CN110482866B - Glass ceramic product, glass ceramic and manufacturing method thereof - Google Patents

Glass ceramic product, glass ceramic and manufacturing method thereof Download PDF

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CN110482866B
CN110482866B CN201910774198.1A CN201910774198A CN110482866B CN 110482866 B CN110482866 B CN 110482866B CN 201910774198 A CN201910774198 A CN 201910774198A CN 110482866 B CN110482866 B CN 110482866B
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microcrystalline
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CN110482866A (en
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原保平
于天来
陈雪梅
聂小兵
刘振禹
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides a microcrystalline glass product, which comprises the following components in percentage by weight: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 : 0 to 10 percent. Through reasonable component design, the microcrystalline glass product has high transmittance and low haze, and is suitable for electronic equipment or display equipment.

Description

Glass ceramic product, glass ceramic and manufacturing method thereof
Technical Field
The present invention relates to a microcrystalline glass product and a microcrystalline glass, and particularly to a microcrystalline glass product having high transmittance and low haze, a microcrystalline glass, and a method for producing the same.
Background
The glass ceramics is a material in which crystals are precipitated inside the glass by heat treatment of a matrix glass, has higher mechanical properties than the matrix glass, and has significant advantages in toughness, wear resistance, and the like over general glasses because crystallites are formed in the glass, and further obtains higher strength by chemical strengthening.
Based on the advantages, the microcrystalline glass or the microcrystalline glass product is applied to display equipment or electronic equipment with high requirements on falling resistance, pressure resistance and scratch resistance. Because the microcrystalline glass contains a certain amount of crystals, the haze of the glass can be improved, the transmittance of the glass can be reduced, and the use of equipment with high requirements on the transmittance is not facilitated. Therefore, the development of a microcrystalline glass product with higher strength, low haze and high transmittance becomes a goal pursued by the majority of researchers.
Disclosure of Invention
The invention aims to provide a microcrystalline glass product with higher strength, low haze and high transmittance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) a microcrystalline glass article having the composition, expressed in weight percent, comprising: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％。
(2) The glass-ceramic product according to (1), which comprises the following components in percentage by weight: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2 percent.
(3) Microcrystalline glass product, the composition of which contains SiO 2 、Al 2 O 3 、Li 2 O and Na 2 O, the composition of which is expressed in weight percent, wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, and the haze of a 0.55mm thick glass-ceramic product is 0.3% or less.
(4) Microcrystalline glass product containing SiO 2 、Al 2 O 3 、Li 2 O and Na 2 O is used as an essential component, and the height of the ball drop test of the microcrystalline glass product is more than 1000 mm.
(5) The crystallized glass product according to any one of (3) to (4), which comprises the following components in percentage by weight: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％；ZnO：0～10％；MgO：0～10％；K 2 O：0～10％；SrO：0～5％；BaO：0～5％；TiO 2 ：0～5％；Y 2 O 3 ：0～5％；B 2 O 3 : 0-6%; a clarifying agent: 0 to 2 percent.
(6) The crystallized glass product according to any one of (1) to (5), which comprises the following components in percentage by weight: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
(7) The crystallized glass product according to any one of (1) to (6), which comprises the following components in percentage by weight: ZrO (ZrO) 2 : 0.5 to 6%, preferably ZrO 2 : 1-4%; and/or Li 2 O: 5-7%; and/or P 2 O 5 ：1～4％。
(8) The crystallized glass product of any one of (1) to (7), wherein the composition is represented by weight percentage of (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.17 to 0.30.
(9) The crystallized glass product of any one of (1) to (8), wherein the composition is represented by weight percentage of (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4, preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
(10) The crystallized glass product of any one of (1) to (9), wherein the composition is represented by weight percentage, Li 2 O/Na 2 O is 0.28 to 1.2, and Li is preferable 2 O/Na 2 O is 0.29 to 1.1, and Li is more preferable 2 O/Na 2 O is 0.30 to 1.0.
(11) The crystallized glass product according to any one of (1) to (10), wherein the crystallized glass product having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 88% or more, and more preferably 90% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 85% or more, preferably 89% or more, and more preferably 91% or more.
(12) The crystallized glass product according to any one of (1) to (11), wherein the crystallized glass product has a surface stress of 300MPa or more, preferably 500MPa or more, and more preferably 700MPa or more; and/or the depth of the ion exchange layer is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more.
(13) The crystallized glass product according to any one of (1) to (12), wherein a falling ball test height of the crystallized glass product is 1000mm or more, preferably 1100mm or more, and more preferably 1200mm or more; and/or a fracture toughness of 1MPa m 1/2 Above, preferably 1.3MPa · m 1/2 More preferably 1.5MPa · m or more 1/2 The above; and/or Vickers hardness (H) v ) Is 600kgf/mm 2 Above, preferably 650kgf/mm 2 Above, more preferably 700kgf/mm 2 The above.
(14) The crystallized glass product according to any one of (1) to (13), wherein a crystallinity of the crystallized glass product is 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more; and/or the crystal grain size is 70nm or less, preferably 50nm or less, more preferably 40nm or less, further preferably 30nm or less, and further preferably 20nm or less.
(15) The crystallized glass article according to any one of (1) to (14), wherein a crystal phase of the crystallized glass article contains lithium monosilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals.
(16) The crystallized glass product according to any one of (1) to (15), wherein the crystallized glass product further contains a colorant, and the crystallized glass product can be made to exhibit different colors.
(17) The crystallized glass article according to (16), which contains the following colorants in percentage by weight: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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％。
(18) The crystallized glass product of any one of (16) to (17), wherein the coloring agent contains, in terms of weight percent: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3％。
The invention also provides the microcrystalline glass.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(19) the microcrystalline glass comprises the following components in percentage by weight: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％。
(20) The glass-ceramic according to claim 19, which further comprises, in terms of weight percent: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2 percent.
(21) Microcrystalline glass having a composition comprising SiO 2 、Al 2 O 3 、Li 2 O and Na 2 O, the composition of which is expressed in weight percent, wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) The microcrystalline glass has a thickness of 0.15-0.35 and 0.55mmThe haze is 0.3% or less.
(22) The glass-ceramic according to (21), which comprises the following components in percentage by weight: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％；ZnO：0～10％；MgO：0～10％；K 2 O：0～10％；SrO：0～5％；BaO：0～5％；TiO 2 ：0～5％；Y 2 O 3 ：0～5％；B 2 O 3 : 0-6%; a clarifying agent: 0 to 2 percent.
(23) The crystallized glass according to any one of (19) to (22), which comprises the following components in percentage by weight: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
(24) The crystallized glass according to any one of (19) to (23), which comprises the following components in percentage by weight: ZrO (ZrO) 2 : 0.5 to 6%, preferably ZrO 2 : 1-4%; and/or Li 2 O: 5-7%; and/or P 2 O 5 ：1～4％。
(25) The crystallized glass of any one of (19) to (24), wherein the composition is represented by weight percentage of (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.17 to 0.30.
(26) The crystallized glass according to any one of (19) to (24), which isThe components are expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4, preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
(27) The crystallized glass of any one of (19) to (26), which has a composition comprising, in weight percent, Li 2 O/Na 2 O is 0.28 to 1.2, and Li is preferable 2 O/Na 2 O is 0.29 to 1.1, and Li is more preferable 2 O/Na 2 O is 0.30 to 1.0.
(28) The crystallized glass of any one of (19) to (27), wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and/or microcrystalline glass with a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400-800 nm is more than 85%, preferably more than 88%, and more preferably more than 90%; and/or 0.55mm thick glass ceramics, having a 550nm wavelength transmittance of 85% or more, preferably 89% or more, and more preferably 91% or more.
(29) The crystallized glass of any one of (19) to (28), wherein the crystallized glass has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more; and/or the crystal grain size is 70nm or less, preferably 50nm or less, more preferably 40nm or less, further preferably 30nm or less, and further preferably 20nm or less.
(30) The microcrystalline glass according to any one of (19) to (29), wherein the microcrystalline glass has a refractive index (nd) of 1.500 to 1.540, preferably 1.510 to 1.530; and/or coefficient of thermal expansion (alpha) 20℃-120℃ ) 70 to 120 x 10 -7 Preferably 86 to 100 × 10 in terms of/K -7 /K。
(31) The crystallized glass of any one of (19) to (30), wherein the crystalline phase of the crystallized glass contains lithium monosilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals.
(32) The glass ceramics according to any one of (19) to (31), wherein the glass ceramics further contains a colorant, and the glass ceramics can be made to exhibit different colors.
(33) The glass ceramic according to (32), wherein the glass ceramic has a colorant containing, in terms of weight percent: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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 to 8 percent; and/or CeO 2 ：0～4％。
(34) The glass-ceramic according to any one of (32) to (33), wherein the glass-ceramic has a colorant containing, in terms of weight percent: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3％。
The invention also provides a matrix glass.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(35) a matrix glass, the composition of which, expressed in weight percent, comprises: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％。
(36) The base glass according to (34), which further comprises, in terms of weight percent: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2％。
(37) The matrix glass according to any one of (35) and (36), which comprises, in terms of weight percent: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
(38) The matrix glass according to any one of (35) to (37), which comprises, in terms of weight percent: ZrO (ZrO) 2 : 0.5 to 6%, preferably ZrO 2 : 1-4%; and/or Li 2 O: 5-7%; and/or P 2 O 5 ：1～4％。
(39) The matrix glass according to any one of (35) to (38), wherein the composition is represented by weight percentage of (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.17 to 0.30.
