of shaped portions; the size of each sizing part is 5-100 nm; the average size of all of the shaped portions is less than 50nm; the average size of all of the shaped portions is less than 30nm. Preferably, the average size of all the shaped portions is 10 to 30nm. Preferably, the shaped portion comprises nepheline and ZrO 2 One or more of cordierite, spinel, a beta-quartz solid solution, petalite and lithium silicate.
In some embodiments, the soda glass includes Al 2 O 3 Is 9 to 15.5 percent, and the sodium glass also comprises the following oxides in percentage by mol: 0.5-2% of rare earth oxide and 0.5-4% of K 2 O,0 to 7% of P 2 O 5 (ii) a Wherein the rare earth oxide at least comprises CeO 2 And CeO 2 The content of (A) is more than or equal to 0.5 percent; k 2 O、Na 2 O and Li 2 The sum of the contents of O is 1 to 20 percent.
The soda glass according to the above embodiment, wherein the soda glass has an elastic modulus of 65.6 to 75.4GPa and a Vickers hardness of 510 to 592kgf/mm 2 The sodium glass has an expansion coefficient of 60 multiplied by 10 under the temperature condition of 20-400 DEG C -7 /℃～100.3×10 -7 The density at 20 ℃ is 2.39-2.491 g/cm 3 . By adding appropriate amount of rare earth oxide and reacting with K 2 O、Na 2 O and Li 2 The sum of the contents of O is controlled so that the density of the soda glass can be reduced while maintaining the elastic modulus, vickers hardness, and expansion coefficient of the soda glass at a satisfactory level.
The soda glass described in the above examples has a viscosity lg3 (visc./(Poise)) corresponding to a temperature of 1299 to 1493 ℃, a liquidus temperature of 1112 to 1300 ℃, a softening point temperature of 745 to 876 ℃ and a transition point Tg temperature of 515 to 579 ℃.
The sodium glass described in the above examples had a brittleness of 60 to 69.2. By adding appropriate amount of rare earth oxide and reacting with K 2 O、Na 2 O and Li 2 The sum of the contents of O is controlled, so that the brittleness of the sodium glass is stabilized at a reliable level.
In some embodiments, the soda glass is Na 2 The content of O is 9-15.5%, li 2 The content of O is 2-5%. Preferably, in the soda glass, na 2 The content of O is 11 to 15.5 percent.
The soda glass described in the above examples has an elastic modulus of 67.2 to 75.4GPa, a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 at a frequency of 1MHZ to 3.5GHZ, and an expansion coefficient of 71X 10 at a temperature of 20 to 400 ℃ -7 /℃～100.3×10 -7 The density at 20 ℃ is 2.42-2.48 g/cm 3 (ii) a The temperature corresponding to the viscosity of the sodium glass is lg3 (visc./(Poise)), the temperature is 1330-1450 ℃, the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.
In some embodiments, the soda glass further includes, in mole percent, 0.01 to 0.25% S. Preferably, the mole percentage content of S in the soda glass is 0.01 to 0.22%, and more preferably, the mole percentage content of S in the soda glass is 0.01 to 0.15%.
The preparation method of the chemically strengthened glass provided by the invention is a process for preparing the chemically strengthened glass provided by the invention after the sodium glass provided by the invention is placed in a mixed salt bath for ion exchange.
The mixed salt bath contains at least three metal ions which are respectively K + 、Na + 、Li + Wherein, K is + The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na + The content in the mixed salt bath is not less than 500ppm + The content in the mixed salt bath is 20-1000 ppm. Using said mixed salt bath to pass K + -Na + Ion deviceThe main chemical reaction forms CS less than 50 microns on the surface of the sodium glass, so that the impact strength of the glass can be improved, and the safety of the glass can be ensured. During ion exchange, K is introduced + 、Na + 、Li + Ternary ion whose main ion exchange reaction is foreign K + With Na in glass + Carrying out a displacement reaction; alkali metal ion K in salt bath + 、Na + 、Li + Can be exchanged with each other, and Na is introduced into the salt bath + And Li + To balance K + -Na + Ion exchange reaction, control of K + The speed and the degree of the sodium glass entering the sodium glass control the size and the total amount of CS formed on the surface of the sodium glass, so that overhigh internal stress CT is avoided, and the safety of the glass is reduced. Preferably, K + Molar amount of (A)>Na + Molar amount of (A)>Li + The molar amount of (c). Wherein due to Li + The activity of the ion is greatest, therefore Li + The mol content of the ions is set to be the lowest among the alkali metal ions; introduction of Li into salt bath + Another important reason for the lower ion content is the control of Na in the salt bath + Ion-displacing Li in glass + Additional CS is formed, resulting in excessive internal stress CT, reducing the safety of the glass. Further preferably, na + Is less than 30%, even less than 25%, of the total molar amount of alkali metal ions. More preferably, li in the mixed salt bath + The content of (B) is 20-600ppm.
