CN113402173B - Glass ceramics, glass ceramics product and method for producing the same - Google Patents

Glass ceramics, glass ceramics product and method for producing the same Download PDF

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CN113402173B
CN113402173B CN202110901905.6A CN202110901905A CN113402173B CN 113402173 B CN113402173 B CN 113402173B CN 202110901905 A CN202110901905 A CN 202110901905A CN 113402173 B CN113402173 B CN 113402173B
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CN113402173A (en
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原保平
于天来
李赛
粟勇
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/02—Tempering or quenching glass products using liquid
    • C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details
    • H05K5/03—Covers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses microcrystalline glass, a microcrystalline glass product and a manufacturing method thereof. The microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more. Through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by the invention have lower haze and excellent optical performance, and are suitable for electronic equipment or display equipment with higher requirements.

Description

Glass ceramics, glass ceramics product and method for producing the same
Technical Field
The present invention relates to glass ceramics, and more particularly, to glass ceramics and glass ceramics products having excellent optical properties and a method for manufacturing the same.
Background
In recent years, with the continuous rise and development of consumer electronic products (such as display devices or electronic devices), glass ceramics as a transparent and excellent material have a tendency to be applied to such electronic products. When glass ceramics are used as a front cover plate for display surfaces of electronic products (such as mobile phones, watches, PADs, portable media players, personal computers, cameras, etc.), glass ceramics are required to have excellent optical properties so as to satisfy good display definition of the electronic products. The microcrystalline glass in the prior art has the problems of high haze, low light transmittance and the like, and is difficult to apply to display equipment or electronic equipment with higher requirements.
Disclosure of Invention
The invention aims to provide glass ceramics and glass ceramics products with excellent optical performance.
The technical scheme adopted for solving the technical problems is as follows:
(1) The microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more.
(2) The glass ceramic product according to (1), wherein the glass ceramic product further comprises the following components in percentage by weight: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(3) Microcrystalline glass product, its components are expressed by weight percentage, and is composed of SiO 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0 to 2%, wherein Li 2 O/(ZnO+MgO) is 9.5 or more.
(4) The microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％。
(5) The glass ceramic product according to (4), wherein the glass ceramic product further comprises the following components in percentage by weight: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(6) The microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％，Al 2 O 3 ：2～15％，Li 2 O: 7-15%, wherein the crystalline phase of the microcrystalline glass product contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.
(7) The microcrystalline glass product comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％，Al 2 O 3 ：2～15％，Li 2 O: and 7 to 15% of a glass-ceramic product, wherein the crystal phase contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a weight percentage higher than that of other crystal phases, and the haze of the glass-ceramic product with a thickness of less than 1mm is less than 0.2%.
(8) The glass-ceramic article according to any one of (6) or (7), which comprises the following components in weight percent: znO+MgO: 0-5%; and/or P 2 O 5 +ZrO 2 :1 to 10 percent; and/or Na 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(9) The glass ceramic product according to any one of (1) to (8), wherein the glass ceramic product comprises, in weight percent, one or more of the following 4 cases:
1)Li 2 O/(ZnO+MgO) is 10 to 50, preferably Li 2 O/(ZnO+MgO) is 11 to 40, more preferably Li 2 O/(ZnO+MgO) is 13-30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 at least 26, preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is 28 to 50, more preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is more preferably 30 to 45 (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.1 to 0.8, preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.2 to 0.62, more preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.3 to 0.6, more preferably (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55;
4)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 at least 24, preferably (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is 25 to 50, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is in the range of 26 to 45, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40.
(10) The glass ceramic product according to any one of (1) to (8), wherein the components are represented by weight percent: siO (SiO) 2 :70 to 80%, preferably SiO 2 : 71-76%; and/or Al 2 O 3 :4 to 12%, preferably Al 2 O 3 : 6-11%; and/or Li 2 O:8 to 14%, preferably Li 2 O: 9-13%; and/or zno+mgo:0.1 to 3%, preferably ZnO+MgO:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 :2 to 8%, preferably P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 3%, preferably Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 3%, preferably B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 2 percent; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or BaO: 0-3%, preferably BaO:0 to 1 percent; and/or CaO:0 to 3%, preferably CaO:0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.
(11) The glass ceramic product according to any one of (1) to (8), wherein the components are represented by weight percent: znO:0 to 3%, preferably ZnO:0 to 2%, more preferably ZnO:0 to 1 percent; and/or MgO:0 to 3%, preferably MgO:0 to 2%, more preferably MgO:0 to 1 percent; and/or P 2 O 5 :0 to 5%, preferably P 2 O 5 :0.5 to 5%, more preferably P 2 O 5 :1 to 3%, more preferably P 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 :0 to 7%, preferably ZrO 2 : from 0.5 to 7%, more preferably ZrO 2 :1 to 6%, more preferably ZrO 2 ：1.5～5％。
(12) The glass-ceramic product according to any one of (1) to (8), wherein a crystal phase of the glass-ceramic product contains lithium silicate; and/or quartz and a quartz solid solution; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a higher weight percentage than other crystalline phases, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50 to 80 weight percent of the glass-ceramic product, still more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 75 weight percent of the glass-ceramic product, still more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 70 weight percent of the glass-ceramic product.
(13) The glass-ceramic product according to any one of (1) to (8), wherein the lithium disilicate crystal phase accounts for 15-40% by weight of the glass-ceramic product, preferably the lithium disilicate crystal phase accounts for 20-35% by weight of the glass-ceramic product, and more preferably the lithium disilicate crystal phase accounts for 25-35% by weight of the glass-ceramic product; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramic product; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramics, preferably Dan Yingji quartz solid solution crystalline phase accounts for 7-20% of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0-10% of the weight of the glass-ceramic product, preferably the lithium silicate crystalline phase accounts for 0-7% of the weight of the glass-ceramic product, and more preferably the lithium silicate crystalline phase accounts for 0-5% of the weight of the glass-ceramic product.
(14) The glass-ceramic product according to any one of (1) to (8), wherein the glass-ceramic product has a four-point bending strength of 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more; and/or the surface stress of the glass-ceramic product is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or the glass-ceramic product has a falling ball test height of 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more; and/or the fracture toughness of the glass ceramic product is 1MPa 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 glass ceramic product has a Vickers hardness of 730kgf/mm 2 Above, preferably 750kgf/mm 2 Above, more preferably 780kgf/mm 2 The above; and/or the crystallinity of the glass-ceramic product is 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystallite size of the glass-ceramic product is 40nm or less, preferably 30nm or less, more preferably 25nm or less.
(15) The glass-ceramic product according to any one of (1) to (8), wherein the glass-ceramic product has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less, with a thickness of 1mm or less; and/or a glass-ceramic product having a thickness of 1mm or less, wherein the average transmittance at a wavelength of 400 to 800nm is 87% or more, preferably 88% or more, and more preferably 89% or more; and/or a glass ceramic product having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a glass-ceramic product having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less; and/or the glass ceramic product having a thickness of 1mm or less has a drop resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and still more preferably 2000mm or more.
(16) The glass-ceramic article according to (15), wherein the thickness of the glass-ceramic article 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.
(17) The glass-ceramic product according to any one of (1) to (8), further comprising: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(18) The microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more.
(19) The glass ceramic according to (18), which comprises the following components in percentage by weight: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(20) Microcrystalline glass comprises the following components in percentage by weight 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0 to 2%, wherein Li 2 O/(ZnO+MgO) is 9.5 or more.
(21) The microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％。
(22) The glass ceramic according to (21), which comprises the following components in percentage by weight: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(23) The microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％，Al 2 O 3 ：2～15％，Li 2 O: 7-15%, wherein the crystalline phase of the microcrystalline glass contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.
(24) The microcrystalline glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％，Al 2 O 3 ：2～15％，Li 2 O: 7-15%, wherein the crystalline phase of the glass-ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a weight percentage higher than that of other crystalline phases, and the haze of the glass-ceramics with a thickness of less than 1mm is less than 0.2%.
(25) The glass-ceramic according to any one of (23) and (24), further comprising, in weight percent: znO+MgO: 0-5%; and/or P 2 O 5 +ZrO 2 :1 to 10 percent; and/or Na 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO:05 percent; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(26) The glass ceramic according to any one of (18) to (25), wherein the glass ceramic comprises, in weight percent, one or more of the following 4 cases:
1)Li 2 O/(ZnO+MgO) is 10 to 50, preferably Li 2 O/(ZnO+MgO) is 11 to 40, more preferably Li 2 O/(ZnO+MgO) is 13-30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 at least 26, preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is 28 to 50, more preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is more preferably 30 to 45 (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.1 to 0.8, preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.2 to 0.62, more preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.3 to 0.6, more preferably (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55;
4)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 at least 24, preferably (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is 25 to 50, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is in the range of 26 to 45, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40.
(27) The glass ceramic according to any one of (18) to (25), wherein the components are represented by weight percent: siO (SiO) 2 ：70About 80%, preferably SiO 2 : 71-76%; and/or Al 2 O 3 :4 to 12%, preferably Al 2 O 3 : 6-11%; and/or Li 2 O:8 to 14%, preferably Li 2 O: 9-13%; and/or zno+mgo:0.1 to 3%, preferably ZnO+MgO:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 :2 to 8%, preferably P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 3%, preferably Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 3%, preferably B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 2 percent; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or BaO: 0-3%, preferably BaO:0 to 1 percent; and/or CaO:0 to 3%, preferably CaO:0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.
(28) The glass ceramic according to any one of (18) to (25), wherein the components are represented by weight percent: znO:0 to 3%, preferably ZnO:0 to 2%, more preferably ZnO:0 to 1 percent; and/or MgO:0 to 3%, preferably MgO:0 to 2%, more preferably MgO:0 to 1 percent; and/or P 2 O 5 :0 to 5%, preferably P 2 O 5 :0.5 to 5%, more preferably P 2 O 5 :1 to 3%, more preferably P 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 :0 to 7%, preferably ZrO 2 : from 0.5 to 7%, more preferably ZrO 2 :1 to 6%, more preferably ZrO 2 ：1.5～5％。
(29) The glass-ceramic according to any one of (18) to (25), wherein a crystal phase of the glass-ceramic contains lithium silicate; and/or quartz and a quartz solid solution; and/or petalite, preferably, the crystalline phase in the glass-ceramic contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite has a higher weight percentage than other crystalline phases, more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 50 to 80 weight percent of the glass-ceramic, still more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 75 weight percent of the glass-ceramic, still more preferably, the total content of the lithium disilicate and the petalite crystalline phase accounts for 55 to 70 weight percent of the glass-ceramic.
