CN115259672B - Transparent glass ceramics and transparent glass ceramics products - Google Patents

Transparent glass ceramics and transparent glass ceramics products Download PDF

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CN115259672B
CN115259672B CN202210723613.2A CN202210723613A CN115259672B CN 115259672 B CN115259672 B CN 115259672B CN 202210723613 A CN202210723613 A CN 202210723613A CN 115259672 B CN115259672 B CN 115259672B
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ceramic
transparent glass
glass
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sio
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CN115259672A (en
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原保平
李赛
于天来
苏学剑
蒋焘
聂小兵
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Cdgm LLC
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Cdgm LLC
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

Abstract

The invention provides transparent glass ceramics and transparent glass ceramics products with higher light transmittance. The transparent glass ceramic product comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: 5% or more but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 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 products
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, electronic book readers, notepads, tablets, notebook computers, etc.) have become powerful, small and light in weight through rapid development. In order to achieve the above-mentioned effects, a case material (such as a cover plate material) of an electronic device is required to have excellent mechanical properties at a small thickness in order to cope with unavoidable dropping, scratches, etc. during use. In recent years, the glass ceramics made into shell materials are reported to be used for electronic equipment, because the properties of bending resistance, wear resistance and the like are obviously superior to those of common high-aluminum cover plate glass. In addition, the glass or glass ceramics can be widely applied to the fields of optical equipment, display equipment, lighting equipment and the like for automobiles. The glass or glass ceramics used in the above fields are required to have high visible light transmittance in order to improve the user experience comfort in addition to excellent mechanical properties to meet the requirements of shatter resistance, compression resistance, scratch resistance and the like in the use process.
Disclosure of Invention
The invention aims to provide transparent glass ceramics and transparent glass ceramics products with higher light transmittance.
The technical scheme adopted for solving the technical problems is as follows:
(1) The transparent glass ceramic product comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 15.0.
(2) The transparent glass ceramic product comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%.
(3) The transparent glass-ceramic product according to (1) or (2), which comprises the following components in percentage by weight: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(4) Transparent glass-ceramic product containing SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The components are expressed in weight percent, wherein SiO 2 /ZrO 2 The transparent glass ceramic product has a thickness of 5.0-15.0, 1mm or less, and an average light transmittance of 88.0% or more at a wavelength of 400-800 nm.
(5) Transparent glass-ceramic product containing SiO 2 、Al 2 O 3 、Li 2 O, wherein the crystal phase contains lithium silicate crystal phase, and the transparent glass ceramic product with the thickness of less than 1mm has light transmittance of more than 89.0% at 550nm wavelength.
(6) Transparent glass-ceramic product containing SiO 2 、Al 2 O 3 、Li 2 And O, wherein the crystal phase of the O contains a lithium silicate crystal phase, and the drop 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), comprising, in weight percent: siO (SiO) 2 : 60-80%; and/or Al 2 O 3 : 3-15%; and/or Li 2 O: greater than or equal to 5% but less than 10%; and/or Na 2 O: 4-8%; and/or P 2 O 5 : 0-5%; and/or ZrO 2 : greater than 5% but less than or equal to 15%; and/or P 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(8) Transparent glass ceramic product comprising SiO as the component in weight percentage 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；P 2 O 5 ：0～5％；ZrO 2 : greater than 5% but less than or equal to 15%; p (P) 2 O 5 ：0～5％；ZnO：0～2％；MgO：0～2％；B 2 O 3 ：0～4％；K 2 O：0～3％；Ln 2 O 3 :0 to 2 percent; clarifying agent: 0 to 2 percent of composition, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(9) According to (1) to (8)) The transparent microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 /ZrO 2 From 6.0 to 13.0, preferably SiO 2 /ZrO 2 From 6.5 to 12.0, more preferably SiO 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 4.0 to 15.5, preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 5.0 to 13.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 6.0 to 11.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0 to 18.0, preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5 to 15.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5 to 13.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 0.85 to 5.0, preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 0.9 to 4.0, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0 to 3.5, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.10 to 0.27, preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.12 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.14 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
(10) The transparent glass-ceramic product according to any one of (1) to (8), comprising, in weight percent: siO (SiO) 2 :62 to 78%, preferably SiO 2 : 64-75%; and/or Al 2 O 3 :5 to 12%, preferably Al 2 O 3 : 5-10%; and/or Li 2 O: greater than or equal to 6% but less than 10%; and/or Na 2 O:4 to 7.5%, preferably Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1 to 4.5%, preferably P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 :5.5 to 13%, preferably ZrO 2 : 6-12%; 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 B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 2%, preferably K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 1%, preferably Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(11) The transparent glass-ceramic article according to any one of (1) to (8), which contains a lithium silicate crystal phase having a higher weight percentage than other crystal phases, preferably a lithium silicate crystal phase accounting for 5 to 50 weight percent of the transparent glass-ceramic article, more preferably a lithium silicate crystal phase accounting for 5 to 40 weight percent of the transparent glass-ceramic article, and even more preferably a lithium silicate crystal phase accounting for 10 to 30 weight percent of the transparent glass-ceramic article.
(12) The transparent glass-ceramic article according to any one of (1) to (8), which 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 accounting for 5 to 50% by weight of the transparent glass-ceramic article, more preferably the lithium silicate crystal phase accounting for 5 to 40% by weight of the transparent glass-ceramic article, and still more preferably the lithium silicate crystal phase accounting for 10 to 30% by weight of the transparent glass-ceramic article.
(13) The transparent glass-ceramic product according to any one of (1) to (8), wherein the transparent glass-ceramic product contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase is 20% by weight or less of the transparent glass-ceramic product, preferably 10% by weight or less of the transparent glass-ceramic product, more preferably 5% by weight or less of the transparent glass-ceramic product, and even more preferably does not contain a lithium disilicate crystal phase.
(14) The transparent glass-ceramic article according to any one of (1) to (8), which contains petalite crystal phase, the petalite crystal phase is 15% by weight or less of the transparent glass-ceramic article, preferably 10% by weight or less of the transparent glass-ceramic article, more preferably 5% by weight or less of the transparent glass-ceramic article, and even more preferably does not contain petalite crystal phase.
(15) The transparent glass-ceramic product according to any one of (1) to (8), wherein the falling ball test height of the transparent glass-ceramic product is 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more; and/or fracture toughness of 1 MPa.m 1/2 The above is preferably 1.1 MPa.m 1/2 The above is more preferably 1.2 MPa.m 1/2 The above; and/or the four-point bending strength is 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or a Vickers hardness of 670kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above; and/or the ion exchange layer depth is 80 μm or more, preferably 90 μm or more, more preferably 100 μm or more; and/or the surface stress is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or crystallinity of 10% or more, preferably 15% or more, more preferably 20% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the drop resistance is 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more.
(16) The transparent glass-ceramic product according to any one of (1) to (8), wherein the transparent glass-ceramic product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less; and/or an average light transmittance of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, still more preferably 90.5% or more at a wavelength of 400 to 800 nm; 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, still more preferably 91.5% or more; and/or an average light-B-value of 400 to 800nm of 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.
(17) The transparent glass-ceramic product according to (16), wherein the thickness of the transparent glass-ceramic product is 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
(18) The transparent glass ceramics comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 15.0.
(19) The transparent glass ceramics comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : 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: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(21) Transparent glass ceramics containing SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The components are expressed in weight percent, wherein SiO 2 /ZrO 2 The transparent glass ceramics with the thickness of less than 1mm and the average light transmittance of 400-800 nm is more than 88.0 percent.
(22) Transparent glass ceramics containing SiO 2 、Al 2 O 3 、Li 2 O, wherein the crystal phase contains lithium silicate crystal phase, and the light transmittance of transparent glass ceramics with a thickness of less than 1mm and a wavelength of 550nm is more than 89.0%.
(23) Transparent glass ceramics containing SiO 2 、Al 2 O 3 、Li 2 And O, wherein the crystal phase of the O contains a lithium silicate crystal phase, and the body falling ball height of the transparent glass ceramics is more than 1700 mm.