The ion exchange time is 3-12 hours, and the temperature of the mixed salt bath is kept at 390-500 ℃ in the ion exchange process.
In some embodiments, the mixed salt bath comprises nitrate ion NO 3 - ，NO 3 - The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH - ，OH - The molar amount of (a) is less than 2.5% of the total molar amount of anions; the mixed salt bath also comprises other anions: CO 2 3 2- Or/and PO 4 3- . The effect of anions in the mixed salt bath cannot be ignored and is the present hairThe invention introduces a plurality of anions which have adsorption and precipitation effects on ions released from glass in ion exchange, thereby avoiding toxic and side effects in salt bath.
In some embodiments, the manufacturing process is a single ion exchange, that is, the soda glass is only chemically strengthened once during the manufacturing process. Because the salt bath is a mixed salt bath, two ion exchanges of potassium-sodium ion exchange and sodium-lithium ion exchange are included in the single ion exchange process.
The chemically strengthened glass provided by the invention is obtained by chemically strengthening sodium glass provided by the invention as raw material glass according to the preparation method provided by the invention. The detection analysis of the chemically strengthened glass by using the conventional detection means in the field can find that: the thickness of the compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to 50 mu m, and the surface compressive stress is more than or equal to 600MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has the tensile stress linear density of 20000-75000 Mpa/mm, the thickness of 0.4-10 mm, the Vickers hardness of more than 520HV, the visible light average transmittance of 90-92 percent and the temperature of 1300 ℃ or less when the viscosity is lg4 (visc./(Poise)). The chemical strengthened glass has higher surface compressive stress CS and lower tensile stress CT, which shows that the chemical strengthened glass with higher CS and lower CT can be effectively formed by effectively controlling the degree of ion exchange reaction through the quaternary ion exchange salt bath. The chemically strengthened glass retains the elasticity endowed by the unique component design of the corresponding sodium glass, and simultaneously obtains higher impact resistance and safety through ion exchange.
In some embodiments, the chemically strengthened glass has a surface compressive stress of 650 to 1100MPa, preferably 700 to 900MPa.
In some embodiments, the chemically strengthened glass has a tensile stress linear density of 28000 to 58000MPa/mm, preferably 28000 to 50000MPa/mm.
In some embodiments, the depth of the ion exchange layer formed by ion exchange at the surface of the chemically strengthened glass is at least 20um greater than the depth of the compressive stress layer. The maximum depth DOI of alkali metal ions entering the chemically strengthened glass through ion exchange can be detected by an electron probe or SEM + EDS, and the maximum depth DOL of surface compressive stress, the maximum depth CS of surface compressive stress and the maximum depth CT of internal tensile stress can be detected by a waveguide optical surface stress meter, wherein the value of DOI is far larger than that of DOL (see figure 1).
In some embodiments, the chemically strengthened glass has a coefficient of expansion of 50 × 10 at a temperature of-100 to 100 ℃ -7 /℃～100×10 -7 V. C. The application scene of the chemically strengthened glass is that when the chemically strengthened glass is extremely cold and hot, the small expansion size ensures the safety of the product.
In some embodiments, the area of the largest fragments formed by fracture of the chemically strengthened glass having a length by width by thickness dimension of 50mm by 0.7mm when tested in a hydrostatic destructive test is between 5% and 45% of the total area of the chemically strengthened glass being tested.
The chemically strengthened glass provided by the present invention can be used as cover glass for mobile electronic devices and touch enabled displays, and can also be used in displays (or as display articles) (e.g., billboards, points of sale systems, computers, navigation systems, etc.), building articles (walls, fixtures, panels, windows, etc.), transportation articles (e.g., in automotive applications, trains, airplanes, ships, etc.), appliances (e.g., washing machines, dryers, dishwashers, refrigerators, etc.), or any article that requires some resistance to breakage.
