CN115259672A - Transparent glass ceramics and transparent glass ceramics product - Google Patents

Abstract

The invention provides transparent microcrystalline glass with high light transmittance and a transparent microcrystalline glass product. A transparent glass-ceramic product comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂5.0 to 15.0. Through reasonable component design, the microcrystalline glass product obtained by the invention has higher light transmittance, and is suitable for display equipment or electronic equipment with higher light transmittance requirement.

Description

Transparent glass ceramics and transparent glass ceramics product

Technical Field

The invention relates to microcrystalline glass, in particular to transparent microcrystalline glass with high light transmittance and a transparent microcrystalline glass product.

Background

Portable electronic devices (e.g., smart phones, music players, e-book readers, notepads, tablets, laptops, etc.) have become powerful, small, and lightweight through high-speed development. In order to achieve the above effects, a housing material (e.g., a cover material) of an electronic device is required to have excellent mechanical properties with a small thickness in order to cope with dropping, scratching, and the like which are inevitable during use. In recent years, microcrystalline glass is made into a shell material for electronic equipment, and the properties of bending resistance, wear resistance and the like of the microcrystalline glass are obviously superior to those of common high-aluminum cover plate glass. In addition, these glasses or glass ceramics are widely used in the fields of optical devices for automobiles, display devices, lighting devices, and the like. The glass or glass ceramics used in the above fields need to have excellent mechanical properties to meet the requirements of drop resistance, pressure resistance, scratch resistance and the like in the use process, and also need to have higher visible light transmittance to improve the experience comfort of users.

Disclosure of Invention

The invention aims to solve the technical problem of providing transparent glass ceramics with high light transmittance and a transparent glass ceramics product.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) A transparent glass-ceramic product comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂5.0 to 15.0.

(2) A transparent glass-ceramic product comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15%.

(3) The transparent glass-ceramic article according to (1) or (2), which comprises the following components in percentage by weight: p is₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2%, what is meantLn₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(4) Transparent glass-ceramic article containing SiO₂、Al₂O₃、Li₂O、Na₂O and ZrO₂The components of which are expressed in weight percent, wherein SiO₂/ZrO₂A transparent glass-ceramic product having a thickness of 5.0 to 15.0, and a wavelength of 400 to 800nm and an average light transmittance of 88.0% or more.

(5) Transparent glass-ceramic article containing SiO₂、Al₂O₃、Li₂O, a crystalline phase of which contains a crystalline phase of lithium silicate, and a light transmittance at a wavelength of 550nm of the transparent glass-ceramic product having a thickness of 1mm or less of 89.0% or more.

(6) Transparent glass-ceramic article comprising SiO₂、Al₂O₃、Li₂And O, wherein the crystal phase contains a lithium silicate crystal phase, and the falling resistance of the transparent microcrystalline glass product is more than 1500 mm.

(7) The transparent glass-ceramic product according to any one of (4) to (6), which comprises the following components in percentage by weight: siO 2₂:60 to 80 percent; and/or Al₂O₃:3 to 15 percent; and/or Li₂O: greater than or equal to 5% but less than 10%; and/or Na₂O:4 to 8 percent; and/or P₂O₅:0 to 5 percent; and/or ZrO₂: greater than 5% but less than or equal to 15%; and/or P₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(8) Transparent glass-ceramic product, the composition of which is expressed in weight percentage and is made of SiO₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；P₂O₅：0～5％；ZrO₂: greater than 5% but less than or equal to 15%; p₂O₅：0～5％；ZnO：0～2％；MgO：0～2％；B₂O₃：0～4％；K₂O：0～3％；Ln₂O₃:0 to 2 percent; a clarifying agent: 0 to 2 percent of the composition, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(9) The transparent glass-ceramic product according to any one of (1) to (8), which comprises the following components in percentage by weight: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, and (SiO) is more preferable₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, and (ZrO) is more preferable₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (L)i₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

(10) The transparent glass-ceramic product according to any one of (1) to (8), which comprises the following components in percentage by weight: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(11) The transparent glass-ceramic article according to any one of (1) to (8), wherein the transparent glass-ceramic article contains a lithium silicate crystal phase, the lithium silicate crystal phase having a higher weight percentage than other crystal phases, preferably the lithium silicate crystal phase accounts for 5 to 50% by weight of the transparent glass-ceramic article, more preferably the lithium silicate crystal phase accounts for 5 to 40% by weight of the transparent glass-ceramic article, and still more preferably the lithium silicate crystal phase accounts for 10 to 30% by weight of the transparent glass-ceramic article.

(12) The transparent glass-ceramic article according to any one of (1) to (8), wherein the transparent glass-ceramic article contains a lithium monosilicate crystal phase, the lithium monosilicate crystal phase having a higher weight percentage than other crystal phases, preferably the lithium monosilicate crystal phase accounts for 5 to 50% by weight of the transparent glass-ceramic article, more preferably the lithium monosilicate crystal phase accounts for 5 to 40% by weight of the transparent glass-ceramic article, and still more preferably the lithium monosilicate crystal phase accounts for 10 to 30% by weight of the transparent glass-ceramic article.

(13) The transparent glass-ceramic article according to any one of (1) to (8), which contains a lithium disilicate crystal phase, wherein the lithium disilicate crystal phase accounts for 20% or less by weight of the transparent glass-ceramic article, preferably the lithium disilicate crystal phase accounts for 10% or less by weight of the transparent glass-ceramic article, more preferably the lithium disilicate crystal phase accounts for 5% or less by weight of the transparent glass-ceramic article, and further preferably does not contain the lithium disilicate crystal phase.

(14) The transparent glass-ceramic product according to any one of (1) to (8), wherein the transparent glass-ceramic product contains petalite crystal phase, the weight percentage of the petalite crystal phase in the transparent glass-ceramic product is less than 15%, preferably the weight percentage of the petalite crystal phase in the transparent glass-ceramic product is less than 10%, more preferably the weight percentage of the petalite crystal phase in the transparent glass-ceramic product is less than 5%, and further preferably the petalite crystal phase is not contained.

(15) The transparent glass-ceramic product according to any one of (1) to (8), wherein the transparent glass-ceramic product has a falling ball test height of 1400mm or more, preferably 1500mm or more, and more preferably 1600mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1 MPa.m^1/2More preferably 1.2 MPa.m^1/2The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or a Vickers hardness of 670kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or the depth of the ion exchange layer is 80 μm or more, preferably 90 μm or more, more preferably 100More than mum; and/or a surface stress of 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or a crystallinity of 10% or more, preferably 15% or more, more preferably 20% or more; and/or a crystal grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or a fall-resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more.

(16) The transparent crystallized glass product according to any one of (1) to (8), wherein the haze of the transparent crystallized glass product having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and further preferably 90.5% or more; and/or a light transmittance at a wavelength of 550nm of 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more; and/or an average light | B | value of 400-800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.

(17) The transparent glass-ceramic article according to (16), wherein the thickness of the transparent glass-ceramic article is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

(18) The transparent microcrystalline glass comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂5.0 to 15.0.

(19) The transparent microcrystalline glass comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15%.

(20) The transparent glass-ceramic according to (18) or (19), which comprises the following components in percentage by weight: p₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(21) Transparent glass ceramics containing SiO₂、Al₂O₃、Li₂O、Na₂O and ZrO₂The components of which are expressed in weight percent, wherein SiO₂/ZrO₂A transparent glass ceramics having a thickness of 5.0 to 15.0 and a thickness of 1mm or less and having an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more.

(22) Transparent microcrystalline glass containing SiO₂、Al₂O₃、Li₂O, a crystalline phase of which contains a crystalline phase of lithium silicate, and a light transmittance of the transparent glass ceramics having a thickness of 1mm or less at a wavelength of 550nm of 89.0% or more.

(23) Transparent glass ceramics containing SiO₂、Al₂O₃、Li₂And O, wherein the crystal phase contains a lithium silicate crystal phase, and the bulk falling sphere height of the transparent glass ceramics is more than 1700 mm.

(24) The transparent glass-ceramic according to any one of (21) to (23), which comprises, in terms of weight percent: siO 2₂:60 to 80 percent; and/or Al₂O₃:3 to 15 percent; and/or Li₂O: greater than or equal to 5% but less than 10%; and/or Na₂O:4 to 8 percent; and/or P₂O₅:0 to 5 percent; and/or ZrO₂: greater than 5% but less than or equal to 15%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(25) Transparent glass-ceramic product, the composition of which is expressed in weight percentage and is made of SiO₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；P₂O₅：0～5％；ZrO₂: greater than 5% but less than or equal to 15%; p is₂O₅：0～5％；ZnO：0～2％；MgO：0～2％；B₂O₃：0～4％；K₂O：0～3％；Ln₂O₃:0 to 2 percent; a clarifying agent: 0 to 2 percent of the composition, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(26) The transparent glass-ceramic according to any one of (18) to (25), which comprises, in terms of weight percent: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, and (SiO) is more preferable₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

(27) The transparent glass-ceramic according to any one of (18) to (25), which comprises, in terms of weight percent: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(28) The transparent glass ceramics according to any one of (18) to (25), wherein the transparent glass ceramics contains a lithium silicate crystal phase having a higher weight percentage than other crystal phases, preferably the lithium silicate crystal phase accounts for 5 to 50% by weight of the transparent glass ceramics, more preferably the lithium silicate crystal phase accounts for 5 to 40% by weight of the transparent glass ceramics, and further preferably the lithium silicate crystal phase accounts for 10 to 30% by weight of the transparent glass ceramics.