(30) The glass ceramic according to any one of (18) to (25), wherein the lithium disilicate crystal phase accounts for 15 to 40 weight percent of the glass ceramic, preferably the lithium disilicate crystal phase accounts for 20 to 35 weight percent of the glass ceramic, and more preferably the lithium disilicate crystal phase accounts for 25 to 35 weight percent of the glass ceramic; and/or the petalite crystal phase accounts for 30-55% of the glass ceramics in weight, preferably the petalite crystal phase accounts for 35-55% of the glass ceramics in weight, more preferably the petalite crystal phase accounts for 35-50% of the glass ceramics in weight; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramics, preferably Dan Yingji quartz solid solution crystalline phase accounts for 7-20% of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0-10% of the glass ceramics by weight, preferably the lithium silicate crystalline phase accounts for 0-7% of the glass ceramics by weight, and more preferably the lithium silicate crystalline phase accounts for 0-5% of the glass ceramics by weight.
(31) The glass-ceramic according to any one of (18) to (25), wherein the glass-ceramic has a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystallite size of the glass ceramics is 40nm or less, preferably 30nm or less, preferably 25nm or less; and/or the glass ceramic body has a ball height of 1700mm or more, preferably 1900mm or more, more preferably 2000mm or more; and/or the glass ceramic has a Vickers hardness of 650kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above; and/or the glass-ceramic has a thermal expansion coefficient of 65X 10 -7 /K～85×10 -7 K; and/or the refractive index of the glass ceramics is 1.5300-1.5420.
(32) The glass-ceramic according to any one of (18) to (25), wherein the glass-ceramic has a thickness of 1mm or less and a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or glass ceramics having a thickness of 1mm or less, and an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or glass ceramics having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or glass ceramics having a thickness of 1mm or less, and an average light-B-value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less.
(33) The glass ceramic according to (32), wherein the thickness of the 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.
(34) The glass-ceramic according to any one of (18) to (25), further comprising: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(35) The substrate glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more.
(36) The matrix glass according to (35), which further comprises, in weight percent: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
(37) The substrate glass comprises the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0 to 2 percent.
(38) Matrix glass, the components of which are represented by weight percentage and are composed of SiO 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0-2%.
(39) The matrix glass according to any one of (35) to (38), wherein the matrix glass comprises, in weight percent, one or more of the following 4 cases:
1)Li 2 O/(ZnO+MgO) is 10 to 50, preferably Li 2 O/(ZnO+MgO) is 11 to 40, more preferably Li 2 O/(ZnO+MgO) is 13-30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 at least 26, preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is 28 to 50, more preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is more preferably 30 to 45 (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.1 to 0.8, preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.2 to 0.62, more preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.3 to 0.6, more preferably (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55;
4)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 at least 24, preferably (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is 25 to 50, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is in the range of 26 to 45, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40.
(40) The matrix glass according to any one of (35) to (38), wherein the components are represented by weight percent: siO (SiO) 2 :70 to 80%, preferably SiO 2 : 71-76%; and/or Al 2 O 3 :4 to 12%, preferably Al 2 O 3 : 6-11%; and/or Li 2 O:8 to 14%, preferably Li 2 O: 9-13%; and/or zno+mgo:0.1 to 3%, preferably ZnO+MgO:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 :2 to 8%, preferably P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 3%, preferably Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 3%, preferably B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 3%, preferably K 2 O:0 to 2 percent; and/or SrO: 0-3%, preferably SrO:0 to 1 percent; and/or BaO: 0-3%, preferably BaO:0 to 1 percent; and/or CaO:0 to 3%, preferably CaO:0 to 1 percent; and/or TiO 2 :0 to 3%, preferably TiO 2 :0 to 1 percent; and/or clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.
(41) The matrix glass according to any one of (35) to (38)The glass comprises the following components in percentage by weight: znO:0 to 3%, preferably ZnO:0 to 2%, more preferably ZnO:0 to 1 percent; and/or MgO:0 to 3%, preferably MgO:0 to 2%, more preferably MgO:0 to 1 percent; and/or P 2 O 5 :0 to 5%, preferably P 2 O 5 :0.5 to 5%, more preferably P 2 O 5 :1 to 3%, more preferably P 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 :0 to 7%, preferably ZrO 2 : from 0.5 to 7%, more preferably ZrO 2 :1 to 6%, more preferably ZrO 2 ：1.5～5％。
(42) The matrix glass according to any one of (35) to (38), which has a thermal expansion coefficient of 50X 10 -7 /K～70×10 -7 And/or refractive index of 1.5200-1.5300.
(43) The base glass according to any one of (35) to (37), further comprising: niO:0 to 4%, preferably NiO:0.1 to 3 percent; and/or Ni 2 O 3 :0 to 4%, preferably Ni 2 O 3 :0.1 to 3 percent; and/or CoO: 0-2%, preferably CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0 to 2%, preferably Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0 to 7%, preferably Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0 to 4%, preferably MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0 to 8%, preferably Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0 to 8%, preferably Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0 to 4%, preferably Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0 to 8%, preferably Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 :0 to 4%, preferably CeO 2 ：0.5～3％。
(44) The glass cover plate is made of the microcrystalline glass product of any one of (1) to (17), and/or made of the microcrystalline glass of any one of (18) to (34), and/or made of the matrix glass of any one of (35) to (43).
(45) Glass components made of the glass-ceramic product of any one of (1) to (17), and/or made of the glass-ceramic of any one of (18) to (34), and/or made of the matrix glass of any one of (35) to (43).
(46) A display device comprising the glass-ceramic product according to any one of (1) to (17), and/or comprising the glass-ceramic according to any one of (18) to (34), and/or comprising the matrix glass according to any one of (35) to (43), and/or comprising the glass cover plate according to (44), and/or comprising the glass component according to (45).
(47) An electronic device comprising the glass-ceramic product according to any one of (1) to (17), and/or comprising the glass-ceramic according to any one of (18) to (34), and/or comprising the matrix glass according to any one of (35) to (43), and/or comprising the glass cover plate according to (44), and/or comprising the glass component according to (45).
(48) The method for producing a glass ceramic product according to any one of (1) to (17), comprising the steps of: generating matrix glass, forming microcrystalline glass on the matrix glass through a crystallization process, and forming a microcrystalline glass product on the microcrystalline glass through a chemical strengthening process.
(49) The method for producing a glass-ceramic product according to (48), wherein the base glass is produced into a glass-ceramic molded body, and the glass-ceramic molded body is crystallized to form a glass-ceramic product, and the glass-ceramic is chemically strengthened to form a glass-ceramic product, or the glass-ceramic is produced into a glass-ceramic molded body, and the glass-ceramic molded body is chemically strengthened to form a glass-ceramic product.
(50) The method for producing a glass-ceramic article according to (48), 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 600-750 ℃, preferably 650-720 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(51) The method for producing a glass-ceramic article according to (48), wherein the crystallization process comprises the steps of: the nucleation process is carried out at a 1 st temperature, followed by the crystal growth process at a 2 nd temperature, the 1 st temperature being 470 to 600 ℃, the holding time at the 1 st temperature being 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature being 600 to 750 ℃, the holding time at the 2 nd temperature being 0 to 10 hours, preferably 0.5 to 6 hours.
(52) The method for producing a glass-ceramic article according to (48), wherein the crystallization process comprises the steps of: the nucleation process is performed at a 1 st temperature, and then the crystal growth process is performed at a 2 nd temperature and a 3 rd temperature, wherein the 1 st temperature is 470 to 550 ℃, the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature is 570 to 630 ℃, the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours, the 3 rd temperature is 650 to 750 ℃, and the holding time at the 3 rd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
(53) The method of manufacturing a glass-ceramic article according to (48), the chemical strengthening process comprising: the glass ceramics are immersed in the salt bath of molten Na salt at the temperature of 320 ℃ to 470 ℃ for 6 to 20 hours, the preferable temperature range is 360 ℃ to 460 ℃, and the preferable time range is 8 to 13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 340-450 ℃ for 1-24 hours, preferably for 2-10 hours; and/or the glass ceramics are immersed in a salt bath of mixed salt of molten K salt and molten Na salt at the temperature of 340-500 ℃ for 1-24 hours, and the preferable time range is 2-10 hours.
(54) The method for producing a glass ceramic according to any one of (18) to (34), comprising the steps of: and generating matrix glass, and forming microcrystalline glass on the matrix glass through a crystallization process.
(55) The method for producing a glass ceramic according to (54), wherein a glass matrix is produced as a glass molded body, and then the glass ceramic is formed on the glass matrix molded body by a crystallization process.
(56) The method for producing glass-ceramic according to (54), 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 600-750 ℃, preferably 650-720 ℃, and the maintaining time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(57) The method for producing glass-ceramic according to (54), wherein the crystallization process comprises the steps of: the nucleation process is carried out at a 1 st temperature, followed by the crystal growth process at a 2 nd temperature, the 1 st temperature being 470 to 600 ℃, the holding time at the 1 st temperature being 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature being 600 to 750 ℃, the holding time at the 2 nd temperature being 0 to 10 hours, preferably 0.5 to 6 hours.
(58) The method for producing glass-ceramic according to (54), wherein the crystallization process comprises the steps of: the nucleation process is performed at a 1 st temperature, and then the crystal growth process is performed at a 2 nd temperature and a 3 rd temperature, wherein the 1 st temperature is 470 to 550 ℃, the holding time at the 1 st temperature is 0 to 24 hours, preferably 2 to 15 hours, the 2 nd temperature is 570 to 630 ℃, the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours, the 3 rd temperature is 650 to 750 ℃, and the holding time at the 3 rd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
The beneficial effects of the invention are as follows: through reasonable component design, the microcrystalline glass and microcrystalline glass products obtained by the invention have lower haze and excellent optical performance, and are suitable for electronic equipment or display equipment with higher requirements.
Detailed Description
The glass ceramics and glass ceramics products of the present invention are materials having a crystalline phase and a glass phase, as opposed to amorphous solids. The crystalline phases of glass ceramics and glass ceramics articles can be distinguished by the angle of the peaks that occur in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.