(24) The transparent glass-ceramic according to any one of (21) to (23), comprising, in weight percent: siO (SiO) 2 : 60-80%; and/or Al 2 O 3 : 3-15%; and/or Li 2 O: greater than or equal to 5% but less than 10%; and/or Na 2 O: 4-8%; and/or P 2 O 5 : 0-5%; and/or ZrO 2 : 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 B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(25) Transparent glass ceramic product comprising SiO as the component in weight percentage 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；P 2 O 5 ：0～5％；ZrO 2 : greater than 5% but less than or equal to 15%; p (P) 2 O 5 ：0～5％；ZnO：0～2％；MgO：0～2％；B 2 O 3 ：0～4％；K 2 O：0～3％；Ln 2 O 3 :0 to 2 percent; clarifying agent: 0 to 2 percent of composition, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(26) The transparent glass-ceramic according to any one of (18) to (25), wherein the components are represented by weight percent: siO (SiO) 2 /ZrO 2 From 6.0 to 13.0, preferably SiO 2 /ZrO 2 From 6.5 to 12.0, more preferably SiO 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 4.0 to 15.5, preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 5.0 to 13.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 6.0 to 11.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0 to 18.0, preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5 to 15.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5 to 13.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 0.85 to 5.0, preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 0.9 to 4.0, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0 to 3.5, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.10 to 0.27, preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.12 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.14 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
(27) The transparent glass-ceramic according to any one of (18) to (25), wherein the glass-ceramic comprises the following components in parts by weightThe percentages are expressed as: siO (SiO) 2 :62 to 78%, preferably SiO 2 : 64-75%; and/or Al 2 O 3 :5 to 12%, preferably Al 2 O 3 : 5-10%; and/or Li 2 O: greater than or equal to 6% but less than 10%; and/or Na 2 O:4 to 7.5%, preferably Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1 to 4.5%, preferably P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 :5.5 to 13%, preferably ZrO 2 : 6-12%; 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 B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 2%, preferably K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 1%, preferably Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(28) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic 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 is 5 to 50% by weight of the transparent glass-ceramic, more preferably the lithium silicate crystal phase is 5 to 40% by weight of the transparent glass-ceramic, and still more preferably the lithium silicate crystal phase is 10 to 30% by weight of the transparent glass-ceramic.
(29) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic 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 is 5 to 50% by weight of the transparent glass-ceramic, more preferably the lithium silicate crystal phase is 5 to 40% by weight of the transparent glass-ceramic, and still more preferably the lithium silicate crystal phase is 10 to 30% by weight of the transparent glass-ceramic.
(30) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase is 20% by weight or less of the transparent glass-ceramic, preferably 10% by weight or less of the transparent glass-ceramic, more preferably 5% by weight or less of the transparent glass-ceramic, and still more preferably does not contain a lithium disilicate crystal phase.
(31) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic contains petalite crystal phase, the petalite crystal phase accounts for 15% by weight or less of the transparent glass-ceramic, preferably 10% by weight or less of the transparent glass-ceramic, more preferably 5% by weight or less of the transparent glass-ceramic, and even more preferably does not contain petalite crystal phase.
(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, more preferably 20% or more; and/or the grain size is 50nm or less, preferably 40nm or less, more preferably 30nm or less; and/or the body ball drop height is 1700mm or more, preferably 1900mm or more, more preferably 2000mm or more; and/or a Vickers hardness of 600kgf/mm 2 Above, preferably 620kgf/mm 2 Above, more preferably 630kgf/mm 2 The above; and/or a refractive index of 1.520 to 1.545; and/or Young's modulus of 80-100 GPa.
(33) The transparent glass-ceramic according to any one of (18) to (25), wherein the transparent glass-ceramic has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less, with a thickness of 1mm or less; and/or an average light transmittance of 88.0% or more, preferably 89.0% or more, more preferably 90.0% or more, still more preferably 90.5% or more at a wavelength of 400 to 800 nm; 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, still more preferably 91.5% or more; and/or an average light-B-value of 400 to 800nm of 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.
(34) The transparent glass ceramic according to (33), 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, still more 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 (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: 5% or more but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 15.0.
(36) The matrix glass comprises the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: 5% or more but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%.
(37) The matrix glass according to (35) or (36), which further comprises, in weight percent: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(38) Matrix glass, the components of which are represented by weight percentage and consist of SiO 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: 5% or more but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 5% but less than or equal to 15%; p (P) 2 O 5 ：0～5％；ZnO：0～2％；MgO：0～2％；B 2 O 3 ：0～4％；K 2 O：0～3％；Ln 2 O 3 :0 to 2 percent; clarifying agent: 0 to 2 percent of composition, ln is as follows 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 In (a) and (b)One or more of them.
(39) The matrix glass according to any one of (35) to (38), wherein the components are represented by weight percent: siO (SiO) 2 /ZrO 2 From 6.0 to 13.0, preferably SiO 2 /ZrO 2 From 6.5 to 12.0, more preferably SiO 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 4.0 to 15.5, preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 5.0 to 13.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 6.0 to 11.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0 to 18.0, preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5 to 15.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5 to 13.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 0.85 to 5.0, preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 0.9 to 4.0, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0 to 3.5, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.10 to 0.27, preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.12 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.14 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
(40) The matrix glass according to any one of (35) to (38), which comprises, in weight percent: siO (SiO) 2 :62 to 78%, preferably SiO 2 : 64-75%; and/orAl 2 O 3 :5 to 12%, preferably Al 2 O 3 : 5-10%; and/or Li 2 O: 6% or more but less than 10%; and/or Na 2 O:4 to 7.5%, preferably Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1 to 4.5%, preferably P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 :5.5 to 13%, preferably ZrO 2 : 6-12%; 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 B 2 O 3 :0 to 3%, preferably B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 2%, preferably K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 1%, preferably Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
(41) The matrix glass according to any one of (35) to (38), wherein the refractive index of the matrix glass is 1.510 to 1.530.
(42) A glass ceramic molded article comprising the transparent glass ceramic according to any one of (18) to (34).
(43) A glass cover sheet 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 article according to (42).
(44) A glass component 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 article according to (42).
(45) Display device 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 formed 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 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 article according to (42), and/or the glass cover plate according to (43), and/or the glass component according to (44).
(47) The method for producing a transparent glass-ceramic product according to any one of (1) to (17), comprising the steps of: forming matrix glass, forming transparent microcrystalline glass by the matrix glass through a crystallization process, and forming a transparent microcrystalline glass product by the transparent microcrystalline glass through a chemical strengthening process.
(48) The method for producing a transparent glass-ceramic product according to (47), wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 550-700 ℃, preferably 580-650 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(49) The method for producing a transparent glass-ceramic product according to (47), 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.
(50) The method for producing a transparent glass-ceramic product 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 product according to any one of (47) to (50), wherein the chemical strengthening process comprises: the transparent glass ceramics are immersed in the salt bath of molten Na salt at the temperature of 350-470 ℃ for 1-36 hours, preferably at the temperature of 380-460 ℃ and preferably for 2-24 hours; and/or immersing the transparent glass ceramics in a salt bath for melting K salt at 360-450 ℃ for 1-36 hours, preferably for 2-24 hours; and/or the transparent glass ceramics are immersed in a mixed salt bath of molten K salt and Na salt at the temperature of 360-450 ℃ for 1-36 hours, and the preferable time range is 2-24 hours.
(52) The method for producing a transparent glass ceramic according to any one of (18) to (34), comprising the steps of: forming matrix glass, and then forming transparent microcrystalline glass by the matrix glass through a crystallization process.
(53) The method for producing a transparent glass ceramic according to (52), wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain period of time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 550-700 ℃, preferably 580-650 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(54) The method for producing a transparent glass ceramic according to (52), 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.
(55) The method for producing a transparent glass ceramic according to (54), 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.
(56) The method for producing a glass ceramic molded body according to (42), which comprises grinding or polishing a transparent glass ceramic to produce a glass ceramic molded body, or subjecting a base glass or a transparent glass ceramic to a hot bending process or a pressing process at a predetermined temperature to produce a glass ceramic molded body.
(57) The method for producing a glass ceramic molded body according to (56), comprising the steps of: performing primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation and nucleation, heating, heat preservation and crystallization and cooling to room temperature to form pre-crystallized glass; and carrying out thermal processing molding on the pre-crystallized glass to obtain the microcrystalline glass forming body.
(58) The method for producing a glass ceramic molded body according to (56), comprising the steps of:
1) Heating and preheating: placing matrix glass or pre-crystallized glass or transparent glass ceramics into a mould, sequentially passing the mould through each heating station in a hot bending machine, keeping the temperature at each station for a certain time, 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) compression molding: the mould is transferred to a forming station after being preheated, a hot bending machine applies certain pressure to the mould, 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 reducing: transferring the die to a cooling station for cooling by station, wherein the cooling temperature is 750-500 ℃, the pressure is 0.01-0.05 Mpa, and the time is 40-200 s.
The beneficial effects of the invention are as follows: through reasonable component design, the microcrystalline glass or 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 glass-ceramic and transparent glass-ceramic articles of the present invention are materials having a crystalline phase (sometimes also referred to as a crystal) and a glass phase, as opposed to an amorphous solid. The crystalline phases of glass ceramics and glass ceramics articles can be distinguished by the angle of the peaks that occur in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.
Through repeated experiments and researches, the inventor of the present invention obtains the transparent glass ceramics or the transparent glass ceramics product of the present invention at a lower cost by defining the content and the content ratio of the specific components constituting the transparent glass ceramics and the transparent glass ceramics product to specific values and precipitating the specific crystalline phases.
The ranges of the respective components (ingredients) of the matrix glass, transparent glass-ceramic and transparent glass-ceramic product of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of substances of the matrix glass, or the glass-ceramic product, in terms of the composition of the oxides. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the constituent components of the matrix glass, glass ceramic or glass ceramic product of the present invention is 100% based on the total amount of oxide when the oxide, composite salt, hydroxide or the like is decomposed and converted into oxide by melting. In the present specification, the term "glass" refers to a base glass before crystallization (i.e., crystallization process treatment), the term "transparent glass ceramics" refers to a transparent glass ceramics (hereinafter, also referred to as "glass ceramics") after crystallization (i.e., crystallization process treatment), and the term "transparent glass ceramics" refers to a product obtained by chemically strengthening transparent glass ceramics.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "about" as used herein means that the formulations, parameters and other quantities and characteristics are not, and need not be, exact, and may be approximated and/or greater or lesser, if desired, reflecting tolerances, conversion factors, measurement errors and the like. The term "and/or" as referred to herein is inclusive, e.g. "a; and/or B ", means either a alone, B alone, or both a and B.