(29) The transparent crystallized glass according to any one of (18) to (25), wherein the transparent crystallized glass contains a lithium monosilicate crystal phase having a higher weight percentage than other crystal phases, preferably the lithium monosilicate crystal phase accounts for 5 to 50% by weight of the transparent crystallized glass, more preferably the lithium monosilicate crystal phase accounts for 5 to 40% by weight of the transparent crystallized glass, and still more preferably the lithium monosilicate crystal phase accounts for 10 to 30% by weight of the transparent crystallized glass.

(30) The transparent glass ceramics according to any one of (18) to (25), wherein the transparent glass ceramics contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase accounts for 20% by weight or less of the transparent glass ceramics, preferably the lithium disilicate crystal phase accounts for 10% by weight or less of the transparent glass ceramics, more preferably the lithium disilicate crystal phase accounts for 5% by weight or less of the transparent glass ceramics, and further preferably the lithium disilicate crystal phase is not contained.

(31) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic contains petalite crystal phase, the weight percentage of the petalite crystal phase in the transparent glass-ceramic is 15% or less, preferably the weight percentage of the petalite crystal phase in the transparent glass-ceramic is 10% or less, more preferably the weight percentage of the petalite crystal phase in the transparent glass-ceramic is 5% or less, and further preferably the petalite crystal phase is not contained.

(32) The transparent glass-ceramic according to any one of (18) to (25), wherein the crystallinity of the transparent glass-ceramic is 10% or more, preferably 15% or more, and more preferably 20% or more; and/or a crystal grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the ball falling height of the body is 1700mm or more, preferably 1900mm or more, more preferably 2000mm or more; and/or a Vickers hardness of 600kgf/mm²Above, it is preferably 620kgf/mm²Above, more preferably 630kgf/mm²The above; and/or a refractive index of 1.520 to 1.545; and/or a Young's modulus of 80 to 100GPa.

(33) The transparent glass ceramics according to any one of (18) to (25), wherein the haze of the transparent glass ceramics having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and further preferably 90.5% or more; and/or a light transmittance at a wavelength of 550nm of 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more; and/or an average light | B | value of 400-800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.

(34) The transparent glass ceramics according to (33), wherein the thickness of the transparent glass ceramics is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

(35) The matrix glass comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂Is 5.0 to 15.0.

(36) The matrix glass comprises the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15%.

(37) The base glass according to (35) or (36), which comprises the following components in percentage by weight: p₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(38) A matrix glass, the composition of which is expressed in weight percentage, is composed of SiO₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15%; p₂O₅：0～5％；ZnO：0～2％；MgO：0～2％；B₂O₃：0～4％；K₂O：0～3％；Ln₂O₃:0 to 2 percent; a clarifying agent: 0 to 2 percent of the composition, the Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(39) The matrix glass according to any one of (35) to (38), which comprises, in terms of weight percent: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, and (SiO) is more preferable₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, and (SiO) is more preferable₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, and (ZrO) is more preferable₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

(40) The matrix glass according to any one of (35) to (38), which comprises, in terms of weight percent: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

(41) The matrix glass according to any one of (35) to (38), wherein the matrix glass has a refractive index of 1.510 to 1.530.

(42) A crystallized glass molded article comprising the transparent crystallized glass according to any one of (18) to (34).

(43) A glass cover plate comprising the transparent glass-ceramic product according to any one of (1) to (17), and/or the transparent glass-ceramic according to any one of (18) to (34), and/or the matrix glass according to any one of (35) to (41), and/or the glass-ceramic molded body according to (42).

(44) A glass component comprising the transparent glass-ceramic product according to any one of (1) to (17), the transparent glass-ceramic according to any one of (18) to (34), the matrix glass according to any one of (35) to (41), and/or the glass-ceramic molded body according to (42).

(45) A display device comprising the transparent glass-ceramic article according to any one of (1) to (17), and/or the transparent glass-ceramic according to any one of (18) to (34), and/or the matrix glass according to any one of (35) to (41), and/or the glass-ceramic molded body according to (42), and/or the glass cover plate according to (43), and/or the glass component according to (44).

(46) An electronic device comprising the transparent glass-ceramic article according to any one of (1) to (17), and/or the transparent glass-ceramic according to any one of (18) to (34), and/or the matrix glass according to any one of (35) to (41), and/or the glass-ceramic molded body according to (42), and/or the glass cover plate according to (43), and/or the glass component according to (44).

(47) (1) A method for producing a transparent glass-ceramic article according to any one of (1) to (17), the method comprising the steps of: forming matrix glass, forming transparent glass ceramics by the matrix glass through a crystallization process, and forming a transparent glass ceramics product by the transparent glass ceramics through a chemical strengthening process.

(48) The method for manufacturing a transparent glass ceramic article according to (47), wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 550-700 ℃, preferably 580-650 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(49) The method for manufacturing a transparent glass-ceramic article according to (47), the crystallization process comprising 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.

(50) The method for producing a transparent glass-ceramic article according to (39), wherein the crystallization process comprises the steps of: the 1 st temperature is 450-550 ℃, and the 2 nd temperature is 550-700 ℃; 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.

(51) The method for producing a transparent glass-ceramic article according to any one of (47) to (50), wherein the chemical strengthening process comprises: immersing the transparent microcrystalline glass in a salt bath of molten Na salt at the temperature of 350-470 ℃ for 1-36 hours, wherein the preferable temperature range is 380-460 ℃, and the preferable time range is 2-24 hours; and/or the transparent glass ceramics is immersed in the salt bath for melting the K salt at the temperature of 360-450 ℃ for 1-36 hours, and the preferred time range is 2-24 hours; and/or the transparent glass ceramics is immersed in the mixed salt bath of the molten K salt and the molten Na salt at the temperature of 360-450 ℃ for 1-36 hours, and the preferred time range is 2-24 hours.

(52) The method for producing a transparent glass ceramics according to any of (18) to (34), comprising the steps of: forming matrix glass, and then forming the matrix glass into transparent microcrystalline glass through a crystallization process.

(53) The method for manufacturing transparent glass ceramics according to (52), the crystallization process comprising the steps of: raising the temperature to a predetermined crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then lowering the temperature, wherein the crystallization temperature is 550 to 700 ℃, preferably 580 to 650 ℃, and the retention time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

(54) The method for manufacturing transparent glass ceramics according to (52), the crystallization process comprising 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.

(55) The method for producing transparent glass ceramics according to (54), wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 450-550 ℃, and the temperature of the No. 2 is 550-700 ℃; 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.

(56) The method for producing a glass-ceramic shaped body according to (42), which comprises grinding or polishing a transparent glass-ceramic to obtain a glass-ceramic shaped body, or subjecting a base glass or a transparent glass-ceramic to a hot bending process or a pressing process at a certain temperature to obtain a glass-ceramic shaped body.

(57) The method for producing a glass-ceramic shaped body according to (56), comprising the steps of: carrying out primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation nucleation, heating, heat preservation crystallization and cooling to room temperature to form pre-crystallized glass; and carrying out hot-forming on the pre-crystallized glass to obtain a microcrystalline glass forming body.

(58) The method for producing a glass-ceramic shaped body according to (56), comprising the steps of:

1) Heating and preheating: placing matrix glass or pre-crystallized glass or transparent microcrystalline glass into a mold, enabling the mold to sequentially pass through each temperature rising station in a hot bending machine, and staying at each station for a certain time for heat preservation, wherein the temperature of a preheating zone is 400-800 ℃, the pressure is 0.01-0.05 MPa, and the time is 40-200 s;

2) And (3) pressure forming: transferring the preheated mould to a forming station, and applying a certain pressure to the mould by a hot bending machine, wherein the pressure range is 0.1-0.8 Mpa, the temperature range of the forming station is 600-850 ℃, and the forming time range is 40-200 s;

3) Pressure maintaining and temperature reduction: and transferring the mold to a cooling station for cooling station by station, wherein the cooling temperature range is 750-500 ℃, the pressure is 0.01-0.05 Mpa, and the time is 40-200 s.

The invention has the beneficial effects that: through reasonable component design, the microcrystalline glass or the microcrystalline glass product obtained by the invention has higher light transmittance, and is suitable for display equipment or electronic equipment with higher light transmittance requirement.

Detailed Description

The transparent crystallized glass and the transparent crystallized glass article of the present invention are materials having a crystalline phase (sometimes also referred to as a crystal) and a glass phase, which are distinguished from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.

The inventors of the present invention have made extensive experiments and studies to obtain a transparent crystallized glass or a transparent crystallized glass product of the present invention at a low cost by specifying the content and content ratio of specific components constituting the transparent crystallized glass and the transparent crystallized glass product to specific values and precipitating specific crystal phases.