Through repeated experiments and researches, the inventors of the present invention have obtained the glass ceramics or glass ceramics products of the present invention at a low cost by specifying the content and the content ratio of the specific components constituting the glass ceramics and glass ceramics to specific values and precipitating the specific crystal phases.
The ranges of the respective components (ingredients) of the matrix glass, the glass-ceramic and the glass-ceramic product of the present invention are described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of substances of the matrix glass, or the glass-ceramic product, in terms of the composition of the oxides. The term "composition converted into oxide" as used herein means that the total amount of oxide used as a raw material of the constituent components of the matrix glass, glass ceramic or glass ceramic product of the present invention is 100% based on the total amount of oxide when the oxide, composite salt, hydroxide or the like is decomposed and converted into oxide by melting. In the present specification, the term "glass" refers to a base glass before crystallization, and the term "glass ceramics" refers to a glass ceramics after crystallization of a base glass, and a glass ceramics product refers to a glass ceramics after chemical strengthening.
Unless otherwise indicated in a particular context, numerical ranges set forth herein include upper and lower limits, and "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values set forth in the defined range. The term "about" as used herein means that the formulations, parameters and other quantities and characteristics are not, and need not be, exact, and may be approximated and/or greater or lesser, if desired, reflecting tolerances, conversion factors, measurement errors and the like. The term "and/or" as referred to herein is inclusive, e.g. "a; and/or B ", means either a alone, B alone, or both a and B.
In the glass ceramics or glass ceramics products of the invention, the crystalline phase contains lithium silicate; and/or quartz and a quartz solid solution; and/or petalite. The lithium silicate crystal phase of the invention comprises lithium monosilicate and/or lithium disilicate. The crystalline phase of the present invention is sometimes referred to as a crystal.
In some embodiments of the invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains lithium disilicate, the content of which has a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the invention.
In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains petalite, the petalite content having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains lithium silicate in an amount that is higher in weight percent than the other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise quartz and a quartz solid solution, the content of quartz and quartz solid solution having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains lithium disilicate and petalite, the combined content of lithium disilicate and petalite having a higher weight percent than other crystalline phases, resulting in excellent performance of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains lithium silicate and petalite, the combined content of lithium silicate and petalite having a higher weight percentage than the other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article contain lithium disilicate and quartz and a solid solution of quartz, the total content of lithium disilicate and quartz and solid solution of quartz having a higher weight percent than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article contain petalite and quartz and a solid solution of quartz, the combined content of petalite and quartz and solid solution of quartz having a higher weight percent than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments, the lithium disilicate crystalline phase comprises 15 to 40 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium disilicate crystalline phase comprises 20 to 35 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium disilicate crystalline phase comprises 25 to 35 weight percent of the glass-ceramic or glass-ceramic article.
In some embodiments, the quartz and quartz solid solution crystalline phases comprise 5 to 25 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the quartz and quartz solid solution crystalline phases comprise 7 to 20 weight percent of the glass-ceramic or glass-ceramic article.
In some embodiments, the petalite crystalline phase comprises 30-55% by weight of the glass-ceramic or glass-ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 55 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 50 weight percent of the glass ceramic or glass ceramic article.
In some embodiments, the lithium silicate crystalline phase comprises 0 to 10 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium silicate crystalline phase comprises 0 to 7 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium silicate crystalline phase comprises 0 to 5% by weight of the glass-ceramic or glass-ceramic article.
In some embodiments, the combined content of lithium disilicate and petalite crystalline phases is 50 to 80 weight percent of the glass ceramic or glass ceramic article. In some embodiments, the combined content of lithium disilicate and petalite crystalline phases is 55 to 75 weight percent of the glass ceramic or glass ceramic article. In some embodiments, the combined content of lithium disilicate and petalite crystalline phases is 55 to 70 weight percent of the glass ceramic or glass ceramic article.
SiO 2 Is the basic component of the matrix glass, the glass ceramics and the glass ceramics products, is one of the main components forming the crystal phase of the glass ceramics and the glass ceramics products, if SiO 2 The content of (2) is lower than 68%, and the formed crystals in the microcrystalline glass and microcrystalline glass products are less and are easy to thicken, so that the falling ball test height and haze of the microcrystalline glass and microcrystalline glass products are affected. Thus, siO 2 The lower limit of the content is 68%, preferably 70%, more preferably 71%. On the other hand, if SiO 2 If the content exceeds 82%, the glass melting temperature is high, the melting is difficult, and the glass is not easy to form in the manufacturing process, so that the uniformity and consistency of the glass are affected. Thus, siO 2 The upper limit of the content is 82%, preferably 80%, more preferably 76%. In some embodiments, about 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%, 80.5%, 81%, 81.5%, 82% SiO may be included 2 。
Al 2 O 3 Is a component forming a glass network structure and is one of components forming petalite crystal phase, which is favorable for chemical strengthening of glass and improves the falling ball test height of microcrystalline glass products, but if the content is less than 2%, the effect is not good. Thus, al 2 O 3 The lower limit of the content is 2%, preferably 4%, more preferably 6%. On the other hand, if Al 2 O 3 If the content exceeds 15%, the glass will have reduced meltability and devitrification resistance, and crystals will tend to increase during crystallization of the glass, thereby reducing the strength of the glass-ceramic product and glass-ceramic. Thus, al 2 O 3 The upper limit of the content is 15%, preferably 12%, more preferably 11%. In some embodiments, about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, and/or,14%, 14.5%, 15% Al 2 O 3 。
Li 2 O is an essential component for forming crystals of the glass ceramics and glass ceramics products in the invention, and is also an essential component for participating in chemical strengthening and improving the mechanical property of the glass ceramics products, if Li 2 If the O content is less than 7%, the microcrystalline glass and the microcrystalline glass product have insufficient crystal content, and the strength of the microcrystalline glass and the microcrystalline glass product is reduced. Thus Li 2 The lower limit of the O content is 7%, preferably 8%, more preferably 9%. On the other hand, if Li is contained excessively 2 O, the haze of the glass-ceramic and glass-ceramic article increases. Thus Li 2 The upper limit of the O content is 15%, preferably 14%, more preferably 13%. In some embodiments, about 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% Li may be included 2 O。
ZnO and MgO can promote the formation of quartz and quartz solid solution in the glass ceramics, and when the total content of ZnO and MgO is too high, the haze of the glass ceramics and glass ceramics products is increased. Therefore, zno+mgo is limited to 5% or less. If ZnO and MgO are too low, the microcrystalline glass and the microcrystalline glass product cannot form quartz and a quartz solid solution under the condition of low haze, and the excellent mechanical properties of the microcrystalline glass and the microcrystalline glass product are not facilitated to be realized. Therefore, it is preferable that ZnO+MgO is 0.1 to 5%, more preferable that ZnO+MgO is 0.1 to 3%, and still more preferable that ZnO+MgO is 0.2 to 1.5%. In some embodiments, the content of ZnO is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0 to 1%. In some embodiments, the MgO content is preferably 0 to 3%, more preferably 0 to 2%, and even more preferably 0 to 1%. In some embodiments, the value of zno+mgo may be 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%. 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%, 1.5%, 2%, 2.5%, 3% ZnO may be included. 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%, 1.5%, 2%, 2.5%, 3% MgO may be included.
The inventors have found from a number of experimental studies that in some embodiments of the invention Li is 2 Ratio Li between O and the sum of ZnO and MgO content ZnO+MgO 2 The O/(ZnO+MgO) is controlled to be more than 9.5, so that the haze and the value of the microcrystalline glass and microcrystalline glass products can be reduced, and the light transmittance of the microcrystalline glass and microcrystalline glass products can be improved. Therefore, li is preferred 2 O/(ZnO+MgO) is 9.5 or more, more preferably Li 2 O/(ZnO+MgO) is 10 to 50. Further, by controlling Li 2 O/(ZnO+MgO) is in the range of 11-40, the Vickers hardness of the microcrystalline glass and microcrystalline glass products can be further improved, the chemical strengthening performance of the microcrystalline glass can be improved, the ion exchange layer depth and the surface stress of the microcrystalline glass products can be improved, and the drop resistance of the microcrystalline glass products can be improved. Therefore, li is more preferable 2 O/(ZnO+MgO) is 11 to 40, and Li is more preferable 2 O/(ZnO+MgO) is 13 to 30. In some embodiments, li 2 The value of O/(zno+mgo) may be 9.5, 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.
P 2 O 5 And ZrO(s) 2 Has nucleation effect when the total content P 2 O 5 +ZrO 2 Above 1%, the desired crystals of the present invention are advantageously formed to achieve excellent mechanical and optical properties of the glass-ceramics and glass-ceramic articles of the present invention. If the total content P 2 O 5 +ZrO 2 When the content exceeds 10%, the crystal grain size in the glass ceramics or glass ceramics products becomes large, the haze and transmittance of the glass ceramics and glass ceramics are increased, and the mechanical properties are lowered. Thus, P 2 O 5 +ZrO 2 1 to 10%, preferably P 2 O 5 +ZrO 2 From 2 to 8%, more preferably P 2 O 5 +ZrO 2 3 to 7 percent. In some embodiments, P 2 O 5 +ZrO 2 The value of (2) may be 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%.
P 2 O 5 Can form crystal nucleus in glass, promote crystal formation, improve the strength of microcrystalline glass and microcrystalline glass products, and is favorable for reducing the haze of microcrystalline glass and microcrystalline glass products. On the other hand, if too much P is contained 2 O 5 Devitrification is easily generated in the process of generating the matrix glass, and the molding difficulty of the glass is increased. Thus, P 2 O 5 The content of (c) is preferably 0 to 5%, more preferably 0.5 to 5%, even more preferably 1 to 3%, and still more preferably 1.5 to 2.5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% P may be included 2 O 5 。
ZrO 2 Has the function of crystallizing and separating out to form crystal nucleus, can refine crystal grains and reduce the haze of microcrystalline glass and microcrystalline glass products. On the other hand, if ZrO is contained in an excessive amount 2 The haze of glass ceramics and glass ceramics products instead increases. Thus, zrO 2 The content of (2) is preferably 0 to 7%, more preferably 0.5 to 7%, still more preferably 1 to 6%, still more preferably 1.5 to 5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7% ZrO may be included 2 。
In some embodiments, siO 2 、Al 2 O 3 And Li (lithium) 2 Total content of O SiO 2 +Al 2 O 3 +Li 2 O and ZrO 2 Ratio between the contents of (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 The four-point bending strength and the fracture toughness of the microcrystalline glass and microcrystalline glass products can be improved by controlling the temperature to be more than 26. Therefore, it is preferable that (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is 26 or more, more preferably (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 28 to 50. Further, by controlling (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 30-45, the Vickers hardness and falling ball test height of the microcrystalline glass and microcrystalline glass products can be further improved, and the ion exchange layer depth and surface stress of the microcrystalline glass products can be improved. Therefore, it is more preferable that (SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 Is 30 to 45, more preferably (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5. In some embodiments, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 The values of (c) may be 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50.
