CN114671619B - Glass ceramics and glass ceramics products - Google Patents

Glass ceramics and glass ceramics products Download PDF

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Publication number
CN114671619B
CN114671619B CN202210207454.0A CN202210207454A CN114671619B CN 114671619 B CN114671619 B CN 114671619B CN 202210207454 A CN202210207454 A CN 202210207454A CN 114671619 B CN114671619 B CN 114671619B
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glass
percent
ceramic
sio
temperature
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CN114671619A (en
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原保平
于天来
陈雪梅
聂小兵
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Abstract

The application provides microcrystalline glass, which comprises the following components in percentage by weight: siO (SiO) 2 ：40～65％；Al 2 O 3 ：15～30％；Li 2 O：5～15％；ZnO：0.5～10％；P 2 O 5 ：2～12％；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.15 to 0.8. Through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by the application have excellent mechanical properties.

Description

Glass ceramics and glass ceramics products
The application is a divisional application of the application patent application with the application number of 202010603489.7 and the application date of 2020, 06 and 29, named as microcrystalline glass and microcrystalline glass products.
Technical Field
The present application relates to a glass ceramic, and more particularly, to a glass ceramic and a glass ceramic product having excellent mechanical properties suitable for use in electronic devices or display devices.
Background
In recent years, with the continuous rise and development of consumer electronics, glass is used as a transparent material with good performance in a large number of such electronic devices. Since electronic devices have many precise electronic components inside, it is necessary to provide a cover plate or a case to protect the electronic components inside. In the prior art, metal is used as a cover plate material, but the metal has the defects of easy oxidation, electromagnetic signal shielding and the like. There are also documents that disclose the use of glass as a cover plate, for example, chinese patent CN101508524a discloses a chemically strengthened glass whose properties such as drop resistance and fracture toughness are hardly satisfactory. As a ceramic material that does not affect a signal, it has a good texture and a high thermal conductivity, but is inferior in workability and high in cost as compared with glass.
The glass ceramics can have physical properties which cannot be obtained in glass by crystallization dispersed in the glass, and have remarkable advantages over general glass in terms of bending resistance, abrasion resistance, and the like due to the formation of crystallites in the glass. Based on the advantages, the microcrystalline glass or the microcrystalline glass product processed by the microcrystalline glass is applied to display equipment or electronic equipment with high requirements on shatter resistance, compression resistance and scratch resistance. Therefore, the development of glass ceramics and glass ceramics products which have excellent mechanical properties and are suitable for display equipment or electronic equipment with high requirements on shatter resistance, compression resistance and scratch resistance is a target pursued by technological staff.
Disclosure of Invention
The technical problem to be solved by the invention is to provide microcrystalline glass with excellent mechanical properties and a microcrystalline glass product.
The technical scheme adopted for solving the technical problems is as follows:
(1) The microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：40～65％；Al 2 O 3 ：15～30％；Li 2 O：5～15％；ZnO：0.5～10％；P 2 O 5 ：2～12％；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.15 to 0.8.
(2) The glass ceramic according to (1), wherein the glass ceramic further comprises the following components in percentage by weight: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(3) Microcrystalline glass containing SiO in its composition 2 、Al 2 O 3 、Li 2 O, znO and ZrO 2 The components are expressed in weight percent, wherein (Li 2 O+ZrO 2 +ZnO)/SiO 2 And 0.15-0.8, wherein the microcrystalline glass contains quartz and quartz solid solution crystalline phases, and the quartz and quartz solid solution crystalline phases have a higher weight percentage than other crystalline phases existing in the microcrystalline glass.
(4) The glass ceramic according to (3), wherein the glass ceramic comprises the following components in percentage by weight: siO (SiO) 2 : 40-65%; and/or Al 2 O 3 : 15-30%; and/or Na 2 O:0 to 6 percent; and/or ZnO: 0.5-10%; and/or TiO 2 : 0-5%; and/or Li 2 O: 5-15%; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or P 2 O 5 : 2-12%; and/or ZrO 2 : 1-15%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(5) The microcrystalline glass contains quartz and quartz solid solution crystalline phases, and the components of the microcrystalline glass are as follows in percentage by weight: siO (SiO) 2 ：40～65％；Al 2 O 3 ：15～30％；ZnO：0.5～10％；TiO 2 ：0～5％；P 2 O 5 ：2～12％；Li 2 O：5～15％；ZrO 2 ：1～15％；MgO：0～8％；Na 2 O：0～6％；K 2 O：0～5％；SrO：0～5％；BaO：0～5％；CaO：0～5％；Ln 2 O 3 ：0～5％；B 2 O 3 : 0-5%; clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(6) The glass ceramic according to any one of (1) to (5), wherein the glass ceramic comprises, in weight percent, one or more of the following 6:
1)Al 2 O 3 /SiO 2 0.25 to 0.7;
2)ZnO/Li 2 o is 0.1-1.8;
3)(P 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.05 to 0.5;
4)P 2 O 5 /Al 2 O 3 0.15 to 0.75;
5)(ZrO 2 +MgO+ZnO)/Al 2 O 3 0.1 to 1.5;
6)(Li 2 O+ZrO 2 )/SiO 2 0.1 to 0.7.
(7) The glass ceramic according to any one of (1) to (6), comprising, in weight percent: siO (SiO) 2 : 45-60%; and/or Al 2 O 3 : 18-26%; and/or Na 2 O:0 to 3 percent; and/or ZnO:1 to 8 percent; and/or TiO 2 :0 to 2 percent; and/or Li 2 O: 6-12%; and/or MgO:0.5 to 5 percent; and/or K 2 O:0 to 4 percent; and/or SrO:0 to 2 percent; and/or BaO:0 to 2 percent; and/or CaO:0 to 2 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or B 2 O 3 :0 to 3 percent; and/or P 2 O 5 : 3-10%; and/or ZrO 2 :2.5 to 12 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(8) The glass ceramic according to any one of (1) to (7), wherein the glass ceramic comprises, in weight percent, one or more of the following 7:
1)Al 2 O 3 /SiO 2 0.3 to 0.6;
2)ZnO/Li 2 o is 0.2-1.5;
3)(P 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.1 to 0.4;
4)P 2 O 5 /Al 2 O 3 0.2 to 0.6;
5)(ZrO 2 +MgO+ZnO)/Al 2 O 3 0.2 to 1.2;
6)(Li 2 O+ZrO 2 )/SiO 2 0.15 to 0.6;
7)(Li 2 O+ZrO 2 +ZnO)/SiO 2 0.2 to 0.7.
(9) The glass ceramic according to any one of (1) to (8), comprising, in weight percent: siO (SiO) 2 : 45-54%; and/or Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 2 percent; and/or ZnO:2 to 6 percent; and/or TiO 2 :0 to 1 percent; and/or Li 2 O: 7-10%; and/or MgO:1 to 4 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 1 percent; and/or P 2 O 5 : 6-10%; and/or ZrO 2 : 3-10%; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(10) The glass ceramic according to any one of (1) to (9), wherein the glass ceramic comprises, in weight percent, one or more of the following 7:
1)Al 2 O 3 /SiO 2 0.4 to 0.55;
2)ZnO/Li 2 o is 0.3-1.0;
3)(P 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.15 to 0.3;
4)P 2 O 5 /Al 2 O 3 0.3 to 0.5;
5)(ZrO 2 +MgO+ZnO)/Al 2 O 3 0.3 to 0.8;
6)(Li 2 O+ZrO 2 )/SiO 2 0.2 to 0.45;
7)(Li 2 O+ZrO 2 +ZnO)/SiO 2 0.25 to 0.55.
(11) The glass ceramic according to any one of (1) to (10), comprising, in weight percent: agO: 0-2%, preferably AgO:0 to 1 percent; and/or CuO:0 to 2%, preferably CuO:0 to 1 percent; and/or Cu 2 O:0 to 2%, preferably Cu 2 O：0～1％。
(12) The glass-ceramic according to any one of (1) to (11), wherein the component does not contain B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Gd 2 O 3 。
(13) The glass-ceramic according to any one of (1) to (12), wherein the glass-ceramic contains quartz and a quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.
(14) The glass-ceramic according to any one of (1) to (13), wherein the total amount of crystal phases in the glass-ceramic is in the range of 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight.
(15) The glass-ceramic according to any one of (1) to (14), wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, preferably the quartz and the quartz solid solution crystal phase account for 20 to 70% by weight of the glass-ceramic, more preferably the Dan Yingji quartz solid solution crystal phase accounts for 25 to 65% by weight of the glass-ceramic, and even more preferably the quartz and the quartz solid solution crystal phase account for 30 to 60% by weight of the glass-ceramic.
(16) The glass-ceramic according to any one of (1) to (15), wherein the glass-ceramic does not contain petalite; and/or does not contain a lithium silicate crystalline phase.
(17) The glass ceramic according to any one of (1) to (16), wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or glass ceramics with a thickness of 0.6mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or glass ceramics with a thickness of 0.6mm, and a transmittance at a wavelength of 550nm is 85% or more, preferably 90% or more, and more preferably 91% or more.
(18) The glass-ceramic according to any one of (1) to (17), wherein the glass-ceramic has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the falling ball test height is 1000mm or more, preferably 1100mm or more, more preferably 1200mm or more.
(19) The glass-ceramic according to any one of (1) to (18), which has a coefficient of thermal expansion of 70X 10 -7 /K～120×10 -7 K, preferably with a lower limit of 75X 10 -7 /K～110×10 -7 K, more preferably 80X 10 -7 /K～100×10 -7 K; and/or a refractive index of 1.51 to 1.57, preferably 1.52 to 1.56, more preferably 1.53 to 1.55.
(20) The glass-ceramic according to any one of (1) to (19), further comprising a colorant, which makes the glass-ceramic exhibit different colors.
(21) The glass ceramic according to (20), wherein the colorant comprises, in weight percent: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(22) A glass ceramic product made of the glass ceramic according to any one of (1) to (21).
(23) The glass-ceramic product according to (22), wherein the glass-ceramic product having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or a glass ceramic product having a thickness of 0.6mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass ceramic product having a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.
(24) The glass-ceramic product according to any one of (22) or (23), wherein the glass-ceramic product has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less.
(25) The glass-ceramic product according to any one of (22) to (24), wherein the glass-ceramic product has a surface stress of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or the ion exchange layer depth is 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more.
(26) The glass-ceramic product according to any one of (22) to (25), wherein the glass-ceramic product has a falling ball test height of 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or fracture toughness of 1 MPa.m 1/2 The above is preferably 1.1 MPa.m 1/2 Above, betterSelected to be 1.2 MPa.m 1/2 The above; and/or a Vickers hardness of 650kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above; and/or the four-point bending strength is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.
The invention also provides a glass cover plate:
(27) The glass cover plate, which is made of the glass ceramics according to any one of (1) to (21); and/or is made of the glass-ceramic product according to any one of (22) to (26).
The invention also provides a glass component:
(28) A glass component made of the glass-ceramic according to any one of (1) to (21); and/or is made of the glass-ceramic product according to any one of (22) to (26).
The invention also provides a display device:
(29) A display device comprising the glass-ceramic of any one of (1) to (21); and/or the glass-ceramic product according to any one of (22) to (26); and/or contain the glass cover plate of (27), and/or contain the glass component of (28).
The invention also provides an electronic device:
(30) An electronic device comprising the glass-ceramic of any one of (1) to (21); and/or the glass-ceramic product according to any one of (22) to (26); and/or contain the glass cover plate of (27), and/or contain the glass component of (28).
The invention also provides a manufacturing method of the microcrystalline glass product, which comprises the following steps:
(31) A method of making a glass-ceramic article, the method comprising the steps of:
forming a matrix glass, the matrix glass comprising, in weight percent: siO (SiO) 2 ：40～65％；Al 2 O 3 ：15～30％；Li 2 O：5～15％；ZnO：0.5～10％；P 2 O 5 ：2～12％；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.15 to 0.8;
and forming microcrystalline glass on the matrix glass through a crystallization process, and forming a microcrystalline glass product on the microcrystalline glass through a chemical strengthening process.