The ranges of the respective components (components) of the matrix glass, the transparent glass ceramics and the transparent glass ceramics product of the present invention will be described below. In the present specification, the contents of the respective components are all expressed in weight percent (wt%) with respect to the total amount of the substance of the matrix glass, or the glass ceramics product converted into the composition of the oxide, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the composition components of the matrix glass, the crystallized glass, or the crystallized glass product of the present invention are decomposed and converted into oxides at the time of melting, the total amount of the oxides is defined as 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization (i.e., crystallization process treatment), the term "matrix glass" refers to a transparent glass ceramic (hereinafter, also simply referred to as "glass ceramic"), and the term "transparent glass ceramic product (hereinafter, also simply referred to as" glass ceramic product ") refers to a product obtained by chemically strengthening a transparent glass ceramic.

Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited 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 can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means only A, only B, or both A and B.

In some embodiments of the invention, the crystalline phase in the transparent glass-ceramic or transparent glass-ceramic article comprises a crystalline phase of lithium silicate (one or both of lithium monosilicate and lithium disilicate). In some embodiments, the lithium silicate crystalline phase has a higher weight percentage than the other crystalline phases. In some embodiments, the lithium silicate crystalline phase comprises from 5 to 50% by weight of the transparent glass ceramic or transparent glass ceramic article, preferably the lithium silicate crystalline phase comprises from 5 to 40% by weight of the transparent glass ceramic or transparent glass ceramic article, and more preferably the lithium silicate crystalline phase comprises from 10 to 30% by weight of the transparent glass ceramic or transparent glass ceramic article. In some embodiments, the lithium silicate crystalline phase comprises 5%, 6%, 7%, 8%, 9%, 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% by weight of the transparent glass ceramic or transparent glass ceramic article.

In some embodiments of the invention, the crystalline phase in the transparent glass ceramic or transparent glass ceramic article comprises a crystalline phase of lithium orthosilicate. In some embodiments, the lithium monosilicate crystalline phase has a higher weight percentage than the other crystalline phases. In some embodiments, the lithium monosilicate crystalline phase comprises from 5 to 50% by weight of the transparent glass ceramic or transparent glass ceramic article, preferably the lithium monosilicate crystalline phase comprises from 5 to 40% by weight of the transparent glass ceramic or transparent glass ceramic article, and more preferably the lithium monosilicate crystalline phase comprises from 10 to 30% by weight of the transparent glass ceramic or transparent glass ceramic article. In some embodiments, the lithium monosilicate crystalline phase constitutes 5%, 6%, 7%, 8%, 9%, 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% by weight of the transparent glass ceramic or transparent glass ceramic article.

In some embodiments of the invention, the crystalline phase in the transparent glass ceramic or transparent glass ceramic article comprises a crystalline phase of lithium disilicate. In some embodiments, the lithium disilicate crystalline phase accounts for 20% or less by weight of the transparent glass ceramic or transparent glass ceramic article, preferably the lithium disilicate crystalline phase accounts for 10% or less by weight of the transparent glass ceramic or transparent glass ceramic article, more preferably the lithium disilicate crystalline phase accounts for 5% or less by weight of the transparent glass ceramic or transparent glass ceramic article, and even more preferably the lithium disilicate crystalline phase is not contained in the transparent glass ceramic or transparent glass ceramic article. In some embodiments, the lithium disilicate crystalline phase constitutes 0%, greater than 0%, 0.1%, 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%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20% by weight of the transparent glass ceramic or transparent glass ceramic article.

In some embodiments of the present invention, the crystalline phase in the transparent glass ceramics or transparent glass ceramics product contains petalite crystalline phase, and the weight percentage of the petalite crystalline phase in the transparent glass ceramics or transparent glass ceramics product is less than 15%, preferably the weight percentage of the petalite crystalline phase in the transparent glass ceramics or transparent glass ceramics product is less than 10%, more preferably the weight percentage of the petalite crystalline phase in the transparent glass ceramics or transparent glass ceramics product is less than 5%, and further preferably the transparent glass ceramics or transparent glass ceramics product does not contain the petalite crystalline phase. In some embodiments, the petalite crystalline phase comprises 0%, greater than 0%, 0.1%, 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%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% by weight of the transparent glass ceramic or transparent glass ceramic article.

SiO₂Is a basic component of the glass, glass-ceramic and glass-ceramic articles of the invention, which is one of the components forming the lithium silicate crystalline phase, if SiO₂When the content of (A) is less than 60%, crystals are easily coarsened in the microcrystalline glass, and the light transmittance of the microcrystalline glass and the microcrystalline glass product is affected. Thus, siO₂The lower limit of the content is 60%, the preferred lower limit is 62%, and the more preferred lower limit is 64%. If SiO₂The content is more than 80 percent, the glass melting temperature is high, the material melting is difficult, and the haze of the microcrystalline glass and the microcrystalline glass product is increased. Thus, siO₂The upper limit of the content is 80%, preferably 78%, more preferably 75%. In some embodiments, about 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80% SiO may be included₂。

Al₂O₃Is a component for forming a glass network structure, is beneficial to chemical strengthening of the microcrystalline glass, and improves the falling resistance of the microcrystalline glass product, and if the content of the component is less than 3 percent, the effect is poor. Thus, al₂O₃The lower limit of the content is 3%, and the preferable lower limit is 5%. On the other hand, if Al₂O₃The content of the microcrystalline glass exceeds 15 percent, and fragments of the microcrystalline glass product obtained after the microcrystalline glass is chemically strengthened after being crushed are small (generally in a granular shape), so that the microcrystalline glass product is not beneficial to continuous use. Thus, al₂O₃The upper limit of the content is 15%, preferably 12%, more preferably 10%. In some embodiments, about 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% of Al₂O₃。

Li₂O is an essential component for forming a crystal phase of the microcrystalline glass of the present invention and is also an essential component for chemical strengthening, but if the content thereof is less than 5%, the kind of the formed crystal changes, and the strength of the microcrystalline glass and the microcrystalline glass product is affected. Thus, li₂The lower limit of the O content is 5%, and the preferable lower limit is 6%. On the other hand, if Li is contained excessively₂And O, the haze of the microcrystalline glass and the microcrystalline glass product is increased, and the raw material cost is higher. Thus, li₂The upper limit of the O content is less than 10%. In some embodiments, about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 9.8%, less than 10% Li may be included₂O。

Na₂O is favorable for forming a lithium monosilicate crystal phase in the glass ceramics and can improve the stability of the glass ceramics after chemical strengthening, and the content of Na is more than 4 percent in the invention₂O to achieve the above effects, and preferably 4.5% or more of Na₂And (O). However, if Na is contained excessively₂O, the formation of a lithium silicate crystal phase in the microcrystalline glass is difficult, and the light transmittance of the microcrystalline glass and the microcrystalline glass product is influenced. Thus, na₂The upper limit of the O content is 8%, preferably 7.5%, more preferably 7%. In some embodiments, about 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% Na may be included₂O。

In some embodiments, the SiO is₂、Al₂O₃、Na₂Total content of O SiO₂+Al₂O₃+Na₂O and Li₂Ratio between contents of O (SiO)₂+Al₂O₃+Na₂O)/Li₂The O is controlled within the range of 7.0-18.0, which is beneficial to refining crystal grains, improving the fracture toughness of the microcrystalline glass and the microcrystalline glass product and improving the depth and the surface stress of an ion exchange layer of the microcrystalline glass product. Therefore, (SiO) is preferable₂+Al₂O₃+Na₂O)/Li₂O is7.0 to 18.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0. In some embodiments, (SiO)₂+Al₂O₃+Na₂O)/Li₂The value of O may be 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5, 15.7, 16.0, 16.3, 16.5, 16.7, 17.0, 17.3, 17.5, 17.7, 18.0.

ZrO₂Can prevent crystallization during glass molding, can refine crystal grains during crystallization heat treatment, and reduce the haze of the microcrystalline glass and the microcrystalline glass product. ZrO in the invention₂The lower limit of the content is more than 5%, preferably 5.5% or more, and more preferably 6% or more. But if too much ZrO is contained₂，ZrO₂Is not easy to melt in the glass, is easy to form calculus, and weakens the heat treatment crystallization capacity of the glass. Thus, zrO₂The upper limit of the content is 15%, preferably 13%, more preferably 12%. In some embodiments, greater than about 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 included₂。

In some embodiments, the SiO is₂With ZrO₂Ratio between contents of (SiO)₂/ZrO₂And the control range is between 5.0 and 15.0, which is favorable for improving the light transmittance and four-point bending strength of the microcrystalline glass and the microcrystalline glass product, improving the ball drop test height of the microcrystalline glass product and the body ball drop height of the microcrystalline glass, and preventing the haze and the | B | value from increasing. Therefore, siO is preferable₂/ZrO₂5.0 to 15.0, and SiO is more preferable₂/ZrO₂Is 6.0 to 13.0, more preferablySiO 2 is selected₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂Is 7.0 to 11.0. In some embodiments, the SiO₂/ZrO₂The value of (a) may be 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0.