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 12
In examples 1-12, 12 different soda glasses were provided, and the soda glasses of examples 1-12 were all produced using float lines using commercial products as starting materials. The soda glass components in examples 1 to 12 are shown in tables 1 and 2.
TABLE 1
TABLE 2
| Components | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| SiO 2 (mol％) | 69.22％ | 72.30％ | 64.80％ | 60.20％ | 67.40％ | 66.16％ |
| Al 2 O 3 (mol％) | 12.03％ | 9.10％ | 9.50％ | 15.57％ | 12.80％ | 12.04％ |
| P 2 O 5 (mol％) | 0.30％ | |||||
| B 2 O 3 (mol％) | 0.70％ | 0.70％ | 1.50％ | 0.38％ | ||
| MgO(mol％) | 1.52％ | 3.00％ | 7.80％ | 4.80％ | 2.10％ | 2.37％ |
| Li 2 O(mol％) | 4.50％ | 3.80％ | 5.60％ | 3.05％ | 2.50％ | 5.60％ |
| Na 2 O(mol％) | 11.00％ | 10.10％ | 12.00％ | 15.58％ | 11.20％ | 10.70％ |
| K 2 O(mol％) | 0.10％ | 1.40％ | ||||
| ZnO(mol％) | 0.05％ | 0.03％ | ||||
| ZrO 2 (mol％) | 0.50％ | 2.00％ | 1.15％ | |||
| TiO 2 (mol％) | 0.05％ | |||||
| SnO 2 (mol％) | 0.83％ | 0.50％ | 0.24％ | |||
| Tm 2 O 3 (mol％) | 0.20％ | |||||
| CeO 2 (mol％) | 0.03％ | 0.50％ | 0.50％ | |||
| Total | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ |
| β | 2.444 | 2.658 | 2.143 | 5.108 | 4.480 | 1.911 |
In tables 1 and 2, β means Na 2 Content of O and Li 2 The ratio of the content of O.
The mole percent content of each element contained in the soda glass of examples 1 to 12 can be obtained by calculation and is shown in tables 3 and 4.
TABLE 3
| Kind of element | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Si(mol％) | 18.38％ | 23.67％ | 17.62％ | 20.67％ | 20.10％ | 19.20％ |
| Al(mol％) | 9.38％ | 5.68％ | 10.50％ | 7.11％ | 6.91％ | 6.61％ |
| P(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| B(mol％) | 0.00％ | 0.59％ | 2.33％ | 0.00％ | 0.00％ | 0.36％ |
| Mg(mol％) | 1.19％ | 0.95％ | 0.29％ | 3.87％ | 4.90％ | 2.98％ |
| Li(mol％) | 1.23％ | 3.79％ | 1.75％ | 0.65％ | 2.29％ | 2.59％ |
| Na(mol％) | 11.03％ | 3.79％ | 6.93％ | 7.42％ | 5.88％ | 9.28％ |
| K(mol％) | 0.00％ | 0.00％ | 0.80％ | 0.00％ | 0.00％ | 0.11％ |
| Zn(mol％) | 0.09％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Zr(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Ti(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Sn(mol％) | 0.16％ | 0.02％ | 0.05％ | 0.06％ | 0.07％ | 0.35％ |
| Tm(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Ce(mol％) | 0.00％ | 0.00％ | 0.04％ | 0.06％ | 0.06％ | 0.00％ |
| O(mol％) | 58.55％ | 61.52％ | 59.69％ | 60.16％ | 59.80％ | 58.52％ |
| total | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ |
| θ | 51.11％ | 107.78％ | 36.12％ | 74.87％ | 68.92％ | 62.50％ |
TABLE 4
| Kind of element | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Si(mol％) | 21.37％ | 22.84％ | 20.82％ | 18.38％ | 20.64％ | 20.53％ |
| Al(mol％) | 7.43％ | 5.75％ | 6.11％ | 9.51％ | 7.84％ | 7.47％ |
| P(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.18％ | 0.00％ | 0.00％ |
| B(mol％) | 0.43％ | 0.44％ | 0.00％ | 0.00％ | 0.92％ | 0.24％ |
| Mg(mol％) | 0.47％ | 0.95％ | 2.51％ | 1.47％ | 0.64％ | 0.74％ |
| Li(mol％) | 2.78％ | 2.40％ | 3.60％ | 1.86％ | 1.53％ | 3.48％ |
| Na(mol％) | 6.79％ | 6.38％ | 7.71％ | 9.51％ | 6.86％ | 6.64％ |
| K(mol％) | 0.06％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.87％ |
| Zn(mol％) | 0.02％ | 0.00％ | 0.01％ | 0.00％ | 0.00％ | 0.00％ |
| Zr(mol％) | 0.00％ | 0.16％ | 0.00％ | 0.00％ | 0.61％ | 0.36％ |