(32) The method for producing a glass-ceramic product according to (31), wherein the matrix glass further comprises, in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(33) The method for producing a glass-ceramic article according to any one of (31) and (32), wherein the matrix glass comprises, in weight percent: siO (SiO) 2 :45 to 60%, preferably SiO 2 : 45-54%; and/or Al 2 O 3 :18 to 26%, preferably Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 3%, preferably Na 2 O:0 to 2 percent; and/or ZnO:1 to 8%, preferably ZnO:2 to 6 percent; and/or TiO 2 :0 to 2%, preferably TiO 2 :0 to 1 percent; and/or Li 2 O:6 to 12%, preferably Li 2 O: 7-10%; and/or MgO:0.5 to 5%, preferably MgO:1 to 4 percent; and/or K 2 O:0 to 4%, preferably K 2 O:0 to 3 percent; and/or SrO: 0-2%, preferably SrO:0 to 1 percent; and/or BaO: 0-2%, preferably BaO:0 to 1 percent; and/or CaO:0 to 2%, preferably CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 4%, preferably Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 1 percent; and/or P 2 O 5 :3 to 10%, preferably P 2 O 5 : 6-10%; and/or ZrO 2 :2.5 to 12%, preferably ZrO 2 : 3-10%; and/or clarifying agent: 0 to 1%, preferably clarifyingCleaning agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(34) The method for producing a glass-ceramic product according to any one of (31) to (33), wherein the matrix glass comprises the following components in percentage by weight: al (Al) 2 O 3 /SiO 2 From 0.25 to 0.7, preferably Al 2 O 3 /SiO 2 From 0.3 to 0.6, more preferably Al 2 O 3 /SiO 2 0.4 to 0.55; and/or ZnO/Li 2 O is 0.1 to 1.8, preferably ZnO/Li 2 O is 0.2 to 1.5, more preferably ZnO/Li 2 O is 0.3-1.0; and/or (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.05 to 0.5, preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.1 to 0.4, more preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.15 to 0.3; and/or P 2 O 5 /Al 2 O 3 From 0.15 to 0.75, preferably P 2 O 5 /Al 2 O 3 From 0.2 to 0.6, more preferably P 2 O 5 /Al 2 O 3 0.3 to 0.5; and/or (ZrO) 2 +MgO+ZnO)/Al 2 O 3 Is 0.1 to 1.5, preferably (ZrO 2 +MgO+ZnO)/Al 2 O 3 Is 0.2 to 1.2, more preferably (ZrO 2 +MgO+ZnO)/Al 2 O 3 0.3 to 0.8; and/or (Li) 2 O+ZrO 2 )/SiO 2 Is 0.1 to 0.7, preferably (Li) 2 O+ZrO 2 )/SiO 2 Is 0.15 to 0.6, more preferably (Li) 2 O+ZrO 2 )/SiO 2 0.2 to 0.45; and/or (Li) 2 O+ZrO 2 +ZnO)/SiO 2 Is 0.15 to 0.8, preferably (Li) 2 O+ZrO 2 +ZnO)/SiO 2 Is 0.2 to 0.7, more preferably (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.25 to 0.55.
(35) The method for producing a glass-ceramic product according to any one of (31) to (34), wherein the matrix glass comprises, in weight percent: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(36) The method for producing a glass-ceramic product according to any one of (31) to (35), wherein the resultant matrix glass has a melting temperature of 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5 to 24 hours, preferably 8 to 12 hours.
(37) The method for producing a glass-ceramic product according to any one of (31) to (36), wherein the crystallization process comprises the steps of: heating to a predetermined crystallization temperature, maintaining the temperature for a certain time after the crystallization temperature is reached, and then cooling. The crystallization temperature is preferably 580 to 950 ℃, more preferably 600 to 850 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours.
(38) The method for producing a glass-ceramic product according to any one of (31) to (37), wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
(39) The method for producing a glass-ceramic article according to (38), wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
(40) The method for producing a glass-ceramic product according to any one of (31) to (39), wherein the chemical strengthening process comprises: the glass ceramics are immersed in the salt bath of molten Na salt at the temperature of 430 ℃ to 470 ℃ for 6 to 20 hours, preferably at the temperature of 435 ℃ to 460 ℃ and preferably at the time of 8 to 13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 400-450 ℃ for 1-8 hours, and the preferable time range is 2-4 hours; and/or the glass ceramic is immersed in a salt bath in which a K salt and a Na salt are mixed at a temperature of about 350 ℃ to 450 ℃ for 0.5 to 8 hours, preferably for 1 to 4 hours.
(41) The method for producing a glass-ceramic product according to any one of (31) to (40), wherein the total amount of crystal phases in the glass-ceramic product is in the range of 10 to 80% by weight, preferably 15 to 75% by weight, more preferably 20 to 70% by weight of the glass-ceramic product.
(42) The method for producing a glass-ceramic product according to any one of (31) to (41), wherein the glass-ceramic product contains a quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, preferably the quartz and the quartz solid solution crystal phase account for 20 to 70 weight percent of the glass-ceramic product, more preferably the Dan Yingji quartz solid solution crystal phase accounts for 25 to 65 weight percent of the glass-ceramic product, and even more preferably the quartz and the quartz solid solution crystal phase account for 30 to 60 weight percent of the glass-ceramic product.
(43) The method for producing a glass-ceramic product according to any one of (31) to (42), wherein the glass-ceramic product having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or a glass ceramic product having a thickness of 0.6mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or a glass ceramic product having a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, more preferably 91% or more; and/or a junction of a glass-ceramic article The crystallinity is 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the surface stress of the glass-ceramic product is 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or the ion exchange layer depth is 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more; and/or the glass-ceramic product has a falling ball test height of 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more; and/or fracture toughness of 1 MPa.m 1/2 The above is preferably 1.1 MPa.m 1/2 The above is more preferably 1.2 MPa.m 1/2 The above; and/or a Vickers hardness of 650kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above; and/or the four-point bending strength is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.
The invention also provides a manufacturing method of the glass ceramics, which comprises the following steps:
(44) A method for producing glass ceramics, comprising the steps of:
forming a matrix glass, the matrix glass comprising, in weight percent: siO (SiO) 2 ：40～65％；Al 2 O 3 ：15～30％；Li 2 O：5～15％；ZnO：0.5～10％；P 2 O 5 ：2～12％；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.15 to 0.8;
and forming microcrystalline glass on the substrate glass through a crystallization process.
(45) The method for producing a glass ceramic according to (44), wherein the matrix glass comprises the following components in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(46) The method for producing a glass ceramic according to any one of (44) and (45), wherein the matrix glass comprises, in weight percent: siO (SiO) 2 :45 to 60%, preferably SiO 2 : 45-54%; and/or Al 2 O 3 :18 to 26%, preferably Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 3%, preferably Na 2 O:0 to 2 percent; and/or ZnO:1 to 8%, preferably ZnO:2 to 6 percent; and/or TiO 2 :0 to 2%, preferably TiO 2 :0 to 1 percent; and/or Li 2 O:6 to 12%, preferably Li 2 O: 7-10%; and/or MgO:0.5 to 5%, preferably MgO:1 to 4 percent; and/or K 2 O:0 to 4%, preferably K 2 O:0 to 3 percent; and/or SrO: 0-2%, preferably SrO:0 to 1 percent; and/or BaO: 0-2%, preferably BaO:0 to 1 percent; and/or CaO:0 to 2%, preferably CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 4%, preferably Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 1 percent; and/or P 2 O 5 :3 to 10%, preferably P 2 O 5 : 6-10%; and/or ZrO 2 :2.5 to 12%, preferably ZrO 2 : 3-10%; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(47) The method for producing a glass ceramic according to any one of (44) to (46), wherein the matrix glass comprises the following components in percentage by weight: al (Al) 2 O 3 /SiO 2 From 0.25 to 0.7, preferably Al 2 O 3 /SiO 2 From 0.3 to 0.6, more preferably Al 2 O 3 /SiO 2 0.4 to 0.55; and/or ZnO/Li 2 O is 0.1 to 1.8, preferably ZnO/Li 2 O is 0.2-1.5, more preferablySelecting ZnO/Li 2 O is 0.3-1.0; and/or (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.05 to 0.5, preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.1 to 0.4, more preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.15 to 0.3; and/or P 2 O 5 /Al 2 O 3 From 0.15 to 0.75, preferably P 2 O 5 /Al 2 O 3 From 0.2 to 0.6, more preferably P 2 O 5 /Al 2 O 3 0.3 to 0.5; and/or (ZrO) 2 +MgO+ZnO)/Al 2 O 3 Is 0.1 to 1.5, preferably (ZrO 2 +MgO+ZnO)/Al 2 O 3 Is 0.2 to 1.2, more preferably (ZrO 2 +MgO+ZnO)/Al 2 O 3 0.3 to 0.8; and/or (Li) 2 O+ZrO 2 )/SiO 2 Is 0.1 to 0.7, preferably (Li) 2 O+ZrO 2 )/SiO 2 Is 0.15 to 0.6, more preferably (Li) 2 O+ZrO 2 )/SiO 2 0.2 to 0.45; and/or (Li) 2 O+ZrO 2 +ZnO)/SiO 2 Is 0.15 to 0.8, preferably (Li) 2 O+ZrO 2 +ZnO)/SiO 2 Is 0.2 to 0.7, more preferably (Li) 2 O+ZrO 2 +ZnO)/SiO 2 0.25 to 0.55.
(48) The method for producing a glass ceramic according to any one of (44) to (47), wherein the matrix glass comprises, in weight percent: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(49) The method for producing a glass ceramic according to any one of (44) to (48), wherein the resultant matrix glass has a melting temperature of 1250 to 1650 ℃, preferably 1380 to 1600 ℃; and/or the melting time is 5 to 24 hours, preferably 8 to 12 hours.
(50) The method for producing a glass ceramic according to any one of (44) to (49), wherein the crystallization process comprises the steps of: heating to a predetermined crystallization temperature, maintaining the temperature for a certain time after the crystallization temperature is reached, and then cooling. The crystallization temperature is preferably 580 to 950 ℃, more preferably 600 to 850 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours.
(51) The method for producing a glass ceramic according to any one of (44) to (49), wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
(52) The method for producing glass ceramics according to (51), wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
(53) The method for producing a glass-ceramic according to any one of (44) to (52), wherein the total amount of crystal phases in the glass-ceramic is in the range of 10 to 80% by weight, preferably 15 to 75% by weight, and more preferably 20 to 70% by weight.
(54) The method for producing a glass-ceramic according to any one of (44) to (53), wherein the glass-ceramic contains a quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, preferably the quartz and the quartz solid solution crystal phase account for 20 to 70 weight percent of the glass-ceramic, more preferably the Dan Yingji quartz solid solution crystal phase accounts for 25 to 65 weight percent of the glass-ceramic, and even more preferably the quartz and the quartz solid solution crystal phase account for 30 to 60 weight percent of the glass-ceramic.
(55) The method for producing a glass ceramic according to any one of (44) to (54), wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and still more preferably 0.1% or less; and/or glass ceramics with a thickness of 0.6mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more; and/or glass ceramics with a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, more preferably 91% or more; and/or the crystallinity of the glass ceramic is 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the falling ball test height is 1000mm or more, preferably 1100mm or more, more preferably 1200mm or more; and/or the glass ceramics has a thermal expansion coefficient of 70 x 10 -7 /K～120×10 -7 K, preferably with a lower limit of 75X 10 -7 /K～110×10 -7 K, more preferably 80X 10 -7 /K～100×10 -7 K; and/or a refractive index of 1.51 to 1.57, preferably 1.52 to 1.56, more preferably 1.53 to 1.55.
The beneficial effects of the invention are as follows: through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by the invention have excellent mechanical properties.
Detailed Description
The glass ceramics and glass ceramics products of the present invention are materials having a crystalline phase and a glass phase, as opposed to amorphous solids. The crystalline phases of glass ceramics and glass ceramics articles can be distinguished by the angle of the peaks that occur in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.
Through repeated experiments and researches, the inventors of the present invention have obtained the glass ceramics or glass ceramics products of the present invention at a low cost by specifying the content and the content ratio of the specific components constituting the glass ceramics and glass ceramics to specific values and precipitating the specific crystal phases.