In some embodiments, zrO is reacted₂And Al₂O₃In total content of ZrO₂+Al₂O₃With Li₂Ratio between contents of O (ZrO)₂+Al₂O₃)/Li₂And the O is controlled within the range of 0.85-5.0, so that the ball falling height of the body of the microcrystalline glass can be improved, the ball falling test height and the ion exchange layer depth of the microcrystalline glass product can be improved, and the reduction of the light transmittance and the crystallinity of the microcrystalline glass and the microcrystalline glass product can be prevented. Therefore, (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.0. In some embodiments, (ZrO)₂+Al₂O₃)/Li₂The value of O may be 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.

In some embodiments, li is substituted with one or more substituents selected from the group consisting of alkyl, aryl, heteroaryl, and heteroaryl₂O and Na₂Total content of O Li₂O+Na₂O and SiO₂And ZrO₂SiO in total content₂+ZrO₂BetweenRatio of (Li)₂O+Na₂O)/(SiO₂+ZrO₂) The control range is 0.10-0.27, which is beneficial to improving the surface stress and the ion exchange layer depth of the microcrystalline glass product, improving the four-point bending strength and the hardness of the microcrystalline glass and the microcrystalline glass product, and preventing the fracture toughness and the falling resistance of the microcrystalline glass and the microcrystalline glass product from being reduced. Therefore, (Li) is preferable₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.10 to 0.27, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23. In some embodiments, (Li)₂O+Na₂O)/(SiO₂+ZrO₂) May be 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27.

P₂O₅The non-uniform nucleation can be carried out in the glass, the formation of crystals is promoted, and the light transmittance of the microcrystalline glass and the microcrystalline glass product is improved; but if too much P is contained₂O₅The glass is easy to be directly crystallized during the forming process, and the heat treatment process is not easy to control. Thus, P₂O₅The content of (b) is 0 to 5%, preferably 1 to 4.5%, more preferably 1.5 to 4%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of P may be included₂O₅。

In some embodiments, the SiO is₂And Li₂SiO as the total content of O₂+Li₂O and ZrO₂And P₂O₅In total content of ZrO₂+P₂O₅Ratio (SiO) between₂+Li₂O)/(ZrO₂+P₂O₅) The control is in the range of 4.0 to 15.5, the haze and the | B | value of the microcrystalline glass and the microcrystalline glass product can be reduced, and the shatter resistance of the microcrystalline glass and the microcrystalline glass product is improvedAnd the crystallinity of the microcrystalline glass and the microcrystalline glass product are optimized. Therefore, (SiO) is preferable₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, and (SiO) is more preferable₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5. In some embodiments, (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) The value of (a) may be 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.7, 6.0, 6.3, 6.5, 6.7, 7.0, 7.3, 7.5, 7.7, 8.0, 8.3, 8.5, 8.7, 9.0, 9.3, 9.5, 9.7, 10.0, 10.3, 10.5, 10.7, 11.0, 11.3, 11.5, 11.7, 12.0, 12.3, 12.5, 12.7, 13.0, 13.3, 13.5, 13.7, 14.0, 14.3, 14.5, 14.7, 15.0, 15.3, 15.5.

ZnO can lower the melting temperature of the glass, but too much can result in increased haze in the microcrystalline glass and microcrystalline glass articles. Therefore, the content of ZnO is limited to 2% or less, preferably 1.5% or less, and more preferably 1% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 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% ZnO may be included.

MgO can lower the melting temperature of the glass, but too much content thereof can cause the haze of the glass ceramics and the glass ceramics products to increase. Therefore, the content of MgO is limited to 2% or less, preferably 1.5% or less, and more preferably 1% or less. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 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% MgO may be included.

B₂O₃Can reduce the melting temperature of glass and increase the microcrystalline glassThe content of the glass phase in the glass is beneficial to the hot bending of the microcrystalline glass and the microcrystalline glass product. However, if the glass contains B excessively₂O₃Phase separation is easy to occur during crystallization heat treatment, which causes the light transmittance of the microcrystalline glass and the microcrystalline glass product to be reduced. Thus, B₂O₃The content is 0 to 4%, preferably 0 to 3%, more preferably 0 to 2%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 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%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% B may be included₂O₃。

K₂O can reduce the viscosity of the glass and promote the growth of crystals during crystallization heat treatment, but if it is too much, K is contained₂O, the crystal in the glass is easy to grow rapidly, and the light transmittance of the microcrystalline glass and the microcrystalline glass product is reduced. Thus, K₂The content of O is 3% or less, preferably 2%, more preferably 1% or less. In some embodiments, K may be included at about 0%, greater than 0%, 0.01%, 0.05%, 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%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%₂O。

Ln₂O₃(Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of) can reduce the smelting difficulty of the glass, when the content is too much, the difficulty of forming crystals during glass crystallization can be caused, the crystallinity of the microcrystalline glass and the microcrystalline glass product is reduced, and the body falling ball height of the microcrystalline glass and the falling ball test height of the microcrystalline glass product are reduced. Thus, ln₂O₃The upper limit of the content is 2%, preferably 1%, more preferably has an upper limit of 0.5%, and further preferably contains no Ln₂O₃. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 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% Ln may be included₂O₃。

In some embodiments, the glass, glass-ceramic, or glass-ceramic article may further comprise 0-2% of a fining agent to enhance the bubble removal capability of the glass, glass-ceramic, or glass-ceramic article, such fining agent including but not limited to Sb₂O₃、SnO₂、SnO、CeO₂One or more of F (fluorine), cl (chlorine) and Br (bromine), preferably Sb₂O₃As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent is preferably 1%, more preferably 0.5% when it is present alone or in combination. In some embodiments, one or more of the above clarifying agents are present in an amount of about 0%, greater than 0%, 0.01%, 0.05%, 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 As₂O₃Are toxic substances and do not meet the environmental requirements even when contained in small amounts, and thus the present invention preferably does not contain PbO and As in some embodiments₂O₃。

"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the matrix glass, the glass ceramic or the glass ceramic product of the present invention; it is within the scope of the present invention that certain impurities or components not intentionally added may be present as raw materials and/or equipment for the production of the matrix glass, microcrystalline glass or microcrystalline glass article and may be present in small or trace amounts in the final matrix glass, microcrystalline glass or microcrystalline glass article.

In some embodiments of the present invention, the microcrystalline glass and microcrystalline glass articles contain lithium monosilicate as a crystalline phase, which provides high strength to the microcrystalline glass and microcrystalline glass articles of the present invention, and the microcrystalline glass and microcrystalline glass articles have high fracture toughness; the height of the body falling ball of the microcrystalline glass, the height of the falling ball test of the microcrystalline glass product and the four-point bending strength are increased. The microcrystalline glass has excellent chemical strengthening performance, and can be treated by a chemical strengthening process to obtain excellent mechanical strength. Through reasonable component design, the microcrystalline glass and the microcrystalline glass product can obtain proper grain size, and the microcrystalline glass product 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 is the integrity of the crystallization, the arrangement of mass points in the crystal with complete crystallization is regular, the diffraction line is strong, sharp and symmetrical, and the half-height width of the diffraction peak is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation and the like, so that diffraction line peaks are wide and diffuse. The poorer the crystallinity, the weaker the diffraction power, the wider the diffraction peak until it disappears in the background. In some embodiments, the microcrystalline glass article or microcrystalline glass has a crystallinity of 10% or more, preferably 15% or more, and more preferably 20% or more.

The size and the type of crystal phase of the microcrystalline glass or the microcrystalline glass product can influence the haze and the light transmittance of the microcrystalline glass or the microcrystalline glass product, and the smaller the crystal grain is, the higher the light transmittance is; the smaller the haze, the higher the light transmittance. In some embodiments, the haze of the microcrystalline glass article or microcrystalline glass having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. In some embodiments, the crystallite glass article or crystallite glass has a grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less.

In some embodiments, the content of crystalline phases and the refractive index in the microcrystalline glass or the microcrystalline glass product according to the invention influence the | B | value of the microcrystalline glass or the microcrystalline glass product, the occurrence of bluish or yellowish coloration of the microcrystalline glass or the microcrystalline glass product in the visible range is observed, which influences the optical properties of the product, and is denoted by the | B | value in LAB (chromaticity values of colors of substances). The microcrystalline glass or microcrystalline glass product of the present invention has a low | B | value in the visible light range, and in some embodiments the microcrystalline glass product or microcrystalline glass having a thickness of less than 1mm has an average light | B | value of 400-800 nm of less than 1.0, preferably less than 0.9, more preferably less than 0.8.

The transparent glass ceramics or transparent glass ceramics products of the invention exhibit high transparency in the visible range (i.e. the glass ceramics or glass ceramics products are transparent). The transparent glass ceramics or transparent glass ceramics product exhibits high transmittance in the visible light range, and in some embodiments, the transparent glass ceramics or transparent glass ceramics having a thickness of 1mm or less preferably has an average light transmittance of 90.5% or more in the range of 400 to 800 nm. In some preferred embodiments, the light transmittance of 550nm of the transparent glass-ceramic article or the transparent glass-ceramic having a thickness of 1mm or less is preferably 91.5% or more.