| Ti(mol％) | 0.02％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Sn(mol％) | 0.26％ | 0.16％ | 0.08％ | 0.00％ | 0.00％ | 0.00％ |
| Tm(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.12％ |
| Ce(mol％) | 0.00％ | 0.00％ | 0.01％ | 0.15％ | 0.15％ | 0.00％ |
| O(mol％) | 60.38％ | 60.93％ | 59.15％ | 58.94％ | 60.80％ | 59.56％ |
| total | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ |
| θ | 83.17％ | 99.84％ | 81.63％ | 49.48％ | 71.64％ | 75.74％ |
In the case of tables 3 and 4,
wherein X is the ratio of the content of O to the content of Si.
It can be seen that the contents of the O element and the Si element in the soda glasses of examples 1 to 12 have the following characteristics:
the ratio of the content of O to the content of Si is X, wherein X satisfies:
individual also satisfies:
individual also satisfies:
examples 13 to 28
In examples 13 to 28, 16 different soda glasses were provided, and all of the soda glasses of examples 13 to 28 were produced from commercially available products by using a float line. The soda glass components in examples 13 to 28 are shown in tables 5 to 7.
TABLE 5
TABLE 6
TABLE 7
In tables 5 to 7, β means Na 2 Content of O and Li 2 The ratio of the content of O; na (Na) 2 O+Li 2 O represents Na 2 Content of O and Li 2 Sum of the contents of O; r 2 O represents the total content of alkali metal oxides, i.e., na 2 O、Li 2 O and K 2 The total content of O; (R) 2 O-Al 2 O 3 )/B 2 O 3 The ratio of the difference between the alkali metal oxide content and the alumina content to the boron oxide content is shown.
It can be seen that Na is contained in the soda glasses of examples 13 to 28 2 O、Li 2 The content of O has the following characteristics: na (Na) 2 Content of O and Li 2 The sum of the contents of O and Na is 9 to 20 percent 2 Content of O and Li 2 The ratio of the content of O is 1 to 9.
Total alkali metal oxide content, al, in the soda glasses of examples 13 to 28 2 O 3 Content of (A) and B 2 O 3 Has the following characteristics: the total content of alkali metal oxide is greater than Al 2 O 3 And the total content of alkali metal oxides and Al 2 O 3 Difference of contents of (A) and (B) 2 O 3 The absolute value of the ratio of the contents of (b) is 1 or more.
Examples 29 to 47
In examples 29 to 47, 19 different soda glasses were provided, and all of the soda glasses of examples 29 to 47 can be produced from a commercially available product by using a float line. The soda glass components in examples 29 to 47 are shown in tables 8 to 10.
TABLE 8
TABLE 9
Watch 10
In tables 8 to 10, beta means Na 2 Content of O and Li 2 The ratio of the content of O; na (Na) 2 O+Li 2 O represents Na 2 Content of O and Li 2 Sum of the contents of O; r 2 O represents the total content of alkali metal oxides, i.e., na 2 O、Li 2 O and K 2 The total content of O; (R) 2 O-Al 2 O 3 )/B 2 O 3 Expressing the ratio of the difference between the content of alkali metal oxide and the content of alumina to the content of boron oxide; REO represents the total content of rare earth oxides, i.e., ceO 2 And Tm 2 O 3 The total content of (a).
It can be seen that Na is contained in the soda glasses of examples 29 to 47 2 O、Li 2 The content of O has the following characteristics: na (Na) 2 Content of O and Li 2 The sum of the contents of O is 9 to 20 percent, and Na 2 Content of O and Li 2 The ratio of the content of O is 1 to 9.