In the glass ceramics and glass ceramics products of the invention, the crystalline phase contains quartz and quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or lithium silicate, etc.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise mainly quartz and quartz solid solutions, the quartz and quartz solid solutions having a higher weight percentage than other crystalline phases, preferably the quartz and quartz solid solutions comprise 20 to 70 weight percent of the glass-ceramic or glass-ceramic article, more preferably the Dan Yingji quartz solid solution crystalline phases comprise 25 to 65 weight percent of the glass-ceramic or glass-ceramic article, and even more preferably the quartz and quartz solid solution crystalline phases comprise 30 to 60 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the quartz and quartz solid solution crystalline phases comprise about 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% by weight of the glass-ceramic or glass-ceramic article.
In some embodiments of the present invention, to achieve the desired superior properties of the present invention, the glass-ceramic or glass-ceramic article preferably does not contain petalite; and/or does not contain a lithium silicate crystalline phase.
In some embodiments of the present invention, it is preferred that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 10 to 80 weight percent of the glass-ceramic or glass-ceramic article; in some embodiments, more preferably the total amount of crystalline phases in the glass-ceramic or glass-ceramic article ranges from 15 to 75 weight percent of the glass-ceramic or glass-ceramic article; in some embodiments, it is further preferred that the total amount of crystalline phases in the glass-ceramic or glass-ceramic article is in the range of 20 to 70 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the total amount of crystalline phase comprises about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80% by weight of the glass-ceramic or glass-ceramic article.
The ranges of the respective components (ingredients) of the matrix glass, the glass-ceramic and the glass-ceramic product of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of substances of the matrix glass, or the glass-ceramic product, in terms of the composition of the oxides. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the constituent components of the matrix glass, glass ceramic or glass ceramic product of the present invention is 100% based on the total amount of oxide when the oxide, composite salt, hydroxide or the like is decomposed and converted into oxide by melting. In the present specification, the term "glass" refers to a base glass before crystallization, and the term "glass ceramics" refers to a glass ceramics after crystallization of a base glass, and a glass ceramics product refers to a glass ceramics after chemical strengthening.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "about" as used herein means that the formulations, parameters and other quantities and characteristics are not, and need not be, exact, and may be approximated and/or greater or lesser, if desired, reflecting tolerances, conversion factors, measurement errors and the like. The term "and/or" as referred to herein is inclusive, e.g. "a; and/or B ", means either a alone, B alone, or both a and B.
SiO 2 Is an essential component for forming the glass, glass ceramics and glass ceramics products of the invention, is one of the main components forming crystalline phases after glass heat treatment, if SiO 2 At a content of 40% or less, the devitrification resistance and strength of the matrix glass become poor, so SiO 2 The lower limit of the content is 40%, preferably 45%. If SiO is 2 The content is more than 65 percent, the glass smelting difficulty is increased, and the forming of the glass is not facilitated, thus SiO 2 The upper limit of the content is 65%, preferably 60%. Further, by making SiO 2 The content is below 54%, which is favorable for obtaining quartz and quartz solid solution crystal phase and expected quartz and quartz solid solution crystal phase content, and can also reduce the haze of microcrystalline glass and microcrystalline glass products and improve the transmittance of microcrystalline glass and microcrystalline glass products, thus further optimizing SiO 2 The upper limit of the content is 54%. In some embodiments, about 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60% SiO may be included 2 。
Al 2 O 3 Is one of the components capable of forming crystalline phase of glass ceramics, can form a network structure of glass, is favorable for chemical strengthening of the glass ceramics, increases the depth of ion exchange layer of the glass ceramics product, but if the content is less than 15%, the effect is poor, and Al is preferred 2 O 3 The lower limit of the content is 18%. Further, if the Al content is 20.5% or more 2 O 3 Is favorable for forming glass, reduces the crystallization temperature of the glass and is favorable for the crystallization process of the glass, so Al is further preferable 2 O 3 The lower limit of the content of (2) is 20.5%. On the other hand, if Al 2 O 3 If the content exceeds 30%, the glass becomes difficult to melt, and defects in the glass are large, which tends to decrease the strength of the matrix glass. Thus, al 2 O 3 Upper limit of contentThe upper limit is preferably 30%, more preferably 26%, and still more preferably 24%. In some embodiments, about 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30% Al may be included 2 O 3 。
In some embodiments of the invention, the metal is prepared by reacting Al with 2 O 3 /SiO 2 Within the range of 0.25-0.7, the structure of the matrix glass is more compact, the strength of the matrix glass is improved, the falling ball test height of the microcrystalline glass is increased, the ion exchange layer depth and the surface stress of the microcrystalline glass product are improved, and the Vickers hardness of the microcrystalline glass product is improved. Therefore, al is preferable 2 O 3 /SiO 2 From 0.25 to 0.7, more preferably Al 2 O 3 /SiO 2 From 0.3 to 0.6, al being more preferred 2 O 3 /SiO 2 0.4 to 0.55. In some embodiments, al 2 O 3 /SiO 2 The values of (2) may be 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7.
Li 2 O can promote glass melting, reduce the melting temperature of the glass, promote the formation of crystals in the crystallization process, is a component which is mainly replaced by sodium, potassium and other ions in the chemical strengthening process, can increase the surface stress of the microcrystalline glass product after chemical strengthening, and improves the falling ball test height of the microcrystalline glass product, but if the content is less than 5%, the effect is poor. Thus Li 2 The lower limit of the O content is 5%, preferably 6%, more preferably 7%. If too much Li is contained 2 When O is used for crystallization of glass, crystals tend to be large, and haze of glass ceramics and glass ceramics products increases, and light transmittance decreases. Thus Li 2 The upper limit of the O content is 15%, preferably 12%, more preferably 10%. In some embodiments, about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8.0%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, and may be included,11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Li 2 O。
Na 2 O can reduce the crystallization temperature of the glass, is beneficial to the crystallization process of the glass, is beneficial to improving the chemical strengthening performance of the microcrystalline glass, and is beneficial to improving the hot bending process of the microcrystalline glass and microcrystalline glass products in some embodiments; however, in the present invention, if Na is excessively contained 2 O easily causes more glass breaking bonds, and the strength of matrix glass is reduced, which affects the strength of glass ceramics and glass ceramics products. Therefore, na is preferred in the present invention 2 The upper limit of the O content is 6%, more preferably 3%, still more preferably 2%. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% Na may be included 2 O。
K 2 The O is beneficial to expanding the range of the glass forming temperature and the crystallization temperature, is beneficial to chemical strengthening, and can improve the ion exchange layer depth of the microcrystalline glass product; but if too much K is contained 2 O, the chemical stability of the glass is easily lowered and the hardness is easily lowered. Thus, K is 2 The upper limit of the content of O is preferably 5%, more preferably 4%, and still more preferably 3%. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% K may be included 2 O。
ZnO can improve the melting property of glass, can enter into the glass to form crystalline phase, improves the crystalline phase content of the glass, increases the falling ball test height of microcrystalline glass and microcrystalline glass products, and the invention obtains the effect by containing more than 0.5 percent of ZnO, preferably more than 1 percent of ZnO, more preferably more than 2 percent of ZnO. On the other hand, if ZnO is contained excessively, the coefficient of thermal expansion of the crystallized or chemically strengthened glass ceramic or glass ceramic product becomes large, which is disadvantageous for subsequent further processing. Therefore, the upper limit of the ZnO content is preferably 10%, more preferably 8%, and still more preferably 6%. In some embodiments, about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10% ZnO may be included.
In some embodiments of the invention, if ZnO/Li 2 O is less than 0.1, the crystalline phase content of the microcrystalline glass and microcrystalline glass products is reduced, and the four-point bending strength is poor; if ZnO/Li 2 O exceeds 1.8, and the hardness and fracture toughness of glass ceramics and glass ceramics products are reduced. Thus, znO/Li is preferred in the present invention 2 O is 0.1 to 1.8, more preferably ZnO/Li 2 O is 0.2 to 1.5, and ZnO/Li is more preferable 2 O is 0.3-1.0. In some embodiments, znO/Li 2 The value of O may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8.
MgO can enter the glass to participate in forming crystalline phase, so that the crystalline phase content of the glass is improved, and the falling ball test height of the microcrystalline glass and microcrystalline glass products is increased; however, if the MgO content is too high, the devitrification resistance of the glass is lowered, the crystallization temperature range of the glass is narrowed, the crystallization process is not easy to control, and the desired glass ceramics and glass ceramics products are difficult to obtain. Accordingly, the MgO content in the present invention is 0 to 8%, preferably 0.5 to 5%, more preferably 1 to 4%. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% MgO may be included.
P 2 O 5 The glass can be easily melted at low temperature to form crystal nucleus in the glass, and can enter into the network structure of the glass to reduce the haze of the glass ceramics and glass ceramics products. In the invention, the P content is more than 2% 2 O 5 To obtain the above effect, it preferably contains 3% or more of P 2 O 5 More preferably, the content of P is 6% or more 2 O 5 . But if too much P is contained 2 O 5 The phase separation of the matrix glass is easily increased, and the chemical stability of the matrix glass, the glass ceramics and glass ceramics products is reduced. Thus, P 2 O 5 The upper limit of the content is 12%, preferably 10%.In some embodiments, about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12% P may be included 2 O 5 。
In some embodiments of the invention, if (P 2 O 5 +ZnO)/(SiO 2 +MgO) is less than 0.05, the crystallinity of the glass ceramics and glass ceramics products is reduced, and the grain size is enlarged; if (P) 2 O 5 +ZnO)/(SiO 2 +MgO) exceeds 0.5, the devitrification resistance of the matrix glass decreases, and at the same time, the strength of the glass ceramics and glass ceramics products decreases, and the falling ball test height decreases. Therefore, it is preferable that (P 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.05 to 0.5, more preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.1 to 0.4, more preferably (P) 2 O 5 +ZnO)/(SiO 2 +MgO) is 0.15 to 0.3. In some embodiments of the invention, (P) 2 O 5 +ZnO)/(SiO 2 +mgo) may be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5.
In some embodiments of the invention, the method is performed by causing P to be 2 O 5 /Al 2 O 3 The value of (2) is in the range of 0.15-0.75, the forming property of matrix glass can be optimized, the processing property of microcrystalline glass and microcrystalline glass products can be optimized, the haze of microcrystalline glass and microcrystalline glass products can be reduced, the transmittance of microcrystalline glass and microcrystalline glass products can be improved, and preferably P 2 O 5 /Al 2 O 3 The value of (C) is 0.2 to 0.6, more preferably P 2 O 5 /Al 2 O 3 The value of (2) is 0.3 to 0.5. In some embodiments, P 2 O 5 /Al 2 O 3 The values of (c) may be 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75.
ZrO 2 Can reduce the formation crystallization of matrix glass and P 2 O 5 Can cooperate with each other, widen the crystallization temperature range of glass, improve the nucleation of glass ceramics, reduce the nucleation of glass ceramics and micro-glass ceramicsHaze of the crystalline glass article. In the present invention, the ZrO is contained by more than 1% 2 To obtain the above effects, it is preferable to contain ZrO 2.5% or more 2 More preferably, zrO is contained in an amount of 3% or more 2 . On the other hand, if ZrO is contained excessively 2 The glass is difficult to melt, so that inclusions are easily formed in the glass, and the strength and the transmittance of the glass are reduced. Thus, zrO 2 The upper limit of the content is 15%, preferably 12%, more preferably 10%. In some embodiments, about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% ZrO may be included 2 。
In some embodiments of the invention, the metal oxide is formed by reacting (ZrO 2 +MgO+ZnO)/Al 2 O 3 The value of (2) is more than 0.1, the crystal grains of the microcrystalline glass can be thinned, the crystal phase variety in the microcrystalline glass is increased, and the crystallinity and the strength of the microcrystalline glass are improved. But if (ZrO 2 +MgO+ZnO)/Al 2 O 3 The value of (2) exceeds 1.5, the thermal expansion coefficients of the matrix glass and the microcrystalline glass are increased, and the subsequent processing difficulty is increased; on the other hand, the chemical strengthening performance of the glass ceramics is reduced, the depth of the ion exchange layer is reduced, and the surface stress is reduced. Therefore, (ZrO 2 +MgO+ZnO)/Al 2 O 3 The value of (2) is 0.1 to 1.5, more preferably (ZrO 2 +MgO+ZnO)/Al 2 O 3 The value of (2) is 0.2 to 1.2, and (ZrO 2 +MgO+ZnO)/Al 2 O 3 The value of (2) is 0.3 to 0.8. In some embodiments, (ZrO 2 +MgO+ZnO)/Al 2 O 3 The values of (2) may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5.