In some embodiments, an antimicrobial component may be added to the matrix glass, microcrystalline glass, or microcrystalline glass article. The microcrystalline glass or microcrystalline glass articles described herein may be used in applications such as kitchens or countertops where exposure to harmful bacteria is likely. The matrix glass, glass-ceramic or glass-ceramic article contains an antimicrobial component including, but not limited to, ag, agO, cu, cuO, cu₂O, and the like. In some embodiments, the antimicrobial components described above are present at 2% or less, preferably 1% or less, alone or in combination.

The matrix glass, the glass-ceramic and the glass-ceramic product of the invention can be produced and manufactured by the following methods:

and (3) generation of matrix glass: the raw materials are evenly mixed according to the component proportion, the evenly mixed raw materials are put into a crucible made of platinum or quartz, the raw materials are 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 the glass composition, the mixture is cooled to proper temperature after being stirred evenly, and the mixture is cast into a mould and slowly cooled to obtain the glass.

The matrix glass of the present invention can be shaped by a well-known method.

The matrix glass of the invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass. The crystallization may be performed in 1 stage or 2 stages, and preferably 2 stages. 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 process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.

In order to obtain desired physical and chemical properties of the glass ceramics, the crystallization process is preferably as follows:

the above-mentioned 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 crystallization temperature, the temperature is maintained for a predetermined time, and then the temperature is lowered. The crystallization temperature is preferably 550 to 700 ℃, more preferably 580 to 650 ℃ in order to allow the desired crystal phase to be precipitated, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours.

When the crystallization is performed in 2 stages, the 1 st temperature is preferably 450 to 550 ℃ and the 2 nd temperature is preferably 550 to 700 ℃. 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 above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.

In some embodiments, the matrix or microcrystalline glasses described herein can be fabricated 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 a float process or a roll process as is well known in the art. The molded article of the present invention further includes a lens, a prism, and the like.

The matrix glass or glass ceramics of the present invention can be produced by a method such as grinding or polishing to produce a glass molded article or a glass ceramics molded article of sheet material, but the method for producing a glass molded article or a glass ceramics molded article is not limited to these methods.

The matrix glass or the glass ceramics of the present invention can be produced by a method such as a hot bending process or a press molding process at a certain temperature to form glass shaped bodies or glass ceramics shaped bodies having various shapes, but is not limited to these methods.

In some embodiments, a hot bending process can be used to form a glass shaped body or a glass ceramic shaped body. The hot bending process is a process of putting 2D or 2.5D glass or microcrystalline glass into a mold, and sequentially carrying out the steps of heating up, preheating, pressure forming, pressure maintaining, temperature reducing and the like in a hot bending machine to obtain a 3D curved glass forming body or microcrystalline glass forming body.

In some embodiments, the microcrystalline glass shaped body has a 2.5D or 3D configuration, i.e., the microcrystalline glass shaped body has a non-planar configuration. As used herein, "non-planar configuration" means that in one 2.5D or 3D shape, at least a portion of the glass-ceramic shaped body extends outwardly or along an angle with a plane defined by the original, laid out configuration of the 2D matrix glass. A 2.5D or 3D glass-ceramic shaped body formed from a matrix glass may have one or more convex or curved portions.

In some embodiments, the method for manufacturing the glass-ceramic shaped body is a thermal bending process method in combination with characteristics such as growth of a crystal phase and transformation of the crystal phase in the glass-ceramic. Specifically, the method includes pre-crystallization and hot forming. The pre-crystallization is to form pre-crystallized glass by controlling a crystallization process on matrix glass, wherein the crystallinity of the pre-crystallized glass does not reach the crystallinity required by the performance index of a target microcrystalline glass forming body. And forming the microcrystalline glass forming body by the pre-crystallized glass through a hot working forming process.

In some embodiments, a method of manufacturing a microcrystalline glass shaped body comprises the steps of:

1) Carrying out primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation nucleation, heating, heat preservation crystallization and cooling to room temperature to form pre-crystallized glass;

2) And carrying out hot-forming on the pre-crystallized glass to obtain a microcrystalline glass forming body.

The crystallization heat treatment process comprises the step of enabling the matrix glass to be at a certain temperature T_hAnd time t_hNucleating at a certain temperature T_cAnd time t_cThen, the pre-crystallized glass is crystallized to obtain a pre-crystallized glass having a crystallinity lower than that required for the performance index of the objective glass-ceramic molded body. Calculating the total content of main crystal phase I in the crystallinity of the pre-crystallized glass by a Rietveld full-spectrum fitting fine modification method by using XRD test data_c1. The pre-crystallization of the invention is a complete process in terms of the process, which comprises a nucleation process step, and the crystallization process comprises one, two or more sections, and the like, and is a complete process comprising temperature rise, heat preservation, temperature rise and heat preservation again, wherein the temperature rise and heat preservation is 82308230, and the temperature is reduced to room temperature according to the process. The method is different from the primary crystallization and the secondary crystallization which are mentioned in partial documents or patents, wherein the crystallization is carried out for 82308230, the crystallization is carried out for the first section and the second section in the complete crystallization process, the crystallization is carried out for the 8230, and the process of raising the temperature and crystallizing again after the temperature is reduced to the room temperature is not carried out.

The hot working forming of the invention refers to forming the pre-crystallized glass by a hot working process under the conditions of certain temperature, time, pressure and the like, wherein the hot working forming comprises more than one hot working process, and the hot working process comprises but is not limited to press forming, bending forming or drawing forming the pre-crystallized glass under the conditions of certain temperature, time, pressure and the like. In the hot forming process, sometimes a formed body with a complicated shape cannot be finished by one hot working, and it may be necessary to perform hot working twice or more.

In some embodiments, the method of manufacturing the microcrystalline glass shaped body is a hot bending process. Specifically, in some embodiments, a method of manufacturing a glass-ceramic shaped body includes the steps of:

1) Heating and preheating: the matrix glass or the pre-crystallized glass or the microcrystalline glass is placed in a mould, the mould sequentially passes through each temperature-raising station in a hot bending machine, and the mould stays at each station for a certain time for heat preservation. The temperature of the preheating zone is 400-800 ℃, the pressure is 0.01-0.05 MPa, and the time is 40-200 s. In some embodiments, for a hot bending machine with 5 preheating stations, the initial temperature rise is generally set to be about 500 ℃, the temperature of the subsequent stations is gradually increased, the temperature gradient between two adjacent stations is gradually reduced from low temperature to high temperature, and the temperature difference between the last preheating station and the first pressing station is within 20 ℃.

2) Pressure molding: the mould is preheated and then transferred to a forming station, a hot bending machine applies a certain pressure to the mould, the pressure range is 0.1-0.8 Mpa, the pressure is determined according to factors such as glass thickness, radian and the like, the temperature range of the forming station is 600-850 ℃, and the forming time range is 40-200 s.

3) Pressure maintaining and temperature reduction: and transferring the die to a cooling station for cooling station by station. The temperature range of the temperature is controlled to be 750-500 ℃, the pressure is 0.01-0.05 Mpa, and the time is 40-200 s.

The microcrystalline glass forming body is formed by adopting a hot bending process, the appearance quality of common high-alumina glass needs to be controlled, and the influence of crystal growth and development in the hot bending process on the performance of the microcrystalline glass also needs to be controlled, for example, 3D curved microcrystalline glass used for a display device or an electronic device shell needs to pay close attention to the light transmittance, the haze, the | B | value, the uniformity and the like after the hot bending.

The matrix glass, microcrystalline glass, and microcrystalline glass articles of the present invention may have any thickness that is reasonably useful.

The microcrystalline glass of the present invention can improve mechanical properties by precipitation crystallization, and can also obtain more excellent mechanical properties by forming a compressive stress layer, thereby producing a microcrystalline glass product.

In some embodiments, the matrix glass or glass-ceramic may be formed into a sheet, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or polished, and chemically strengthened by a chemical strengthening process.

The chemical strengthening method of the invention is an ion exchange method. In the ion exchange process, smaller metal ions in the matrix glass or glass ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are closer to the matrix glass or glass ceramic. And replacing the smaller ions with the larger ions to build a compressive stress in the matrix glass or the microcrystalline glass 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 for replacing the smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag⁺、Tl⁺、Cu⁺Etc. 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: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.

In some embodiments, the matrix glass or glass-ceramic can be formed by immersing a molten Na salt (e.g., naNO) at a temperature of about 350 ℃ to 470 ℃₃) The salt bath of (a) is subjected to ion exchange for about 1 to 36 hours, preferably at a temperature in the range of 380 to 460 c, preferably for a time in the range of 2 to 24 hours. In this embodiment, na ions replace part of Li ions in the matrix glass or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 360 ℃ to 450 ℃₃) The salt bath of (3) is subjected to ion exchange for 1 to 36 hours, preferably for a time ranging from 2 to 24 hours. In some embodiments, the matrix glass or glass-ceramic may be ion exchanged by melting a mixed salt bath of a K salt and a Na salt for 1 to 36 hours, preferably in the time range of 2 to 24 hours, at a temperature of about 360 to 450 ℃.