(40) The matrix glass according to any one of (35) to (39), wherein the composition is represented by weight percentage of (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4, preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
(41) The matrix glass according to any one of (35) to (40), wherein the matrix glass comprises, in terms of weight%, Li 2 O/Na 2 O is 0.28 to 1.2, and Li is preferable 2 O/Na 2 O is 0.29 to 1.1, and Li is more preferable 2 O/Na 2 O is 0.30 to 1.0.
(42) The matrix glass according to any one of (35) to (41), wherein the matrix glass has a refractive index (nd) of 1.500 to 1.530, preferably 1.505 to 1.525; and/or coefficient of thermal expansion (alpha) 20℃-120℃ ) 60 to 85 x 10 -7 Preferably 70 to 85 × 10 in terms of/K -7 /K。
(43) The matrix glass according to any one of (35) to (42), wherein the matrix glass further contains a colorant, and the microcrystalline glass product can be rendered into different colors.
(44) The base glass according to (43), wherein the coloring agent comprises, in weight%: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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％。
(45) The base glass according to any one of (43) to (44), wherein the coloring agent comprises, in weight%: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3％。
The invention also provides a glass cover plate.
(46) A glass cover plate made of the crystallized glass product according to any one of (1) to (18), and/or made of the crystallized glass according to any one of (19) to (34), and/or made of the matrix glass according to any one of (35) to (45).
The invention also provides a glass component.
(47) A glass component produced from the glass-ceramic product according to any one of (1) to (18), and/or produced from the glass-ceramic according to any one of (19) to (34), and/or produced from the base glass according to any one of (35) to (45).
The invention also provides a glass display device.
(48) A display device comprising the crystallized glass article according to any one of (1) to (18), and/or comprising the crystallized glass according to any one of (19) to (34), and/or comprising the matrix glass according to any one of (35) to (45), and/or comprising the glass cover plate according to (46).
The invention also provides electronic equipment.
(49) An electronic device comprising the glass-ceramic article according to any one of (1) to (18), and/or comprising the glass-ceramic according to any one of (19) to (34), and/or comprising the matrix glass according to any one of (35) to (45), and/or comprising the glass cover plate according to (46), and/or comprising the glass component according to (47).
The invention also provides a manufacturing method of the microcrystalline glass product.
(50) A method of making a crystallized glass article, the method comprising the steps of:
forming a matrix glass having the composition, expressed in weight percent, comprising: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％；ZnO：0～10％；MgO：0～10％；K 2 O：0～10％；SrO：0～5％；BaO：0～5％；TiO 2 ：0～5％；Y 2 O 3 ：0～5％；B 2 O 3 : 0-6%; a clarifying agent: 0-2%;
and forming microcrystalline glass by crystallizing the matrix glass, and forming a microcrystalline glass product by chemically strengthening the microcrystalline glass.
(51) The method for producing a glass-ceramic article according to (50), wherein the matrix glass comprises, in terms of weight percent, the following components: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4 to 8%, preferably Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1 to 10%, preferably ZrO 2 : 0.5 to 6%, more preferably ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.17 to 0.30; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4, preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2; and/or Li 2 O/Na 2 O is 0.28 to 1.2, and Li is preferable 2 O/Na 2 O is 0.29 to 1.1, and Li is more preferable 2 O/Na 2 O is 0.30 to 1.0.
(52) The method for producing a crystallized glass article according to any one of (50) and (51), wherein the matrix glass comprises, in terms of weight percent, the following components: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0 to 2 percent; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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％。
(53) The method for producing a crystallized glass product according to any one of (50) to (52), wherein the matrix glass comprises the following components by weightExpressed in percent, contains: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3％。
(54) The method for producing a crystallized glass product according to any one of (50) to (53), wherein the crystallization process includes the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 480-700 ℃, preferably 520-600 ℃, and the holding time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(55) The method for producing a crystallized glass product according to any one of (50) to (53), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
(56) The method for manufacturing a crystallized glass article according to (55), wherein the crystallization process includes the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
(57) The method for producing a crystallized glass product according to any one of (50) to (56), wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours, preferably at the temperature of 435-460 ℃ for 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting the K salt at the temperature of 400-450 ℃ for 1-8 hours, wherein the preferable time range is 2-4 hours.
(58) The method for producing a crystallized glass product according to any one of (50) to (57), wherein a crystal phase of the crystallized glass product contains lithium monosilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals.
(59) And (5) according to the method for producing a crystallized glass product of any one of (50) to (58), the crystallized glass product having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 88% or more, and more preferably 90% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 85% or more, preferably 89% or more, more preferably 91% or more; and/or the surface stress of the glass-ceramic product is 300MPa or more, preferably 500MPa or more, more preferably 700MPa or more; and/or the ion exchange layer depth of the crystallized glass product is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more; and/or the height of the microcrystalline glass product in a falling ball test is more than 1000mm, preferably more than 1100mm, and more preferably more than 1200 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m 1/2 Above, preferably 1.3 MPa.m 1/2 More preferably 1.5MPa · m or more 1/2 The above; and/or Vickers hardness (H) of the microcrystalline glass article v ) Is 600kgf/mm 2 Above, preferably 650kgf/mm 2 Above, more preferably 700kgf/mm 2 The above; and/or the crystallite glass product has a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, still more preferably 30nm or less, and yet still more preferably 20nm or less.
(60) The method for producing a crystallized glass product according to any one of (50) to (59), wherein the crystallized glass product has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.
The invention also provides a manufacturing method of the microcrystalline glass.
(61) A method for producing a crystallized glass, comprising the steps of:
forming a matrix glass having the components in weight percentThe ratio, expressed, contains: SiO 2 2 ：50～59.5％；Al 2 O 3 ：15～25％；Li 2 O：4～10％；Na 2 O：5～15％；P 2 O 5 ：0.1～10％；ZrO 2 ：0～10％；ZnO：0～10％；MgO：0～10％；K 2 O：0～10％；SrO：0～5％；BaO：0～5％；TiO 2 ：0～5％；Y 2 O 3 ：0～5％；B 2 O 3 : 0-6%; a clarifying agent: 0 to 2 percent;
and forming microcrystalline glass by the matrix glass through a crystallization process.
(62) The method for producing a glass ceramic according to (61), wherein the matrix glass comprises, in terms of the components by weight percent: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4 to 8%, preferably Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1 to 10%, preferably ZrO 2 : 0.5 to 6%, more preferably ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.15 to 0.35, preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.17 to 0.30; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4, preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2; and/or Li 2 O/Na 2 O is 0.28 to 1.2, and Li is preferable 2 O/Na 2 O is 0.29 to 1.1, and Li is more preferable 2 O/Na 2 O is 0.30 to 1.0.
(63) The method for producing a glass-ceramic according to any one of (60) and (61), wherein the matrix glass comprises, in terms of the components by weight: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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％。
(64) The method for producing a glass-ceramic according to any one of (60) and (61), wherein the matrix glass comprises, in terms of the components by weight: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3％。
(65) The method for producing crystallized glass according to any one of (60) to (64), wherein the crystallization process includes the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 480-700 ℃, preferably 520-600 ℃, and the holding time at the crystallization temperature is 0-8 hours, preferably 1-6 hours.
(66) The method for producing crystallized glass according to any one of (60) to (64), wherein the crystallization process includes the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
(67) The method for producing a crystallized glass according to (66), the crystallization process comprising the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the 2 nd temperature is 0 to 10 hours, preferably 0.5 to 6 hours.
(68) The method for producing a glass ceramics according to any of (60) to (67), wherein the crystalline phase of the glass ceramics contains lithium monosilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals.
(69) According to the process for producing a crystallized glass of any one of (60) to (68), the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and/or a microcrystalline glass product having a thickness of 0.55mm, wherein the average transmittance at a wavelength of 400 to 800nm is 85% or more, preferably 88% or more, and more preferably 90% or more; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 85% or more, preferably 89% or more, more preferably 91% or more; and/or the crystallite size of the glass ceramics is 70nm or less, preferably 50nm or less, more preferably 40nm or less, further preferably 30nm or less, further preferably 20nm or less; and/or the coefficient of thermal expansion (alpha) of the glass-ceramic 20℃-120℃ ) 70 to 120 x 10 -7 Preferably 86 to 100 × 10 in terms of/K -7 /K。
(70) According to the method for producing a glass ceramic of any one of (60) to (69), the degree of crystallinity of the glass ceramic is 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.
The beneficial effects of the invention are: through reasonable component design, the microcrystalline glass and the microcrystalline glass product have high transmittance and low haze, and are suitable for electronic equipment or display equipment.
Detailed Description
The crystallized glass and the crystallized glass article of the present invention are materials having a crystal phase and a glass phase, which are different from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.
The inventors of the present invention have made extensive experiments and studies, and have obtained a crystallized glass or a crystallized glass product of the present invention at a low cost by specifying the content and content ratio of specific components constituting a crystallized glass or a crystallized glass product to specific values and precipitating specific crystal phases.