Na 2 O can reduce the haze of glass ceramics and glass ceramics products, improve the glass phase in the glass ceramics, and is beneficial to the hot bending forming of the glass ceramics, but if too much Na is contained 2 O, can lead to coarsening of crystals in the glass-ceramics and glass-ceramic products, and instead, to deterioration of haze and transmittance of the glass-ceramics and glass-ceramic products. Thus, na 2 The content of O is in the range of 0 to 4%, preferably 0.5 to 3%, more preferably 0.5 to 2.5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% Na may be included 2 O。
In some embodiments, the (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) The control is in the range of 0.1-0.8, which is favorable for forming lithium disilicate and petalite crystalline phases in the crystallization process of the matrix glass, and improves the crystallinity and the Vickers hardness of the microcrystalline glass and microcrystalline glass products. Therefore, it is preferable that (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.1 to 0.8, more preferably (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.2 to 0.62. Further, by controlling (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) In the range of 0.3-0.6, the crystal grains can be refined, the drop resistance of the microcrystalline glass and microcrystalline glass products can be improved, and the falling ball test height of the microcrystalline glass products and microcrystalline glass can be improved. Therefore, it is more preferable that (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) Is 0.3 to 0.6, and more preferably (Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55. In some embodiments, (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) The values of (2) may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8.
B 2 O 3 The glass phase in the glass can be increased to be beneficial to the hot bending forming of the glass ceramics without participating in the formation of crystals, but if too much B is contained 2 O 3 The grains are promoted to grow rapidly, and the crystallization treatment is not easy to control. Thus B 2 O 3 The content is in the range of 0 to 4%, preferably 0.5 to 3%, more preferably 0.5 to 2.5%. 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% B may be included 2 O 3 。
In some embodiments, the (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 The grain size of the microcrystalline glass and microcrystalline glass products can be reduced by controlling the grain size to be more than 24, the value of |B| and haze are reduced, and the light transmittance is improved. Therefore, it is preferable that (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 More preferably at least 24 (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 25 to 50. Further, a (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 The crystallization degree and the drop resistance of the glass ceramics and glass ceramics products can be improved by controlling the temperature within the range of 26-45. Therefore, it is more preferable that (SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 Is 26 to 45, more preferably (SiO) 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40. In some embodiments of the present invention, in some embodiments,
(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 the values of (3) may be 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50.
K 2 O can reduce the viscosity of the glass and promote crystal formation during heat treatment, but if K is contained in excess 2 And O, the coarsening of glass crystals is easy to cause, and the transmittance and falling ball test height of microcrystalline glass and microcrystalline glass products are reduced. Thus, K is 2 The content of O is 4% or less, preferably 3% or less, and more preferably 2% 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%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% K may be included 2 O。
SrO is an optional component that improves the low-temperature meltability of glass and suppresses crystallization during glass molding, but is unfavorable for glass molding when the content is too large. Accordingly, the SrO content in the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably not containing SrO. 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% SrO may be included.
BaO is an optional component that helps to improve the glass forming properties of the glass, and when present in excess, is detrimental to glass forming. Accordingly, in the present invention, the BaO content is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably no BaO is contained. 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% BaO may be included.
CaO can increase the hardness of the glass, and the glass is easy to generate milk when being molded when the content is excessive. Therefore, the CaO content in the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and even more preferably no CaO is contained. In some embodiments, caO may be included at 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%.
TiO 2 Is an optional component which helps to reduce the melting temperature of glass and improve chemical stability, and in the invention, the glass comprises less than 5% of TiO 2 The crystallization process of the glass can be easily controlled, and TiO is preferable 2 The content of (2) is 3% or less, more preferably 1% or less. In some embodiments, it is further preferred that TiO is absent 2 . 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% TiO may be included 2 。
In some embodiments, the glass, glass-ceramic, or glass-ceramic article may further include 0-2% fining agent to improve the bubble removal ability of the glass, glass-ceramic, or glass-ceramic article. Such clarifying agents include, but are not limited toOn Sb 2 O 3 、SnO 2 SnO and CeO 2 One or more of (a), 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%, 0.1%, 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%.
In order to achieve desirable mechanical, optical, production, chemical strengthening, and other excellent properties for the glass, glass-ceramic, or glass-ceramic articles of the present invention, it is preferred in some embodiments of the present invention that F is absent; and/or does not contain Ta 2 O 5 。
PbO and As 2 O 3 Is a toxic substance, and even a small amount of the addition does not meet the environmental requirements, so that the invention in some embodiments preferably does not contain PbO and As 2 O 3 。
In some embodiments of the present invention, a colored base glass, glass-ceramic, or glass-ceramic article can be prepared by including a colorant that can cause the base glass, glass-ceramic, or glass-ceramic article to exhibit different colors, the colorant including: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 :0 to 4 percent. The weight percentage of the colorant and the function thereof are as follows:
the brown or green matrix glass, glass ceramics or glass ceramics products prepared by the invention use NiO and Ni 2 O 3 Or Pr (Pr) 2 O 5 Is a colorant. NiO and Ni 2 O 3 To do it withThe colorant is used for preparing brown or green matrix glass, microcrystalline glass or microcrystalline glass products, the two components can be used singly or mixed, the respective content of the two components is generally below 4 percent, preferably below 3 percent, if the content exceeds 4 percent, the colorant cannot be well dissolved in the matrix glass, the microcrystalline glass or the microcrystalline glass products, the lower limit of the respective content is above 0.1 percent, such as below 0.1 percent, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass products is not obvious. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO, or Ni may be included 2 O 3 . When used in combination, niO and Ni 2 O 3 The total amount is generally 4% or less, and the lower limit of the total amount is 0.1% or more. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO and Ni may be included 2 O 3 . Pr is used 2 O 5 The colorant used alone is generally 8% or less, preferably 6% or less, and the lower limit of the colorant is 0.4% or more, for example, less than 0.4%, and the color of the substrate glass, glass ceramic or glass ceramic product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7 may be included.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Pr 2 O 5 。
The blue matrix glass, glass ceramics or glass ceramics products prepared by the invention use CoO or Co 2 O 3 As the colorant, the two colorant components may be used singly or in combination, and the respective contents thereof are generally 2% or less, preferably 1.8% or less, and if the content exceeds 2%, the colorant is not well dissolved in the base glass, the glass-ceramic or the glass-ceramic product, and the respective lower limit of the content thereof is 0.05% or more, such as less than 0.05%, and the color of the base glass, the glass-ceramic or the glass-ceramic product is not obvious. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO or Co may be included 2 O 3 . When used in combination, coO and Co 2 O 3 The total amount is not more than 2%, and the lower limit of the total amount is not less than 0.05%. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO and Co may be included 2 O 3 。
The yellow matrix glass, glass ceramics or glass ceramics products prepared by the invention use Cu 2 O or CeO 2 As the colorant, the two colorant components are used singly or in combination, the lower limit of the respective content is more than 0.5 percent, such as less than 0.5 percent, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious, and the Cu is used singly 2 O is 4% or less, preferably 3% or less, and if the content exceeds 4%, the matrix glass is liable to be devitrified. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3 may be included. 7%, 3.8%, 3.9%, 4.0% Cu 2 O. Using CeO alone 2 The content is generally 4% or less, preferably 3% or less, for example, the content exceeds 4%, and the substrate glass, glass ceramics or glass ceramics is poor in gloss. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO may be included 2 . At the same time, a small amount of CeO 2 The CeO has the effect of removing bubbles when being added into glass 2 The glass can also be used as a clarifying agent. When the two colorants are mixed and used, the total amount thereof is generally 4% or less, and the lower limit of the total amount is 0.5% or more. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO may be included 2 And Cu 2 O。
The black or soot-colored matrix glass, glass ceramics or glass ceramics products prepared by the invention independently use Fe 2 O 3 Is a colorant; or Fe is used 2 O 3 And CoO, two colorants used in combination; or Fe is used 2 O 3 And Co 2 O 3 Two colorants used in combination; or Fe is used 2 O 3 Coloring agents used in combination of three types, coO and NiO; or Fe is used 2 O 3 、Co 2 O 3 And three kinds of NiO. The colorants for preparing black and soot-colored base glass, glass-ceramic or glass-ceramic articles are mainly Fe 2 O 3 Coloring at a level of 7% or less, preferably 5% or less, with a lower limit of 0.2% or more, and in some embodiments may comprise about 0.2%, 0.3%, 04%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0% Fe 2 O 3 . CoO and Co 2 O 3 Can absorb visible light and deepen the coloring degree of matrix glass, glass ceramics or glass ceramics products, and is generally similar to Fe 2 O 3 The respective contents are 0.6% or less and the lower limit is 0.2% or more when mixed. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% CoO and/or Co may be included 2 O 3 . NiO absorbs visible light and can enhance the coloration degree of the base glass, glass ceramic or glass ceramic product, and the content thereof is generally 1% or less when mixed for use, and the total lower limit is 0.2% or more. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% NiO may be included.