In some embodiments of the invention, if (Li 2 O+ZrO 2 )/SiO 2 Below 0.1, the falling ball test height of the glass ceramics and glass ceramics products becomes poor, if (Li 2 O+ZrO 2 )/SiO 2 Over 0.7, glass ceramics and grain rules of glass ceramics productsThe haze and the haze increase, and the transmittance decreases. Therefore, it is preferable that (Li 2 O+ZrO 2 )/SiO 2 Is 0.1 to 0.7, more preferably (Li) 2 O+ZrO 2 )/SiO 2 Is 0.15 to 0.6, more preferably (Li) 2 O+ZrO 2 )/SiO 2 0.2 to 0.45. In some embodiments, (Li) 2 O+ZrO 2 )/SiO 2 The values of (2) may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7.
In some embodiments of the invention, the method is performed by reacting (Li 2 O+ZrO 2 +ZnO)/SiO 2 The value of (C) is in the range of 0.15 to 0.8, and the fracture toughness and four-point bending strength of glass ceramics and glass ceramics products can be improved, preferably (Li 2 O+ZrO 2 +ZnO)/SiO 2 The value of (2) is 0.2 to 0.7, more preferably (Li) 2 O+ZrO 2 +ZnO)/SiO 2 The value of (2) is 0.25 to 0.55. In some embodiments, (Li) 2 O+ZrO 2 +ZnO)/SiO 2 The values of (2) may be 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8.
TiO 2 Is an optional ingredient which helps to reduce the melting temperature of the matrix glass and improve chemical stability. If TiO 2 The too high content of the glass, the glass ceramics and the glass ceramics products have reduced transmittance, which is unfavorable for preparing products with high transparency, thus, tiO 2 The content is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably no TiO is contained 2 . In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% TiO may be included 2 。
SrO is an optional component for improving the low-temperature meltability of the glass and inhibiting crystallization during forming of the matrix glass, and is unfavorable for forming of the matrix glass when the content is too high. Therefore, the SrO content in the present invention is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably not containing SrO. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% SrO may be included.
BaO is an optional component which contributes to improving glass forming performance of glass, and when the BaO content is too high, the BaO is unfavorable for chemical strengthening performance of glass ceramics, and the strength of glass ceramics is easily reduced. Therefore, in the present invention, the BaO content is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably no BaO is contained. In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% BaO may be included.
CaO can increase the hardness of glass, and when the content is too much, the glass can be milky during forming, which is unfavorable for obtaining qualified glass products. Therefore, the CaO content in the present invention is in the range of 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%, and even more preferably no CaO is contained. In some embodiments, caO may be included at about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
B 2 O 3 Helps to optimize the melting properties of the matrix glass, and when the content is too high, the chemical stability of the matrix glass is reduced, thus B 2 O 3 The content of (C) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably B is not contained 2 O 3 . In some embodiments, about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% B may be included 2 O 3 。
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of (a) is an optional component for improving the hardness and chemical stability of glass ceramics and inhibiting glass molding crystallization, and the glass is easy to become opaque after crystallization when the content is excessive. Thus Ln in the present invention 2 O 3 The content is in the range of 0 to 5%, preferably 0 to 4%, more preferably 0 to 3%. In the present invention, for obtaining excellent properties, la is preferably not contained 2 O 3 And/or does not contain Gd 2 O 3 . In some embodiments, may comprise about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% Ln 2 O 3 。
In some embodiments, the glass, glass-ceramic, or glass-ceramic article may further include 0-2% fining agent to improve the bubble removal ability of the glass, glass-ceramic, or glass-ceramic article. Such fining agents include, but are not limited to, sb 2 O 3 、SnO 2 、SnO、CeO 2 One or more of F, cl and Br, preferably Sb 2 O 3 、SnO 2 SnO as a fining agent. When the above clarifying agents are present alone or in combination, the upper limit of the content thereof is preferably 1%, more preferably 0.5%. In some embodiments, one or more of the above-described clarifying agents is present in an amount of about 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.
PbO and As 2 O 3 Is a toxic substance, and even a small amount of the toxic substance does not meet the environmental requirements, so that the present invention in some embodiments preferably does not contain PbO and As 2 O 3 。
In some embodiments of the present invention, a colored base glass, glass-ceramic, or glass-ceramic article is produced by including a colorant that comprises: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 :0 to 4 percent. The weight percentage of the colorant and the function thereof are as follows:
the brown or green matrix glass, glass ceramics or glass ceramics products prepared by the invention use NiO and Ni 2 O 3 Or Pr (Pr) 2 O 5 Is a colorant. NiO and Ni 2 O 3 The colorant is used for preparing brown or green matrix glass, glass ceramics or glass ceramics products, the two components can be used singly or mixed, the respective content of the two components is generally below 4 percent, preferably below 3 percent, if the content exceeds 4 percent, the colorant cannot be well dissolved in the matrix glass, glass ceramics or glass ceramics products, the respective lower limit of the two components is above 0.1 percent, such as below 0.1 percent, and the color of the matrix glass, glass ceramics or glass ceramics products is not obvious. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO, or Ni may be included 2 O 3 . When used in combination, niO and Ni 2 O 3 The total amount is generally 4% or less, and the lower limit of the total amount is 0.1% or more. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO and Ni may be included 2 O 3 . Pr is used 2 O 5 The colorant used alone is generally 8% or less, preferably 6% or less, and the lower limit of the colorant is 0.4% or more, for example, less than 0.4%, and the color of the substrate glass, glass ceramic or glass ceramic product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8% 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Pr 2 O 5 。
The blue matrix glass, glass ceramics or glass ceramics products prepared by the invention use CoO or Co 2 O 3 As the colorant, the two colorant components may be used singly or in combination, and the respective contents thereof are generally 2% or less, preferably 1.8% or less, and if the content exceeds 2%, the colorant is not well dissolved in the base glass, the glass-ceramic or the glass-ceramic product, and the respective lower limit of the content thereof is 0.05% or more, such as less than 0.05%, and the color of the base glass, the glass-ceramic or the glass-ceramic product is not obvious. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO or Co may be included 2 O 3 . When used in combination, coO and Co 2 O 3 The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO and Co may be included 2 O 3 。
The yellow matrix glass, glass ceramics or glass ceramics products prepared by the invention use Cu 2 O or CeO 2 As the colorant, the two colorant components are used singly or in combination, the lower limit of the respective content is more than 0.5 percent, such as less than 0.5 percent, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious, and the Cu is used singly 2 O is 4% or less, preferably 3% or less, and if the content exceeds 4%, the matrix glass is liable to be devitrified. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6% may be included3.7%, 3.8%, 3.9%, 4.0% Cu 2 O. Using CeO alone 2 The content is generally 4% or less, preferably 3% or less, for example, the content exceeds 4%, and the substrate glass, glass ceramics or glass ceramics is poor in gloss. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO may be included 2 . At the same time, a small amount of CeO 2 The CeO has the effect of removing bubbles when being added into glass 2 The glass can also be used as a clarifying agent. When the two colorants are mixed and used, the total amount thereof is generally 4% or less, and the lower limit of the total amount is 0.5% or more. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO may be included 2 And Cu 2 O。
The black or soot-colored matrix glass, glass ceramics or glass ceramics products prepared by the invention independently use Fe 2 O 3 Is a colorant; or Fe is used 2 O 3 And CoO, two colorants used in combination; or Fe is used 2 O 3 And Co 2 O 3 Two colorants used in combination; or Fe is used 2 O 3 Coloring agents used in combination of three types, coO and NiO; or Fe is used 2 O 3 、Co 2 O 3 And three kinds of NiO. The colorants for preparing black and soot-colored base glass, glass-ceramic or glass-ceramic articles are mainly Fe 2 O 3 Coloring at a level of 7% or less, preferably 5% or less, with a lower limit of 0.2% or more, and in some embodiments may comprise about 0.2%, 0.3%0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.5%, 6.0%, 6.5%, 7.0% Fe 2 O 3 . CoO and Co 2 O 3 Can absorb visible light and deepen the coloring degree of matrix glass, glass ceramics or glass ceramics products, and is generally similar to Fe 2 O 3 The respective contents are 0.6% or less and the lower limit is 0.2% or more when mixed. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% CoO and/or Co may be included 2 O 3 . NiO absorbs visible light and can enhance the coloration degree of the base glass, glass ceramic or glass ceramic product, and the content thereof is generally 1% or less when mixed for use, and the total lower limit is 0.2% or more. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% NiO may be included.
The purple matrix glass, glass ceramics or glass ceramics products prepared by the invention use MnO 2 As the colorant, a colorant is used in an amount of generally 4% or less, preferably 3% or less, and the lower limit of the amount is 0.1% or more, for example, less than 0.1%, and the color of the base glass, glass-ceramic or glass-ceramic product is not noticeable. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% MnO may be included 2 。
The pink matrix glass, microcrystalline glass or microcrystalline glass product prepared by the invention uses Er 2 O 3 The content of the colorant is generally 8% or less, preferably 6% or less.Due to rare earth element Er 2 O 3 The coloring efficiency is low, and when the content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, but the cost is increased, and the lower limit of the content is more than 0.4%, for example, less than 0.4%, so that the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Er may be included 2 O 3 。
The purple-red matrix glass, glass ceramics or glass ceramics products prepared by the invention use Nd 2 O 3 The content of the colorant is generally 8% or less, preferably 6% or less. Due to rare earth element Nd 2 O 3 The coloring efficiency is low, the use content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, the cost is increased, the lower limit of the content is more than 0.4%, for example, less than 0.4%, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd may be included 2 O 3 。
The red matrix glass, microcrystalline glass or microcrystalline glass product prepared by the invention uses Er 2 O 3 、Nd 2 O 3 And MnO 2 Mixed colorant, er ion in glass is absorbed at 400-500nm, mn ion is mainly absorbed at 500nm, nd ion is mainly absorbed at 580nm, and three substances are mixed Can be used for preparing red matrix glass, microcrystalline glass or microcrystalline glass products due to Er 2 O 3 And Nd 2 O 3 Coloring rare earth with weaker coloring power Er 2 O 3 The usage amount is within 6 percent, nd 2 O 3 The usage amount is within 4%, mnO 2 The coloring is strong, the amount of the coloring agent is within the range of 2%, and the lower limit of the total amount of the coloring agents to be mixed is more than 0.9%.
The term "not containing" or "0%" as used herein means that the compound, molecule, element, or the like is not intentionally added as a raw material to the base glass, glass ceramic, or glass ceramic product of the present invention; however, it is within the scope of the present invention that certain other impurities or components may be present that are not intentionally added as raw materials and/or equipment for producing the base glass, glass-ceramic or glass-ceramic article, and that may be present in minor or trace amounts in the final base glass, glass-ceramic or glass-ceramic article.
In some embodiments of the invention, the crystalline phases in the glass-ceramic and glass-ceramic articles comprise quartz and a solid solution of quartz; and/or eucryptite; and/or lithium zinc phosphate, provide high strength for the glass ceramics and glass ceramics products of the invention, the glass ceramics and glass ceramics products break the toughness and become high; the falling ball test height and four-point bending strength of the microcrystalline glass and microcrystalline glass products become large. The glass ceramics of the present invention may also be ion exchanged to obtain additional mechanical strength. The invention can lead the microcrystalline glass and the microcrystalline glass product to obtain proper grain size through reasonable component design, and lead the microcrystalline glass and the microcrystalline glass product to have high strength. The microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity refers to the degree of crystallization, the arrangement of particles in the crystals with complete crystallization is more regular, diffraction lines are strong, sharp and symmetrical, and the half-width of diffraction peaks is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation, so that the diffraction lines have wide peak shapes and are dispersed. The worse the crystallinity, the weaker the diffraction power, the broader the diffraction peak until disappeared in the background.