In some embodiments of the invention, the crystalline phase in the transparent glass-ceramic or transparent glass-ceramic article comprises a lithium silicate crystalline phase (one or both of lithium monosilicate and lithium disilicate). In some embodiments, the lithium silicate crystalline phase has a higher weight percent than the other crystalline phases. In some embodiments, the lithium silicate crystalline phase comprises 5 to 50% by weight of the transparent glass-ceramic or transparent glass-ceramic article, preferably the lithium silicate crystalline phase comprises 5 to 40% by weight of the transparent glass-ceramic or transparent glass-ceramic article, more preferably the lithium silicate crystalline phase comprises 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 lithium silicate crystalline phase. In some embodiments, the lithium monosilicate crystalline phase has a higher weight percent than the other crystalline phases. In some embodiments, the lithium silicate crystalline phase comprises 5 to 50% by weight of the transparent glass ceramic or transparent glass ceramic article, preferably the lithium silicate crystalline phase comprises 5 to 40% by weight of the transparent glass ceramic or transparent glass ceramic article, more preferably the lithium silicate crystalline phase comprises 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 lithium disilicate crystalline phase. In some embodiments, the lithium disilicate crystalline phase comprises less than 20% by weight of the transparent glass ceramic or transparent glass ceramic article, preferably less than 10% by weight of the lithium disilicate crystalline phase comprises less than 5% by weight of the transparent glass ceramic or transparent glass ceramic article, more preferably no lithium disilicate crystalline phase is present in the transparent glass ceramic or transparent glass ceramic article. In some embodiments, the lithium disilicate 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%, 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-ceramic or transparent glass-ceramic article contains petalite crystalline phase, the petalite crystalline phase comprises less than 15% by weight of the transparent glass-ceramic or transparent glass-ceramic article, preferably less than 10% by weight of the petalite crystalline phase comprises less than 5% by weight of the transparent glass-ceramic or transparent glass-ceramic article, more preferably no petalite crystalline phase is present in the transparent glass-ceramic or transparent glass-ceramic article. 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.
SiO 2 Is the basic component of the glass, glass-ceramic and glass-ceramic products of the invention, which is one of the components forming the crystalline phase of lithium silicate, if SiO 2 The content of (2) is below 60%, and the crystals are easy to coarsen in the microcrystalline glass, so that the light transmittance of the microcrystalline glass and microcrystalline glass products is affected. Thus, siO 2 The lower limit of the content is 60%, preferably 62%, more preferably 64%. If SiO is 2 The content is more than 80%, the glass melting temperature is high, the material melting is difficult, and the haze of glass ceramics and glass ceramics products is increased. Thus, siO 2 The 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% of SiO may be included 2 。
Al 2 O 3 Is a component forming a glass network structure, is favorable for chemical strengthening of microcrystalline glass and improves the drop resistance of microcrystalline glass products, and if the content is less than 3 percent, the effect is poor. Thus, al 2 O 3 The lower limit of the content is 3%, preferably 5%. On the other hand, if Al 2 O 3 The content of the glass ceramics exceeds 15 percent, and the broken fragments (generally in the shape of particles) of the glass ceramics obtained by chemical strengthening of the glass ceramics are small, which is not beneficial to continuous use. Thus, al 2 O 3 The 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% Al may be included 2 O 3 。
Li 2 O is an essential component for forming a crystalline phase of the glass-ceramic of the present invention and is also an essential component for chemical strengthening, but if the content thereof is less than 5%, the type of crystals formed changes, affecting the strength of the glass-ceramic and glass-ceramic products. Thus Li 2 The lower limit of the O content is 5%, preferably 6%. On the other hand, if too much Li is contained 2 And the haze of O, glass ceramics and glass ceramics products is increased, and the raw material cost is higher. Thus Li 2 The upper limit of the O content is less than 10 percent. 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 included 2 O。
Na 2 O is favorable for forming a lithium silicate crystalline phase in the glass ceramics, and can improve the stability of the glass ceramics after chemical strengthening, and the glass ceramics contains more than 4 percent of Na 2 O is preferably Na in an amount of 4.5% or more to achieve the above effect 2 O. But if too much Na is contained 2 O, the formation of a lithium silicate crystalline phase in glass ceramics is difficult, and the light transmittance of glass ceramics and glass ceramics products is affected. Thus, na 2 The 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 included 2 O。
In some embodiments, siO 2 、Al 2 O 3 、Na 2 Total content of O SiO 2 +Al 2 O 3 +Na 2 O and Li 2 Ratio between O contents (SiO 2 +Al 2 O 3 +Na 2 O)/Li 2 O is controlled within the range of 7.0-18.0, which is favorable for refining grains, improving the fracture toughness of microcrystalline glass and microcrystalline glass products and improving the depth of ion exchange layers and surface stress of microcrystalline glass products. Therefore, it is preferable that (SiO 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0 to 18.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5 to 15.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5 to 13.0, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0. In some embodiments, (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 The 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。
ZrO 2 Can prevent crystallization during glass forming, refine crystal grains during crystallization heat treatment, and reduce haze of glass ceramics and glass ceramics products. ZrO in the present invention 2 The lower limit of the content is more than 5%, preferably 5.5% or more, more preferably 6% or more. But if too much ZrO is contained 2 ，ZrO 2 Is not easy to be melted in glass, is easy to form stones, and reduces the crystallization capability of the glass in heat treatment. Thus, zrO 2 The upper limit of the content is 15%, preferably 13%, more preferably 12%. In some embodiments, zrO may be included in an amount of about greater than 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% 2 。
In some embodiments, siO 2 Content of (3) and ZrO 2 Ratio between the contents of SiO 2 /ZrO 2 The glass ceramics is controlled within the range of 5.0-15.0, which is beneficial to improving the light transmittance and four-point bending strength of the glass ceramics and glass ceramics products, improving the falling ball test height of the glass ceramics products and the falling ball height of the glass ceramics body, and preventing the increase of haze and the value of |B|. Therefore, siO is preferred 2 /ZrO 2 From 5.0 to 15.0, more preferably SiO 2 /ZrO 2 From 6.0 to 13.0, siO is more preferable 2 /ZrO 2 From 6.5 to 12.0, siO is more preferable 2 /ZrO 2 7.0 to 11.0. In some embodiments, siO 2 /ZrO 2 The values of (3) 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 2 And Al 2 O 3 Is based on the sum of ZrO 2 +Al 2 O 3 With Li 2 Ratio between O contents (ZrO 2 +Al 2 O 3 )/Li 2 O is controlled within the range of 0.85-5.0, so that the falling ball height of the body of the glass ceramics can be improved, the falling ball test height and the ion exchange layer depth of the glass ceramics product are improved, and the light transmittance and the crystallinity of the glass ceramics and the glass ceramics product are prevented from being reduced. Therefore, (ZrO 2 +Al 2 O 3 )/Li 2 O is 0.85 to 5.0, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 0.9 to 4.0, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0 to 3.5, more preferably (ZrO 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0. In some embodiments, (ZrO 2 +Al 2 O 3 )/Li 2 The O value 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, 4.5, 4.9, 4.5, 4.0.
In some embodiments, li 2 O and Na 2 Total content of O Li 2 O+Na 2 O and SiO 2 And ZrO(s) 2 Is the total content of SiO 2 +ZrO 2 Ratio between (Li 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) The control of the surface stress and the ion exchange layer depth of the microcrystalline glass products is in the range of 0.10-0.27, which is beneficial to improving the four-point bending strength and hardness of the microcrystalline glass and the microcrystalline glass products and preventing the fracture toughness and the drop resistance of the microcrystalline glass and the microcrystalline glass products from being reduced. Therefore, it is preferable that (Li 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.10 to 0.27, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.12 to 0.25, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) Is 0.14 to 0.25, more preferably(Li 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23. In some embodiments, (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) The values of (2) 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.
P 2 O 5 The heterogeneous nucleation can be carried out in glass, the formation of crystals is promoted, and the light transmittance of microcrystalline glass and microcrystalline glass products is improved; but if too much P is contained 2 O 5 The glass is easy to directly devitrify during forming, and the heat treatment process is not easy to control. Thus, P 2 O 5 The content of (2) 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% P may be included 2 O 5 。
In some embodiments, siO 2 And Li (lithium) 2 Total content of O SiO 2 +Li 2 O and ZrO 2 And P 2 O 5 Is based on the sum of ZrO 2 +P 2 O 5 Ratio between (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) The haze and the value of the microcrystalline glass and the microcrystalline glass product can be reduced within the range of 4.0-15.5, the drop resistance and the hardness of the microcrystalline glass and the microcrystalline glass product are improved, and the crystallinity of the microcrystalline glass and the microcrystalline glass product is optimized. Therefore, it is preferable that (SiO 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 4.0 to 15.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 5.0 to 13.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) Is 6.0 to 11.5, more preferably (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5. In some embodiments, (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) The values of (2) 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 glass, but excessive amounts can result in increased haze in glass-ceramics and glass-ceramic 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 excessive amounts can result in increased haze in glass ceramics and glass ceramic articles. 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.