The ranges of the respective components (components) of the matrix glass, the glass ceramics and the glass ceramics product of the present invention will be described below. In the present specification, unless otherwise specified, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of the substance of the matrix glass, or the glass ceramics product converted into the composition of the oxide. Here, the "composition in terms of oxide" means that when an oxide, a complex salt, a hydroxide, or the like used as a raw material of a composition component of a matrix glass, a glass-ceramic, or a glass-ceramic product of the present invention is decomposed at melting and converted into an oxide, the total amount of the oxide is 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization, the term "glass matrix" refers to a crystallized glass after crystallization, and the term "glass-ceramic product" refers to a chemically strengthened glass-ceramic.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include endpoints, all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means only A, only B, or both A and B.
The crystalline phase in the glass-ceramic or glass-ceramic product of the invention contains lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals, and the like.
The weight percentage of the crystalline phase in the microcrystalline glass or the microcrystalline glass product is 20-80%; in some embodiments, the weight percent ranges from 25 to 70%; in some embodiments, the weight percentage ranges from 30 to 70%.
SiO 2 Is an essential component of the glass of the invention, which is one of the components which form crystals after heat treatment, if SiO 2 When the content of (A) is less than 50%, glass forming performance of the glass is poor and the glass is not easily formed. Thus, SiO 2 The lower limit of the content is 50%, and the preferable lower limit is 52%. If SiO 2 The content of 59.5% or more is not favorable for chemical strengthening of the glass, and the falling ball test height of the glass-ceramic product and the glass-ceramic is reduced. Thus, SiO 2 The upper limit of the content is 59.5%, and the preferable upper limit is 58%. In some embodiments, about 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 59.5% SiO may be included 2 。
Al 2 O 3 The glass is an essential component for forming a glass network structure, the expansion coefficients of matrix glass and microcrystalline glass are reduced, crystal grains can be refined, the haze of the microcrystalline glass and microcrystalline glass products is reduced, the chemical strengthening of the microcrystalline glass is facilitated, and the ion exchange capacity is improved, but if the content of the glass is less than 15%, the effect is not good. Thus, Al 2 O 3 The lower limit of the content is 15%, and the preferable lower limit is 16%. On the other hand, if Al 2 O 3 When the content of (b) exceeds 25%, the degree of difficulty in melting the glass increases, formation of crystals is inhibited, and the fracture toughness and the falling ball test height of the glass-ceramic and the glass-ceramic article are lowered. Thus Al 2 O 3 The upper limit of the content is 25%, preferably 23%. In some embodiments, about 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% Al may be included 2 O 3 。
Li 2 O can reduce the viscosity of the glass and promote the formation of crystals, is an essential component for the composition of a crystal phase and is also a component mainly substituted with sodium and potassium ions in the ion exchange process, can increase the surface stress after chemical strengthening, but can also increase the surface stress after chemical strengtheningIf the content is less than 4%, the effect is not good, and therefore, Li 2 The lower limit of the O content is 4%, and the preferable lower limit is 5%. On the other hand, if Li is contained excessively 2 O, adversely affects the ion exchange layer depth and surface stress of the glass-ceramic article, resulting in a decrease in the strength of the glass-ceramic article. Thus, Li 2 The upper limit of the O content is 10%, preferably 8%, and more preferably 7%. In some embodiments, about 4%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 8%, 9%, 10% Li may be included 2 O。
Na 2 O can reduce the melting temperature of glass raw materials, reduce the solid low-temperature viscosity of the glass, effectively promote the crystal precipitation during the heat treatment of the glass, and is beneficial to the chemical strengthening of the microcrystalline glass, but the glass contains excessive Na 2 And O, the moisture resistance stability of the matrix glass and the microcrystalline glass is reduced, the crystallization speed of the microcrystalline glass is easy to be too high, and the strength of the microcrystalline glass is reduced. Thus, Na 2 The upper limit of the O content is 15%, and the preferable upper limit is 12%. On the other hand, the glass contains too little Na 2 O, the matrix glass and the microcrystalline glass cannot obtain the expected thermal expansion coefficient, are unfavorable for subsequent processing, reduce the Na ion and K ion exchange content in the microcrystalline glass, reduce the surface stress of the microcrystalline glass product, and further reduce the strength of the microcrystalline glass product, so that Na is used for reducing the strength of the microcrystalline glass product 2 The lower limit of the O content is 5%, and the preferable lower limit is 8%. In some embodiments, about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Na may be included 2 O。
The inventor of the invention has found that through controlling SiO 2 、Al 2 O 3 、Na 2 O and Li 2 The introduction of O in a certain proportion can influence the thermal expansion coefficient of the matrix glass and the microcrystalline glass, the hardness, the bending strength and the fracture toughness of the microcrystalline glass and the microcrystalline glass products, especially (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) In the range of 0.15 to 0.35, the matrix glass or the glass ceramics can have a suitable thermal expansion coefficient, and more crystal grains can be obtained after crystallization, and the hardness and fracture toughness of the glass ceramics and the glass ceramics product can be improved, and in some embodiments, (Li) is preferable 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.16 to 0.32, more preferably 0.17 to 0.30, and high bending strength, and in some embodiments, the four-point bending strength is 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more. In some embodiments, (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) May be 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35.
By controlling (Li) in the present invention 2 O+Na 2 O)/Al 2 O 3 The value of (A) is within the range of 0.5-1.4, the chemical strengthening performance of the glass ceramics can be optimized, and the depth and the surface stress of an ion exchange layer of the glass ceramics product, especially (Li) 2 O+Na 2 O)/Al 2 O 3 The value of (B) is preferably in the range of 0.53 to 1.3, and the falling ball test height of the glass-ceramic product can be increased, more preferably (Li) 2 O+Na 2 O)/Al 2 O 3 The value of (b) is 0.55 to 1.2. In some embodiments, (Li) 2 O+Na 2 O)/Al 2 O 3 May be 0.5, 0.53, 0.55, 0.57, 0.60, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.4.
In the present invention, when Li is controlled 2 O and Na 2 O introduction amount ratio Li 2 O/Na 2 When the O is within the range of 0.28-1.2, the crystallization performance of the matrix glass can be optimized, and the microcrystalline glass product have proper grain size, so that the microcrystalline glass and the microcrystalline glass product have excellent performance, preferably Li 2 O/Na 2 O is 0.29 to 1.1, more preferably 0.30 to 1.0, and the height of the ball drop test of the microcrystalline glass and the microcrystalline glass productIn some embodiments, the height of the crystallized glass product in the falling ball test is preferably 1000mm or more, more preferably 1100mm or more, still more preferably 1200mm or more, and still more preferably 1500mm or more. In some embodiments, Li 2 O/Na 2 The value of O may be 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, 0.52, 0.54, 0.56, 0.58, 0.60, 0.62, 0.64, 0.66, 0.68, 0.70, 0.72, 0.74, 0.76, 0.78, 0.80, 0.82, 0.84, 0.86, 0.88, 0.90, 0.92, 0.94, 0.96, 0.98, 1.0, 1.02, 1.04, 1.06, 1.08, 1.10, 1.12, 1.14, 1.16, 1.18, 1.20.
K 2 O is an optional component which contributes to the improvement of the melting property and the moldability of the matrix glass, but if K is contained excessively 2 O, a decrease in chemical stability and an increase in thermal expansion coefficient of the matrix glass or the glass ceramics are easily caused. Thus, K 2 The content of O is 0 to 10%, preferably 0 to 5%. In some embodiments, K may be included at about 0%, greater than 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% 2 O。
ZrO 2 The glass is an optional component in the invention, has the function of crystallizing out to form crystal nucleus, and simultaneously contributes to improving the chemical stability of matrix glass and microcrystalline glass. It was found that ZrO 2 The risk of devitrification of the glass can also be significantly reduced by forming the matrix glass. ZrO in the invention 2 The lower limit of the content is preferably 0.1%, more preferably 0.5%, and further preferably 1%; but if it contains ZrO excessively 2 The devitrification resistance of the matrix glass is rather easily lowered, and at the same time, the difficulty of controlling the crystallization process of the matrix glass is increased. Thus, ZrO 2 The upper limit of the content is 10%, preferably 6%, more preferably 4%. In some embodiments, ZrO may be included at about 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% 2 。
P 2 O 5 Is a component contributing to improvement of the meltability of the matrix glass and can be applied to the matrix glassForm crystal nucleus in glass, raise the heat expansion stability of matrix glass during crystallization, P 2 O 5 The lower limit of the content is preferably 0.1%, more preferably 0.5%, and further preferably 1%; but if it contains P excessively 2 O 5 The devitrification resistance of the matrix glass tends to be lowered, and the mechanical properties of the glass ceramics and glass ceramics products tend to be deteriorated. Thus, P 2 O 5 The upper limit of the content is 10%, preferably 5%, more preferably 4%. In some embodiments, about 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% P may be included 2 O 5 。
MgO contributes to lowering the viscosity of glass, inhibits crystallization of glass during molding, refines crystal grains during crystallization, and has the effect of improving melting performance, and MgO is an optional component in the invention, and the preferable lower limit is 0.5%; however, if the MgO content is too high, devitrification resistance is lowered, and undesirable crystals are obtained after crystallization, resulting in deterioration of the properties of the glass ceramics and glass ceramics products. Therefore, the upper limit of the MgO content is 10%, preferably 5%. In some embodiments, MgO may be included at about 0%, greater than 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
ZnO can improve the melting performance of matrix glass, improve the chemical stability of the matrix glass, refine crystal grains during crystallization, and is an optional component in the invention, and the content is preferably more than 1%; the upper limit of the ZnO content is controlled to 10% or less to prevent the matrix glass from being excessively large in the crystallization process, and therefore, the upper limit of the ZnO content is 10%, preferably 8%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% ZnO may be included.