The purple matrix glass, glass ceramics or glass ceramics products prepared by the invention use MnO 2 As the colorant, a colorant is used in an amount of generally 4% or less, preferably 3% or less, and the lower limit of the amount is 0.1% or more, for example, less than 0.1%, and the color of the base glass, glass-ceramic or glass-ceramic product is not noticeable. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% MnO may be included 2 。
The pink matrix glass, microcrystalline glass or microcrystalline glass product prepared by the invention uses Er 2 O 3 The content of the colorant is generally 8% or less, preferably 6% or less. From the following componentsIn rare earth element Er 2 O 3 The coloring efficiency is low, and when the content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, but the cost is increased, and the lower limit of the content is more than 0.4%, for example, less than 0.4%, so that the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Er may be included 2 O 3 。
The purple-red matrix glass, glass ceramics or glass ceramics products prepared by the invention use Nd 2 O 3 The content of the colorant is generally 8% or less, preferably 6% or less. Due to rare earth element Nd 2 O 3 The coloring efficiency is low, the use content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, the cost is increased, the lower limit of the content is more than 0.4%, for example, less than 0.4%, and the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd may be included 2 O 3 。
The red matrix glass, microcrystalline glass or microcrystalline glass product prepared by the invention uses Er 2 O 3 、Nd 2 O 3 And MnO 2 Mixing colorant, er ion in glass has absorption at 400-500nm, mn ion has absorption at 500nm, nd ion has strong absorption at 580nm, mixing three substances,can be used for preparing red matrix glass, microcrystalline glass or microcrystalline glass products due to Er 2 O 3 And Nd 2 O 3 Coloring rare earth with weaker coloring power Er 2 O 3 The usage amount is within 6 percent, nd 2 O 3 The usage amount is within 4%, mnO 2 The coloring is strong, the amount of the coloring agent is within the range of 2%, and the lower limit of the total amount of the coloring agents to be mixed is more than 0.9%.
The term "not containing" or "0%" as used herein means that the compound, molecule, element, or the like is not intentionally added as a raw material to the base glass, glass ceramic, or glass ceramic product of the present invention; however, it is within the scope of the present invention that certain other impurities or components may be present that are not intentionally added as raw materials and/or equipment for producing the base glass, glass-ceramic or glass-ceramic article, and that may be present in minor or trace amounts in the final base glass, glass-ceramic or glass-ceramic article.
In some embodiments of the invention, the crystalline phases in the glass-ceramic and glass-ceramic products contain lithium disilicate and petalite, and/or quartz and quartz solid solutions, which provide high strength for the glass-ceramic and glass-ceramic products of the invention, and the glass-ceramic and glass-ceramic products have high fracture toughness; the falling ball test height and four-point bending strength of the microcrystalline glass and microcrystalline glass products become large; the haze decreases and the light transmittance increases. The glass ceramics of the invention has excellent chemical strengthening performance, and can obtain more excellent mechanical strength through chemical strengthening. 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 product or glass-ceramic has a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more.
The grain size and the kind of the microcrystalline glass or the microcrystalline glass product can influence the haze and the transmittance of the microcrystalline glass or the microcrystalline glass product, and the smaller the grain, the higher the transmittance; the smaller the haze, the higher the 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 0.15% or less, more preferably 0.12% or less. In some embodiments, the glass-ceramic article or glass-ceramic has a grain size of 40nm or less, preferably 30nm or less, more preferably 25nm or less.
In some embodiments, the glass-ceramic or glass-ceramic article of the present invention exhibits a high transmittance in the visible light range, and in some embodiments a glass-ceramic article having a thickness of 1mm or less, or a glass-ceramic 400-800 nm, preferably has an average light transmittance of 89% or more. In some preferred embodiments, the glass ceramic product or glass ceramic having a thickness of 1mm or less preferably has a light transmittance of 550nm of 91% or more.
In some embodiments, the antimicrobial component may be added to a base glass, glass-ceramic, or glass-ceramic article. The glass-ceramic or glass-ceramic article described herein may be used in applications such as kitchen or restaurant countertops, where exposure to harmful bacteria is likely. Antimicrobial components that may be added to the matrix glass, glass-ceramic, or glass-ceramic article include, but are not limited to, ag, agO, cu, cuO, cu 2 O, etc. In some embodiments, the antimicrobial component is present in an amount of 2% or less, preferably 1% or less, alone or in combination.
The matrix glass, glass-ceramic and glass-ceramic products of the present invention can be produced and manufactured by the following methods:
generating a matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, and the mixture is carried out in an electric furnace or a gas furnace for 5 to 24 hours at the temperature of 1400 to 1650 ℃ according to the melting difficulty of the glass composition. Melting, stirring to make it uniform, cooling to proper temperature, casting into mould, and slowly cooling.
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, 2 stages, or 3 stages. In order to obtain desired physical properties of the glass ceramics, a preferred crystallization process is:
the crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after the 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 600 to 750 ℃, more preferably 650 to 720 ℃, 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 by 2 stages, the nucleation process is performed at the 1 st temperature and then the crystal growth process is performed at the 2 nd temperature. The 1 st temperature is preferably 470 to 600℃and the 2 nd temperature is preferably 600 to 750 ℃. 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.
In the crystallization treatment in 3 stages, the nucleation process is performed at the 1 st temperature, and then the crystal growth process is performed at the 2 nd and 3 rd temperatures, wherein the 1 st temperature is preferably 470 to 550 ℃, the 2 nd temperature is preferably 570 to 630 ℃, and the 3 rd temperature is preferably 650 to 750 ℃. 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 at the 3 rd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.
The holding time of 0 hours means that the temperature starts to be lowered or raised again less than 1 minute after the temperature thereof is reached.
In some embodiments, the matrix glass or glass-ceramic described herein can be manufactured into shaped bodies, including but not limited to sheets, by various processes including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by float or roll processes as are known in the art.
The base glass or the glass ceramic of the present invention may be a glass molded product of a sheet material manufactured by a method such as grinding or polishing, but the method for manufacturing the glass molded product is not limited to these methods.
The matrix glass or glass ceramic molded article of the present invention can be formed into various shapes by a method such as hot bending or pressing at a certain temperature, and is not limited to these methods.
The substrate glass, glass-ceramic, and glass-ceramic articles of the present invention can have any thickness that is reasonably useful.
The microcrystalline glass of the invention not only improves mechanical properties through precipitation crystallization, but also can obtain higher strength through forming a compressive stress layer, thereby preparing microcrystalline glass products.
In some embodiments, the substrate glass or glass-ceramic may be processed into a sheet and/or shaped (e.g., punched, heat bent, etc.), shaped, polished and/or polished, and then chemically strengthened by a chemical strengthening process.
The chemical strengthening is ion exchange method. During ion exchange, smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" with larger metal ions of the same valence state in close proximity to the matrix glass or glass-ceramic. And replacing smaller ions with larger ions to construct compressive stress in the matrix glass or the microcrystalline glass, so as to form a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metalIons (e.g. Na + 、K + 、Rb + 、Cs + Plasma), ion exchange is performed by immersing the matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions that are used to displace smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag + 、Tl + 、Cu + And the like may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths of the same or different composition, with washing and/or annealing steps between immersion.
In some embodiments, the matrix glass or glass-ceramic may be produced by immersing a molten Na salt (e.g., naNO) in a temperature of about 320℃to 470 DEG C 3 ) Ion exchange is carried out in a salt bath of about 6 to 20 hours, preferably at a temperature in the range of 360 to 460 c, preferably for a time in the range of 8 to 13 hours. In this embodiment, na ions replace part of Li ions in the matrix glass or the glass-ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be prepared by melting a K-salt (e.g., KNO) at a temperature immersed in the range of about 340 ℃ to 450 DEG C 3 ) The ion exchange is carried out in the salt bath for 1 to 24 hours, preferably for 2 to 10 hours. 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 340 ℃ to 500 DEG C 3 ) And molten Na salts (e.g. NaNO) 3 ) The ion exchange is carried out in the mixed salt bath for 1 to 24 hours, preferably for 2 to 10 hours.
In some embodiments, there are also ion implantation methods for implanting ions into the surface layer of the base glass or glass-ceramic, and thermal strengthening methods for heating the base glass or glass-ceramic and then rapidly cooling.
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 EEL57D is adopted, the haze tester EEL57D is prepared by a sample with the thickness of less than 1mm, and the haze tester EEL57D 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.
[ surface stress ] and [ depth of ion exchange layer ]
Surface stress measurement was performed by using a glass surface stress meter SLP-2000.
Ion exchange layer depth measurements were performed using a glass surface stress meter SLP-2000.
The measurement conditions were calculated by using a sample having a refractive index of 1.54 and an optical elastic constant of 25.3[ (nm/cm)/MPa ].
[ falling ball test height ]
A sample of a glass ceramic product of 150mm by 57mm 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 150mm multiplied by 57mm 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 examples with "body drop height", glass ceramics were the subject of the test. 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 sample is tested by taking ASTM C158-2002 as a standard.
The thickness of the sample 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.
[ 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 set to 100 (N) and the retention time was set to be 100 (N)15 (seconds). The vickers hardness is sometimes referred to simply as hardness in the present invention.
[ coefficient of thermal expansion ]
Coefficient of thermal expansion (alpha) 20℃-300℃ ) The test was performed according to the test method of GB/T7962.16-2010.
[ refractive index ]
Refractive index (n) d ) Tested according to the method of GB/T7962.1-2010.
[ |B|value ]
B-value measurements were performed using Meidad CM-700 d. And (3) respectively carrying out zero calibration and whiteboard calibration on the instrument by using the matched calibration long cylinder and the short cylinder, carrying out an empty test by using the long cylinder after calibration, judging the stability calibration reliability (B is less than or equal to 0.05) of the instrument, and placing the product on the zero long cylinder for testing after the instrument is qualified for calibration.
The value of |b| is the absolute value of the B value.
[ 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.
The microcrystalline glass product has the following properties:
1) In some embodiments, the four-point bending strength of the glass-ceramic article is 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more.
2) In some embodiments, the ion exchange layer depth of the glass-ceramic article is 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more.
3) In some embodiments, the surface stress of the glass-ceramic article is 100MPa or more, preferably 150MPa or more, and more preferably 200MPa or more.
4) In some embodiments, the 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 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 glass-ceramic article has a Vickers hardness of 730kgf/mm 2 Above, preferably 750kgf/mm 2 Above, more preferably 780kgf/mm 2 The above.
7) In some embodiments, the glass-ceramic article has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.
8) In some embodiments, the glass-ceramic article has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.
9) In some embodiments, the glass-ceramic article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% 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.
10 In some embodiments, the glass-ceramic product has a thickness of 1mm or less, and an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, and more preferably 89% 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.
11 In some embodiments, the glass-ceramic product has a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% 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, a glass-ceramic article having a thickness of 1mm or less, and an average light-B-value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, more preferably 0.7 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.
13 In some embodiments, the glass-ceramic product having a thickness of 1mm or less has a shatter resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and even more preferably 2000mm 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.
The microcrystalline glass has the following properties:
1) In some embodiments, the glass-ceramic has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.
2) In some embodiments, the glass-ceramic has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.