Total alkali Metal oxide content, al, in the soda glasses of examples 29 to 47 2 O 3 Content of (A) and B 2 O 3 Has the following characteristics: the total content of alkali metal oxide is greater than Al 2 O 3 The content of (A) is 1%About 20% and the total content of alkali metal oxides and Al 2 O 3 Difference of contents of (A) and (B) 2 O 3 The absolute value of the ratio of the contents of (a) is 1 or more.
The content of the rare earth oxide in the soda glasses of examples 29 to 47 has the following characteristics: the rare earth oxide at least comprises CeO 2 And CeO 2 The content of (A) is more than or equal to 0.5 percent; the total content of the rare earth oxide is 0.5-2%.
The soda glasses of examples 1 to 47 were subjected to physicochemical property tests using the above-mentioned test methods, and the results are shown in tables 11 to 18.
TABLE 11
TABLE 12
Watch 13
TABLE 14
Watch 15
TABLE 16
TABLE 17
Watch 18
The viscosity-temperature properties of the soda glasses of examples 1 to 47 were computationally analyzed based on the Herbert formula, and the results are shown in Table 19 below.
Watch 19
TABLE 21
TABLE 22
TABLE 23
Watch 24
TABLE 25
Watch 26
Watch 27
Watch 28
Watch 29
Watch 30
The viscosity-temperature properties of the soda glasses of examples 1 to 47 were computationally analyzed based on the Fluegel formula, and the results are shown in Table 31 below.
Watch 31
Watch 32
Watch 33
Watch 34
Watch 35
Watch 36
Watch 37
Watch 38
Watch 39
Table 41
Watch 42
Examples 48 to 58
Examples 48 to 58 provide 11 mixed salt baths which can be used in the preparation process according to the invention. The components of the mixed salt bath provided in examples 48 to 58 and the amounts of solid alumina added are shown in tables 43 to 44.
Watch 43
Watch 44
In the mixed salt bath provided in examples 48 to 58, the amount of solid alumina added was 0.8% by mass or more of the mixed salt bath.
By computational analysis, it can be concluded that the contents of the respective ions per mole of the mixed salt bath in the mixed salt baths provided in examples 48 to 58 are shown in tables 45 and 46.
TABLE 45
TABLE 46
In the mixed salt bath provided in examples 48 to 58, K + Molar amount of (A)>Na + Molar amount of (A)>Li + The molar amount of (c).
Further analysis revealed that the percentages of each type of cation in the total amount of cations and the percentages of each type of anion in the total amount of anions in the mixed salt baths provided in examples 48 to 58 are shown in tables 47 and 48.
Watch 47
Watch 48
In the mixed salt bath provided in examples 48 to 58, K + Molar amount of (A)>Na + Molar amount of (A)>Li + Molar amount of (A), K + The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na + Is less than 30% (even less than 25%) of the total molar amount of alkali metal ions. NO 3 - The molar weight of (a) is more than 95 percent of the total molar weight of anions，OH - The molar amount of (a) is 2.5% or less of the total molar amount of anions.
Further analysis can lead to the concentrations of each type of cation in the mixed salt baths provided in examples 48 to 58 being shown in tables 49 and 50.
Watch 49
Watch 50
Examples 48 to 58 provide a mixed salt bath of Na + The content in the mixed salt bath is not less than 500ppm + The content of Al in the mixed salt bath is 20-1000ppm 3+ The content in the mixed salt bath is 2000ppm or less.
Examples 59 to 76
Examples 59-76 provide 18 chemically strengthened glasses according to the present invention. The raw materials for the chemically strengthened glass provided in examples 59 to 76 and the parameters during the strengthening process are shown in tables 59 to 76.
Watch 51
Table 52
Watch 53
Watch 54
Watch 55
Watch 56
The chemical strengthening of examples 59-76 was examined using the above-mentioned examination method, and the results are shown in tables 57-59.
Watch 57
Watch 58
Watch 59
In tables 57-59, dol _ K represents the depth of penetration of potassium ions in the salt bath into the glass, i.e., dol corresponding to chemically strengthened glass; dol Na represents the depth of sodium ions in the salt bath penetrating into the glass, namely the DOI of the corresponding chemically strengthened glass.