SrO is an optional component for improving the melting property of the matrix glass and suppressing the devitrification during the shaping of the matrix glass, and in the present invention, SrO is preferably controlled to 5% or less, so that a microcrystalline glass and a microcrystalline glass product can easily have an excellent crystal grain size, and more preferably, the content thereof is 1% or less. In some embodiments, it is preferred not to introduce SrO. In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% SrO may be included.
BaO is an optional component contributing to improvement of glass forming property of the matrix glass, and when the content thereof exceeds 5%, devitrification resistance of the matrix glass is lowered, so that the BaO content is preferably controlled to 5% or less, more preferably 1% or less in the present invention. In some embodiments, it is preferred not to incorporate BaO. In some embodiments, BaO may be included at about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%.
TiO 2 Is an optional component which is helpful for reducing the melting temperature of matrix glass and improving the chemical stability, and TiO less than 5 percent is introduced into the invention 2 The crystallization process of the matrix glass can be easily controlled, and is preferably 1% or less. In some embodiments, it is preferred not to incorporate TiO 2 . In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% TiO may be included 2 。
Y 2 O 3 The content of the glass is 5% or less, preferably 1% or less, although the content is an optional component for improving the hardness and chemical stability of the matrix glass, and the matrix glass tends to be devitrified when the content is too large. In some embodiments, it is preferred not to introduce Y 2 O 3 . In some embodiments, about 0%, greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% Y may be included 2 O 3 。
B 2 O 3 Helps to optimize the melting property of the matrix glass, and when the content thereof is too high, the chemical stability of the matrix glass is lowered, so that B 2 O 3 The content is less than 6%, preferably B 2 O 3 Is 0.1 to 4%, and in some embodiments may comprise about 0%, greater than 0%, 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%, 5.0%, 5.5%, 6% of B 2 O 3 。
Sb 2 O 3 、SnO 2 、SnO、CeO 2 One or more of Sb is added as a clarifying agent 2 O 3 The upper limit of the content is 2%, preferably 1%, more preferably 0.5%. SnO 2 、SnO、CeO 2 The upper limit of the content of each is 2%, preferably 1%, and more preferably 0.5%. In some embodiments, one or more of the above 4 fining agents are 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%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
In some embodiments, As may also be used 2 O 3 The content of each of the clarifying agents is 2% or less, preferably 1% or less, and more preferably 0.5% or less.
In order to obtain suitable grain size and crystalline phase type in the present invention, La may be introduced in some embodiments 2 O 3 、Cs 2 O、Tb 2 O 3 、GeO 2 And CaO, the content of each of these components alone or in combination is preferably 2% or less. PbO and As 2 O 3 Are toxic substances and are not environmentally friendly even when added in small amounts, and thus the present invention preferably does not contain PbO and As in some embodiments 2 O 3 。
In some embodiments of the present invention, a colored matrix glass, glass-ceramic, or glass-ceramic article is prepared by adding a colorant to a raw material, wherein the colorant comprises: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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 content of the colorant in percentage by weight and the function thereof are detailed as follows:
NiO and Ni are used for preparing the brown or green matrix glass, the microcrystalline glass or the microcrystalline glass product 2 O 3 Or Pr 2 O 5 Is a colorant. NiO and Ni 2 O 3 For the colouring agent, for the preparation of a brown or green matrix glass, glass ceramic or glass ceramic product, the two components can be used individually or in admixture, each in a content of generally less than 4%, preferably less than 3%, and if the content exceeds 4%, the colouring agent is not very soluble in the matrix glass, glass ceramic or glass ceramic product, each in a content below 0.1%, such as below 0.1%, and the matrix glass, glass ceramic or glass ceramic product is not visibly coloured. 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 . NiO and Ni, if used in admixture 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% of NiO and Ni may be included 2 O 3 . Using Pr 2 O 5 As a colorant for green matrix glass, glass ceramics or glass ceramics, the colorant is used alone, and the content is generally 8 percentThe content is preferably 6% or less, and the lower limit of the content is 0.4% or more, for example, less than 0.4%, and the color of the matrix glass, the glass ceramics or the glass ceramics product is not conspicuous. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Pr may be included 2 O 5 。
The blue matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses CoO or Co 2 O 3 The two colorant components may be used alone or in combination as a colorant, and their respective contents are generally 2% or less, preferably 1.8% or less, and if the content exceeds 2%, the colorant is not well soluble in the matrix glass, the crystallized glass or the crystallized glass product, and its respective lower limit is 0.05% or more, e.g., less than 0.05%, and the matrix glass, the crystallized glass or the crystallized glass product is not conspicuous in color. 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% of CoO or Co may be included 2 O 3 . CoO and Co, if used in admixture 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% of CoO and Co may be included 2 O 3 。
The yellow matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Cu 2 O or CeO 2 The two colorant components are used alone or in combination as colorant, and have a lower limit of 0.5% or more, such as less than 0.5%, matrix glass, and microcrystalline glassOr the microcrystalline glass product has no obvious color and the Cu is used alone 2 O is 4% or less, preferably 3% or less, and if the content exceeds 4%, the matrix glass is easily crystallized. 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% Cu may be included 2 And O. Using CeO alone 2 The content is generally 4% or less, preferably 3% or less, and if the content exceeds 4%, the substrate glass, the crystallized glass or the crystallized glass product is poor in gloss. In some embodiments, CeO of 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% may be included 2 . At the same time, a small amount of CeO 2 Added to glass with a defoaming effect, CeO 2 Can also be used as a clarifying agent in glass. When two kinds of colorants are used in combination, the total amount is generally 4% or less, and the lower limit of the total amount is 0.5% or more. In some embodiments, CeO of 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% may be included 2 And Cu 2 O。
The black or smoke gray matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention independently uses Fe 2 O 3 Is a colorant; or using Fe 2 O 3 And CoO; or using Fe 2 O 3 And Co 2 O 3 Two kinds ofA colorant used in combination; or using Fe 2 O 3 Three colorants mixed together, CoO and NiO; or using Fe 2 O 3 、Co 2 O 3 And NiO. Colorants for the production of black and smoky grey matrix glass, glass ceramics or glass ceramic articles using predominantly Fe 2 O 3 Coloration, less than 7%, preferably less than 5%, with a lower limit of 0.2% or more, and in some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0% or more of Fe can be included 2 O 3 . CoO and Co 2 O 3 Can absorb visible light to increase the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products, and is generally combined with Fe 2 O 3 The content of each component is 0.6% or less, and the lower limit is 0.2% or more. 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 increase the degree of coloration of the base glass, glass ceramic or glass ceramic product, and is generally used in a mixture in which the content is 1% or less and the lower limit of the total amount is 0.2% or more. In some embodiments, NiO may be included at about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.
The purple matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses MnO 2 As a coloring agent, it is used in an amount of generally 4% or less, preferably 3% or less, and the lower limit thereof is 0.1% or more, for example, less than 0.1%, and the color of the matrix glass, the glass ceramics or the glass ceramics article is not conspicuous. 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 may be included.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 2 。
Er is used in the pink substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention 2 O 3 The content of the colorant used is generally 8% or less, preferably 6% or less. Because of rare earth element Er 2 O 3 The coloring efficiency is low, when the content exceeds 8%, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, and the cost is increased, and the lower limit of the content is more than 0.4%, such as 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% Er may be included 2 O 3 。
The mauve substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Nd 2 O 3 The content of the colorant used 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 is more than 8 percent, 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 percent, such as less than 0.4 percent, 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%, (iii) may be included,6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd 2 O 3 。
Er is used for the red matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention 2 O 3 、Nd 2 O 3 And MnO 2 The mixed colorant, Er ion in the glass has absorption at 400-500nm, Mn ion has absorption mainly at 500nm, Nd ion has strong absorption mainly at 580nm, and the mixture of the three substances can prepare red matrix glass, microcrystalline glass or microcrystalline glass product 2 O 3 And Nd 2 O 3 Coloring rare earth, relatively weak coloring ability, Er 2 O 3 The usage amount is less than 6 percent, Nd 2 O 3 The usage amount is less than 4 percent, MnO 2 The coloring is strong, the usage amount is within 2 percent, and the lower limit of the total amount of the mixed coloring agent is more than 0.9 percent.
The term "not introduced", "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 matrix glass, the glass ceramic or the glass ceramic product of the present invention; it is within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the matrix glass, microcrystalline glass or microcrystalline glass article and may be present in small or trace amounts in the final matrix glass, microcrystalline glass or microcrystalline glass article.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass and microcrystalline glass articles comprises lithium monosilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or quartz crystals; and/or zirconium silicate crystals and the like, which provide high strength to the microcrystalline glass and the microcrystalline glass product of the present invention, and the fracture toughness of the microcrystalline glass and the microcrystalline glass product becomes high; the height of the falling ball test and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product become large. The glass-ceramic of the invention can also be ion exchanged to obtain additional mechanical strength. The invention can make the microcrystalline glass and the microcrystalline glass product obtain proper grain size through reasonable component design, and make the microcrystalline glass and the microcrystalline glass product have high strength.