The performance indexes of the microcrystalline glass and/or the microcrystalline glass product and/or the matrix glass are tested by adopting the following method:

[ haze ]

A haze tester, namely Meinenda CM3600A, is adopted, samples with the thickness of less than 1mm are prepared, and GB2410-80 is used as a standard for testing.

[ grain size ]

And (3) determining by using an SEM (scanning electron microscope), carrying out surface treatment on the microcrystalline glass in HF (hydrofluoric acid), carrying out gold spraying on the surface of the microcrystalline glass, and carrying out surface scanning under the SEM, so as to determine the size of the crystal grains.

[ light transmittance ]

The light transmittance described herein is the external transmittance, sometimes referred to simply as the transmittance.

The sample was processed to 1mm or less and polished in parallel with the opposite surface, and the average light transmittance at 400 to 800nm was measured by Hitachi U-41000 spectrophotometer.

The sample was processed to 1mm or less and the opposed faces were polished in parallel, and the light transmittance at 550nm was measured by Hitachi U-41000 spectrophotometer.

[ degree of crystallinity ]

The XRD diffraction peaks were compared with the database pattern, and the crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the entire pattern, and internal calibration was performed by using a pure quartz crystal.

[ depth of ion exchange layer ]

Ion exchange layer depth was measured using a glass surface stress meter SLP-2000.

The refractive index of the sample was 1.56 and the optical elastic constant was 29[ (nm/cm)/MPa, which were used as the measurement conditions.

[ surface stress ]

Surface stress measurement was carried out using a glass surface stress meter SLP-2000.

The refractive index of the sample was 1.52 and the optical elastic constant was 29[ (nm/cm)/MPa as the measurement conditions.

[ shatter resistance ]

The drop resistance test was carried out using a directional drop tester WH-2101. The 2D glass ceramic product is loaded with glass products with the same specification (each glass product is 20g in weight and is loaded with 2 glass sheets), 60-80 meshes of sand paper is laid on a base, the sand paper freely falls from the specified height, a sample is directly hammered on the sand paper, and the height which can bear the impact without breaking is the falling resistance. Specifically, the test was conducted from a height of 600mm, and the height was changed in the order of 700mm, 800mm, 900mm, 1000mm and more without breaking. For the examples having "drop-resistance", a glass ceramic product was used as a test object. The test data recorded as 2000mm in the examples indicates that even a loaded nucleated glass article does not break and withstand impact from a height of 2000mm, the maximum test height of the drop test machine WH-2101 is 2000mm.

[ falling ball test height ]

A microcrystalline glass product sample of 145mm by 67mm by 0.7mm was placed on a glass holder, and 132g of a steel ball was dropped from a predetermined height to obtain a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 800mm, and the height was changed in the order of 850mm, 900mm, 950mm, 1000mm and more without breaking. For the examples having the "falling ball test height", a crystallized glass article was used as a test object. The test data recorded as 1000mm in the examples indicates that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from a height of 1000 mm. The drop test height is sometimes referred to herein as the drop height.

[ height of falling ball of body ]

A microcrystalline glass sample of 145mm by 67mm by 0.7mm is placed on a glass carrying jig, 32g of a steel ball is dropped from a predetermined height, and the maximum ball drop test height at which the sample can withstand without breaking is the body ball drop height. Specifically, the test was conducted from a ball drop test height of 500mm, and the height was changed in the order of 550mm, 600mm, 650mm, 700mm and more without breaking. For the embodiment with the "body ball drop height", the microcrystalline glass is taken as a test object, namely the ball drop test height of the microcrystalline glass. The test data recorded as 1000mm in the examples shows that the glass ceramics were not broken and received impact even when the steel ball was dropped from a height of 1000 mm.

[ fracture toughness ]

The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.

[ four-point bending Strength ]

A microcomputer-controlled electronic universal tester CMT6502 is adopted, the sample specification is below 1mm in thickness, and the test is carried out by taking ASTM C158-2002 as a standard. In the present invention, the four-point bending strength is sometimes simply referred to as bending strength.

[ Vickers hardness ]

The load (N) when a pyramid-shaped indentation was pressed into the test surface by a diamond quadrangular pyramid indenter having an included angle of 136 degrees with respect to the opposite surface was divided by the surface area (mm) calculated from the length of the indentation²) The values of (b) indicate (a). The test load was set to 100 (N) and the holding time was set to 15 (sec). In the present invention, vickers hardness is sometimes referred to simply as hardness.

[ | B | value ]

B value detection was performed using Mentenda CM-700 d. The sample specification is less than 1mm, instrument zero calibration and white board calibration are respectively carried out by using a matched long correction cylinder and a short correction cylinder, an empty test is carried out by using the long cylinder after calibration, the stability and calibration reliability (B is less than or equal to 0.05) of the instrument is judged, and a product is placed on the zero long cylinder for testing after the instrument is qualified in calibration.

| B | the value is the absolute value of the value B.

[ Young's modulus ]

The Young modulus (E) is obtained by testing the longitudinal wave speed and the transverse wave speed of the Young modulus by adopting ultrasonic waves and then calculating according to the following formula.

G＝V_S ²ρ

In the formula: e is Young's modulus, pa;

g is shear modulus, pa;

V_Tis the transverse wave velocity, m/s;

V_Sis the longitudinal wave velocity, m/s;

rho is the density of the glass, g/cm³。

[ refractive index ]

Refractive index (n)_d) The test was carried out according to the method specified in GB/T7962.1-2010.

The transparent glass-ceramic product has the following properties:

1) In some embodiments, the transparent glass-ceramic article has a four-point bending strength of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.

2) In some embodiments, the ion exchange layer depth of the transparent glass-ceramic article is 80 μm or more, preferably 90 μm or more, and more preferably 100 μm or more.

3) In some embodiments, the surface stress of the transparent glass-ceramic article is 100MPa or greater, preferably 150MPa or greater, and more preferably 200MPa or greater.

4) In some embodiments, the transparent glass-ceramic article has a ball drop test height of 1400mm or more, preferably 1500mm or more, and more preferably 1600mm or more.

5) In some embodiments, the transparent microcrystalline glass article has a fracture toughness of 1 MPa-m^1/2Above, preferably 1.1 MPa.m^1/2More preferably 1.2 MPa.m^1/2The above.

6) In some embodiments, the vickers hardness (H) of the transparent microcrystalline glass article_v) Is 670kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²As described above.

7) In some embodiments, the transparent crystallized glass article has a crystallinity of 10% or more, preferably 15% or more, and more preferably 20% or more.

8) In some embodiments, the transparent 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 shatter resistance of the transparent glass-ceramic article is 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more.

10 In some embodiments, the haze of a transparent crystallized glass article having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

11 In some embodiments, a transparent glass-ceramic article having a thickness of 1mm or less has an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and still more preferably 90.5% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

12 In some embodiments, a transparent crystallized glass product having a thickness of 1mm or less has a light transmittance at a wavelength of 550nm of 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

13 In some embodiments the average | B | value of 400-800 nm is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less, for a transparent microcrystalline glass product having a thickness of 1mm or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

The transparent glass ceramics of the invention has the following properties:

1) In some embodiments, the crystallinity of the transparent glass ceramics is 10% or more, preferably 15% or more, and more preferably 20% or more.

2) In some embodiments, the crystal grain size of the transparent glass-ceramic is 50nm or less, preferably 40nm or less, and more preferably 30nm or less.

3) In some embodiments, the haze of the transparent glass ceramics having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, and more preferably 0.15% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

4) In some embodiments, the transparent glass-ceramic having a thickness of 1mm or less has an average light transmittance at a wavelength of 400 to 800nm of 87.0% or more, preferably 88.0% or more, and more preferably 88.5% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

5) In some embodiments, the transparent glass ceramics having a thickness of 1mm or less has a light transmittance of 89.0% or more, preferably 90.0% or more, and more preferably 90.5% or more at a wavelength of 550 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

6) In some embodiments, the transparent glass ceramics have a body drop height of 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more.

7) In some embodiments, the transparent glass-ceramic has a thickness of 1mm or less and an average light | B | value of 400-800 nm of 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and yet more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

8) In some embodiments, the vickers hardness (H) of the transparent glass-ceramic_v) Is 600kgf/mm²Above, it is preferably 620kgf/mm²Above, more preferably 630kgf/mm²As described above.

9) In some embodiments, the refractive index (n) of the transparent glass-ceramic_d) Is 1.520 to 1.545.

10 In some embodiments, the transparent glass-ceramic article has a young's modulus (E) of 80 to 100GPa.

The matrix glass of the present invention has the following properties:

1) In some embodiments, the refractive index (n) of the matrix glass_d) Is 1.510 to 1.530.

The transparent glass ceramics, the transparent glass ceramics product, the matrix glass, the glass forming body and the glass ceramics forming body of the invention can be widely made into glass cover plates or glass components and parts due to the excellent performance; meanwhile, the transparent glass ceramics, the matrix glass, the glass formed body and the glass ceramics formed body of the invention can be applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens and the like, and are used for manufacturing protective glass of mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or are used for manufacturing touch screens, protective windows, automobile windows, train windows, aircraft mechanical windows and touch screen protective glass, 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 kitchenware.