3) In some embodiments, the glass-ceramic having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% 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 average transmittance of the glass ceramics having a thickness of 1mm or less at a wavelength of 400 to 800nm is 87% or more, preferably 88% or more, and more preferably 89% 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 glass ceramic has a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% 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 glass-ceramic article has a thickness of 1mm or less and an average light-B-value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, more preferably 0.7 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.
7) In some embodiments, the glass-ceramic body drop height is 1700mm or greater, preferably 1900mm or greater, and more preferably 2000mm or greater.
8) In some embodiments, the glass-ceramic has a Vickers hardness of 650kgf/mm 2 Above, preferably 680kgf/mm 2 The above is more preferably 700kgf/mm 2 The above.
9) In some embodiments, the coefficient of thermal expansion (α) of glass-ceramic 20℃-120℃ ) 65X 10 -7 /K～85×10 -7 /K。
10 In some embodiments, the refractive index of the glass-ceramic (n d ) 1.5300-1.5420.
The substrate glass has the following properties:
1) In some embodiments, the coefficient of thermal expansion (α) of the matrix glass 20℃-120℃ ) 50X 10 -7 /K～70×10 -7 /K。
2) In some embodiments, the refractive index (n d ) 1.5200 to 1.5300.
The microcrystalline glass, microcrystalline glass products and matrix glass have the excellent performances, so that the microcrystalline glass, microcrystalline glass products and matrix glass can be widely manufactured into glass cover plates or glass components; meanwhile, the glass ceramics, glass ceramics products and matrix glass of the invention are applied to electronic devices or display devices, 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, aero-mechanical windows and touch screen, 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.
< glass-ceramic example >
In this example, glass ceramics having compositions shown in tables 3 to 4 were obtained by using the above-described 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 test thickness of the glass ceramic sample in examples was 0.7mm.
Table 3.
Table 4.
< microcrystalline glass article example >
In this example, glass-ceramic products having compositions shown in tables 5 to 6 were obtained by using the above-described method for producing glass-ceramic products. The characteristics of each glass-ceramic product were measured by the test method of the present invention, and the measurement results are shown in tables 5 to 6, with the test thickness of the glass-ceramic product sample in the examples being 0.7mm.
Table 5.
Table 6.

Claims (104)

1. The microcrystalline glass product is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 26 to 38.5, (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55.
2. The glass-ceramic article according to claim 1, further comprising, in weight percent: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
3. A glass ceramic product is characterized in that the components of the glass ceramic product are represented by weight percentage and are SiO 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0 to 2%, wherein Li 2 O/(ZnO+MgO) is 9.5 or more, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 26 to 38.5, (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55.
4. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof, expressed in weight percent, satisfy one or more of the following 3 conditions:
1)Li 2 O/(ZnO+MgO) is 10-50;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 28 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 is more than 24.
5. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof, expressed in weight percent, satisfy one or more of the following 3 conditions:
1)Li 2 O/(ZnO+MgO) is 11-40;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 30 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 25 to 50.
6. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof, expressed in weight percent, satisfy one or more of the following 3 conditions:
1)Li 2 O/(ZnO+MgO) is 13-30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 26 to 45.
7. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof, expressed in weight percent, satisfy the following conditions:
(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40。
8. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: siO (SiO) 2 : 70-80%; and/or Al 2 O 3 : 4-12%; and/or Li 2 O: 8-14%; and/or zno+mgo:0.1 to 3 percent; and/or P 2 O 5 +ZrO 2 : 2-8%; and/or Na 2 O:0.5 to 3 percent; and/or B 2 O 3 :0.5 to 3 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO 2 :0 to 3 percent; and/or clarifying agent: 0 to 1 percent.
9. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: siO (SiO) 2 : 71-76%; and/or Al 2 O 3 : 6-11%; and/or Li 2 O: 9-13%; and/or zno+mgo:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 2 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or TiO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5 percent.
10. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: znO:0 to 3 percent; and/or MgO:0 to 3 percent; and/or P 2 O 5 : 0-5%; and/or ZrO 2 ：0～7％。
11. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: znO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or P 2 O 5 :0.5 to 5 percent; and/or ZrO 2 ：0.5～7％。
12. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: znO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or P 2 O 5 :1 to 3 percent; and/or ZrO 2 ：1～6％。
13. A glass-ceramic product according to any one of claims 1 to 3, characterized in that the components thereof are expressed in weight percent, wherein: p (P) 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 ：1.5～5％。
14. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product comprises lithium silicate in a crystalline phase; and/or quartz and a quartz solid solution; and/or petalite.
15. A glass-ceramic article according to any one of claims 1 to 3, wherein the crystalline phase in the glass-ceramic article comprises lithium disilicate and petalite, the combined content of lithium disilicate and petalite having a higher weight percentage than the other crystalline phases.
16. A glass-ceramic product according to any one of claims 1 to 3, wherein the crystalline phase in the glass-ceramic product comprises lithium disilicate and petalite, the total content of the lithium disilicate and petalite crystalline phases being 50 to 80% by weight of the glass-ceramic product.
17. A glass-ceramic product according to any one of claims 1 to 3, wherein the crystalline phase in the glass-ceramic product comprises lithium disilicate and petalite, the total content of the lithium disilicate and petalite crystalline phases being 55 to 75% by weight of the glass-ceramic product.
18. A glass-ceramic product according to any one of claims 1 to 3, wherein the crystalline phase in the glass-ceramic product comprises lithium disilicate and petalite, the total content of the lithium disilicate and petalite crystalline phases being 55 to 70% by weight of the glass-ceramic product.
19. A glass-ceramic product according to any one of claims 1 to 3, wherein the lithium disilicate crystalline phase comprises 15 to 40% by weight of the glass-ceramic product; and/or petalite crystalline phase accounts for 30-55% of the glass ceramic product by weight; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramic product; and/or the lithium silicate crystalline phase accounts for 0-10% of the weight of the glass ceramic product.
20. A glass-ceramic product according to any one of claims 1 to 3, wherein the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic product; and/or petalite crystalline phase accounts for 35-55% of the glass ceramic product by weight; and/or the quartz and quartz solid solution crystalline phase accounts for 7-20 percent of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0 to 7 percent of the weight of the glass ceramic product.
21. A glass-ceramic product according to any one of claims 1 to 3, wherein the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic product; and/or petalite crystalline phase accounts for 35-50% of the weight of the glass ceramic product; and/or the lithium silicate crystalline phase accounts for 0 to 5 percent of the weight of the glass ceramic product.
22. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a four-point bending strength of 600MPa or more; and/or the ion exchange layer depth of the glass ceramic product is more than 80 mu m; and/or the surface stress of the glass ceramic product is more than 100 MPa; and/or the falling ball test height of the microcrystalline glass product is more than 1400 mm; and/or the fracture toughness of the glass ceramic product is 1MPa m 1/2 The above; and/or the glass ceramic product has a Vickers hardness of 730kgf/mm 2 The above; and/or the crystallinity of the glass ceramic product is more than 50%; and/or the crystallite size of the glass ceramic product is below 40 nm.
23. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a four-point bending strength of 650MPa or more; and/or the ion exchange layer depth of the glass ceramic product is more than 100 mu m; and/or the surface stress of the glass ceramic product is more than 150 MPa; and/or the falling ball test height of the microcrystalline glass product is more than 1500 mm; and/or the fracture toughness of the glass ceramic product is 1.1MPa m 1/2 The above; and/or the glass ceramic product has a Vickers hardness of 750kgf/mm 2 The above; and/or the crystallinity of the glass ceramic product is more than 60%; and/or the crystallite size of the glass ceramic product is below 30 nm.
24. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a four-point bending strength of 700MPa or more; and/or the ion exchange layer depth of the glass ceramic product is more than 120 mu m; and/or the surface stress of the glass ceramic product is more than 200 MPa; and/or the falling ball test height of the microcrystalline glass product is more than 1600 mm; and/or the fracture toughness of the glass ceramic product is 1.2MPa m 1/2 The above; and/or the glass ceramic product has a Vickers hardness of 780kgf/mm 2 The above; and/or the crystallinity of the glass ceramic product is more than 70%; and/or the crystallite size of the glass ceramic product is below 25 nm.
25. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a haze of 0.2% or less with a thickness of 1mm or less; and/or a glass ceramic product having a thickness of 1mm or less, wherein the average transmittance at a wavelength of 400 to 800nm is 87% or more; and/or a glass ceramic product having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 88% or more; and/or a glass ceramic product having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.9 or less; and/or the shatter resistance of the microcrystalline glass product with the thickness of less than 1mm is more than 1500 mm.
26. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a haze of 0.15% or less with a thickness of 1mm or less; and/or a glass ceramic product having a thickness of 1mm or less, wherein the average transmittance at a wavelength of 400 to 800nm is 88% or more; and/or a glass ceramic product having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 90% or more; and/or a glass ceramic product having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.8 or less; and/or the shatter resistance of the microcrystalline glass product with the thickness of less than 1mm is more than 1600 mm.
27. A glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a haze of 0.12% or less, with a thickness of 1mm or less; and/or a glass ceramic product having a thickness of 1mm or less, wherein the average transmittance at a wavelength of 400 to 800nm is 89% or more; and/or a glass ceramic product having a thickness of 1mm or less, and a transmittance at a wavelength of 550nm of 91% or more; and/or a glass ceramic product having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.7 or less; and/or the shatter resistance of the microcrystalline glass product with the thickness of less than 1mm is more than 1800 mm.
28. The glass-ceramic product according to any one of claims 1 to 3, wherein the glass-ceramic product has a shatter resistance of 2000mm or more and a thickness of 1mm or less.
29. The glass-ceramic article according to claim 25, wherein the glass-ceramic article has a thickness of 0.2 to 1mm.
30. The glass-ceramic article according to claim 25, wherein the glass-ceramic article has a thickness of 0.3 to 0.9mm.
31. The glass-ceramic article according to claim 25, wherein the glass-ceramic article has a thickness of 0.5 to 0.8mm.
32. The glass-ceramic article according to claim 25, wherein the glass-ceramic article has a thickness of 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
33. The glass-ceramic article according to claim 1 or 2, further comprising: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4％。
34. The glass-ceramic article according to claim 1 or 2, further comprising: niO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3％。
35. The microcrystalline glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 26 to 38.5, (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55.