The grain size and haze of the microcrystalline glass or the microcrystalline glass product can influence the transmittance of the microcrystalline glass or the microcrystalline glass product, namely the light transmittance is influenced, and the smaller the grain is, the higher the transmittance is; the smaller the haze, the higher the transmittance. In some embodiments, the 0.55mm thick devitrified glass article or glass-ceramic has a haze of 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less. In some embodiments, the crystallite glass product or crystallite glass has a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, even more preferably 30nm or less, and even more preferably 20nm or less. On the other hand, it has been found through research that the smaller the difference in refractive index between the crystal phase and the glass phase in the crystallized glass, the higher the transmittance of the crystallized glass or the crystallized glass product.
The crystallized glass or the crystallized glass product of the invention has high transmittance in a visible light range. In some embodiments, the microcrystalline glass product or microcrystalline glass with a thickness of 0.55mm has an average light transmission of 85% or more, preferably 88% or more, and more preferably 90% or more at 400 to 800 nm. In some preferred embodiments, the microcrystalline glass product or microcrystalline glass having a thickness of 0.55mm has a light transmittance of 80% or more, preferably 85% or more, more preferably 89% or more, and still more preferably 91% or more at 550 nm.
In some embodiments, an antimicrobial component may be added to the matrix glass, microcrystalline glass, or microcrystalline glass article.
The matrix glass, the glass-ceramic and the glass-ceramic product of the invention can be produced and manufactured by the following methods:
and (3) generation of matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, the mixture is melted in an electric furnace or a gas furnace within the temperature range of 1250-1650 ℃ for 5-24 hours according to the melting difficulty of glass composition, the mixture is stirred to be uniform, the temperature is reduced to a proper temperature, the mixture is cast into a mold, and the mixture is slowly cooled to obtain the glass.
The matrix glass of the present invention can be shaped by a well-known method. In some embodiments, the matrix glass of the present invention has a refractive index (nd) of 1.500 to 1.530, preferably 1.505 to 1.525.
The matrix glass of the invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass. The crystallization may be performed in 1 stage, or may be performed in 2 stages, and preferably, the crystallization is performed in 2 stages. The treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1 st temperature is referred to as a 1 st crystallization process, and the crystallization process performed at the 2 nd temperature is referred to as a 2 nd crystallization process.
In order to obtain desired physical properties of the glass-ceramic, the preferred crystallization process is:
the above-described crystallization process is performed in 1 stage, and thus 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 reaching the crystallization temperature, the temperature is maintained for a predetermined time, and then the temperature is lowered. The crystallization temperature is preferably 480 to 700 ℃, and the holding time at the crystallization temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours, in order to precipitate a desired crystal phase, more preferably 520 to 600 ℃.
When the crystallization is performed in 2 stages, the 1 st temperature is preferably 480 to 550 ℃, and the 2 nd temperature is preferably 550 to 700 ℃. The holding time at the temperature of 1 st is preferably 0 to 24 hours, more preferably 2 to 15 hours. The holding time at the 2 nd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.
The above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.
In some embodiments, the microcrystalline glass obtained by the crystallization process has a refractive index (nd) of 1.500 to 1.540, preferably 1.510 to 1.530.
In some embodiments, the matrix or glass-ceramic described herein can be fabricated into shaped bodies, including but not limited to sheets, by various processes, including but not limited to slot draw, float, roll, and other sheet forming processes known in the art. Alternatively, the matrix glass or glass-ceramic may be formed by a float process or a roll process as is well known in the art.
The substrate glass or the glass ceramics of the present invention can be produced into a sheet glass molded body by a method such as grinding or polishing, but the method for producing the glass molded body is not limited to these methods.
The matrix glass or glass-ceramic shaped article of the present invention can be produced into various shapes at a certain temperature by a method such as hot bending or press molding, and is not limited to these methods.
The matrix glass, microcrystalline glass, and microcrystalline glass articles of the present invention may have any thickness that is reasonably useful.
The crystallized glass of the present invention can be produced into a crystallized glass product by forming a compressive stress layer to obtain higher strength in addition to improving mechanical properties by precipitation crystallization.
In some embodiments, the substrate glass or glass ceramic may be formed into a sheet, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or scanned, and then chemically strengthened by a chemical strengthening process.
The chemical strengthening method is an ion exchange method. The matrix glass and the glass ceramics of the present invention can be ion-exchanged by a method known in the art. During the ion exchange process, the smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are adjacent to the matrix glass or glass-ceramic. And replacing smaller ions with larger ions to build a compressive stress in the matrix glass or the microcrystalline glass to form a compressive stress layer.
In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na) + 、K + 、Rb + 、Cs + Etc.), ion exchange by immersing the matrix glass or glass ceramic in at least one melt comprising larger metal ionsIn a salt bath of molten salt, the larger metal ions being used to replace the smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag + 、Tl + 、Cu + Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.
In some embodiments, the matrix glass or glass-ceramic may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 430 ℃ to 470 ℃ 3 ) The salt bath is subjected to ion exchange for about 6 to 20 hours, preferably at a temperature of between 435 and 460 ℃ for 8 to 13 hours. In this embodiment, Na ions replace part of Li ions in the matrix glass or the glass ceramics, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 400 ℃ to 450 ℃ 3 ) The salt bath is subjected to ion exchange for 1 to 8 hours, and the preferable time range is 2 to 4 hours.
In some preferred embodiments, the Na salt (e.g., NaNO) is melted at 450 deg.C 3 ) The salt bath of (2) has an ion exchange layer depth of 20 μm or more, preferably 25 μm or more, for about 8 hours.
In some embodiments, there are also an ion implantation method of implanting ions into a surface layer of a base glass or a glass ceramics, and a thermal tempering method of heating a base glass or a glass ceramics and then rapidly cooling it.
The matrix glass, the microcrystalline glass and/or the microcrystalline glass product are tested by the following methods:
[ refractive index ]
The refractive index (nd) was measured according to the method specified in GB/T7962.1-2010.
[ haze ]
A haze tester EEL57D was used, prepared from 0.55mm thick glass samples and tested according to GB 2410-80.
[ grain size ]
And (3) determining by using an SEM (scanning electron microscope), carrying out surface treatment on the microcrystalline glass in HF (hydrofluoric acid), carrying out gold spraying on the surface of the microcrystalline glass, and carrying out surface scanning under the SEM, so as to determine the size of the crystal grains.
[ light transmittance ]
The light transmittances described herein are external transmittances, sometimes simply referred to as transmittances.
The sample is processed into a thickness of 0.55mm, the opposite surfaces are polished in parallel, and the average light transmittance of 400-800 nm is measured by a Hitachi U-41000 spectrophotometer.
The sample was processed to a thickness of 0.55mm and the opposed faces were polished in parallel, and the light transmittance at 550nm was measured by means of a Hitachi U-41000 spectrophotometer.
[ degree of crystallinity ]
The XRD diffraction peaks were compared with the database spectra, and the degree of crystallinity was obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the entire spectrum, and was internally calibrated by using pure quartz crystals.
[ surface stress ] and [ depth of ion exchange layer ]
And (4) measuring the surface stress by using a glass surface stress meter FSM-6000 LEUV.
Ion exchange layer depth was measured using a glass surface stress meter SLP-2000.
The refractive index of the sample was 1.54 and the optical elastic constant was 25.3[ (nm/cm)/MPa, which were used as the measurement conditions.
[ falling ball test height ]
A150X 57X 0.55mm sample was placed on a glass carrier jig, and 132g of a steel ball was dropped from a predetermined height to a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 800mm, and the height was changed in the order of 850mm, 900mm, 950mm, 1000mm and more without breaking. For the examples having the "falling ball test height", a crystallized glass article was used as a test object. The test data recorded as 1000mm in the examples shows that the crystallized glass product was not broken and received an impact even when the steel ball was dropped from the height of 1000 mm.
[ fracture toughness ]
The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, chamfering, grinding and polishing are carried out, after the sample is prepared, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining for 30s, after the indentation is made, the breaking strength of the sample is measured by a three-point bending method.
[ four-point bending Strength ]
The test is carried out by adopting a microcomputer control electronic universal tester CMT6502, the glass specification is 150 multiplied by 57 multiplied by 0.55mm and the ASTM C158-2002 is taken as a standard.
[ Vickers hardness ]
The load (N) when a pyramid-shaped depression was pressed into a test surface by a diamond quadrangular pyramid indenter having an included angle of 136 degrees with respect to the surface was divided by the surface area (mm) calculated from the length of the depression 2 ) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec).
[ expansion coefficient ]
Coefficient of thermal expansion (alpha) 20℃-120℃ ) The test was carried out according to the method specified in GB/T7962.16-2010.
The matrix glass of the present invention has the following properties:
1) in some embodiments, the refractive index (nd) is 1.500 to 1.530, preferably 1.505 to 1.525.
2) In some embodiments, the coefficient of thermal expansion (α) 20℃-120℃ ) 60 to 85 x 10 -7 Preferably 70 to 85 × 10 in terms of/K -7 /K。
The microcrystalline glass has the following properties:
1) in some embodiments, the microcrystalline glass has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.