To further illustrate that the depth of ion exchange layer (DOI) in the chemically strengthened glass provided by the present invention is at least 20um greater than the depth of compressive stress layer (DOL). We also plot the DOI and DOL profiles within the chemically strengthened glass provided in example 75, see fig. 2, where the dashed curve is the DOI profile within the chemically strengthened glass provided in example 75 and the solid curve is the DOL profile within the chemically strengthened glass provided in example 75.
While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and many modifications may be made by those skilled in the art without departing from the spirit and the scope of the invention as defined by the appended claims.
Claims (17)
1. Sodium glass, characterized in that it comprises the following elements in mol percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 6.91 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein, the content of S is 0.01 to 0.22 percent, and the ratio of the content of Na to the content of Li is 1 to 11.5; the sodium glass has an elastic modulus of 65 to 88.2GPa and a Vickers hardness of 490 to 592kgf/mm 2 The brittleness is 57.5-72.3; the thickness of the sodium glass is 1.2-10 mm.
2. The soda glass according to claim 1, characterised in that it comprises, in mole percentages, the following oxides: 6 to 18 percent of Na 2 O, siO 60% or more 2 9% or more of Al 2 O 3 1 to 6% of Li 2 O, mgO with the concentration of more than or equal to 1 percent and SO with the concentration of 0.01 to 0.2 percent 3 。
3. The soda glass as claimed in claim 1, wherein the soda glass has a dielectric constant of 1MHZ to 3.5GHZ5.5-7.75, and the expansion coefficient of 57 multiplied by 10 under the temperature condition of 20-400 DEG C -7 /℃～101×10 -7 /° c; the temperature corresponding to the viscosity of the sodium glass lg3 (visc./(Poise)) is 1250-1493 ℃, the liquidus temperature is 1060-1300 ℃, the softening point temperature is 710-880 ℃, and the transition point Tg temperature is 515-620 ℃.
4. The soda glass according to claim 1, further comprising, in mole percent, the following oxides: 0.5% -2% of ZrO 2 (ii) a Wherein Li 2 O content of 2% or more, siO 2 The content of (A) is 62 to 75 percent, and Al 2 O 3 9 to 17 percent of Na 2 Content of O and Li 2 The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent.
5. The soda glass of claim 4, wherein a blending index θ of O and Si in the soda glass is 0.35 to 1.10.
6. The soda glass of claim 4, wherein the soda glass has a total alkali metal oxide content greater than Al 2 O 3 Content of (A), na 2 Content of O and Li 2 The ratio of the content of O is 1 to 9.
7. The soda glass according to claim 4, further comprising, in mole percent, the following oxides: 1% -4% of B 2 O 3 (ii) a Wherein the total content of alkali metal oxide and Al 2 O 3 Difference of contents of (A) and (B) 2 O 3 The absolute value of the ratio of the contents of (a) is 1 or more.
8. The soda glass according to claim 4, wherein the soda glass has an elastic modulus of 65 to 77GPa and a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5 GHz; the temperature corresponding to the viscosity of the soda glass is 1274-1493 ℃ when the viscosity of the soda glass is lg3 (visc./(Poise)),the liquidus temperature is 1086-1300 ℃, and the softening point temperature is 726-876 ℃; the soda glass comprises an amorphous part and a plurality of shaped parts; the size of each sizing part is 5-100 nm; the average size of all of the shaped portions is less than 50nm; the average size of all the shaped portions is less than 30nm; the average size of all the fixed parts is 10-30 nm; the shaped part comprises nepheline and ZrO 2 One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.
9. The soda glass of claim 4, wherein Al in the soda glass 2 O 3 Is 9 to 15.5 percent, and the sodium glass also comprises the following oxides in percentage by mol: 0.5-2% of rare earth oxide and 0.5-4% of K 2 O,0 to 7% of P 2 O 5 (ii) a Wherein the rare earth oxide at least comprises CeO 2 And CeO 2 The content of (A) is more than or equal to 0.5 percent; k 2 O、Na 2 O and Li 2 The sum of the contents of O is 1 to 20 percent.
10. The soda glass as claimed in claim 9, wherein the soda glass has an elastic modulus of 65.6 to 75.4GPa and a vickers hardness of 510 to 592kgf/mm 2 The brittleness is 60-69.2, and the expansion coefficient of the sodium glass under the temperature condition of 20-400 ℃ is 60 multiplied by 10 -7 /℃～100.3×10 -7 /° c; the temperature corresponding to the viscosity of the sodium glass lg3 (visc./(Poise)) is 1299-1493 ℃, the liquidus temperature is 1112-1300 ℃, the softening point temperature is 745-876 ℃, and the transition point Tg temperature is 515-579 ℃.