B 2 O 3 The glass melting temperature can be reduced, the content of glass phase in the glass ceramics can be increased, and the glass ceramics and glass ceramics products can be heated and bent. However, if too much B is contained in the glass 2 O 3 Phase separation is easy during crystallization heat treatment, and light transmittance of glass ceramics and glass ceramics products is reduced. Thus B 2 O 3 The 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%, a,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 2 O 3 。
K 2 O can reduce the viscosity of the glass and promote the growth of crystals during crystallization heat treatment, but if too much K is contained 2 And O, crystals in the glass can be easily grown rapidly, and the light transmittance of the glass ceramics and glass ceramics products is reduced. Thus, K is 2 The content of O is 3% or less, preferably 2% 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%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% K may be included 2 O。
Ln 2 O 3 (Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the above) can reduce the smelting difficulty of glass, and when the content is too high, the difficulty of forming crystals during glass crystallization can be caused, the crystallinity of glass ceramics and glass ceramics products is reduced, and the falling ball height of the body of the glass ceramics and the falling ball test height of the glass ceramics products are reduced. Thus Ln 2 O 3 The upper limit of the content is 2%, preferably 1%, more preferably 0.5%, and even more preferably Ln is not contained 2 O 3 . 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 included 2 O 3 。
In some embodiments, the glass, glass-ceramic, or glass-ceramic article may further contain 0-2% of a fining agent, including but not limited to Sb, to enhance the bubble removal ability of the glass, glass-ceramic, or glass-ceramic article 2 O 3 、SnO 2 、SnO、CeO 2 One or more of F (fluorine), cl (chlorine) and Br (bromine), preferably Sb 2 O 3 As a clarifying agent. When the above clarifying agents are present alone or in combination, the upper limit of the content thereof is preferably 1%, more preferably 0.5%. In some embodiments, one or more of the above-described clarifying agents is present in an amount of about 0%, 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 As 2 O 3 Is a toxic substance, and even a small amount of the toxic substance does not meet the environmental requirements, so that the present invention in some embodiments preferably does not contain PbO and As 2 O 3 。
The term "not containing" or "0%" as used herein means that the compound, molecule, element, or the like is not intentionally added as a raw material to the base glass, glass ceramic, or glass ceramic product of the present invention; however, it is within the scope of the present invention that certain other impurities or components may be present that are not intentionally added as raw materials and/or equipment for producing the base glass, glass-ceramic or glass-ceramic article, and that may be present in minor or trace amounts in the final base glass, glass-ceramic or glass-ceramic article.
In some embodiments of the present invention, the crystalline phase of the glass-ceramic and glass-ceramic article comprises lithium silicate, which provides the glass-ceramic and glass-ceramic article of the present invention with high strength and high fracture toughness; the falling ball height of the body of the microcrystalline glass and the falling ball test height of the microcrystalline glass product and the four-point bending strength become larger. The glass ceramics of the invention 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 microcrystalline glass products of the invention can obtain proper grain size, and the microcrystalline glass and microcrystalline glass products of the invention have high strength. The microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity refers to the degree of crystallization, the arrangement of particles in the crystals with complete crystallization is more regular, diffraction lines are strong, sharp and symmetrical, and the half-width of diffraction peaks is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation, so that the diffraction lines have wide peak shapes and are dispersed. The worse the crystallinity, the weaker the diffraction power, the broader the diffraction peak until disappeared in the background. In some embodiments, the glass-ceramic article or glass-ceramic has a crystallinity of 10% or more, preferably 15% or more, more preferably 20% or more.
The grain size and the crystal phase type in 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 grain, the higher the light transmittance; the smaller the haze, the higher the light transmittance. In some embodiments, the glass-ceramic product or glass-ceramic having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, more preferably 0.15% or less. In some embodiments, the glass-ceramic article or glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, more preferably 30nm or less.
In some embodiments, the crystalline phase content and refractive index of the glass-ceramic or glass-ceramic article of the present invention affect the value of l B for glass-ceramic or glass-ceramic article, and blue or yellow appearance of glass-ceramic or glass-ceramic article in the visible range affects the optical properties of the product, indicated by the value of l B in LAB (chromaticity value of material color). The glass-ceramic or glass-ceramic product of the present invention exhibits a low value of l, B in the visible light range, and in some embodiments a glass-ceramic product of 1mm or less thickness or a glass-ceramic 400-800 nm average value of l, B is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less.
The transparent glass-ceramic or transparent glass-ceramic article of the present invention exhibits high transparency in the visible range (i.e., the glass-ceramic or glass-ceramic article is transparent). The transparent glass ceramic or transparent glass ceramic product exhibits a high transmittance in the visible light range, and in some embodiments, the transparent glass ceramic product or transparent glass ceramic product having a thickness of 1mm or less has an average light transmittance of 400 to 800nm of preferably 90.5% or more. In some preferred embodiments, the transparent glass-ceramic product or transparent glass-ceramic having a thickness of 1mm or less preferably has a light transmittance of 91.5% or more at 550 nm.
In some embodiments, the antimicrobial component may be added to a base glass, glass-ceramic, or glass-ceramic article. The glass-ceramic or glass-ceramic article described herein may be used in applications such as kitchen or restaurant countertops, where exposure to harmful bacteria is likely. The antimicrobial component contained in the base glass, glass-ceramic or glass-ceramic article includes, but is not limited to, ag, agO, cu, cuO, cu 2 O, etc. In some embodiments, the antimicrobial component is present in an amount of 2% or less, preferably 1% or less, alone or in combination.
The matrix glass, glass-ceramic and glass-ceramic products of the present invention can be produced and manufactured by the following methods:
Generating a matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixed raw materials are put into a crucible made of platinum or quartz, and are melted for 5 to 24 hours in an electric furnace or a gas furnace at the temperature of 1250 to 1650 ℃ according to the melting difficulty of the glass composition, and the mixture is stirred to be uniform, cooled to a proper temperature, cast into a mold and slowly cooled.
The substrate glass of the present invention can be molded by a well-known method.
The substrate glass of the invention is crystallized by crystallization process after molding or processing, and crystals are uniformly precipitated in the glass. The crystallization treatment may be performed in 1 stage or 2 stages, and preferably 2 stages are used. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization treatment performed at the 1 st temperature is referred to as a 1 st crystallization treatment, and the crystallization treatment performed at the 2 nd temperature is referred to as a 2 nd crystallization treatment.
In order to obtain the desired physicochemical properties of the glass ceramics, the preferred crystallization process is:
the crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after the crystallization temperature is reached, the temperature is maintained for a predetermined period of time, and then the temperature is lowered. The crystallization temperature is preferably 550 to 700 ℃, more preferably 580 to 650 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, more preferably 1 to 6 hours, in order to precipitate a desired crystal phase.
In the crystallization treatment in 2 stages, the 1 st temperature is preferably 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 holding time of 0 hours means that the temperature starts to be lowered or raised again less than 1 minute after the temperature is reached.
In some embodiments, the matrix glass or glass-ceramic described herein can be manufactured into shaped bodies, including but not limited to sheets, by various processes including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by float or roll processes as are known in the art. The molded article of the present invention also includes lenses, prisms, and the like.
The base glass or glass ceramic of the present invention may be a glass molded article or glass ceramic molded article produced by a method such as grinding or polishing, but the method for producing a glass molded article or glass ceramic molded article is not limited to these methods.
The matrix glass or glass ceramic of the present invention may be produced at a predetermined temperature by a method such as a hot bending process or a pressing process to form glass molded bodies or glass ceramic molded bodies of various shapes, but is not limited to these methods.
In some embodiments, glass shaped bodies or glass ceramic shaped bodies may be formed using a hot bending process. The hot bending process is a process of placing 2D or 2.5D glass or glass ceramics in a mould, and sequentially carrying out the steps of heating, preheating, pressurizing, pressure maintaining, cooling and the like in a hot bending machine to obtain a glass forming body or glass ceramics forming body with a 3D curved surface.
In some embodiments, the glass-ceramic shaped body has a 2.5D or 3D configuration, i.e., the glass-ceramic shaped body has a non-planar configuration. As used herein, a "non-planar configuration" refers to at least a portion of the glass-ceramic forming body extending outwardly or along an angle with respect to a plane defined by the original, laid-out configuration of the 2D matrix glass in a 2.5D or 3D shape. A 2.5D or 3D glass-ceramic forming body formed from a matrix glass may have one or more protrusions or curved portions.