2) In some embodiments, the crystallite glass has a crystal grain size of 70nm or less, preferably 50nm or less, preferably 40nm or less, more preferably 30nm or less, and even more preferably 20nm or less.
3) In some embodiments, the 0.55mm thick glass ceramic has a haze of 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less.
4) In some embodiments, the microcrystalline glass having a thickness of 0.55mm has an average transmittance of 85% or more, preferably 88% or more, and more preferably 90% or more at a wavelength of 400 to 800 nm.
5) In some embodiments, the 0.55mm thick glass ceramics have a 550nm wavelength transmittance of 85% or more, preferably 89% or more, and more preferably 91% or more.
6) In some embodiments, the microcrystalline glass has a refractive index (nd) of 1.500 to 1.540, preferably 1.510 to 1.530.
7) In some embodiments, the microcrystalline glass has a coefficient of thermal expansion (α) 20℃-120℃ ) 70 to 120 x 10 -7 Preferably 86 to 100 × 10 in terms of/K -7 /K。
The microcrystalline glass product has the following properties:
1) in some embodiments, the surface stress of the microcrystalline glass article is 300MPa or greater, preferably 500MPa or greater, and more preferably 700MPa or greater.
2) In some embodiments, the microcrystalline glass article has a four-point flexural strength of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.
3) In some embodiments, the ion exchange layer depth of the crystallized glass product is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and still more preferably 25 μm or more.
4) In some embodiments, the crystallized glass article has a falling ball test height of 1000mm or more, preferably 1100mm or more, and more preferably 1200mm or more.
5) In some embodiments, the microcrystalline glass article has a fracture toughness of 1 MPa-m 1/2 Above, preferably 1.3MPa · m 1/2 More preferably 1.5MPa · m or more 1/2 The above.
6) In some embodiments, the microcrystalline glass article has a Vickers hardness (H) v ) Is 600kgf/mm 2 Above, preferably 650kgf/mm 2 Above, more preferably 700kgf/mm 2 The above.
7) In some embodiments, the microcrystalline glass product has a crystallinity of 20% or more, preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.
8) In some embodiments, the crystallite glass product has a crystal grain size of 70nm or less, preferably 50nm or less, more preferably 40nm or less, even more preferably 30nm or less, and even more preferably 20nm or less.
9) In some embodiments, the 0.55mm thick microcrystalline glass article has a haze of 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less.
10) In some embodiments, the microcrystalline glass product having a thickness of 0.55mm has an average transmittance of 85% or more, preferably 88% or more, and more preferably 90% or more at a wavelength of 400 to 800 nm.
11) In some embodiments, the 0.55mm thick glass-ceramic product has a 550nm wavelength transmittance of 85% or more, preferably 89% or more, and more preferably 91% or more.
12) In some embodiments, the microcrystalline glass article has a refractive index (nd) of 1.500 to 1.540, preferably 1.510 to 1.530.
13) In some embodiments, the microcrystalline glass article has a coefficient of thermal expansion (α) 20℃-120℃ ) 70 to 120 x 10 -7 Preferably 86 to 100X 10 in terms of/K -7 /K。
The microcrystalline glass, the microcrystalline glass product and the matrix glass have the excellent performances, so that the microcrystalline glass, the microcrystalline glass product and the matrix glass can be widely made into glass cover plates or glass components; meanwhile, the microcrystalline glass product and the matrix glass are applied to electronic equipment or display equipment, such as a mobile phone, a watch, a computer, a touch display screen and the like.
Examples
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided. Many efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. The composition is itself given in weight% on oxide basis and has been standardized to 100%.
The following tables 1-2 show examples of matrix glasses
Table 1.
Figure GDA0003348851710000301
Figure GDA0003348851710000311
Table 2.
Figure GDA0003348851710000312
Examples of the microcrystalline glass are shown in tables 3 to 4 below
Table 3.
Figure GDA0003348851710000321
Table 4.
Figure GDA0003348851710000322
Figure GDA0003348851710000331
Examples of the glass-ceramic product are shown in tables 5 to 6 below
Table 5.
Figure GDA0003348851710000332
Figure GDA0003348851710000341
Table 6.
Figure GDA0003348851710000342
Figure GDA0003348851710000351
Examples of colored glass-ceramic articles are shown in tables 7-9 below
Table 7.
Figure GDA0003348851710000352
Figure GDA0003348851710000361
Table 8.
Figure GDA0003348851710000362
Figure GDA0003348851710000371
Table 9.
Figure GDA0003348851710000372

Claims (125)

1. A microcrystalline glass product, characterized in that its composition, expressed in weight percent, contains: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 : 0 to 10 percent; wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35; the crystalline phase of the microcrystalline glass article comprises lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
2. The glass-ceramic article according to claim 1, characterized in that it further comprises, in percentages by weight: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2 percent.
3. A crystallized glass product, characterized in that its composition contains SiO 2 ：50～59.5%、Al 2 O 3 ：15～25%、Li 2 O: 4 to 10% and Na 2 O: 5 to 15% by weight of a component of (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24-0.35, wherein the haze of the microcrystalline glass product with the thickness of 0.55mm is less than 0.3%; the crystalline phase of the microcrystalline glass article comprises lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
4. A glass-ceramic article according to claim 3, characterized in that its composition, expressed in weight percentage, comprises: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 ：0～10%；ZnO：0～10%；MgO：0～10%；K 2 O：0～10%；SrO：0～5%；BaO：0～5%；TiO 2 ：0～5%；Y 2 O 3 ：0～5%；B 2 O 3 : 0-6%; a clarifying agent: 0 to 2 percent.
5. A microcrystalline glass product according to any of claims 1-4, characterised in that its composition is by weightExpressed in percent, contains: SiO 2 2 : 52-58 percent; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
6. A microcrystalline glass product according to any of claims 1-4, characterised in that its composition, expressed in weight percentage, contains: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 0.5-6%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
7. A microcrystalline glass product according to any of claims 1-4, characterised in that its composition, expressed in weight percentage, contains: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
8. A crystallized glass product according to any one of claims 1 to 4, wherein the components are expressed by weight percentage (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.32.
9. A crystallized glass product according to any one of claims 1 to 4, wherein the components are expressed by weight percentage (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.30.
10. A crystallized glass product according to any one of claims 1 to 4, wherein the components are expressed by weight percentage (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4.
11. A crystallized glass product according to any one of claims 1 to 4, wherein the components are expressed by weight percentage (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3.
12. A crystallized glass product according to any one of claims 1 to 4, wherein the components are expressed by weight percentage (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
13. A glass-ceramic article according to any one of claims 1 to 4, characterized in that the composition thereof, expressed in weight percentage, is Li 2 O/Na 2 O is 0.28 to 1.2.
14. A microcrystalline glass product according to any of claims 1-4, characterised in that its composition, expressed in weight percentage, is Li 2 O/Na 2 O is 0.29 to 1.1.
15. According to claimA crystallized glass product according to any one of claims 1 to 4, wherein the composition is represented by weight percentage, Li 2 O/Na 2 O is 0.30 to 1.0.
16. A crystallized glass product according to any one of claims 1 to 4, wherein the haze of the crystallized glass product having a thickness of 0.55mm is 0.3% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 85%; and/or a microcrystalline glass product having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 85% or more.
17. A crystallized glass product according to any one of claims 1 to 4, wherein the haze of the crystallized glass product having a thickness of 0.55mm is 0.25% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of 400-800 nm wavelength is more than 88%; and/or a microcrystalline glass product having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 89% or more.
18. A crystallized glass product according to any one of claims 1 to 4, wherein the haze of the crystallized glass product having a thickness of 0.55mm is 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more.
19. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a surface stress of 300MPa or more; and/or the depth of the ion exchange layer is 10 μm or more.
20. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a surface stress of 500MPa or more; and/or the depth of the ion exchange layer is 15 μm or more.
21. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a surface stress of 700MPa or more; and/or the depth of the ion exchange layer is 20 μm or more.
22. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a surface stress of 700MPa or more; and/or the depth of the ion exchange layer is 25 μm or more.
23. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a falling ball test height of 1000mm or more; and/or a fracture toughness of 1MPa m 1/2 The above; and/or Vickers hardness H v Is 600kgf/mm 2 The above.
24. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a falling ball test height of 1100mm or more; and/or a fracture toughness of 1.3 MPa.m 1/2 The above; and/or Vickers hardness H v Is 650kgf/mm 2 The above.
25. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a falling ball test height of 1200mm or more; and/or a fracture toughness of 1.5MPa m 1/2 The above; and/or Vickers hardness H v 700kgf/mm 2 The above.
26. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a crystallinity of 20% or more; and/or the crystal grain size is 70nm or less.
27. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a crystallinity of 30% or more; and/or the crystal grain size is 50nm or less.
28. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a crystallinity of 40% or more; and/or the grain size is 40nm or less.
29. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a crystallinity of 50% or more; and/or the grain size is 30nm or less.
30. A crystallized glass product according to any one of claims 1 to 4, wherein the crystallized glass product has a crystallinity of 50% or more; and/or the grain size is 20nm or less.