Examples

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. The composition is itself given in weight% on oxide basis and has been standardized to 100%.

< matrix glass example >

In this example, the above-described method for producing a matrix glass was used to obtain a matrix glass having a composition shown in tables 1 to 2. The characteristics of each base glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2.

Table 1.

Table 2.

< example of transparent crystallized glass >

In this example, transparent glass ceramics having compositions shown in tables 3 to 4 were obtained by the above method for producing glass ceramics. In addition, the characteristics of each glass-ceramic were measured by the test method of the present invention and the results are shown in tables 3-4, where the measured sample thickness for the haze, the average light transmittance at a wavelength of 400-800 nm, the light transmittance at a wavelength of 550nm, and the average light | B | value of 400-800 nm is 0.7mm in the following examples.

Table 3.

Table 4.

< examples of transparent crystallized glass articles >

In this example, transparent crystallized glass products having compositions shown in tables 5 to 6 were obtained by the above method for producing crystallized glass products. In addition, the characteristics of each transparent glass-ceramic article were measured by the test method according to the present invention, and the measurement results are shown in tables 5 to 6, where the test sample thickness for the haze, the average light transmittance at a wavelength of 400 to 800nm, the light transmittance at a wavelength of 550nm, and the average light | B | value of 400 to 800nm is 0.7mm in the following examples.

Table 5.

Table 6.

Claims (48)

1. The transparent glass-ceramic product is characterized by comprising the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂Is 5.0 to 15.0.

2. The transparent glass-ceramic product according to claim 1, characterized in that the composition further comprises, in weight percent: p₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

3. A transparent glass-ceramic product characterized by containing SiO₂、Al₂O₃、Li₂O、Na₂O and ZrO₂The components are expressed by weight percentage, wherein SiO₂/ZrO₂A transparent glass-ceramic product having a thickness of 5.0 to 15.0 and a thickness of 1mm or less and having an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more.

4. A transparent glass-ceramic article according to claim 3, characterized in that its composition, expressed in weight percentage, comprises: siO 2₂:60 to 80 percent; and/or Al₂O₃:3 to 15 percent; and/or Li₂O: greater than or equal to 5% but less than 10%; and/or Na₂O:4 to 8 percent; and/or P₂O₅:0 to 5 percent; and/or ZrO₂: greater than 5% but less than or equal to 15%; and/or P₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

5. The transparent glass-ceramic article according to any one of claims 1 to 4, characterized in that its composition is expressed in weight percentage, wherein: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, and (SiO) is more preferable₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, and (ZrO) is more preferable₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

6. The transparent glass-ceramic product according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, comprises: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

7. Transparent glass-ceramic article according to any one of claims 1 to 4, characterized in that it contains a crystalline phase of lithium silicate in a higher weight percentage than the other crystalline phases, preferably 5 to 50% by weight of the transparent glass-ceramic article, more preferably 5 to 40% by weight of the transparent glass-ceramic article, and even more preferably 10 to 30% by weight of the transparent glass-ceramic article.

8. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a crystalline phase of lithium monosilicate in a higher weight percentage than the other crystalline phases, preferably the crystalline phase of lithium monosilicate constitutes between 5 and 50% by weight of the transparent glass-ceramic article, more preferably the crystalline phase of lithium monosilicate constitutes between 5 and 40% by weight of the transparent glass-ceramic article, and even more preferably the crystalline phase of lithium monosilicate constitutes between 10 and 30% by weight of the transparent glass-ceramic article.

9. Transparent glass-ceramic article according to any one of claims 1 to 4, characterized in that it contains a lithium disilicate crystalline phase, which constitutes less than 20% by weight of the transparent glass-ceramic article, preferably less than 10% by weight of the transparent glass-ceramic article, more preferably less than 5% by weight of the transparent glass-ceramic article, and even more preferably no lithium disilicate crystalline phase.

10. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises petalite crystal phase, wherein the petalite crystal phase accounts for less than 15% of the transparent glass-ceramic article by weight, preferably the petalite crystal phase accounts for less than 10% of the transparent glass-ceramic article by weight, more preferably the petalite crystal phase accounts for less than 5% of the transparent glass-ceramic article by weight, and even more preferably the petalite crystal phase is not contained.

11. The transparent crystallized glass product according to any one of claims 1 to 4, wherein the transparent crystallized glass product has a ball drop test height of 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more; and/or a fracture toughness of 1MPa m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or a Vickers hardness of 670kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or the depth of the ion exchange layer is 80 μm or more, preferably 90 μm or more, more preferably 100 μm or more; and/or a surface stress of 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or a crystallinity of 10% or more, preferably 15% or more, more preferably 20% or more; and/or a crystal grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or a fall-resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more.

12. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the haze of the transparent glass-ceramic article having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and further preferably 90.5% or more; and/or a light transmittance at a wavelength of 550nm of 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more; and/or the average light | B | value of 400-800 nm is below 1.0, preferably below 0.9, more preferably below 0.8.

13. The transparent glass-ceramic article according to claim 12, wherein the thickness of the transparent glass-ceramic article is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

14. The transparent glass-ceramic is characterized by comprising the following components in percentage by weight: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂5.0 to 15.0.

15. The transparent glass-ceramic according to claim 14, characterized in that it further comprises, in weight percent: p₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

16. A transparent glass-ceramic characterized by containing SiO₂、Al₂O₃、Li₂O、Na₂O and ZrO₂The components are expressed by weight percentage, wherein SiO₂/ZrO₂5.0 to 15.0, and the transparent glass ceramics with a thickness of less than 1mm has an average light transmission rate of 88.0% at a wavelength of 400 to 800nmThe above.

17. The transparent glass-ceramic according to claim 16, characterized in that its composition, expressed in weight percentage, contains: siO 2₂:60 to 80 percent; and/or Al₂O₃:3 to 15 percent; and/or Li₂O: greater than or equal to 5% but less than 10%; and/or Na₂O:4 to 8 percent; and/or P₂O₅:0 to 5 percent; and/or ZrO₂: greater than 5% but less than or equal to 15%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

18. The transparent glass-ceramic according to any one of claims 14 to 17, characterized in that its composition is expressed in weight percentage, wherein: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, and (SiO) is more preferable₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5, and (ZrO) is more preferable₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

19. The transparent glass-ceramic according to any one of claims 14 to 17, characterized in that it comprises, in weight percent: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

20. The transparent glass-ceramic according to any one of claims 14 to 17, wherein the transparent glass-ceramic comprises a lithium silicate crystalline phase having a higher weight percentage than other crystalline phases, preferably the lithium silicate crystalline phase comprises 5 to 50% by weight of the transparent glass-ceramic, more preferably the lithium silicate crystalline phase comprises 5 to 40% by weight of the transparent glass-ceramic, and even more preferably the lithium silicate crystalline phase comprises 10 to 30% by weight of the transparent glass-ceramic.

21. The transparent glass-ceramic according to any one of claims 14 to 17, wherein the transparent glass-ceramic comprises a crystalline phase of lithium monosilicate in a higher weight percentage than the other crystalline phases, preferably the crystalline phase of lithium monosilicate constitutes between 5 and 50% by weight of the transparent glass-ceramic, more preferably the crystalline phase of lithium monosilicate constitutes between 5 and 40% by weight of the transparent glass-ceramic, and even more preferably the crystalline phase of lithium monosilicate constitutes between 10 and 30% by weight of the transparent glass-ceramic.

22. The transparent glass ceramics according to any one of claims 14 to 17, characterized in that the transparent glass ceramics contains lithium disilicate crystal phases, the lithium disilicate crystal phases account for 20% or less by weight of the transparent glass ceramics, preferably the lithium disilicate crystal phases account for 10% or less by weight of the transparent glass ceramics, more preferably the lithium disilicate crystal phases account for 5% or less by weight of the transparent glass ceramics, and further preferably do not contain lithium disilicate crystal phases.

23. The transparent glass-ceramic according to any one of claims 14 to 17, wherein the transparent glass-ceramic comprises petalite crystal phase, wherein the petalite crystal phase accounts for less than 15% of the transparent glass-ceramic by weight, preferably the petalite crystal phase accounts for less than 10% of the transparent glass-ceramic by weight, more preferably the petalite crystal phase accounts for less than 5% of the transparent glass-ceramic by weight, and even more preferably the petalite crystal phase is not contained.

24. The transparent glass-ceramic according to any one of claims 14 to 17, wherein the crystallinity of the transparent glass-ceramic is 10% or more, preferably 15% or more, and more preferably 20% or more; and/or the crystal grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the ball falling height of the body is 1700mm or more, preferably 1900mm or more, more preferably 2000mm or more; and/or a Vickers hardness of 600kgf/mm²Above, it is preferably 620kgf/mm²Above, more preferably 630kgf/mm²The above; and/or a refractive index of 1.520 to 1.545; and/or a Young's modulus of 80 to 100GPa.