The grain size and the haze of the microcrystalline glass or the microcrystalline glass product can influence the transmittance of the microcrystalline glass or the microcrystalline glass product, namely the light transmittance is influenced, and the smaller the grain size is, the higher the transmittance is; the smaller the haze, the higher the transmittance. In some embodiments, the glass-ceramic product or glass-ceramic having a thickness of 0.6mm has a haze of 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less. In some embodiments, the glass-ceramic article or glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less. On the other hand, it has been found through studies that the smaller the refractive index difference between the crystalline phase and the glass phase in the glass-ceramic, the higher the transparency of the glass-ceramic or glass-ceramic product.
In some embodiments, the glass-ceramic or glass-ceramic article of the present invention exhibits high transparency in the visible range (i.e., the glass-ceramic or glass-ceramic article is transparent). The glass-ceramic or glass-ceramic article exhibits a high transmittance in the visible light range, and in some embodiments the glass-ceramic article or glass-ceramic 400 to 800nm has an average light transmittance of 85% or more, preferably 87% or more, more preferably 89% or more, at a thickness of 0.6 mm. In some preferred embodiments, the glass-ceramic product or glass-ceramic 550nm has a light transmittance of 85% or more, preferably 90% or more, more preferably 91% or more, with a thickness of 0.6 mm.
In some embodiments, the antimicrobial component may be added to a base glass, glass-ceramic, or glass-ceramic article. The glass-ceramic or glass-ceramic article described herein may be used in applications such as kitchen or restaurant countertops, where exposure to harmful bacteria is likely. Antimicrobial components that may be added to the matrix glass, glass-ceramic, or glass-ceramic article include, but are not limited to, ag, agO, cu, cuO, cu 2 O, etc. In some embodiments, the antimicrobial component is present in an amount of 2% or less, preferably 1% or less, alone or in combination.
The matrix glass, glass-ceramic and glass-ceramic products of the present invention can be produced and manufactured by the following methods:
generating a matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, and is melted for 5 to 24 hours in an electric furnace or a gas furnace within the temperature range of 1250 to 1650 ℃ according to the melting difficulty of glass composition, preferably the temperature is 1380 to 1600 ℃, preferably the time is 8 to 12 hours, and after stirring to be uniform, the mixture is cooled to a proper temperature and is cast into a mould, and the mould is slowly cooled to obtain the glass.
The substrate glass of the present invention can be molded by a well-known method.
The substrate glass of the invention is crystallized by crystallization process after molding or processing, and crystals are uniformly precipitated in the glass. The crystallization treatment may be performed in 1 stage or 2 stages, and preferably 2 stages are used. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization treatment performed at the 1 st temperature is referred to as a 1 st crystallization treatment, and the crystallization treatment performed at the 2 nd temperature is referred to as a 2 nd crystallization treatment.
In order to obtain desired physical properties of the glass ceramics, a preferred crystallization process is:
the crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after the temperature reaches the heat treatment temperature, the temperature is maintained for a predetermined period of time, and then the temperature is lowered. The crystallization temperature is preferably 580 to 950 ℃, more preferably 600 to 850 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours, in order to precipitate a desired crystal phase.
In the crystallization treatment in 2 stages, the 1 st temperature is preferably 580 to 650℃and the 2 nd temperature is preferably 650 to 850 ℃. The holding time at the 1 st temperature is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.
The holding time of 0 hours means that the temperature starts to be lowered or raised again less than 1 minute after the temperature thereof is reached.
In some embodiments, the matrix glass or glass-ceramic described herein can be manufactured into shaped bodies, including but not limited to sheets, by various processes including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by float or roll processes as are known in the art.
The base glass or the glass ceramic of the present invention may be a glass molded product of a sheet material manufactured by a method such as grinding or polishing, but the method for manufacturing the glass molded product is not limited to these methods.
The matrix glass or glass ceramic molded article of the present invention can be formed into various shapes by a method such as hot bending or pressing at a certain temperature, and is not limited to these methods.
The substrate glass, glass-ceramic, and glass-ceramic articles of the present invention can have any thickness that is reasonably useful.
The microcrystalline glass of the invention not only improves mechanical properties through precipitation crystallization, but also can obtain higher strength through forming a compressive stress layer, thereby preparing microcrystalline glass products.
In some embodiments, the substrate glass or glass-ceramic may be processed into a sheet and/or shaped (e.g., punched, heat bent, etc.), shaped, polished and/or polished, and then chemically strengthened by a chemical strengthening process.
The chemical strengthening is ion exchange method. During ion exchange, smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" with larger metal ions of the same valence state in close proximity to the matrix glass or glass-ceramic. And replacing smaller ions with larger ions to construct compressive stress in the matrix glass or the microcrystalline glass, so as to form a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., na + 、K + 、Rb + 、Cs + Etc.),ion exchange is performed by immersing the matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions that are used to displace smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag + 、Tl + 、Cu + And the like may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different composition, with washing and/or annealing steps between immersion.
In some embodiments, the matrix glass or glass-ceramic may be produced by immersing a molten Na salt (e.g., naNO) in a temperature of about 430 ℃ to 470 DEG C 3 ) Ion exchange is carried out in a salt bath of about 6 to 20 hours, preferably at a temperature in the range of 435 to 460 c, preferably for a time in the range of 8 to 13 hours. In this embodiment, na ions replace part of Li ions in the matrix glass or the glass-ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be prepared by melting a K-salt (e.g., KNO) at a temperature immersed in the range of about 400 ℃ to 450 DEG C 3 ) Ion exchange is carried out for 1 to 8 hours in the salt bath, preferably for 2 to 4 hours. In some embodiments, the matrix glass or glass-ceramic may be mixed by immersing the molten K-salt and Na-salt (e.g., KNO) at a temperature of about 350 ℃ to 450 DEG C 3 And NaNO 3 ) Ion exchange is carried out in the salt bath for 0.5 to 8 hours, preferably for 1 to 4 hours.
In some embodiments, there are also ion implantation methods for implanting ions into the surface layer of the base glass or glass-ceramic, and thermal tempering methods for heating and then rapidly cooling the base glass or glass-ceramic.
The substrate glass and/or microcrystalline glass products of the invention are tested by the following methods:
[ coefficient of thermal expansion ]
Coefficient of thermal expansion (alpha) 20℃-120℃ ) The test was performed according to the GB/T7962.16-2010 test method.
[ refractive index ]
Refractive index (nd) was measured according to the method GB/T7962.1-2010.
[ haze ]
The haze tester EEL57D is adopted, a glass sample with the thickness of 0.6mm is used for preparation, and the test is carried out by taking GB2410-80 as a standard.
[ Crystal grain size ]
And (3) measuring by using an SEM scanning electron microscope, carrying out surface treatment on the microcrystalline glass in HF acid, then carrying out metal spraying on the surface of the microcrystalline glass, carrying out surface scanning under the SEM scanning electron microscope, and determining the size of crystal grains.
[ light transmittance ]
The light transmittance is referred to herein as the external transmittance, sometimes simply referred to as the transmittance.
The samples were processed to a thickness of 0.6mm and polished with the opposite faces in parallel, and the average light transmittance of 400 to 800nm was measured by using a Hitachi U-41000-shaped spectrophotometer.
The sample was processed to a thickness of 0.6mm and subjected to parallel polishing of opposite faces, and the light transmittance at 550nm was measured by using a Hitachi U-41000-shaped spectrophotometer.
[ crystallinity ]
The XRD diffraction peaks were compared with the database spectra, and the crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the overall spectrum, and internal calibration was performed by using pure quartz crystals.
[ falling ball test height of glass ceramics ]
The falling ball test height test method of the glass ceramics comprises the following steps:
a sample of 150X 57X 0.55mm was placed on a glass-carrying jig, and a steel ball of 32g was dropped from a predetermined height, and the sample was subjected to a maximum drop test height of impact that could be received without breaking. Specifically, the test was performed starting from a falling ball test height of 400mm, and the heights were changed in order of 450mm, 500mm, 550mm, 600mm, 650mm, 700mm and above without breaking. For the examples having the "falling ball test height A", glass ceramics were used as the test object. Test data recorded as 800mm in the examples show that the glass ceramic is not broken and receives an impact even if the steel ball is dropped from a height of 800 mm.
[ surface stress ] and [ depth of ion exchange layer ]
Surface stress measurements were performed using a glass surface stress meter FSM-6000 LEUV.
Ion exchange layer depth measurements were performed using a glass surface stress meter SLP-2000.
The measurement conditions were calculated by using a sample having a refractive index of 1.54 and an optical elastic constant of 25.3[ (nm/cm)/MPa ].
[ falling ball test height of glass ceramic product ]
The falling ball test height test method of the microcrystalline glass product comprises the following steps:
a sample of 150X 57X 0.55mm was placed on a glass-carrying jig, and 132g of steel balls were dropped from a prescribed height, and the sample was subjected to a maximum drop test height of impact that could be sustained without breaking. Specifically, the test was performed starting from a falling ball test height of 800mm, and the heights were changed in order of 850mm, 900mm, 950, 1000 and above without breaking. For the examples having the "falling ball test height B", the glass ceramic product was used as a test object. Test data recorded as 1000mm in the examples show that the glass ceramic product is not broken and receives an impact even if the steel ball is dropped from a height of 1000 mm. The falling ball test height is sometimes referred to as falling ball height.
[ fracture toughness ]
The method for directly measuring the size of the indentation expansion crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, chamfering, grinding and polishing are carried out, after the sample preparation is completed, a force of 49N is applied to the sample by a Vickers hardness pressing head for 30s, and after the indentation is made, the breaking strength is measured by a three-point bending method.
[ four-point bending Strength ]
The test was performed using a microcomputer controlled electronic universal tester CMT6502, glass size 150X 57X 0.55mm, with ASTM C158-2002 as standard.
[ Vickers hardness ]
By angle of opposite facesA diamond quadrangular pyramid indenter of 136 ° divided by a load (N) when a pyramid-shaped recess was pressed into a test surface by a surface area (mm) calculated by a length of the recess 2 ) Is represented by a value of (a). The test load was 100 (N) and the holding time was 15 (seconds). The vickers hardness is sometimes referred to simply as hardness in the present invention.
The substrate glass has the following properties:
1) In some embodiments, the coefficient of thermal expansion (α) of the matrix glass 20℃-120℃ ) The lower limit of (2) is 50×10 -7 K, preferably with a lower limit of 55X 10 -7 K, more preferably a lower limit of 60X 10 -7 K, upper limit of 80X 10 -7 K, preferably with an upper limit of 75X 10 -7 K, more preferably an upper limit of 70X 10 -7 /K。
2) In some embodiments, the refractive index (nd) of the matrix glass has a lower limit of 1.50, preferably a lower limit of 1.51, more preferably a lower limit of 1.52, and an upper limit of 1.55, preferably an upper limit of 1.54.
The microcrystalline glass has the following properties:
1) In some embodiments, the glass-ceramic has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
2) In some embodiments, the glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.
3) In some embodiments, the haze of the 0.6mm thick glass-ceramic is 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less.
4) In some embodiments, the average transmittance at wavelengths of 400 to 800nm of the glass ceramic having a thickness of 0.6mm is 85% or more, preferably 87% or more, and more preferably 89% or more.
5) In some embodiments, the glass ceramic having a thickness of 0.6mm has a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.
6) In some embodiments, the glass-ceramic has a falling ball test height of 1000mm or more, preferably 1100mm or more, and more preferably 1200mm or more.
7) In some embodiments, the coefficient of thermal expansion (α) of glass-ceramic 20℃-120℃ ) The lower limit of (2) is 70×10 -7 K, preferably with a lower limit of 75X 10 -7 K, more preferably a lower limit of 80X 10 -7 K, upper limit of 120X 10 -7 K, preferably with an upper limit of 110X 10 -7 K, more preferably an upper limit of 100X 10 -7 /K。
8) In some embodiments, the glass-ceramic has a refractive index (nd) with a lower limit of 1.51, preferably a lower limit of 1.52, more preferably a lower limit of 1.53, and an upper limit of 1.57, preferably an upper limit of 1.56, more preferably an upper limit of 1.55.