11. The soda glass according to claim 9, wherein in said soda glass, na is present in a mole percentage 2 The content of O is 9-15.5%, li 2 The content of O is 2-5%.
12. The soda glass according to claim 11, wherein said soda glass bulletA modulus of 67.2 to 75.4GPa, a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 under the frequency of 1MHZ to 3.5GHZ, and an expansion coefficient of 71 x 10 under the temperature condition of 20 to 400 DEG C -7 /℃～100.3×10 -7 /° c; the temperature corresponding to the viscosity of the sodium glass is lg3 (visc./(Poise)), the temperature is 1330-1450 ℃, the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.
13. The soda glass of claim 1, wherein a size of the soda glass increases by 0.05 to 0.1% after an ion exchange treatment.
14. A chemically strengthened glass formed by ion-exchanging the sodium glass according to any one of claims 1 to 13 in a salt bath, wherein a compressive stress layer formed on a surface of the chemically strengthened glass by the ion-exchange has a thickness of one tenth or less of a thickness of the glass, and a surface compressive stress of 600MPa or more; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000MPa/mm, a thickness of 1.2 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92 percent, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)).
15. The chemically strengthened glass according to claim 14, wherein the surface compressive stress is 650 to 1100 MPa; the tensile stress linear density of the chemically strengthened glass is 28000-58000 MPa/mm; the depth of an ion exchange layer formed on the surface of the chemically strengthened glass by ion exchange is at least 20um greater than the depth of the compressive stress layer; the chemically strengthened glass has an expansion coefficient of 50 multiplied by 10 under the temperature condition of-100 to 100 DEG C -7 /℃～100×10 -7 /℃。
16. Chemical strengthening glassThe method for preparing the glass is characterized in that the method comprises the steps of placing the sodium glass in any one of claims 1 to 13 in a mixed salt bath for ion exchange to obtain the chemically strengthened glass in any one of claims 14 to 15; the mixed salt bath contains at least three metal ions which are respectively K + 、Na + 、Li + Wherein, K is + The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na + The content in the mixed salt bath is not less than 500ppm + The content in the mixed salt bath is 20-1000 ppm.
17. The preparation method according to claim 16, wherein the preparation method is single ion exchange, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃; in the mixed salt bath, na + The molar amount of (b) is less than 30% of the total molar amount of alkali metal ions; the mixed salt bath contains nitrate ions NO 3 - ，NO 3 - The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH - ，OH - The molar weight of the (B) accounts for 1.1 to 2.5 percent of the total molar weight of anions; li in the mixed salt bath + The content of (A) is 20-600ppm; the mixed salt bath also contains other anions: CO 2 3 2- Or/and PO 4 3- 。
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| CN102992600A (en) * | 2011-09-09 | 2013-03-27 | Hoya株式会社 | Method of manufacturing an ion-exchanged glass article |
| CN109071319A (en) * | 2016-04-20 | 2018-12-21 | 康宁股份有限公司 | Glass based articles comprising metal oxide concentration gradient |
| CN110104955A (en) * | 2019-05-27 | 2019-08-09 | 深圳市东丽华科技有限公司 | It is a kind of can chemical strengthening from glass ceramics ceramics and preparation method thereof |
| CN110352180A (en) * | 2017-02-27 | 2019-10-18 | 肖特玻璃科技(苏州)有限公司 | With the alumina silicate glass containing lithium of low bulk after chemical tempering |
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| CN102992600A (en) * | 2011-09-09 | 2013-03-27 | Hoya株式会社 | Method of manufacturing an ion-exchanged glass article |
| CN109071319A (en) * | 2016-04-20 | 2018-12-21 | 康宁股份有限公司 | Glass based articles comprising metal oxide concentration gradient |
| CN110352180A (en) * | 2017-02-27 | 2019-10-18 | 肖特玻璃科技(苏州)有限公司 | With the alumina silicate glass containing lithium of low bulk after chemical tempering |
| CN110104955A (en) * | 2019-05-27 | 2019-08-09 | 深圳市东丽华科技有限公司 | It is a kind of can chemical strengthening from glass ceramics ceramics and preparation method thereof |
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