In some embodiments, the method of manufacturing the glass-ceramic shaped body is a hot bending process method, combining the characteristics of growth of a crystal phase and transformation of the crystal phase in glass-ceramic. In particular, the method includes pre-crystallization and thermoforming. The pre-crystallization is to form pre-crystallized glass by controlling a crystallization process, wherein the crystallinity of the pre-crystallized glass does not reach the crystallinity required by the performance index of the target microcrystalline glass forming body. And forming the microcrystalline glass forming body by the pre-crystallized glass through a thermal processing forming process.
In some embodiments, a method of manufacturing a glass ceramic forming body includes the steps of:
1) Performing primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation and nucleation, heating, heat preservation and crystallization and cooling to room temperature to form pre-crystallized glass;
2) And carrying out thermal processing molding on the pre-crystallized glass to obtain the microcrystalline glass forming body.
The crystallization heat treatment process of the invention comprises the steps of heating the substrate glass at a certain temperature T h And time t h Nucleating at a certain temperature T c And time t c And crystallizing, wherein the crystallinity of the obtained pre-crystallized glass does not reach the crystallinity required by the performance index of the target microcrystalline glass forming body. XRD test data are applied, and the main component in the crystallinity of the pre-crystallized glass is calculated through a Rietveld full spectrum fitting refinement methodThe total content of crystal phase is I c1 . The pre-crystallization of the invention is a complete process in terms of the technological process, comprising one step of a nucleation process, one, two or three or more steps of a crystallization process, and the like, and is a complete process of heating, heat preservation, heating again, heat preservation … … and then cooling to room temperature according to the process. Unlike the first crystallization and the second crystallization … … mentioned in some documents or patents, the present invention is actually only the first crystallization in a complete crystallization process, the second crystallization … …, which is continuous, and there is no process of raising the temperature again after cooling to room temperature.
The hot forming of the invention refers to forming the pre-crystallized glass by a hot forming process under the conditions of a certain temperature, a certain time, a certain pressure and the like, wherein the hot forming comprises more than one hot forming process, and the hot forming process comprises, but is not limited to, press forming, bending forming or drawing forming of the pre-crystallized glass under the conditions of a certain temperature, a certain time, a certain pressure and the like. In the hot forming process, sometimes a formed body having a complicated shape cannot be formed by one hot working, and it may be necessary to perform a plurality of hot working times more than two times.
In some embodiments, the method of making the glass-ceramic 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: and placing the matrix glass or the pre-crystallized glass or the microcrystalline glass into a mould, sequentially passing through each heating station in a hot bending machine, and keeping the temperature at each station for a certain time. The preheating zone is at 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 profiling first station is within 20 ℃.
2) And (3) compression molding: the mould is transferred to a forming station after being preheated, a hot bending machine applies 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 reducing: transferring the die to a cooling station for cooling. The temperature is controlled to be 750-500 ℃, the pressure is 0.01-0.05 Mpa, and the time is 40-200 s.
The glass ceramic forming body is formed by adopting a hot bending process, so that the appearance quality of common high-alumina glass is required to be controlled, and meanwhile, the influence of crystal growth and development in the hot bending process on the performance of glass ceramic is required to be controlled, for example, the 3D curved glass ceramic used for a display device or an electronic device shell is required to pay close attention to the light transmittance, the haze, the |B| value, the uniformity and the like after hot bending.
The substrate glass, glass-ceramic, and glass-ceramic articles of the present invention can have any thickness that is reasonably useful.
The microcrystalline glass of the invention not only improves mechanical properties through precipitation crystallization, but also can obtain more excellent mechanical properties through forming a compressive stress layer, thereby preparing microcrystalline glass products.
In some embodiments, the substrate glass or glass-ceramic may be processed into a sheet and/or shaped (e.g., punched, heat bent, etc.), shaped, polished and/or polished, and then chemically strengthened by a chemical strengthening process.
The chemical strengthening is ion exchange method. During ion exchange, smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" with larger metal ions of the same valence state in close proximity to the matrix glass or glass-ceramic. And replacing smaller ions with larger ions to construct compressive stress in the matrix glass or the microcrystalline glass, so as to form a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., na + 、K + 、Rb + 、Cs + Plasma), ion exchange is performed by immersing a matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ionsThe ions are used to replace smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag + 、Tl + 、Cu + And the like may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different composition, with washing and/or annealing steps between immersion.
In some embodiments, the matrix glass or glass-ceramic may be produced by immersing a molten Na salt (e.g., naNO) in a temperature of about 350 ℃ to 470 DEG C 3 ) Ion exchange is carried out in a salt bath of 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-ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be prepared by melting a K-salt (e.g., KNO) at a temperature immersed in the range of about 360 ℃ to 450 DEG C 3 ) Ion exchange is carried out in the salt bath for 1 to 36 hours, preferably for 2 to 24 hours. In some embodiments, the matrix glass or glass ceramic may be ion exchanged by immersing in a mixed salt bath of molten K and Na salts at a temperature of about 360 to 450 ℃ for 1 to 36 hours, preferably for a time period in the range of 2 to 24 hours.
The microcrystalline glass and/or microcrystalline glass products and/or matrix glass of the invention are tested by the following performance indexes:
[ haze ]
The haze tester Meinada CM3600A is adopted, a sample with the thickness of less than 1mm is prepared, and the haze tester is tested by taking GB2410-80 as a standard.
[ Crystal grain size ]
And (3) measuring by using an SEM scanning electron microscope, carrying out surface treatment on the microcrystalline glass in HF acid, then carrying out metal spraying on the surface of the microcrystalline glass, carrying out surface scanning under the SEM scanning electron microscope, and determining the size of crystal grains.
[ light transmittance ]
The light transmittance is referred to herein as the external transmittance, sometimes simply referred to as the transmittance.
The sample was processed to 1mm or less and polished with the opposite surfaces in parallel, and the average light transmittance of 400 to 800nm was measured by using a Hitachi U-41000-shaped spectrophotometer.
The sample was processed to 1mm or less and polished with the opposite surfaces in parallel, and the light transmittance at 550nm was measured by using a Hitachi U-41000-shaped spectrophotometer.
[ crystallinity ]
The XRD diffraction peaks were compared with the database spectra, and the crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the overall spectrum, and internal calibration was performed by using pure quartz crystals.
[ depth of ion exchange layer ]
Ion exchange layer depth measurements were performed using a glass surface stress meter SLP-2000.
The measurement conditions were calculated by using a sample having a refractive index of 1.56 and an optical elastic constant of 29[ (nm/cm)/MPa ].
[ surface stress ]
Surface stress measurement was performed by using a glass surface stress meter SLP-2000.
The measurement conditions were calculated by using a sample having a refractive index of 1.52 and an optical elastic constant of 29[ (nm/cm)/MPa ].
[ crash resistance ]
The drop resistance test was performed using a directional drop tester WH-2101. By loading glass products with the same specification (each weight is 20g and 2 pieces are loaded) on a 2D microcrystalline glass product, 60-80-mesh sand paper is paved on a base, the sample is freely dropped from a specified height, the sample is directly crashed on the sand paper, and the height of impact which can be borne without breaking is the drop resistance. Specifically, the test was performed starting from a height of 600mm, and the heights were changed in order of 700mm, 800mm, 900mm, 1000mm and above without breaking. For the examples with "shatter resistance", glass-ceramic articles were the subject of the test. Test data recorded as 2000mm in the examples show that even the glass-ceramic product loaded from a height of 2000mm is not broken and receives impact, and the highest test height of the drop tester WH-2101 is 2000mm.
[ falling ball test height ]
A sample of a glass ceramic product of 145mm by 67mm by 0.7mm was placed on a glass-carrying jig, and 132g of steel balls were dropped from a predetermined height, and the sample was subjected to a maximum ball drop test height of impact that could be sustained without breaking. Specifically, the test was performed starting from a falling ball test height of 800mm, and the heights were changed in order of 850mm, 900mm, 950mm, 1000mm and above without breaking. For the examples with "falling ball test height", glass-ceramic articles were the test subjects. Test data recorded as 1000mm in the examples show that the glass ceramic product is not broken and receives an impact even if the steel ball is dropped from a height of 1000 mm. The falling ball test height is sometimes referred to as falling ball height.
[ height of falling ball of body ]
The glass ceramic sample with the thickness of 145mm multiplied by 67mm multiplied by 0.7mm is placed on a glass bearing clamp, so that a 32g steel ball falls from a specified height, and the maximum falling ball test height of the impact which can be born by the sample without breaking is the falling ball height of the body. Specifically, the test was performed starting from a falling ball test height of 500mm, and the heights were changed in order of 550mm, 600mm, 650mm, 700mm and above without breaking. For the embodiment with the body falling ball height, the microcrystalline glass is taken as a test object, namely the falling ball test height of the microcrystalline glass. Test data recorded as 1000mm in the examples show that the glass ceramic is not broken and receives an impact even if the steel ball is dropped from a height of 1000 mm.
[ fracture toughness ]
The method for directly measuring the size of the indentation expansion crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, chamfering, grinding and polishing are carried out, after the sample preparation is completed, a force of 49N is applied to the sample by a Vickers hardness pressing head for 30s, and after the indentation is made, the breaking strength is measured by a three-point bending method.