36. The glass-ceramic according to claim 35, further comprising, in weight percent: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
37. The microcrystalline glass is characterized by comprising the following components in percentage by weight 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 ：1～10％；Na 2 O：0～4％；B 2 O 3 ：0～4％；K 2 O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO 2 : 0-5%; clarifying agent: 0 to 2%, wherein Li 2 O/(ZnO+MgO) is 9.5 or more, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 26 to 38.5, (Al) 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55.
38. The glass-ceramic according to any one of claims 35 to 37, wherein the composition is one or more of the following 3 conditions, expressed in weight percent:
1)Li 2 O/(ZnO+MgO) is 10-50;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 28 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 is more than 24.
39. The glass-ceramic according to any one of claims 35 to 37, wherein the composition is one or more of the following 3 conditions, expressed in weight percent:
1)Li 2 O/(ZnO+MgO) is 11-40;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 30 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 25 to 50.
40. The glass-ceramic according to any one of claims 35 to 37, wherein the composition is one or more of the following 3 conditions, expressed in weight percent:
1)Li 2 O/(ZnO+MgO) is 13-30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 26 to 45.
41. The glass-ceramic according to any one of claims 35 to 37, wherein the components in weight percent satisfy the following conditions:
(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40.
42. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 : 70-80%; and/or Al 2 O 3 : 4-12%; and/or Li 2 O: 8-14%; and/or zno+mgo:0.1 to 3 percent; and/or P 2 O 5 +ZrO 2 : 2-8%; and/or Na 2 O:0.5 to 3 percent; and/or B 2 O 3 :0.5 to 3 percent; and/or K 2 O:0 to 3 percent; and/or SAnd rO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO 2 :0 to 3 percent; and/or clarifying agent: 0 to 1 percent.
43. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: siO (SiO) 2 : 71-76%; and/or Al 2 O 3 : 6-11%; and/or Li 2 O: 9-13%; and/or zno+mgo:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 2 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or TiO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5 percent.
44. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: znO:0 to 3 percent; and/or MgO:0 to 3 percent; and/or P 2 O 5 : 0-5%; and/or ZrO 2 ：0～7％。
45. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: znO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or P 2 O 5 :0.5 to 5 percent; and/or ZrO 2 ：0.5～7％。
46. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: znO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or P 2 O 5 :1 to 3 percent; and/or ZrO 2 ：1～6％。
47. The glass-ceramic according to any one of claims 35 to 37, wherein the components are expressed in weight percent, and wherein: p (P) 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 ：1.5～5％。
48. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic comprises lithium silicate in a crystalline phase; and/or quartz and a quartz solid solution; and/or petalite.
49. The glass-ceramic according to any one of claims 35 to 37, wherein the crystalline phase in the glass-ceramic contains lithium disilicate and petalite, and the total content of lithium disilicate and petalite has a higher weight percentage than other crystalline phases.
50. The glass-ceramic according to any one of claims 35 to 37, wherein the crystalline phase in the glass-ceramic comprises lithium disilicate and petalite, and the total content of the lithium disilicate and petalite crystalline phases is 50 to 80% by weight of the glass-ceramic.
51. The glass-ceramic according to any one of claims 35 to 37, wherein the crystalline phase in the glass-ceramic comprises lithium disilicate and petalite, and the total content of the lithium disilicate and petalite crystalline phases is 55 to 75% by weight of the glass-ceramic.
52. The glass-ceramic according to any one of claims 35 to 37, wherein the crystalline phase in the glass-ceramic comprises lithium disilicate and petalite, and the total content of the lithium disilicate and petalite crystalline phases is 55 to 70% by weight of the glass-ceramic.
53. The glass-ceramic according to any one of claims 35 to 37, wherein the lithium disilicate crystalline phase comprises 15 to 40% by weight of the glass-ceramic; and/or the petalite crystalline phase accounts for 30-55% of the glass ceramics by weight; and/or the quartz and quartz solid solution crystalline phase accounts for 5-25% of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0-10% of the glass ceramics by weight.
54. The glass-ceramic according to any one of claims 35 to 37, wherein the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic; and/or petalite crystalline phase accounts for 35-55% of the glass ceramics by weight; and/or the quartz and quartz solid solution crystalline phase accounts for 7-20 percent of the weight of the glass ceramics; and/or the lithium silicate crystalline phase accounts for 0 to 7 percent of the weight of the glass ceramics.
55. The glass-ceramic according to any one of claims 35 to 37, wherein the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic; and/or petalite crystalline phase accounts for 35-50% of the glass ceramics by weight; and/or the lithium silicate crystalline phase accounts for 0 to 5 percent of the weight of the glass ceramics.
56. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a crystallinity of 50% or more; and/or the grain size of the glass ceramics is below 40 nm; and/or the falling ball height of the glass ceramic body is more than 1700 mm; and/or the glass ceramic has a Vickers hardness of 650kgf/mm 2 The above; and/or the glass-ceramic has a thermal expansion coefficient of 65X 10 -7 /K～85×10 -7 K; and/or the refractive index of the glass ceramics is 1.5300-1.5420.
57. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a crystallinity of 60% or more; and/or the grain size of the glass ceramics is below 30 nm; and/or the falling ball height of the glass ceramic body is above 1900 mm; and/or the glass ceramic has a Vickers hardness of 680kgf/mm 2 The above.
58. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a crystallinity of 70% or more; and/or the grain size of the glass ceramics is below 25 nm; and/or glass ceramic body falling ballThe height is more than 2000 mm; and/or the glass ceramic has a Vickers hardness of 700kgf/mm 2 The above.
59. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a haze of 0.2% or less at a thickness of 1mm or less; and/or microcrystalline glass with the thickness of less than 1mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 87%; and/or microcrystalline glass with the thickness below 1mm, and the transmittance of 550nm wavelength is above 88%; and/or glass ceramics having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.9 or less.
60. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a haze of 0.15% or less at a thickness of 1mm or less; and/or microcrystalline glass with the thickness below 1mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 88%; and/or microcrystalline glass with the thickness of less than 1mm, wherein the transmittance of 550nm wavelength is more than 90%; and/or glass ceramics having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.8 or less.
61. The glass-ceramic according to any one of claims 35 to 37, wherein the glass-ceramic has a haze of 0.12% or less at a thickness of 1mm or less; and/or microcrystalline glass with the thickness of less than 1mm, wherein the average transmittance of the wavelength of 400-800 nm is more than 89%; and/or microcrystalline glass with the thickness of less than 1mm, wherein the transmittance of 550nm wavelength is more than 91%; and/or glass ceramics having a thickness of 1mm or less, and an average light value of 400 to 800nm of 0.7 or less.
62. The glass-ceramic according to claim 59, wherein the glass-ceramic has a thickness of 0.2 to 1mm.
63. The glass-ceramic according to claim 59, wherein the glass-ceramic has a thickness of 0.3 to 0.9mm.
64. The glass-ceramic according to claim 59, wherein the glass-ceramic has a thickness of 0.5 to 0.8mm.
65. The glass-ceramic of claim 59, wherein the glass-ceramic has a thickness of 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75mm.
66. The glass-ceramic according to claim 35 or 36, further comprising: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O:0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4％。
67. The glass-ceramic according to claim 35 or 36, further comprising: niO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3％。
68. The matrix glass is characterized by comprising the following components in percentage by weight: siO (SiO) 2 ：68～82％；Al 2 O 3 ：2～15％；Li 2 O：7～15％；ZnO+MgO：0.1～5％；P 2 O 5 +ZrO 2 :1 to 10 percent of Li 2 O/(ZnO+MgO) is 9.5 or more, (SiO) 2 +Al 2 O 3 +Li 2 O)/ZrO 2 26 to 38.5，(Al 2 O 3 +ZnO)/(Li 2 O+Na 2 O+ZrO 2 ) 0.4 to 0.55.
69. The substrate glass of claim 68, wherein the composition, expressed in weight percent, further comprises: na (Na) 2 O:0 to 4 percent; and/or B 2 O 3 :0 to 4 percent; and/or K 2 O:0 to 4 percent; and/or SrO: 0-5%; and/or BaO: 0-5%; and/or CaO: 0-5%; and/or TiO 2 : 0-5%; and/or clarifying agent: 0 to 2 percent.
70. The substrate glass according to claim 68 or 69, wherein the composition, expressed in weight percent, satisfies one or more of the following 3 conditions:
1)Li 2 O/(ZnO+MgO) is 10-50;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 28 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 is more than 24.
71. The substrate glass according to claim 68 or 69, wherein the composition, expressed in weight percent, satisfies one or more of the following 3 conditions:
1)Li 2 O/(ZnO+MgO) is 11-40;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 30 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 25 to 50.
72. The substrate glass according to claim 68 or 69, wherein the composition, expressed in weight percent, satisfies one or more of the following 3 conditions:
1)Li 2 O/(Zno+mgo) is 13 to 30;
2)(SiO 2 +Al 2 O 3 +Li 2 O)/ZrO 2 31 to 38.5;
3)(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 26 to 45.
73. The substrate glass according to claim 68 or 69, wherein the composition, expressed in weight percent, satisfies the following conditions:
(SiO 2 +Al 2 O 3 +Na 2 O+B 2 O 3 )/ZrO 2 27 to 40.
74. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: siO (SiO) 2 : 70-80%; and/or Al 2 O 3 : 4-12%; and/or Li 2 O: 8-14%; and/or zno+mgo:0.1 to 3 percent; and/or P 2 O 5 +ZrO 2 : 2-8%; and/or Na 2 O:0.5 to 3 percent; and/or B 2 O 3 :0.5 to 3 percent; and/or K 2 O:0 to 3 percent; and/or SrO:0 to 3 percent; and/or BaO:0 to 3 percent; and/or CaO:0 to 3 percent; and/or TiO 2 :0 to 3 percent; and/or clarifying agent: 0 to 1 percent.
75. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: siO (SiO) 2 : 71-76%; and/or Al 2 O 3 : 6-11%; and/or Li 2 O: 9-13%; and/or zno+mgo:0.2 to 1.5 percent; and/or P 2 O 5 +ZrO 2 : 3-7%; and/or Na 2 O:0.5 to 2.5 percent; and/or B 2 O 3 :0.5 to 2.5 percent; and/or K 2 O:0 to 2 percent; and/or SrO:0 to 1 percent; and/or BaO:0 to 1 percent; and/or CaO:0 to 1 percent; and/or TiO 2 :0 to 1 percent; and/or clarifying agent: 0 to 0.5 percent.
76. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: znO:0 to 3 percent; and/or MgO:0 to 3 percent; and/or P 2 O 5 : 0-5%; and/or ZrO 2 ：0～7％。
77. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: znO:0 to 2 percent; and/or MgO:0 to 2 percent; and/or P 2 O 5 :0.5 to 5 percent; and/or ZrO 2 ：0.5～7％。
78. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: znO:0 to 1 percent; and/or MgO:0 to 1 percent; and/or P 2 O 5 :1 to 3 percent; and/or ZrO 2 ：1～6％。
79. The substrate glass according to claim 68 or 69, wherein the composition is expressed in weight percent, wherein: p (P) 2 O 5 :1.5 to 2.5 percent; and/or ZrO 2 ：1.5～5％。
80. The substrate glass of claim 68 or 69, wherein the substrate glass has a coefficient of thermal expansion of 50 x 10 -7 /K～70×10 -7 And/or refractive index of 1.5200-1.5300.
81. The substrate glass of claim 68 or 69, wherein the substrate glass further comprises: niO:0 to 4 percent; and/or Ni 2 O 3 :0 to 4 percent; and/or CoO:0 to 2 percent; and/or Co 2 O 3 :0 to 2 percent; and/or Fe 2 O 3 : 0-7%; and/or MnO 2 :0 to 4 percent; and/or Er 2 O 3 : 0-8%; and/or Nd 2 O 3 : 0-8%; and/or Cu 2 O：0 to 4 percent; and/or Pr 2 O 5 : 0-8%; and/or CeO 2 ：0～4％。
82. The substrate glass of claim 68 or 69, wherein the substrate glass further comprises: niO:0.1 to 3 percent; and/or Ni 2 O 3 :0.1 to 3 percent; and/or CoO:0.05 to 1.8 percent; and/or Co 2 O 3 :0.05 to 1.8 percent; and/or Fe 2 O 3 :0.2 to 5 percent; and/or MnO 2 :0.1 to 3 percent; and/or Er 2 O 3 :0.4 to 6 percent; and/or Nd 2 O 3 :0.4 to 6 percent; and/or Cu 2 O:0.5 to 3 percent; and/or Pr 2 O 5 :0.4 to 6 percent; and/or CeO 2 ：0.5～3％。
83. Glass cover plate, characterized in that it is made of a glass-ceramic product according to any one of claims 1 to 34 and/or of a glass-ceramic according to any one of claims 35 to 67 and/or of a matrix glass according to any one of claims 68 to 82.
84. Glass components, characterized in that they are made of a glass-ceramic product according to any of claims 1 to 34 and/or of a glass-ceramic according to any of claims 35 to 67 and/or of a matrix glass according to any of claims 68 to 82.
85. Display device, characterized in that it comprises a glass-ceramic product according to any one of claims 1 to 34, and/or comprises a glass-ceramic according to any one of claims 35 to 67, and/or comprises a matrix glass according to any one of claims 68 to 82, and/or comprises a glass cover plate according to claim 83, and/or comprises a glass component according to claim 84.
86. An electronic device comprising a glass-ceramic article according to any one of claims 1 to 34, and/or comprising a glass-ceramic according to any one of claims 35 to 67, and/or comprising a matrix glass according to any one of claims 68 to 82, and/or comprising a glass cover plate according to claim 83, and/or comprising a glass component according to claim 84.
87. The method of manufacturing a glass ceramic product according to any one of claims 1 to 34, comprising the steps of: generating matrix glass, forming microcrystalline glass on the matrix glass through a crystallization process, and forming a microcrystalline glass product on the microcrystalline glass through a chemical strengthening process.
88. The method for producing a glass-ceramic article according to claim 87, wherein a base glass is produced into a glass-ceramic molded article, and then a glass-ceramic is formed on the glass-ceramic molded article by a crystallization process, and then a glass-ceramic article is formed on the glass-ceramic by a chemical strengthening process, or a glass-ceramic molded article is produced from a glass-ceramic molded article, and then a glass-ceramic article is formed on the glass-ceramic molded article by a chemical strengthening process.
89. The method of making a glass-ceramic article according to claim 87, wherein the crystallization process comprises the steps of: heating to a prescribed crystallization temperature, maintaining the temperature for a certain time after reaching the crystallization temperature, and then cooling, wherein the crystallization temperature is 600-750 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
90. The method of making a glass-ceramic article according to claim 87, 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 650-720 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
91. The method of making a glass-ceramic article according to claim 87, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature, the 1 st temperature is 470-600 ℃, the holding time at the 1 st temperature is 0-24 hours, the 2 nd temperature is 600-750 ℃, and the holding time at the 2 nd temperature is 0-10 hours.
92. The method of making a glass-ceramic article according to claim 87, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature, the 1 st temperature is 470-600 ℃, the holding time at the 1 st temperature is 2-15 hours, the 2 nd temperature is 600-750 ℃, and the holding time at the 2 nd temperature is 0.5-6 hours.
93. The method of making a glass-ceramic article according to claim 87, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature and the 3 rd temperature, the 1 st temperature is 470-550 ℃, the holding time at the 1 st temperature is 0-24 hours, the 2 nd temperature is 570-630 ℃, the holding time at the 2 nd temperature is 0-10 hours, the 3 rd temperature is 650-750 ℃, and the holding time at the 3 rd temperature is 0-10 hours.
94. The method of making a glass-ceramic article according to claim 87, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature and the 3 rd temperature, the 1 st temperature is 470-550 ℃, the holding time at the 1 st temperature is 2-15 hours, the 2 nd temperature is 570-630 ℃, the holding time at the 2 nd temperature is 0.5-6 hours, the 3 rd temperature is 650-750 ℃, and the holding time at the 3 rd temperature is 0.5-6 hours.
95. The method of making a glass-ceramic article according to claim 87, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of 320-470 ℃ for 6-20 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 340-450 ℃ for 1-24 hours; and/or the glass ceramics is immersed in a salt bath of mixed salt of molten K salt and molten Na salt for 1 to 24 hours at the temperature of 340 to 500 ℃.
96. The method of making a glass-ceramic article according to claim 87, wherein the chemical strengthening process comprises: immersing the glass ceramics in a salt bath of molten Na salt at the temperature of between 360 and 460 ℃ for 8 to 13 hours; and/or the glass ceramics are immersed in a salt bath of molten K salt at the temperature of 340-450 ℃ for 2-10 hours; and/or the glass ceramics is immersed in a salt bath of mixed salt of molten K salt and molten Na salt for 2 to 10 hours at the temperature of 340 to 500 ℃.
97. The method for producing a glass ceramic according to any one of claims 35 to 67, comprising the steps of: and generating matrix glass, and forming microcrystalline glass on the matrix glass through a crystallization process.
98. The method for producing a glass ceramic according to claim 97, wherein a base glass is produced into a glass molded body, and then the glass molded body is crystallized to form the glass ceramic.
99. The method for producing 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 600-750 ℃, and the maintaining time at the crystallization temperature is 0-8 hours.
100. The method for producing 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 650-720 ℃, and the maintaining time at the crystallization temperature is 1-6 hours.
101. The method for producing glass-ceramic according to claim 97, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature, the 1 st temperature is 470-600 ℃, the holding time at the 1 st temperature is 0-24 hours, the 2 nd temperature is 600-750 ℃, and the holding time at the 2 nd temperature is 0-10 hours.
102. The method for producing glass-ceramic according to claim 97, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature, the 1 st temperature is 470-600 ℃, the holding time at the 1 st temperature is 2-15 hours, the 2 nd temperature is 600-750 ℃, and the holding time at the 2 nd temperature is 0.5-6 hours.
103. The method for producing glass-ceramic according to claim 97, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature and the 3 rd temperature, the 1 st temperature is 470-550 ℃, the holding time at the 1 st temperature is 0-24 hours, the 2 nd temperature is 570-630 ℃, the holding time at the 2 nd temperature is 0-10 hours, the 3 rd temperature is 650-750 ℃, and the holding time at the 3 rd temperature is 0-10 hours.
104. The method for producing glass-ceramic according to claim 97, wherein the crystallization process comprises the steps of: the nucleation process is carried out at the 1 st temperature, then the crystal growth process is carried out at the 2 nd temperature and the 3 rd temperature, the 1 st temperature is 470-550 ℃, the holding time at the 1 st temperature is 2-15 hours, the 2 nd temperature is 570-630 ℃, the holding time at the 2 nd temperature is 0.5-6 hours, the 3 rd temperature is 650-750 ℃, and the holding time at the 3 rd temperature is 0.5-6 hours.
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CN114195394B (en) * 2021-12-24 2022-09-09 深圳市新旗滨科技有限公司 Glass composition, microcrystalline glass, and preparation method and application thereof
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107963815A (en) * 2017-12-01 2018-04-27 成都光明光电股份有限公司 Devitrified glass and its substrate
CN110510879A (en) * 2019-08-21 2019-11-29 成都光明光电股份有限公司 Crystallized glass article, devitrified glass and its manufacturing method
CN111099825A (en) * 2018-10-26 2020-05-05 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN111807706A (en) * 2020-06-29 2020-10-23 成都光明光电股份有限公司 Glass ceramics and glass ceramics product
CN112876082A (en) * 2021-01-28 2021-06-01 李群 Glass ceramics, glass ceramics product and manufacturing method thereof
CN113200678A (en) * 2021-03-18 2021-08-03 常熟佳合显示科技有限公司 Glass material, preparation method thereof and product thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107963815A (en) * 2017-12-01 2018-04-27 成都光明光电股份有限公司 Devitrified glass and its substrate
CN111099825A (en) * 2018-10-26 2020-05-05 成都光明光电股份有限公司 Glass ceramics, glass ceramics product and manufacturing method thereof
CN110510879A (en) * 2019-08-21 2019-11-29 成都光明光电股份有限公司 Crystallized glass article, devitrified glass and its manufacturing method
CN111807706A (en) * 2020-06-29 2020-10-23 成都光明光电股份有限公司 Glass ceramics and glass ceramics product
CN112876082A (en) * 2021-01-28 2021-06-01 李群 Glass ceramics, glass ceramics product and manufacturing method thereof
CN113200678A (en) * 2021-03-18 2021-08-03 常熟佳合显示科技有限公司 Glass material, preparation method thereof and product thereof

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