31. A microcrystalline glass product according to any of claims 1-4, characterised in that the microcrystalline glass product further comprises a colouring agent, which makes the microcrystalline glass product appear different colours.
32. A glass-ceramic article according to claim 31, characterized in that its colouring agent comprises, in percentages by weight: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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%。
33. A glass-ceramic article according to claim 31, characterized in that its colouring agent comprises, in percentages by weight: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3%。
34. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 : 0 to 10 percent; wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35; the crystalline phase of the microcrystalline glass contains lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
35. A glass-ceramic according to claim 34, characterized in that it further comprises, in percentages by weight: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2 percent.
36. The microcrystalline glass is characterized in that the components of the microcrystalline glass contain SiO 2 ：50～59.5%、Al 2 O 3 ：15～25%、Li 2 O: 4 to 10% and Na 2 O: 5 to 15% by weight of a component of (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35, wherein the haze of the microcrystalline glass with the thickness of 0.55mm is less than 0.3%; the crystalline phase of the microcrystalline glass contains lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
37. The microcrystalline glass of claim 36The glass is characterized by comprising the following components in percentage by weight: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 ：0～10%；ZnO：0～10%；MgO：0～10%；K 2 O：0～10%；SrO：0～5%；BaO：0～5%；TiO 2 ：0～5%；Y 2 O 3 ：0～5%；B 2 O 3 : 0-6%; a clarifying agent: 0 to 2 percent.
38. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition, expressed in weight percentage, comprises: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
39. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition, expressed in weight percentage, comprises: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 0.5-6%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
40. An agent according to any one of claims 34 to 37A glass-ceramic according to claim, characterized in that its composition, expressed in weight percentage, comprises: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
41. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition is expressed in weight percent (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.32.
42. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition is expressed in weight percent (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.30.
43. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition is expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4.
44. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition is expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3.
45. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition is expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
46. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition, expressed in weight percentage, is Li 2 O/Na 2 O is 0.28 to 1.2.
47. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition, expressed in weight percentage, is Li 2 O/Na 2 O is 0.29 to 1.1.
48. A glass-ceramic according to any one of claims 34 to 37, characterized in that its composition, expressed in weight percentage, is Li 2 O/Na 2 O is 0.30 to 1.0.
49. The crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.3% or less; and/or microcrystalline glass with the thickness of 0.55mm, wherein the average transmittance of 400-800 nm wavelength is more than 85%; and/or a microcrystalline glass having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 85% or more.
50. The crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.25% or less; and/or microcrystalline glass with the thickness of 0.55mm, wherein the average transmittance of 400-800 nm wavelength is more than 88%; and/or a microcrystalline glass having a thickness of 0.55mm, and has a transmittance at a wavelength of 550nm of 89% or more.
51. The crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.2% or less; and/or microcrystalline glass with the thickness of 0.55mm, wherein the average transmittance of 400-800 nm wavelength is more than 90%; and/or a microcrystalline glass having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more.
52. A crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass has a crystallinity of 20% or more; and/or the crystal grain size is 70nm or less.
53. A crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass has a crystallinity of 30% or more; and/or the crystal grain size is 50nm or less.
54. A crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass has a crystallinity of 40% or more; and/or the grain size is 40nm or less.
55. A crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass has a crystallinity of 50% or more; and/or the grain size is 30nm or less.
56. A crystallized glass according to any one of claims 34 to 37, wherein the crystallized glass has a crystallinity of 50% or more; and/or the grain size is 20nm or less.
57. A microcrystalline glass according to any of claims 34-37, characterised in that the refractive index n of the microcrystalline glass is d 1.500 to 1.540; and/or coefficient of thermal expansion alpha 20℃-120℃ 70 to 120 x 10 -7 /K。
58. A microcrystalline glass according to any of claims 34-37, characterised in that the refractive index n of the microcrystalline glass is d 1.510 to 1.530; and/or coefficient of thermal expansion alpha 20℃-120℃ Is 86 to 100 x 10 -7 /K。
59. A glass-ceramic according to any one of claims 34 to 37, wherein the glass-ceramic further comprises a colorant to make the glass-ceramic show different colors.
60. A glass-ceramic according to claim 59, characterized in that its colouring agents, expressed in weight percentage, contain: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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%。
61. A glass-ceramic according to claim 59, characterized in that its colouring agents, expressed in weight percentage, contain: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3%。
62. Matrix glass, characterized in that its composition, expressed in weight percentages, contains: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 : 0 to 10 percent; wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35.
63. The matrix glass according to claim 62, further comprising, in weight percent: ZnO: 0 to 10 percent; and/or MgO: 0 to 10 percent; and/or K 2 O: 0 to 10 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or TiO 2 : 0 to 5 percent; and/or Y 2 O 3 : 0 to 5 percent; and/or B 2 O 3 : 0-6%; and/or a clarifying agent: 0 to 2 percent.
64. The matrix glass according to claim 62 or 63, wherein the components thereof, expressed in weight percent, comprise: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
65. The matrix glass according to claim 62 or 63, wherein the components thereof, expressed in weight percent, comprise: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 0.5-6%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
66. The matrix glass according to claim 62 or 63, wherein the components thereof, expressed in weight percent, comprise: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 1-4%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent.
67. The matrix glass according to claim 62 or 63, wherein the components thereof are expressed in weight percent (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.32.
68. The matrix glass according to claim 62 or 63, wherein the components thereof are expressed in weight percent (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.30.
69. The matrix glass according to claim 62 or 63, wherein the components thereof are expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4.
70. The matrix glass according to claim 62 or 63, wherein the components thereof are expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3.
71. The matrix glass according to claim 62 or 63, wherein the components thereof are expressed in weight percent (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2.
72. The matrix glass according to claim 62 or 63, wherein the composition thereof is expressed in weight percent, Li 2 O/Na 2 O is 0.28 to 1.2.
73. The matrix glass according to claim 62 or 63, wherein the composition thereof is expressed in weight percent, Li 2 O/Na 2 O is 0.29 to 1.1.
74. The matrix glass according to claim 62 or 63, wherein the constituents are, in weight percent, Li 2 O/Na 2 O is 0.30 to 1.0.
75. The matrix glass of claim 62 or 63, wherein the matrix glass has a refractive index n d 1.500 to 1.530; and/or coefficient of thermal expansion alpha 20℃-120℃ 60 to 85 x 10 -7 /K。
76. The matrix glass of claim 62 or 63, wherein the matrix glass has a refractive index n d 1.505 to 1.525; and/or coefficient of thermal expansion alpha 20℃-120℃ 70 to 85 x 10 -7 /K。
77. The matrix glass of claim 62 or 63, wherein the matrix glass further comprises a colorant to impart a different color to the crystallized glass article.
78. The matrix glass according to claim 77, wherein the colorants comprise, in weight percent: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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%。
79. The matrix glass according to claim 77, wherein the colorants comprise, in weight percent: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 ：0.05～1.8 percent; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3%。
80. Glass cover plate, characterized in that it is made of a glass-ceramic product according to any of claims 1 to 33, and/or made of a glass-ceramic according to any of claims 34 to 61, and/or made of a matrix glass according to any of claims 62 to 79.
81. A glass component, characterized in that it is made of a glass-ceramic product as claimed in any one of claims 1 to 33, and/or a glass-ceramic as claimed in any one of claims 34 to 61, and/or a matrix glass as claimed in any one of claims 62 to 79.
82. Display device, characterized in that it comprises a glass-ceramic article according to any of claims 1 to 33, and/or comprises a glass-ceramic according to any of claims 34 to 61, and/or comprises a matrix glass according to any of claims 62 to 79, and/or comprises a glass cover plate according to claim 80.
83. An electronic device comprising the glass-ceramic article according to any one of claims 1 to 33, and/or comprising the glass-ceramic according to any one of claims 34 to 61, and/or comprising the matrix glass according to any one of claims 62 to 79, and/or comprising the glass cover plate according to claim 80, and/or comprising the glass component according to claim 81.
84. A method for producing a crystallized glass product, characterized by comprising the steps of:
forming a matrix glass having the composition, expressed in weight percent, comprising: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 ：0～10%；ZnO：0～10% ；MgO：0～10%；K 2 O：0～10%；SrO：0～5%；BaO：0～5%；TiO 2 ：0～5%；Y 2 O 3 ：0～5%；B 2 O 3 : 0-6%; a clarifying agent: 0-2%; wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35;
forming microcrystalline glass by a crystallization process on the matrix glass, and forming a microcrystalline glass product by a chemical strengthening process on the microcrystalline glass, wherein the crystalline phase of the microcrystalline glass product contains lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
85. The method for producing a crystallized glass article according to claim 84, wherein the matrix glass has a composition comprising, in weight percent: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4; and/or Li 2 O/Na 2 O is 0.28 to 1.2.
86. The method for producing a crystallized glass article according to claim 84, wherein the matrix glass has a composition comprising, in weight percent: SiO 2 2 ：52～58 percent; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.5-6%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.32; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3; and/or Li 2 O/Na 2 O is 0.29 to 1.1.
87. The method for producing a crystallized glass article according to claim 84, wherein the matrix glass has a composition comprising, in weight percent: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.30; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2; and/or Li 2 O/Na 2 O is 0.30 to 1.0.