[ four-point bending Strength ]
The microcomputer controlled electronic universal tester CMT6502 is adopted, the specification of a sample is less than 1mm, and the test is carried out by taking ASTM C158-2002 as a standard. In the present invention, four-point bending strength is sometimes referred to simply as bending strength.
[ Vickers hardness ]
The load (N) of a diamond quadrangular pyramid indenter having an included angle of 136 DEG with respect to the surface of the test surface when the pyramid-shaped recess was pressed into the test surface was divided by the surface area (mm) calculated by the length of the recess 2 ) Is represented by a value of (a). The test load was 100 (N) and the holding time was 15 (seconds). The vickers hardness is sometimes referred to simply as hardness in the present invention.
[ |B|value ]
B-value measurements were performed using Meidad CM-700 d. The sample specification is below 1mm thickness, with supporting correction long section of thick bamboo and short section of thick bamboo respectively carry out instrument zero calibration and whiteboard calibration, carry out empty test with long section of thick bamboo again after the calibration, judge instrument stability calibration reliability (B is less than or equal to 0.05), place the product on the long section of thick bamboo of zero position and test after the instrument correction is qualified.
The value of |b| is the absolute value of the B value.
Young's modulus
Young's modulus (E) is obtained by measuring longitudinal wave velocity and transverse wave velocity by ultrasonic wave and calculating according to the following formula.
G＝V S 2 ρ
Wherein: e is Young's modulus, pa;
g is the shear modulus, pa;
V T is transverse wave speed, m/s;
V S is longitudinal wave speed, m/s;
ρ is the density of the glass, g/cm 3 。
[ refractive index ]
Refractive index (n) d ) Tested 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 more, preferably 650MPa or more, and more preferably 700MPa or more.
2) In some embodiments, the transparent glass-ceramic article has an ion exchange layer depth of 80 μm or more, preferably 90 μm or more, more preferably 100 μm or more.
3) In some embodiments, the surface stress of the transparent glass-ceramic article is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more.
4) In some embodiments, the transparent glass-ceramic article has a falling ball test height of 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more.
5) In some embodiments, the transparent glass-ceramic article has a fracture toughness of 1 MPa-m 1/2 The above is preferably 1.1 MPa.m 1/2 The above is more preferably 1.2 MPa.m 1/2 The above.
6) In some embodiments, the vickers hardness (H v ) 670kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above.
7) In some embodiments, the transparent glass-ceramic article has a crystallinity of 10% or more, preferably 15% or more, 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 transparent glass-ceramic article has a shatter resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more.
10 In some embodiments, the transparent glass-ceramic article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.17% or less, 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
11 In some embodiments, the transparent glass-ceramic product has a thickness of 1mm or less, and 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
12 In some embodiments, the transparent glass-ceramic product has a thickness of 1mm or less, and 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 still more 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
13 In some embodiments, the transparent glass-ceramic article has a thickness of 1mm or less, and an average light |b| value of 400 to 800nm of 1.0 or less, preferably 0.9 or less, and 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
The transparent glass ceramic has the following properties:
1) In some embodiments, the transparent glass-ceramic has a crystallinity of 10% or more, preferably 15% or more, and more preferably 20% or more.
2) In some embodiments, the transparent glass-ceramic has a grain size of 50nm or less, preferably 40nm or less, and more preferably 30nm or less.
3) In some embodiments, the haze of the transparent glass ceramic 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
4) In some embodiments, the transparent glass ceramic has a thickness of 1mm or less, and 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
5) In some embodiments, the transparent glass ceramic has a thickness of 1mm or less, and a light transmittance at a wavelength of 550nm is 89.0% or more, preferably 90.0% or more, and 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
6) In some embodiments, the bulk drop height of the transparent glass-ceramic is 1700mm or more, preferably 1900mm or more, 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 to 800nm of 1.0 or less, preferably 0.9 or less, and 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, still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
8) In some embodiments, the vickers hardness (H v ) 600kgf/mm 2 Above, preferably 620kgf/mm 2 Above, more preferably 630kgf/mm 2 The above.
9) In some embodiments, the refractive index (n d ) 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 substrate glass has the following properties:
1) In some embodiments, the refractive index (n d ) 1.510 to 1.530.
The transparent glass ceramics, transparent glass ceramics products, matrix glass, glass forming bodies and glass forming bodies have the excellent performances, so that the transparent glass ceramics, transparent glass ceramics products, matrix glass, glass forming bodies and glass forming bodies can be widely manufactured into glass cover plates or glass components; meanwhile, the transparent glass ceramics, transparent glass ceramics products, matrix glass, glass forming bodies and glass ceramics forming bodies can be applied to electronic equipment or display equipment, such as mobile phones, watches, computers, touch display screens and the like, are used for manufacturing protective glass of mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or are used for manufacturing protective glass of touch screens, protective windows, automobile windows, train windows, aviation mechanical windows, 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 kitchen ware.
Examples
In order to further clearly illustrate and describe the technical solutions of the present invention, the following non-limiting examples are provided. Embodiments of the present invention have undergone a number of efforts to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. The composition itself is given in weight% based on the oxide and has been standardized to 100%.
< matrix glass example >
In this example, a substrate glass having the composition shown in tables 1 to 2 was obtained by using the above-mentioned method for producing a substrate glass. The characteristics of each of the matrix glasses were measured by the test method of the present invention, and the measurement results are shown in tables 1 to 2.
Table 1.
Table 2.
< transparent glass-ceramic example >
In this example, transparent glass ceramics having compositions shown in tables 3 to 4 were obtained by using the above-mentioned glass ceramics production method. The characteristics of each glass ceramic were measured by the test method of the present invention, and the measurement results are shown in tables 3 to 4, and the thickness of the test sample, which is 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 at 400 to 800nm in the following examples, was 0.7mm.
Table 3.
Table 4.
< transparent glass-ceramic article example >
In this example, transparent glass ceramics having compositions shown in tables 5 to 6 were obtained by using the above-mentioned method for producing glass ceramics. The characteristics of each transparent glass-ceramic product were measured by the test method of the present invention, and the measurement results are shown in tables 5 to 6, and the thickness of the test sample, which is 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 at 400 to 800nm in the following examples, was 0.7mm.
Table 5.
Table 6.
/>

Claims (105)

1. The transparent glass ceramic product is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 6.7% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 11.9.
2. The transparent glass-ceramic article according to claim 1, further comprising, in weight percent: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
3. A transparent glass ceramic product characterized by comprising SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The components are expressed in weight percent, siO 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 6.7% but less than or equal to 15%, where SiO 2 /ZrO 2 The transparent glass ceramic product has a thickness of 5.0-11.9, and an average light transmittance of 88.0% or more at a wavelength of 400-800 nm.
4. A transparent glass-ceramic article according to claim 3, characterized in that it comprises, in weight percent: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
5. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 /ZrO 2 6.0 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 4.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0-18.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-5.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.10 to 0.27.
6. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 /ZrO 2 6.5 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 5.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5-15.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-4.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.12 to 0.25.
7. The transparent glass-ceramic article according to any one of claims 1 to 4, whereinThe components are expressed in weight percent, wherein: siO (SiO) 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 11.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-13.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.5; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.14 to 0.25.
8. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the components are expressed in weight percent, and wherein: (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
9. The transparent glass-ceramic product according to any one of claims 1 to 4, characterized in that it comprises, in weight percent: siO (SiO) 2 : 62-78%; and/or Al 2 O 3 : 5-12%; and/or Li 2 O: greater than or equal to 6% but less than 10%; and/or Na 2 O:4 to 7.5 percent; and/or P 2 O 5 :1 to 4.5 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 13%; and/or ZnO:0 to 1.5 percent; and/or MgO:0 to 1.5 percent; and/or B 2 O 3 :0 to 3 percent; and/or K 2 O:0 to 2 percent; and/or Ln 2 O 3 :0 to 1 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
10. According to the weightsThe transparent glass-ceramic product according to any one of claims 1 to 4, characterized in that it comprises, in weight percent: siO (SiO) 2 : 64-75%; and/or Al 2 O 3 : 5-10%; and/or Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 12%; and/or ZnO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
11. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a lithium silicate crystalline phase having a higher weight percentage than the other crystalline phases.
12. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a lithium silicate crystalline phase in an amount of 5 to 50% by weight of the transparent glass-ceramic article.
13. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a lithium silicate crystalline phase in an amount of 5 to 40% by weight of the transparent glass-ceramic article.
14. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a lithium silicate crystalline phase in an amount of 10 to 30% by weight of the transparent glass-ceramic article.
15. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article comprises a lithium silicate crystalline phase having a higher weight percentage than the other crystalline phases.
16. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium silicate crystal phase, and the lithium silicate crystal phase accounts for 5 to 50% of the transparent glass-ceramic product by weight.
17. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium silicate crystal phase, and the lithium silicate crystal phase accounts for 5 to 40% of the transparent glass-ceramic product by weight.
18. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium silicate crystal phase, and the lithium silicate crystal phase accounts for 10 to 30% of the transparent glass-ceramic product by weight.
19. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase accounts for 20% by weight or less of the transparent glass-ceramic product.
20. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase accounts for 10% by weight or less of the transparent glass-ceramic product.
21. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase accounts for 5% by weight or less of the transparent glass-ceramic product.
22. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article does not contain a lithium disilicate crystalline phase.
23. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains petalite crystal phase, and the petalite crystal phase accounts for 15% or less of the transparent glass-ceramic product by weight.
24. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains petalite crystal phase, and the petalite crystal phase accounts for 10% or less of the transparent glass-ceramic product by weight.
25. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product contains petalite crystal phase, and the petalite crystal phase accounts for less than 5% by weight of the transparent glass-ceramic product.
26. The transparent glass-ceramic article according to any one of claims 1 to 4, wherein the transparent glass-ceramic article does not contain petalite crystalline phases.
27. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the falling ball test height of the transparent glass-ceramic product is 1400mm or more; and/or fracture toughness of 1 MPa.m 1/2 The above; and/or the four-point bending strength is above 600 MPa; and/or a Vickers hardness of 670kgf/mm 2 The above; and/or the ion exchange layer depth is more than 80 μm; and/or the surface stress is more than 100 MPa; and/or crystallinity of 10% or more; and/or the grain size is 50nm or less; and/or the drop resistance is 1500mm or more.
28. According to claim 1The transparent microcrystalline glass product described in any one of the above-mentioned items 4, wherein the falling ball test height of the transparent microcrystalline glass product is more than 1500 mm; and/or fracture toughness of 1.1 MPa.m 1/2 The above; and/or the four-point bending strength is 650MPa or more; and/or a Vickers hardness of 680kgf/mm 2 The above; and/or the ion exchange layer depth is more than 90 μm; and/or a surface stress of 150MPa or more; and/or crystallinity of 15% or more; and/or the grain size is 40nm or less; and/or the drop resistance is 1600mm or more.
29. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the falling ball test height of the transparent glass-ceramic product is 1600mm or more; and/or fracture toughness of 1.2 MPa.m 1/2 The above; and/or the four-point bending strength is more than 700 MPa; and/or a Vickers hardness of 700kgf/mm 2 The above; and/or the ion exchange layer depth is more than 100 μm; and/or a surface stress of 200MPa or more; and/or crystallinity of 20% or more; and/or the grain size is below 30 nm; and/or the drop resistance is 1800mm or more.
30. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the haze of the transparent glass-ceramic product having a thickness of 1mm or less is 0.2% or less; and/or an average light transmittance of 88.0% or more at a wavelength of 400 to 800 nm; and/or light transmittance at 550nm wavelength of 89.0% or more; and/or an average light-B-value of 400-800 nm of 1.0 or less.
31. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the haze of the transparent glass-ceramic product having a thickness of 1mm or less is 0.17% or less; and/or an average light transmittance of 89.0% or more at a wavelength of 400 to 800 nm; and/or a light transmittance at a wavelength of 550nm of 90.0% or more; and/or an average light-B-value of 400-800 nm of 0.9 or less.
32. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the haze of the transparent glass-ceramic product having a thickness of 1mm or less is 0.15% or less; and/or an average light transmittance of 90.0% or more at a wavelength of 400 to 800 nm; and/or a light transmittance at a wavelength of 550nm of 91.0% or more; and/or an average light-B-value of 400-800 nm of 0.8 or less.
33. The transparent glass-ceramic product according to any one of claims 1 to 4, wherein the transparent glass-ceramic product having a thickness of 1mm or less has an average light transmittance of 90.5% or more at a wavelength of 400 to 800 nm; and/or a light transmittance at a wavelength of 550nm of 91.5% or more.
34. The transparent glass-ceramic article according to claim 30, wherein the transparent glass-ceramic article has a thickness of 0.2 to 1mm.
35. The transparent glass-ceramic article according to claim 30, wherein the transparent glass-ceramic article has a thickness of 0.3 to 0.9mm.
36. The transparent glass-ceramic article according to claim 30, wherein the transparent glass-ceramic article has a thickness of 0.5 to 0.8mm.
37. The transparent glass-ceramic article according to claim 30, wherein the transparent glass-ceramic article has a thickness of 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
38. The transparent glass ceramic is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 6.7% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 11.9.
39. The transparent glass-ceramic according to claim 14, whereinThe components of the composition are expressed in weight percent and also comprise: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
40. A transparent glass ceramic comprising SiO 2 、Al 2 O 3 、Li 2 O、Na 2 O and ZrO 2 The components are expressed in weight percent, siO 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 6.7% but less than or equal to 15%, where SiO 2 /ZrO 2 The transparent glass ceramics with the thickness of less than 1mm and the average light transmittance of 400-800 nm is more than 88.0 percent, wherein the transparent glass ceramics have the thickness of 5.0-11.9.
41. The transparent glass-ceramic according to claim 16, wherein the composition comprises, in weight percent: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
42. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 /ZrO 2 6.0 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 4.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0-18.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-5.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.10 to 0.27.
43. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 /ZrO 2 6.5 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 5.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5-15.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-4.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.12 to 0.25.
44. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 11.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-13.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.5; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.14 to 0.25.
45. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the components are expressed in weight percent, and wherein: (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
46. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the composition comprises, in weight percent: siO (SiO) 2 : 62-78%; and/or Al 2 O 3 : 5-12%; and/or Li 2 O: greater than or equal to 6% but less than 10%; and/or Na 2 O:4 to 7.5 percent; and/or P 2 O 5 :1 to 4.5 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 13%; and/or ZnO:0 to 1.5 percent; and/or MgO:0 to 1.5 percent; and/or B 2 O 3 :0 to 3 percent; and/or K 2 O:0 to 2 percent; and/or Ln 2 O 3 :0 to 1 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
47. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the composition comprises, in weight percent: siO (SiO) 2 : 64-75%; and/or Al 2 O 3 : 5-10%; and/or Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 12%; and/or ZnO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
48. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains a lithium silicate crystal phase having a higher weight percentage than other crystal phases.
49. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic comprises a lithium silicate crystal phase in an amount of 5 to 50% by weight of the transparent glass-ceramic.
50. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic comprises a lithium silicate crystal phase in an amount of 5 to 40% by weight of the transparent glass-ceramic.
51. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic comprises a lithium silicate crystal phase in an amount of 10 to 30% by weight of the transparent glass-ceramic.
52. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic comprises a lithium silicate crystal phase having a higher weight percentage than other crystal phases.
53. The glass-ceramic according to any one of claims 38 to 41, wherein the glass-ceramic comprises a lithium silicate crystal phase, the lithium silicate crystal phase comprising 5 to 50% by weight of the glass-ceramic.
54. The glass-ceramic according to any one of claims 38 to 41, wherein the glass-ceramic comprises a lithium silicate crystal phase, the lithium silicate crystal phase comprising 5 to 40% by weight of the glass-ceramic.
55. The glass-ceramic according to any one of claims 38 to 41, wherein the glass-ceramic comprises a lithium silicate crystal phase, the lithium silicate crystal phase comprising 10 to 30% by weight of the glass-ceramic.
56. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase is 20% by weight or less of the transparent glass-ceramic.
57. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase is 10% by weight or less of the transparent glass-ceramic.
58. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains a lithium disilicate crystal phase, and the lithium disilicate crystal phase is 5% by weight or less of the transparent glass-ceramic.
59. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic does not contain a lithium disilicate crystal phase.
60. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains petalite crystal phase, and the petalite crystal phase accounts for 15% or less by weight of the transparent glass-ceramic.
61. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains petalite crystal phase, and the petalite crystal phase accounts for 10% or less by weight of the transparent glass-ceramic.
62. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic contains petalite crystal phase, and the petalite crystal phase accounts for 5% or less by weight of the transparent glass-ceramic.
63. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic does not contain petalite crystalline phase.
64. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the crystallinity of the transparent glass-ceramic is 10% or more; and/or the grain size is 50nm or less; and/or the falling ball height of the body is more than 1700 mm; and/or a Vickers hardness of 600kgf/mm 2 The above; and/or a refractive index of 1.520 to 1.545; and/or Young's modulus of 80-100 GPa.
65. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the crystallinity of the transparent glass-ceramic is 15% or more; and/or the grain size is 40nm or less; and/or the falling ball height of the body is above 1900 mm; and/or a Vickers hardness of 620kgf/mm 2 The above.
66. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the crystallinity of the transparent glass-ceramic is 20% or more; and/or the grain size is below 30 nm; and/or the falling ball height of the body is more than 2000 mm; and/or a Vickers hardness of 630kgf/mm 2 The above.
67. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic having a thickness of 1mm or less has a haze of 0.2% or less; and/or an average light transmittance of 88.0% or more at a wavelength of 400 to 800 nm; and/or light transmittance at 550nm wavelength of 89.0% or more; and/or an average light-B-value of 400-800 nm of 1.0 or less.
68. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic having a thickness of 1mm or less has a haze of 0.17% or less; and/or an average light transmittance of 89.0% or more at a wavelength of 400 to 800 nm; and/or a light transmittance at a wavelength of 550nm of 90.0% or more; and/or an average light-B-value of 400-800 nm of 0.9 or less.
69. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic having a thickness of 1mm or less has a haze of 0.15% or less; and/or an average light transmittance of 90.0% or more at a wavelength of 400 to 800 nm; and/or a light transmittance at a wavelength of 550nm of 91.0% or more; and/or an average light-B-value of 400-800 nm of 0.8 or less.
70. The transparent glass-ceramic according to any one of claims 38 to 41, wherein the transparent glass-ceramic has a thickness of 1mm or less and an average light transmittance at a wavelength of 400 to 800nm of 90.5% or more; and/or a light transmittance at a wavelength of 550nm of 91.5% or more.
71. The transparent glass-ceramic according to claim 67, wherein the thickness of the transparent glass-ceramic is 0.2 to 1mm.
72. The transparent glass-ceramic according to claim 67, wherein the thickness of the transparent glass-ceramic is 0.3 to 0.9mm.
73. The transparent glass-ceramic according to claim 67, wherein the thickness of the transparent glass-ceramic is 0.5 to 0.8mm.
74. The transparent glass-ceramic according to claim 67, wherein the thickness of the transparent glass-ceramic is 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
75. The matrix glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：60～80％；Al 2 O 3 ：3～15％；Li 2 O: greater than or equal to 5% but less than 10%; na (Na) 2 O：4～8％；ZrO 2 : greater than 6.7% but less than or equal to 15%, where SiO 2 /ZrO 2 5.0 to 11.9.
76. The substrate glass according to claim 75, further comprising, in weight percent: p (P) 2 O 5 : 0-5%; and/or ZnO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 3 percent; and/or Ln 2 O 3 :0 to 2 percent; and/or clarifying agent: 0 to 2 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
77. The substrate glass according to claim 75 or 76, wherein the composition is expressed in weight percent, wherein: siO (SiO) 2 /ZrO 2 6.0 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 4.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.0-18.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-5.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.10 to 0.27.
78. The substrate glass according to claim 75 or 76, wherein the composition is expressed in weight percent, wherein: siO (SiO) 2 /ZrO 2 6.5 to 11.9; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 5.0 to 13.3; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 7.5-15.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-4.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.12 to 0.25.
79. The substrate glass of claim 75 or 76, whereinThe composition is characterized by comprising the following components in percentage by weight: siO (SiO) 2 /ZrO 2 7.0 to 11.0; and/or (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 11.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-13.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.5; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.14 to 0.25.
80. The substrate glass according to claim 75 or 76, wherein the composition is expressed in weight percent, wherein: (SiO) 2 +Li 2 O)/(ZrO 2 +P 2 O 5 ) 6.0 to 10.5; and/or (SiO) 2 +Al 2 O 3 +Na 2 O)/Li 2 O is 8.5-11.0; and/or (ZrO) 2 +Al 2 O 3 )/Li 2 O is 1.0-3.0; and/or (Li) 2 O+Na 2 O)/(SiO 2 +ZrO 2 ) 0.15 to 0.23.
81. The substrate glass according to claim 75 or 76, wherein the composition comprises, in weight percent: siO (SiO) 2 : 62-78%; and/or Al 2 O 3 : 5-12%; and/or Li 2 O: greater than or equal to 6% but less than 10%; and/or Na 2 O:4 to 7.5 percent; and/or P 2 O 5 :1 to 4.5 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 13%; and/or ZnO:0 to 1.5 percent; and/or MgO:0 to 1.5 percent; and/or B 2 O 3 :0 to 3 percent; and/or K 2 O:0 to 2 percent; and/or Ln 2 O 3 :0 to 1 percent; and/or clarifying agent: 0 to 1 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
82. The method according to claim 75 or 76The matrix glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 : 64-75%; and/or Al 2 O 3 : 5-10%; and/or Na 2 O:4.5 to 7 percent; and/or P 2 O 5 :1.5 to 4 percent; and/or ZrO 2 : greater than 6.7% but less than or equal to 12%; and/or ZnO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or B 2 O 3 :0 to 2 percent; and/or K 2 O:0 to 1 percent; and/or Ln 2 O 3 :0 to 0.5 percent; and/or clarifying agent: 0 to 0.5 percent of Ln, the Ln 2 O 3 Is La (La) 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of the following.
83. The substrate glass of claim 75 or 76, wherein the substrate glass has a refractive index of 1.510 to 1.530.
84. A glass ceramic molded article comprising the transparent glass ceramic according to any one of claims 38 to 74.
85. A glass cover sheet comprising the transparent glass-ceramic product according to any one of claims 1 to 37, and/or the transparent glass-ceramic according to any one of claims 38 to 74, and/or the base glass according to any one of claims 75 to 83, and/or the glass-ceramic formed article according to claim 84.
86. Glass component, characterized in that it comprises a transparent glass-ceramic product according to any one of claims 1 to 37, and/or a transparent glass-ceramic according to any one of claims 38 to 74, and/or a matrix glass according to any one of claims 75 to 83, and/or a glass-ceramic shaped body according to claim 84.
87. A display device comprising the transparent glass-ceramic article according to any one of claims 1 to 37, and/or the transparent glass-ceramic according to any one of claims 38 to 74, and/or the matrix glass according to any one of claims 75 to 83, and/or the glass-ceramic formed article according to claim 84, and/or the glass cover plate according to claim 85, and/or the glass component according to claim 86.
88. An electronic device comprising the transparent glass-ceramic product according to any one of claims 1 to 37, and/or the transparent glass-ceramic according to any one of claims 38 to 74, and/or the matrix glass according to any one of claims 75 to 83, and/or the glass-ceramic formed article according to claim 84, and/or the glass cover plate according to claim 85, and/or the glass component according to claim 86.
89. A method of manufacturing a transparent glass-ceramic article according to any one of claims 1 to 37, characterized in that it comprises the steps of: forming matrix glass, forming transparent microcrystalline glass by the matrix glass through a crystallization process, and forming a transparent microcrystalline glass product by the transparent microcrystalline glass through a chemical strengthening process.
90. The method of claim 89, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 550-700 ℃ and the maintaining time at the crystallization temperature is 0-8 hours.
91. The method of claim 89, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-650 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
92. The method of claim 89, 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.
93. The method of making a transparent glass-ceramic article as recited in claim 92, 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; the holding time at the 2 nd temperature is 0 to 10 hours.
94. The method of making a transparent glass-ceramic article as recited in claim 92, 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 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
95. The method of any one of claims 90 to 94, wherein the chemical strengthening process comprises: immersing transparent glass ceramics in a salt bath of molten Na salt at the temperature of 350-470 ℃ for 1-36 hours; and/or immersing the transparent glass ceramics in a salt bath for melting K salt at the temperature of 360-450 ℃ for 1-36 hours; and/or immersing the transparent glass ceramic in a mixed salt bath of molten K salt and Na salt at the temperature of between 360 and 450 ℃ for 1 to 36 hours.
96. The method of any one of claims 90 to 94, wherein the chemical strengthening process comprises: immersing transparent glass ceramics in salt bath of molten Na salt at 380-460 ℃ for 2-24 hours; and/or immersing the transparent glass ceramics in a salt bath for melting K salt at the temperature of 360-450 ℃ for 2-24 hours; and/or immersing the transparent glass ceramic in a mixed salt bath of molten K salt and Na salt at the temperature of between 360 and 450 ℃ for 2 to 24 hours.
97. The method for producing a transparent glass ceramic according to any one of claims 38 to 74, wherein the method comprises the steps of: forming matrix glass, and then forming transparent microcrystalline glass by the matrix glass through a crystallization process.
98. The method for producing a transparent glass ceramic according to claim 97, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 550-700 ℃ and the maintaining time at the crystallization temperature is 0-8 hours.
99. The method for producing a transparent glass ceramic according to claim 97, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 580-650 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
100. The method for producing a transparent glass ceramic according to claim 97, 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.
101. The method for producing a transparent glass ceramic according to claim 100, 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; the holding time at the 2 nd temperature is 0 to 10 hours.
102. The method for producing a transparent glass ceramic according to claim 100, 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 2 to 15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
103. The method of claim 84, wherein the method comprises grinding or polishing the transparent glass ceramic to form a glass ceramic shaped body, or subjecting the base glass or transparent glass ceramic to a thermal bending or pressing process at a temperature to form a glass ceramic shaped body.
104. The method of producing a glass ceramic molded body according to claim 103, comprising the steps of: performing primary crystallization heat treatment process on the matrix glass, wherein the primary crystallization heat treatment process comprises heating, heat preservation and nucleation, heating, heat preservation and crystallization and cooling to room temperature to form pre-crystallized glass; and carrying out thermal processing molding on the pre-crystallized glass to obtain the microcrystalline glass forming body.
105. The method of producing a glass ceramic molded body according to claim 103, comprising the steps of:
1) Heating and preheating: placing matrix glass or pre-crystallized glass or transparent glass ceramics into a mould, sequentially passing the mould through each heating station in a hot bending machine, keeping the temperature at each station for a certain time, 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) compression molding: the mould is transferred to a forming station after being preheated, a hot bending machine applies certain pressure to the mould, 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 reducing: transferring the die to a cooling station for cooling by station, wherein the cooling temperature is 750-500 ℃, the pressure is 0.01-0.05 MPa, and the time is 40-200 s.
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