The microcrystalline glass product has the following properties:
1) In some embodiments, the surface stress of the glass-ceramic article is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.
2) In some embodiments, the four-point bending strength of the glass-ceramic article is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.
3) In some embodiments, the ion exchange layer depth of the glass-ceramic article is 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more.
4) In some embodiments, the glass-ceramic article has a falling ball test height of 1200mm or more, preferably 1300mm or more, more preferably 1400mm or more.
5) In some embodiments, the glass-ceramic article has a fracture toughness of 1 MPa-m 1/2 The above is preferably 1.1 MPa.m 1/2 The above is more preferably 1.2 MPa.m 1/2 The above.
6) In some embodiments, the microcrystalline glass article has a vickers hardness (H v ) 650kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above.
7) In some embodiments, the glass-ceramic article has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
8) In some embodiments, the glass-ceramic article has a grain size of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.
9) In some embodiments, the haze of a 0.6mm thick glass-ceramic article is 0.3% or less, preferably 0.2% or less, more preferably 0.15% or less, and even more preferably 0.1% or less.
10 In some embodiments, the average transmittance at wavelengths of 400 to 800nm is 85% or more, preferably 87% or more, more preferably 89% or more for a glass-ceramic article having a thickness of 0.6 mm.
11 In some embodiments, a glass-ceramic article having a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 85% or more, preferably 90% or more, and more preferably 91% or more.
The microcrystalline glass, microcrystalline glass products and matrix glass have the excellent performances, so that the microcrystalline glass, microcrystalline glass products and matrix glass can be widely manufactured into glass cover plates or glass components; meanwhile, the glass ceramics, glass ceramics products and matrix glass of the invention are applied to electronic equipment or display equipment, such as mobile phones, watches, computers, touch display screens and the like, are used for manufacturing protective glass of mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, unmanned aerial vehicles, personal computers, MTA machines or industrial displays, or are used for manufacturing protective glass of touch screens, protective windows, automobile windows, train windows, aviation mechanical windows, protective glass of touch screens, or are used for manufacturing hard disk substrates or solar cell substrates, or are used for manufacturing white household appliances, such as refrigerator parts or kitchen ware.
Examples
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided. Embodiments of the present invention take numerous efforts to ensure accuracy with respect to numbers but some errors and deviations should be accounted for. The composition itself is given in weight% based on the oxide and has been standardized to 100%.
The examples of the matrix glasses shown in tables 1 to 4 below were manufactured and tested according to the manufacturing method and the performance test method of the matrix glass described above.
Table 1.
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Table 2.
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Table 3.
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Table 4.
Examples of the glass ceramics shown in tables 5 to 6 below were manufactured and tested according to the methods for manufacturing glass ceramics and the methods for testing properties described above.
Table 5.
Table 6.
Table 7.
Table 8.
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Examples of the glass-ceramic products shown in tables 9 to 12 below were obtained by subjecting the glass-ceramics described in tables 5 to 8 above to chemical strengthening according to the chemical strengthening method described above, and were tested according to the performance test method described above.
Table 9.
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Table 10.
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Table 11.
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Table 12.
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Claims (143)

1. The microcrystalline glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；Li 2 O：5～15%；ZnO：0.5～10%；P 2 O 5 ：2～12%；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3 to 1.8, (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5.
2. The glass ceramic according to claim 1, further comprising, in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
3. The microcrystalline glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；Li 2 O：5～15%；ZnO：0.5～10%；P 2 O 5 ：2～12%；ZrO 2 ：1～15%，（Li 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3 to 1.8, (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5; the glass ceramics contains quartz and quartz solid solution crystal phases, wherein the quartz and the quartz solid solution crystal phases have higher weight percentage than other crystal phases existing in the glass ceramics.
4. A glass ceramic according to claim 3, wherein the composition comprises, in weight percent: siO (SiO) 2 : 41-65%; and/or Al 2 O 3 : 15-30%; and/or Na 2 O:0 to 6 percent; and/or ZnO: 0.5-10%; and/or TiO 2 : 0-5%; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO:0 to5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or P 2 O 5 : 2-12%; and/or ZrO 2 : 1-15%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
5. The microcrystalline glass is characterized by comprising quartz and a quartz solid solution crystalline phase, and the microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；ZnO：0.5～10%；TiO 2 ：0～5%；P 2 O 5 ：2～12%；Li 2 O：5～15%；ZrO 2 ：1～15%；MgO：0～8%；Na 2 O：0～6%；K 2 O：0～5%；SrO：0～5%；BaO：0～5%；CaO：0～5%；Ln 2 O 3 ：0～5%；B 2 O 3 : 0-5%; clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of (a) wherein (Li 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3 to 1.8, (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5.
6. The glass-ceramic according to any one of claims 1 to 5, wherein the content of each component in weight percent is one or more of the following cases 7:
1）Al 2 O 3 /SiO 2 0.25 to 0.7;
2）ZnO/Li 2 o is 0.3-1.5;
3）（P 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.05 to 0.5;
4）P 2 O 5 /Al 2 O 3 0.15 to 0.75;
5）（ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.2;
6）（Li 2 O+ZrO 2 ）/SiO 2 0.1 to 0.7;
7）（Li 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.7.
7. The glass-ceramic according to any one of claims 1 to 5, wherein the content of each component in weight percent is one or more of the following cases 7:
1）Al 2 O 3 /SiO 2 0.3 to 0.6;
2）ZnO/Li 2 o is 0.3-1.0;
3）（P 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.1 to 0.4;
4）P 2 O 5 /Al 2 O 3 0.2 to 0.6;
5）（ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 0.8;
6）（Li 2 O+ZrO 2 ）/SiO 2 0.15 to 0.6;
7）（Li 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.55.
8. The glass-ceramic according to any one of claims 1 to 5, wherein the content of each component in weight percent is one or more of the following 4 cases:
1）Al 2 O 3 /SiO 2 0.4 to 0.55;
2）（P 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.15 to 0.3;
3）P 2 O 5 /Al 2 O 3 0.3 to 0.5;
4）（Li 2 O+ZrO 2 ）/SiO 2 0.2 to 0.45.
9. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic comprises the following components in percentage by weight: siO (SiO) 2 : 45-60%; and/or Al 2 O 3 : 18-26%; and/or Na 2 O:0 to 3 percent; and/or ZnO:1 to 8 percent; and/or TiO 2 :0 to 2 percent; and/or Li 2 O: 6-12%; and/or MgO:0.5 to 5 percent; and/or K 2 O:0 to 4 percent; and/or SrO:0 to 2 percent; and/or BaO:0 to 2 percent; and/or CaO:0 to 2 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or B 2 O 3 :0 to 3 percent; and/or P 2 O 5 : 3-10%; and/or ZrO 2 :2.5 to 12 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
10. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic comprises the following components in percentage by weight: siO (SiO) 2 : 45-54%; and/or Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 2 percent; and/or ZnO:2 to 6 percent; and/or TiO 2 :0 to 1 percent; and/or Li 2 O: 7-10%; and/or MgO:1 to 4 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 1 percent; and/or P 2 O 5 : 6-10%; and/or ZrO 2 : 3-10%; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
11. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic comprises the following components in percentage by weight: agO:0 to 2 percent; and/or CuO:0 to 2 percent; and/or Cu 2 O：0～2%。
12. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic comprises the following components in percentage by weight: agO:0 to 1 percent; and/or CuO:0 to 1 percent; and/or Cu 2 O：0～1%。
13. The glass-ceramic according to any one of claims 1 to 5, wherein the component contains no B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Gd 2 O 3 。
14. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic contains quartz and a quartz solid solution; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.
15. The glass-ceramic according to any one of claims 1 to 5, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 10 to 80% by weight of the glass-ceramic.
16. The glass-ceramic according to any one of claims 1 to 5, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 15 to 75% by weight of the glass-ceramic.
17. The glass-ceramic according to any one of claims 1 to 5, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 20 to 70% by weight of the glass-ceramic.
18. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, and the quartz solid solution crystal phase account for 20 to 70 weight percent of the glass-ceramic.
19. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, and the quartz solid solution crystal phase account for 25 to 65 weight percent of the glass-ceramic.
20. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, and the quartz solid solution crystal phase account for 30 to 60 weight percent of the glass-ceramic.
21. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic does not contain petalite; and/or does not contain a lithium silicate crystalline phase.
22. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic having a thickness of 0.6mm has a haze of 0.3% or less; and/or microcrystalline glass with the thickness of 0.6mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 85 percent; and/or glass ceramics with the thickness of 0.6mm, and the transmittance of 550nm wavelength is more than 85 percent.
23. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic having a thickness of 0.6mm has a haze of 0.2% or less; and/or glass ceramics with the thickness of 0.6mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 87 percent; and/or glass ceramics with the thickness of 0.6mm, and the transmittance of 550nm wavelength is more than 90 percent.
24. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic having a thickness of 0.6mm has a haze of 0.15% or less; and/or glass ceramics with the thickness of 0.6mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 89%; and/or glass ceramics with a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 91% or more.
25. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic having a thickness of 0.6mm has a haze of 0.1% or less.
26. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a crystallinity of 20% or more; and/or the grain size is 50nm or less; and/or the falling ball test height is more than 1000 mm.
27. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a crystallinity of 30% or more; and/or the grain size is 40nm or less; and/or the falling ball test height is more than 1100 mm.
28. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a crystallinity of 40% or more; and/or the grain size is below 30 nm; and/or the falling ball test height is more than 1200 mm.
29. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a crystallinity of 50% or more.
30. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a thermal expansion coefficient of 70X 10 -7 /K～120×10 -7 K; and/or a refractive index of 1.51 to 1.57.
31. The glass-ceramic according to any one of claims 1 to 5, wherein the glass-ceramic has a thermal expansion coefficient of 75X 10 -7 /K～110×10 -7 K; and/or a refractive index of 1.52 to 1.56.
32. The glass-ceramic according to any one of claims 1 to 5The glass is characterized in that the thermal expansion coefficient of the glass ceramics is 80 multiplied by 10 -7 /K～100×10 -7 K; and/or a refractive index of 1.53 to 1.55.
33. The glass-ceramic according to any one of claims 1 to 5, further comprising a colorant.
34. The glass-ceramic according to claim 33, wherein the colorant comprises, in weight percent: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4%。
35. The glass-ceramic according to claim 33, wherein the colorant comprises NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3%。
36. A glass ceramic product made from the glass ceramic of any one of claims 1 to 35.
37. The microcrystalline glass product is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；Li 2 O：5～15%；ZnO：0.5～10%；P 2 O 5 ：2～12%；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3 to 1.8, (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5.
38. The glass-ceramic article according to claim 37, further comprising, in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
39. A glass-ceramic article according to claim 37 or 38, wherein the components are present in weight percent in an amount satisfying one or more of the following conditions 7:
1）Al 2 O 3 /SiO 2 0.25 to 0.7;
2）ZnO/Li 2 o is 0.3-1.5;
3）（P 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.05 to 0.5;
4）P 2 O 5 /Al 2 O 3 0.15 to 0.75;
5）（ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.2;
6）（Li 2 O+ZrO 2 ）/SiO 2 0.1 to 0.7;
7) 0.25 to 0.7.
40. A glass-ceramic article according to claim 37 or 38, wherein the components are present in weight percent in an amount satisfying one or more of the following conditions 7:
1）Al 2 O 3 /SiO 2 0.3 to 0.6;
2）ZnO/Li 2 o is 0.3-1.0;
3）（P 2 O 5 +ZnO）/（SiO 2 +MgO）0.1～0.4；
4）P 2 O 5 /Al 2 O 3 0.2 to 0.6;
5）（ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 0.8;
6）（Li 2 O+ZrO 2 ）/SiO 2 0.15 to 0.6;
7）（Li 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.55.