25. The transparent crystallized glass according to any one of claims 14 to 17, wherein the haze of the transparent crystallized glass having a thickness of 1mm or less is 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average light transmittance at a wavelength of 400 to 800nm of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, and further preferably 90.5% or more; and/or a light transmittance at a wavelength of 550nm of 89.0% or more, preferably 90.0% or more, more preferably 91.0% or more, and further preferably 91.5% or more; and/or the average light | B | value of 400-800 nm is below 1.0, preferably below 0.9, more preferably below 0.8.

26. The transparent glass-ceramic according to claim 25, wherein the thickness of the transparent glass-ceramic is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.

27. Matrix glass, characterized in that its composition, expressed in weight percentage, contains: siO 2₂：60～80％；Al₂O₃：3～15％；Li₂O: greater than or equal to 5% but less than 10%; na (Na)₂O：4～8％；ZrO₂: greater than 5% but less than or equal to 15% of SiO₂/ZrO₂5.0 to 15.0.

28. The matrix glass according to claim 27, further comprising, in weight percent: p is₂O₅:0 to 5 percent; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B₂O₃:0 to 4 percent; and/or K₂O:0 to 3 percent; and/or Ln₂O₃:0 to 2 percent; and/or a clarifying agent: 0 to 2 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

29. The matrix glass according to claim 27 or 28, characterized in that its components are expressed in weight percentage, wherein: siO 2₂/ZrO₂6.0 to 13.0, preferably SiO₂/ZrO₂6.5 to 12.0, and SiO is more preferable₂/ZrO₂7.0 to 11.0; and/or (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 4.0 to 15.5, preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 5.0 to 13.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) Is 6.0 to 11.5, more preferably (SiO)₂+Li₂O)/(ZrO₂+P₂O₅) 6.0 to 10.5; and/or (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.0 to 18.0, preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 7.5 to 15.0, more preferably (SiO)₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 13.0, and (SiO) is more preferable₂+Al₂O₃+Na₂O)/Li₂O is 8.5 to 11.0; and/or (ZrO)₂+Al₂O₃)/Li₂O is 0.85 to 5.0, preferably (ZrO)₂+Al₂O₃)/Li₂O is 0.9 to 4.0, more preferably (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.5Further, it is preferable to use (ZrO)₂+Al₂O₃)/Li₂O is 1.0 to 3.0; and/or (Li)₂O+Na₂O)/(SiO₂+ZrO₂) 0.10 to 0.27, preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.12 to 0.25, more preferably (Li)₂O+Na₂O)/(SiO₂+ZrO₂) Is 0.14 to 0.25, and (Li) is more preferable₂O+Na₂O)/(SiO₂+ZrO₂) 0.15 to 0.23.

30. The matrix glass according to claim 27 or 28, comprising, in weight percent: siO 2₂:62 to 78%, preferably SiO₂:64 to 75 percent; and/or Al₂O₃:5 to 12%, preferably Al₂O₃:5 to 10 percent; and/or Li₂O: greater than or equal to 6% but less than 10%; and/or Na₂O:4 to 7.5%, preferably Na₂O:4.5 to 7 percent; and/or P₂O₅:1 to 4.5%, preferably P₂O₅:1.5 to 4 percent; and/or ZrO₂:5.5 to 13%, preferably ZrO₂:6 to 12 percent; and/or ZnO:0 to 1.5%, preferably ZnO:0 to 1 percent; and/or MgO:0 to 1.5%, preferably MgO:0 to 1 percent; and/or B₂O₃:0 to 3%, preferably B₂O₃:0 to 2 percent; and/or K₂O:0 to 2%, preferably K₂O:0 to 1 percent; and/or Ln₂O₃:0 to 1%, preferably Ln₂O₃:0 to 0.5 percent; and/or a clarifying agent: 0 to 1%, preferably a clarifying agent: 0 to 0.5 percent of Ln₂O₃Is La₂O₃、Gd₂O₃、Y₂O₃、Yb₂O₃One or more of (a).

31. The matrix glass according to claim 27 or 28, wherein the matrix glass has a refractive index of 1.510 to 1.530.

32. A glass ceramic molded article comprising the transparent glass ceramic according to any one of claims 14 to 26.

33. A glass cover plate comprising the transparent glass-ceramic product according to any one of claims 1 to 13, and/or the transparent glass-ceramic according to any one of claims 14 to 26, and/or the matrix glass according to any one of claims 27 to 31, and/or the glass-ceramic shaped body according to claim 32.

34. A glass component comprising the transparent glass-ceramic product according to any one of claims 1 to 13, the transparent glass-ceramic according to any one of claims 14 to 26, the matrix glass according to any one of claims 27 to 31, and the glass-ceramic molded body according to claim 32.

35. A display device comprising the transparent glass-ceramic product according to any one of claims 1 to 13, and/or the transparent glass-ceramic according to any one of claims 14 to 26, and/or the matrix glass according to any one of claims 27 to 31, and/or the glass-ceramic shaped body according to claim 32, and/or the glass cover plate according to claim 33, and/or the glass component according to claim 34.

36. An electronic device comprising the transparent glass-ceramic product according to any one of claims 1 to 13, and/or the transparent glass-ceramic according to any one of claims 14 to 26, and/or the matrix glass according to any one of claims 27 to 31, and/or the glass-ceramic shaped body according to claim 32, and/or the glass cover plate according to claim 33, and/or the glass component according to claim 34.

37. A method for producing a transparent glass-ceramic article according to any one of claims 1 to 13, characterized in that the method comprises the steps of: forming matrix glass, forming transparent glass ceramics by the matrix glass through a crystallization process, and forming a transparent glass ceramics product by the transparent glass ceramics through a chemical strengthening process.

38. The method of manufacturing a transparent glass-ceramic article according to claim 37, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 550-700 ℃, preferably 580-650 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

39. The method of manufacturing a transparent glass-ceramic article according to claim 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.

40. The method for manufacturing a transparent glass-ceramic article according to claim 39, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 450-550 ℃, and the temperature of the No. 2 is 550-700 ℃; 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.

41. The method for manufacturing a transparent glass-ceramic article according to any one of claims 37 to 40, wherein the chemical strengthening process comprises: the transparent glass ceramics is immersed in a salt bath of molten Na salt at the temperature of 350-470 ℃ for 1-36 hours, the preferred temperature range is 380-460 ℃, and the preferred time range is 2-24 hours; and/or the transparent glass ceramics is immersed in the salt bath for melting the K salt at the temperature of 360-450 ℃ for 1-36 hours, and the preferred time range is 2-24 hours; and/or the transparent glass ceramics is immersed in the mixed salt bath of the molten K salt and the molten Na salt at the temperature of 360-450 ℃ for 1-36 hours, and the preferred time range is 2-24 hours.

42. The method for producing a transparent glass-ceramic according to any one of claims 14 to 26, characterized by comprising the steps of: forming matrix glass, and then forming the matrix glass into transparent glass ceramics through a crystallization process.

43. The method for manufacturing transparent glass-ceramic according to claim 42, wherein the crystallization process comprises the steps of: raising the temperature to a predetermined crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then lowering the temperature, wherein the crystallization temperature is 550 to 700 ℃, preferably 580 to 650 ℃, and the retention time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

44. The method for manufacturing transparent glass-ceramic according to claim 42, 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.

45. The method for manufacturing transparent glass ceramics according to claim 44, wherein the crystallization process comprises the steps of: the 1 st temperature is 450-550 ℃, and the 2 nd temperature is 550-700 ℃; 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.

46. A method for manufacturing a glass-ceramic shaped body according to claim 32, wherein the method comprises grinding or polishing a transparent glass-ceramic to obtain a glass-ceramic shaped body, or subjecting a base glass or a transparent glass-ceramic to a hot bending process or a pressing process at a certain temperature to obtain a glass-ceramic shaped body.

47. The method for manufacturing a glass-ceramic shaped body according to claim 46, characterized by comprising the steps of: carrying out primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation nucleation, heating, heat preservation crystallization and cooling to room temperature to form pre-crystallized glass; and carrying out hot-forming on the pre-crystallized glass to obtain a microcrystalline glass forming body.

48. The method for manufacturing a glass-ceramic shaped body according to claim 46, characterized by comprising the steps of:

1) Heating and preheating: placing matrix glass or pre-crystallized glass or transparent microcrystalline glass into a mold, enabling the mold to sequentially pass through each temperature-raising station in a hot bending machine, and staying at each station for a certain time for heat preservation, wherein the temperature of a preheating zone is 400-800 ℃, the pressure is 0.01-0.05 MPa, and the time is 40-200 s;

2) And (3) pressure forming: transferring the preheated mould to a forming station, applying a certain pressure to the mould by a hot bending machine, wherein the pressure range is 0.1-0.8 Mpa, the temperature range of the forming station is 600-850 ℃, and the forming time range is 40-200 s;

3) Pressure maintaining and temperature reduction: and transferring the mold to a cooling station for cooling station by station, wherein the cooling temperature range is 750-500 ℃, the pressure is 0.01-0.05 Mpa, and the time is 40-200 s.