41. A glass-ceramic article according to claim 37 or 38, wherein the components are present in weight percent in an amount satisfying one or more of the following conditions 4:
1）Al 2 O 3 /SiO 2 0.4 to 0.55;
2）（P 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.15 to 0.3;
3）P 2 O 5 /Al 2 O 3 0.3 to 0.5;
4）（Li 2 O+ZrO 2 ）/SiO 2 0.2 to 0.45.
42. A glass-ceramic product according to claim 37 or 38, characterized in that it comprises, in weight percent: siO (SiO) 2 : 45-60%; and/or Al 2 O 3 : 18-26%; and/or Na 2 O:0 to 3 percent; and/or ZnO:1 to 8 percent; and/or TiO 2 :0 to 2 percent; and/or Li 2 O: 6-12%; and/or MgO:0.5 to 5 percent; and/or K 2 O:0 to 4 percent; and/or SrO:0 to 2 percent; and/or BaO:0 to 2 percent; and/or CaO:0 to 2 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or B 2 O 3 :0 to 3 percent; and/or P 2 O 5 : 3-10%; and/or ZrO 2 :2.5 to 12 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
43. A glass-ceramic product according to claim 37 or 38, characterized in that it comprises, in weight percent: siO (SiO) 2 : 45-54%; and/or Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 2 percent; and/or ZnO:2 to 6 percent; and/or TiO 2 :0 to 1 percent; and/or Li 2 O: 7-10%; and/or MgO:1 to 4 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 1 percent; and/or P 2 O 5 : 6-10%; and/or ZrO 2 : 3-10%; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
44. A glass-ceramic product according to claim 37 or 38, characterized in that it comprises, in weight percent: agO:0 to 2 percent; and/or CuO:0 to 2 percent; and/or Cu 2 O：0～2%。
45. A glass-ceramic product according to claim 37 or 38, characterized in that it comprises, in weight percent: agO:0 to 1 percent; and/or CuO:0 to 1 percent; and/or Cu 2 O：0～1%。
46. The glass-ceramic article according to claim 37 or 38, wherein the component (a) does not contain B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain CaO; and/or no BaO; and/or does not contain SrO; and/or does not contain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or does not contain Gd 2 O 3 。
47. The glass-ceramic article of claim 37 or 38, wherein the glass-ceramic comprises quartz and a solid solution of quartz; and/or eucryptite; and/or lithium zinc phosphate; and/or petalite; and/or a lithium silicate crystalline phase.
48. The glass-ceramic article of claim 37 or 38, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 10 to 80% by weight of the glass-ceramic.
49. The glass-ceramic article of claim 37 or 38, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 15 to 75 weight percent of the glass-ceramic.
50. The glass-ceramic article of claim 37 or 38, wherein the total amount of crystalline phases in the glass-ceramic is in the range of 20 to 70% by weight of the glass-ceramic.
51. The glass-ceramic article according to claim 37 or 38, wherein the glass-ceramic comprises quartz and quartz solid solution crystal phases, and the quartz and quartz solid solution crystal phases have a higher weight percentage than other crystal phases, the quartz and quartz solid solution crystal phases comprising 20 to 70 weight percent of the glass-ceramic.
52. The glass-ceramic article according to claim 37 or 38, wherein the glass-ceramic comprises quartz and quartz solid solution crystal phases, and the quartz and quartz solid solution crystal phases have a higher weight percentage than other crystal phases, the quartz and quartz solid solution crystal phases comprising 25 to 65 weight percent of the glass-ceramic.
53. The glass-ceramic article according to claim 37 or 38, wherein the glass-ceramic comprises quartz and a quartz solid solution crystal phase, and the quartz and quartz solid solution crystal phase has a higher weight percentage than other crystal phases, and the quartz and quartz solid solution crystal phase accounts for 30-60% of the glass-ceramic by weight.
54. The glass-ceramic article according to claim 37 or 38, wherein the glass-ceramic is free of petalite; and/or does not contain a lithium silicate crystalline phase.
55. The glass-ceramic article according to any one of claims 36 to 38, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.3% or less; and/or a glass ceramic product with a thickness of 0.6mm, wherein the average transmittance of the glass ceramic product at a wavelength of 400-800 nm is more than 85%; and/or a glass ceramic product with a thickness of 0.6mm, wherein the transmittance at a wavelength of 550nm is more than 85%.
56. The glass-ceramic article according to any one of claims 36 to 38, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.2% or less; and/or a glass ceramic product with a thickness of 0.6mm, wherein the average transmittance of the glass ceramic product at a wavelength of 400-800 nm is more than 87%; and/or a glass ceramic product with a thickness of 0.6mm, wherein the transmittance at a wavelength of 550nm is more than 90%.
57. The glass-ceramic article according to any one of claims 36 to 38, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.15% or less; and/or glass ceramic products with the thickness of 0.6mm, wherein the average transmittance of the wavelengths of 400-800 nm is more than 89%; and/or a glass ceramic product with a thickness of 0.6mm, and a transmittance at a wavelength of 550nm of 91% or more.
58. The glass-ceramic article according to any one of claims 36 to 38, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.1% or less.
59. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a crystallinity of 20% or more; and/or the grain size is 50nm or less.
60. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a crystallinity of 30% or more; and/or the grain size is 40nm or less.
61. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a crystallinity of 40% or more; and/or the grain size is 30nm or less.
62. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a crystallinity of 50% or more.
63. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a surface stress of 600MPa or greater; and/or the ion exchange layer depth is 5 μm or more.
64. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a surface stress of 650MPa or more; and/or the ion exchange layer depth is 10 μm or more.
65. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a surface stress of 700MPa or more; and/or the ion exchange layer depth is 20 μm or more.
66. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a falling ball test height of 1200mm or more; and/or fracture toughness of 1 MPa.m 1/2 The above; and/or a Vickers hardness of 650kgf/mm 2 The above; and/or four-point bendingThe strength is more than 600 MPa.
67. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a falling ball test height of 1300mm or more; and/or fracture toughness of 1.1 MPa.m 1/2 The above; and/or a Vickers hardness of 680kgf/mm 2 The above; and/or the four-point bending strength is 650MPa or more.
68. The glass-ceramic article of any one of claims 36 to 38, wherein the glass-ceramic article has a falling ball test height of 1400mm or more; and/or fracture toughness of 1.2 MPa.m 1/2 The above; and/or a Vickers hardness of 700kgf/mm 2 The above; and/or the four-point bending strength is 700MPa or more.
69. A glass cover plate, characterized in that it is made of the glass ceramics according to any one of claims 1 to 35; and/or using the glass-ceramic article of any one of claims 36-68.
70. A glass component, characterized in that it is made of the glass ceramics according to any one of claims 1 to 35; and/or using the glass-ceramic article of any one of claims 36-68.
71. A display device comprising the glass-ceramic of any one of claims 1 to 35; and/or comprising the glass-ceramic article of any one of claims 36 to 68, and/or comprising the glass cover plate of claim 69; and/or contain the glass component of claim 70.
72. An electronic device comprising the glass ceramic according to any one of claims 1 to 35; and/or comprising a glass-ceramic article according to any one of claims 36 to 68; and/or contain the glass cover plate of claim 69; and/or contain the glass component of claim 70.
73. The method for producing a glass ceramic according to any one of claims 1 to 35, characterized by comprising the steps of: forming matrix glass, and forming microcrystalline glass on the matrix glass through a crystallization process.
74. The method of producing glass-ceramic according to claim 73, wherein the melting temperature of the matrix glass is 1250 to 1650 ℃; and/or the melting time is 5 to 24 hours.
75. The method of producing glass-ceramic according to claim 73, wherein the melting temperature of the matrix glass is 1380 to 1600 ℃; and/or the melting time is 8 to 12 hours.
76. The method for producing glass-ceramic according to claim 73, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-950 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
77. The method for producing glass-ceramic according to claim 73, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-850 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
78. The method for producing glass-ceramic according to claim 73, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
79. The method for producing glass-ceramic according to claim 78, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
80. The method for producing glass-ceramic according to claim 78, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
81. The method of making a glass-ceramic article according to any one of claims 36 to 68, comprising the steps of: forming matrix glass, forming microcrystalline glass on the matrix glass through a crystallization process, and forming a microcrystalline glass product on the microcrystalline glass through a chemical strengthening process.
82. The method of manufacturing a glass-ceramic article according to claim 81, wherein the melting temperature of the formed matrix glass is 1250-1650 ℃; and/or the melting time is 5 to 24 hours.
83. The method of manufacturing a glass-ceramic article according to claim 81, wherein the melting temperature of the formed matrix glass is 1380 to 1600 ℃; and/or the melting time is 8 to 12 hours.
84. The method of manufacturing a glass-ceramic article according to claim 81, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-950 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
85. The method of manufacturing a glass-ceramic article according to claim 81, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-850 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
86. The method of manufacturing a glass-ceramic article according to claim 81, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
87. The method of manufacturing a glass-ceramic article according to claim 86, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
88. The method of manufacturing a glass-ceramic article according to claim 86, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
89. The method of making a glass-ceramic article according to claim 81, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 400-450 ℃ for 1-8 hours; and/or the glass ceramics are immersed in a salt bath in which the molten K salt and Na salt are mixed at the temperature of 350-450 ℃ for 0.5-8 hours.
90. The method of making a glass-ceramic article according to claim 81, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of 435-460 ℃ for 8-13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 400-450 ℃ for 2-4 hours; and/or the glass ceramics are immersed in a salt bath in which the K salt and the Na salt are mixed at the temperature of 0350 ℃ to 450 ℃ for 1 to 4 hours.
91. A method of making a glass-ceramic article, the method comprising the steps of:
forming a matrix glass, the matrix glass comprising, in weight percent: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；Li 2 O：5～15%；ZnO：0.5～10%；P 2 O 5 ：2～12%；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3-1.8; (ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5;
and forming microcrystalline glass on the matrix glass through a crystallization process, and forming a microcrystalline glass product on the microcrystalline glass through a chemical strengthening process.
92. The method of manufacturing a glass-ceramic article according to claim 91, wherein the matrix glass comprises the following components in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
93. Manufacture of a glass-ceramic article according to any one of claims 91 or 92The method is characterized in that the matrix glass comprises the following components in percentage by weight: siO (SiO) 2 : 45-60%; and/or Al 2 O 3 : 18-26%; and/or Na 2 O:0 to 3 percent; and/or ZnO:1 to 8 percent; and/or TiO 2 :0 to 2 percent; and/or Li 2 O: 6-12%; and/or MgO:0.5 to 5 percent; and/or K 2 O:0 to 4 percent; and/or SrO:0 to 2 percent; and/or BaO:0 to 2 percent; and/or CaO:0 to 2 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or B 2 O 3 :0 to 3 percent; and/or P 2 O 5 : 3-10%; and/or ZrO 2 :2.5 to 12 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
94. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises, in weight percent: siO (SiO) 2 : 45-54%; and/or Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 2 percent; and/or ZnO:2 to 6 percent; and/or TiO 2 :0 to 1 percent; and/or Li 2 O: 7-10%; and/or MgO:1 to 4 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 1 percent; and/or P 2 O 5 : 6-10%; and/or ZrO 2 : 3-10%; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
95. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises the following components in weight percent: al (Al) 2 O 3 /SiO 2 Is 0.250.7; and/or ZnO/Li 2 O is 0.3-1.5; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.05 to 0.5; and/or P 2 O 5 /Al 2 O 3 0.15 to 0.75; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.1 to 0.7; and/or (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.7.
96. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises the following components in weight percent: al (Al) 2 O 3 /SiO 2 0.3 to 0.6; and/or ZnO/Li 2 O is 0.3-1.0; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.1 to 0.4; and/or P 2 O 5 /Al 2 O 3 0.2 to 0.6; and/or (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.2; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.15 to 0.6; and/or (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.55.
97. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises the following components in weight percent: al (Al) 2 O 3 /SiO 2 0.4 to 0.55; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.15 to 0.3; and/or P 2 O 5 /Al 2 O 3 0.3 to 0.5; and/or (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 0.8; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.2 to 0.45.
98. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises, in weight percent: niO:0 to 4 percent; and/or Ni 2 O 3 ：0～4%；And/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4%。
99. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the matrix glass comprises, in weight percent: niO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3%。
100. The method of making a glass-ceramic article of any one of claims 91 or 92, wherein the substrate glass is formed at a melting temperature of 1250-1650 ℃; and/or the melting time is 5 to 24 hours.
101. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the substrate glass is formed with a melting temperature of 1380 ℃ to 1600 ℃; and/or the melting time is 8 to 12 hours.
102. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-950 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
103. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-850 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
104. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
105. The method of manufacturing a glass-ceramic article according to claim 104, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
106. The method of manufacturing a glass-ceramic article according to claim 104, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
107. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 400-450 ℃ for 1-8 hours; and/or the glass ceramics are immersed in a salt bath in which the molten K salt and Na salt are mixed at the temperature of 350-450 ℃ for 0.5-8 hours.
108. The method of making a glass-ceramic article according to any one of claims 91 or 92, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of 435-460 ℃ for 8-13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 400-450 ℃ for 2-4 hours; and/or the glass ceramics are immersed in a salt bath in which the molten K salt and Na salt are mixed at the temperature of 350-450 ℃ for 1-4 hours.
109. The method of any one of claims 91 or 92, wherein the total amount of crystalline phases in the glass-ceramic article is in the range of 10 to 80% by weight of the glass-ceramic article.
110. The method of any one of claims 91 or 92, wherein the total amount of crystalline phases in the glass-ceramic article is in the range of 15 to 75% by weight of the glass-ceramic article.
111. The method of any one of claims 91 or 92, wherein the total amount of crystalline phases in the glass-ceramic article is in the range of 20 to 70% by weight of the glass-ceramic article.
112. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the glass-ceramic article comprises a crystal phase of quartz and a crystal solid solution, and the crystal phase of quartz and the crystal solid solution has a higher weight percentage than other crystal phases, and the crystal phase of quartz and the crystal solid solution is 20 to 70 weight percentage of the glass-ceramic article.
113. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the glass-ceramic article comprises a crystal phase of quartz and a crystal solid solution, and the crystal phase of quartz and the crystal solid solution has a higher weight percentage than other crystal phases, and the crystal phase of quartz and the crystal solid solution accounts for 25 to 65 weight percent of the glass-ceramic article.
114. The method of manufacturing a glass-ceramic article according to any one of claims 91 or 92, wherein the glass-ceramic article comprises a crystal phase of quartz and a crystal solid solution, and the crystal phase of quartz and the crystal solid solution has a higher weight percentage than other crystal phases, and the crystal phase of quartz and the crystal solid solution accounts for 30 to 60 weight percent of the glass-ceramic article.
115. The method of producing a glass-ceramic article according to any one of claims 91 to 92, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.3% or less; and/or a glass ceramic product with a thickness of 0.6mm, wherein the average transmittance of the glass ceramic product at a wavelength of 400-800 nm is more than 85%; and/or a glass ceramic product with a thickness of 0.6mm, wherein the transmittance of 550nm wavelength is more than 85%; and/or the crystallinity of the glass ceramic product is more than 20%; and/or the grain size is 50nm or less; and/or the surface stress of the glass ceramic product is more than 600 MPa; and/or the ion exchange layer depth is more than 5 μm; and/or the falling ball test height of the microcrystalline glass product is more than 1200 mm; and/or fracture toughness of 1 MPa.m 1/2 The above; and/or a Vickers hardness of 650kgf/mm 2 The above; and/or the four-point bending strength is 600MPa or more.
116. The method of producing a glass-ceramic article according to any one of claims 91 to 92, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.2% or less; and/or a glass ceramic product with a thickness of 0.6mm, wherein the average transmittance of the glass ceramic product at a wavelength of 400-800 nm is more than 87%; and/or a glass ceramic product with a thickness of 0.6mm, wherein the transmittance of 550nm wavelength is more than 90%; and/or the crystallinity of the glass ceramic product is more than 30%; and/or the grain size is 40nm or less; and/or the surface stress of the glass ceramic product is more than 650 MPa; and/or the ion exchange layer depth is more than 10 μm; and/or the falling ball test height of the microcrystalline glass product is more than 1300 mm; and/or fracture toughness of 1.1 MPa.m 1/2 The above; and/or a Vickers hardness of 680kgf/mm 2 The above; and/or the four-point bending strength is 650MPa or more.
117. The method of producing a glass-ceramic article according to any one of claims 91 to 92, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.15% or less; and/or glass ceramic products with the thickness of 0.6mm, wherein the average transmittance of the wavelengths of 400-800 nm is more than 89%; and/or a glass ceramic product with a thickness of 0.6mm, wherein the transmittance of 550nm wavelength is more than 91%; and/or the crystallinity of the glass ceramic product is more than 40%; and/or the grain size is below 30 nm; and/or the surface stress of the glass ceramic product is more than 700 MPa; and/or the ion exchange layer depth is more than 20 μm; and/or the falling ball test height of the microcrystalline glass product is more than 1400 mm; and/or fracture toughness of 1.2 MPa.m 1/2 The above; and/or a Vickers hardness of 700kgf/mm 2 The above; and/or the four-point bending strength is 700MPa or more.
118. The method of producing a glass-ceramic article according to any one of claims 91 to 92, wherein the glass-ceramic article having a thickness of 0.6mm has a haze of 0.1% or less; and/or the crystallinity of the glass ceramic product is more than 50%.
119. The manufacturing method of the microcrystalline glass is characterized by comprising the following steps:
Forming a matrix glass, the matrix glass comprising, in weight percent: siO (SiO) 2 ：41～65%；Al 2 O 3 ：15～30%；Li 2 O：5～15%；ZnO：0.5～10%；P 2 O 5 ：2～12%；ZrO 2 :1 to 15 percent, wherein (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.8, znO/Li 2 O is 0.3-1.8; (ZrO 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.5;
and forming microcrystalline glass on the substrate glass through a crystallization process.
120. The method for producing glass-ceramic according to claim 119, wherein the matrix glass comprises the following components in weight percent: na (Na) 2 O:0 to 6 percent; and/or MgO: 0-8%; and/or K 2 O: 0-5%; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or Ln 2 O 3 : 0-5%; and/or B 2 O 3 : 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
121. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises, in weight percent: siO (SiO) 2 : 45-60%; and/or Al 2 O 3 : 18-26%; and/or Na 2 O:0 to 3 percent; and/or ZnO:1 to 8 percent; and/or TiO 2 :0 to 2 percent; and/or Li 2 O: 6-12%; and/or MgO:0.5 to 5 percent; and/or K 2 O:0 to 4 percent; and/or SrO:0 to 2 percent; and/or BaO:0 to 2 percent; and/or CaO:0 to 2 percent; and/or Ln 2 O 3 :0 to 4 percent; and/or B 2 O 3 :0 to 3 percent; and/or P 2 O 5 : 3-10%; and/or ZrO 2 :2.5 to 12 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
122. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises, in weight percent: siO (SiO) 2 : 45-54%; and/or Al 2 O 3 :20.5 to 24 percent; and/or Na 2 O:0 to 2 percent; and/or ZnO:2 to 6 percent; and/or TiO 2 :0 to 1 percent; and/or Li 2 O: 7-10%; and/or MgO:1 to 4 percent;and/or K 2 O:0 to 3 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3 percent; and/or B 2 O 3 :0 to 1 percent; and/or P 2 O 5 : 6-10%; and/or ZrO 2 : 3-10%; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
123. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises the following components in weight percent: al (Al) 2 O 3 /SiO 2 0.25 to 0.7; and/or ZnO/Li 2 O is 0.3-1.5; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.05 to 0.5; and/or P 2 O 5 /Al 2 O 3 0.15 to 0.75; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.1 to 0.7; and/or (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.7.
124. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises the following components in weight percent: al (Al) 2 O 3 /SiO 2 0.3 to 0.6; and/or ZnO/Li 2 O is 0.3-1.0; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.1 to 0.4; and/or P 2 O 5 /Al 2 O 3 0.2 to 0.6; and/or (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 1.2; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.15 to 0.6; and/or (Li) 2 O+ZrO 2 +ZnO）/SiO 2 0.25 to 0.55.
125. The method for producing a glass ceramic according to any one of claims 119 and 120, which comprisesCharacterized in that the matrix glass comprises the following components in percentage by weight, wherein Al 2 O 3 /SiO 2 0.4 to 0.55; and/or (P) 2 O 5 +ZnO）/（SiO 2 +MgO) is 0.15 to 0.3; and/or P 2 O 5 /Al 2 O 3 0.3 to 0.5; and/or (ZrO) 2 +MgO+ZnO）/Al 2 O 3 0.35 to 0.8; and/or (Li) 2 O+ZrO 2 ）/SiO 2 0.2 to 0.45.
126. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises, in weight percent: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4%。
127. The method for producing a glass-ceramic according to any one of claims 119 to 120, wherein the matrix glass comprises, in weight percent: niO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3%。
128. The method for producing a glass-ceramic according to any one of claims 119 and 120, wherein a melting temperature of the matrix glass is 1250 to 1650 ℃; and/or the melting time is 5 to 24 hours.
129. The method of producing glass-ceramic according to any one of claims 119 to 120, wherein the melting temperature of the matrix glass is 1380 ℃ to 1600 ℃; and/or the melting time is 8 to 12 hours.
130. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-950 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
131. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-850 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
132. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
133. The method for producing glass-ceramic according to claim 132, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 0 to 24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
134. The method for producing glass-ceramic according to claim 132, wherein the crystallization process comprises the steps of: the 1 st temperature is 580-650 ℃, and the 2 nd temperature is 650-850 ℃; the holding time at the 1 st temperature is 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
135. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the total amount of crystal phases in the glass-ceramic is in the range of 10 to 80% by weight of the glass-ceramic.
136. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the total amount of crystal phases in the glass-ceramic is 15 to 75% by weight of the glass-ceramic.
137. The method for producing glass-ceramic according to any one of claims 119 to 120, wherein the total amount of crystal phases in the glass-ceramic is in the range of 20 to 70% by weight of the glass-ceramic.
138. The method for manufacturing glass-ceramic according to any one of claims 119 to 120, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, the quartz and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, and the quartz solid solution crystal phase account for 20 to 70 weight percent of the glass-ceramic.
139. The method for manufacturing glass-ceramic according to any one of claims 119 to 120, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, the quartz and the quartz solid solution crystal phase have a higher weight percentage than other crystal phases, and the quartz solid solution crystal phase account for 25 to 65 weight percent of the glass-ceramic.
140. The method for manufacturing glass-ceramic according to any one of claims 119 to 120, wherein the glass-ceramic contains quartz and a quartz solid solution crystal phase, the quartz and the quartz solid solution crystal phase have a weight percentage higher than other crystal phases, and the quartz solid solution crystal phase account for 30 to 60% by weight of the glass-ceramic.
141. The method for producing a glass ceramic according to any one of claims 119 to 120, wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.3% or less; and/or microcrystalline glass with the thickness of 0.6mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 85 percent; and/or microcrystalline glass with the thickness of 0.6mm, wherein the transmittance of 550nm wavelength is more than 85%; and/or the crystallinity of the glass ceramics is more than 20 percent; and/or the grain size is 50nm or less; and/or the falling ball test height is more than 1000 mm; and/or the glass ceramics has a thermal expansion coefficient of 70 x 10 -7 /K～120×10 -7 K; and/or a refractive index of 1.51 to 1.57.
142. The method for producing a glass ceramic according to any one of claims 119 to 120, wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.2% or less; and/or glass ceramics with the thickness of 0.6mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 87 percent; and/or microcrystalline glass with the thickness of 0.6mm, wherein the transmittance of 550nm wavelength is more than 90%; and/or the crystallinity of the glass ceramics is more than 30 percent; and/or the grain size is 40nm or less; and/or the falling ball test height is more than 1100 mm; and/or glass ceramics having a thermal expansion coefficient of 75 x 10 -7 /K～110×10 -7 K; and/or a refractive index of 1.52 to 1.56.
143. The method for producing a glass ceramic according to any one of claims 119 to 120, wherein the glass ceramic having a thickness of 0.6mm has a haze of 0.1% or less; and/or the crystallinity of the glass ceramics is more than 50 percent.
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