88. A method for manufacturing a glass-ceramic article according to claim 84 or 85, wherein the matrix glass comprises, in weight percent: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0-2%; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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%。
89. A method for manufacturing a glass-ceramic article according to claim 84 or 85, wherein the matrix glass comprises, in weight percent: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3%。
90. The method of manufacturing a glass-ceramic article according to claim 84 or 85, wherein the crystallization process comprises the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 480-700 ℃, and the holding time at the crystallization temperature is 0-8 hours.
91. The method of manufacturing a glass-ceramic article according to claim 84 or 85, wherein the crystallization process comprises the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 520-600 ℃, and the holding time at the crystallization temperature is 1-6 hours.
92. The method of manufacturing a glass-ceramic article according to claim 84 or 85, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
93. The method of making a crystallized glass article of claim 92, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 0-24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
94. The method of making a crystallized glass article of claim 92, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 2-15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
95. The method for manufacturing a glass-ceramic article according to claim 84 or 85, wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 430-470 ℃ for 6-20 hours; and/or immersing the microcrystalline glass in a salt bath for melting the K salt at the temperature of 400-450 ℃ for 1-8 hours.
96. The method for manufacturing a glass-ceramic article according to any of claims 84 or 85, wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at 435-460 ℃ for 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt for 2-4 hours at the temperature of 400-450 ℃.
97. The method for producing a crystallized glass article according to claim 84 or 85, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.3% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 85%;and/or a microcrystalline glass product with a thickness of 0.55mm, wherein the transmittance at a wavelength of 550nm is more than 85%; and/or the surface stress of the microcrystalline glass product is more than 300 MPa; and/or the ion exchange layer depth of the microcrystalline glass product is more than 10 mu m; and/or the height of the microcrystalline glass product in a ball drop test is more than 1000 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m 1/2 The above; and/or Vickers hardness H of the glass-ceramic article v Is 600kgf/mm 2 The above; and/or the crystallite size of the glass-ceramic product is less than or equal to 70 nm.
98. The method for producing a crystallized glass article according to claim 84 or 85, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.25% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of 400-800 nm wavelength is more than 88%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 89% or more; and/or the surface stress of the microcrystalline glass product is more than 500 MPa; and/or the ion exchange layer depth of the microcrystalline glass product is more than 15 mu m; and/or the height of the microcrystalline glass product in a ball drop test is more than 1100 mm; and/or the fracture toughness of the glass-ceramic product is 1.3 MPa.m 1/2 The above; and/or Vickers hardness H of the glass-ceramic article v Is 650kgf/mm 2 The above; and/or the crystallite size of the glass-ceramic product is less than 50 nm.
99. The method for producing a crystallized glass article according to claim 84 or 85, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the surface stress of the microcrystalline glass product is above 700 MPa; and/or the ion exchange layer depth of the microcrystalline glass product is more than 20 mu m; and/or the height of the microcrystalline glass product in a ball drop test is more than 1200 mm; and/or the fracture toughness of the glass-ceramic product is 1.5 MPa.m 1/2 The above; and/or Vickers hardness H of the glass-ceramic article v 700kgf/mm 2 The above; and/or crystallitesThe glass product has a grain size of 40nm or less.
100. The method for producing a crystallized glass article according to claim 84 or 85, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.2% or less; and/or the microcrystalline glass product with the thickness of 0.55mm, the average transmittance of 400-800 nm wavelength is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the surface stress of the microcrystalline glass product is above 700 MPa; and/or the ion exchange layer depth of the microcrystalline glass product is more than 25 μm; and/or the height of the microcrystalline glass product in a ball drop test is more than 1200 mm; and/or the fracture toughness of the glass-ceramic product is 1.5 MPa.m 1/2 The above; and/or Vickers hardness H of the glass-ceramic article v 700kgf/mm 2 The above; and/or the crystallite size of the glass-ceramic product is less than or equal to 30 nm.
101. The method for producing a crystallized glass article according to claim 84 or 85, wherein the haze of the crystallized glass article having a thickness of 0.55mm is 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the surface stress of the microcrystalline glass product is above 700 MPa; and/or the ion exchange layer depth of the microcrystalline glass product is more than 25 μm; and/or the height of the microcrystalline glass product in a ball drop test is more than 1200 mm; and/or the fracture toughness of the glass-ceramic product is 1.5 MPa.m 1/2 The above; and/or Vickers hardness H of the glass-ceramic article v 700kgf/mm 2 The above; and/or the crystallite size of the glass-ceramic product is less than or equal to 20 nm.
102. The method for producing a glass-ceramic product according to claim 84 or 85, wherein a crystallinity of the glass-ceramic product is 20% or more.
103. The method for producing a glass-ceramic product according to claim 84 or 85, wherein a crystallinity of the glass-ceramic product is 30% or more.
104. The method for producing a glass-ceramic product according to claim 84 or 85, wherein a crystallinity of the glass-ceramic product is 40% or more.
105. The method for producing a glass-ceramic product according to claim 84 or 85, wherein a crystallinity of the glass-ceramic product is 50% or more.
106. A method for producing a crystallized glass, characterized by comprising:
forming a matrix glass having the composition, expressed in weight percent, comprising: SiO 2 2 ：50～59.5%；Al 2 O 3 ：15～25%；Li 2 O：4～10%；Na 2 O：5～15%；P 2 O 5 ：0.1～10%；ZrO 2 ：0～10%；ZnO：0～10% ；MgO：0～10%；K 2 O：0～10%；SrO：0～5%；BaO：0～5%；TiO 2 ：0～5%；Y 2 O 3 ：0～5%；B 2 O 3 : 0-6%; a clarifying agent: 0-2%; wherein (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.35;
forming microcrystalline glass by a crystallization process on the matrix glass, wherein the crystalline phase of the microcrystalline glass contains lithium metasilicate; and/or aluminum phosphate; and/or aluminum metaphosphate; and/or lithium phosphate; and/or zirconium silicate crystals.
107. A method for producing glass-ceramic according to claim 106, wherein the matrix glass comprises, in terms of weight percent, the following components: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 4-8%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 0.1-10%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; (Li) 2 O+Na 2 O)/Al 2 O 3 0.5 to 1.4; and/or Li 2 O/Na 2 O is 0.28 to 1.2.
108. A method for producing glass-ceramic according to claim 106, wherein the matrix glass comprises, in terms of weight percent, the following components: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/or a clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.32; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.53 to 1.3; and/or Li 2 O/Na 2 O is 0.29 to 1.1.
109. A method for producing glass-ceramic according to claim 106, wherein the matrix glass comprises, in terms of weight percent, the following components: SiO 2 2 : 52-58%; and/or Al 2 O 3 : 16-23%; and/or Li 2 O: 5-7%; and/or Na 2 O: 8-12%; and/or P 2 O 5 : 0.5-5%; and/or ZrO 2 : 1-4%; and/or ZnO: 1-8%; and/or MgO: 0.5-5%; and/or K 2 O: 0 to 5 percent; and/or SrO: 0 to 1 percent; and/or BaO: 0 to 1 percent; and/or TiO 2 : 0 to 1 percent; and/or Y 2 O 3 : 0 to 1 percent; and/or B 2 O 3 : 0.1-4%; and/orA clarifying agent: 0 to 1 percent; and/or (Li) 2 O+Na 2 O)/(SiO 2 +Al 2 O 3 ) 0.24 to 0.30; and/or (Li) 2 O+Na 2 O)/Al 2 O 3 0.55 to 1.2; and/or Li 2 O/Na 2 O is 0.30 to 1.0.
110. A method for manufacturing glass-ceramic according to claim 106 or 107, wherein the matrix glass comprises, in terms of weight percent, the following components: NiO: 0 to 4 percent; and/or Ni 2 O 3 : 0 to 4 percent; and/or a CoO: 0 to 2 percent; and/or Co 2 O 3 : 0-2%; and/or Fe 2 O 3 : 0 to 7 percent; 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%。
111. A method for producing a glass-ceramic according to any of claims 106 or 107, wherein the matrix glass comprises, in terms of weight percent, the following: NiO: 0.1-3%; and/or Ni 2 O 3 : 0.1-3%; and/or a CoO: 0.05-1.8%; and/or Co 2 O 3 : 0.05-1.8%; and/or Fe 2 O 3 : 0.2-5%; and/or MnO 2 : 0.1-3%; and/or Er 2 O 3 : 0.4-6%; and/or Nd 2 O 3 : 0.4-6%; and/or Cu 2 O: 0.5-3%; and/or Pr 2 O 5 : 0.4-6%; and/or CeO 2 ：0.5～3%。
112. A method for manufacturing glass-ceramic according to claim 106 or 107, wherein the crystallization process comprises the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 480-700 ℃, and the holding time at the crystallization temperature is 0-8 hours.
113. A method for manufacturing glass-ceramic according to claim 106 or 107, wherein the crystallization process comprises the steps of: heating to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then cooling; the crystallization temperature is 520-600 ℃, and the holding time at the crystallization temperature is 1-6 hours.
114. A method for manufacturing glass-ceramic according to claim 106 or 107, wherein the crystallization process comprises the steps of: the treatment of the nucleation process is performed at the 1 st temperature, and then the treatment of the crystal growth process is performed at the 2 nd temperature higher than the nucleation process temperature.
115. A method for manufacturing crystallized glass according to claim 114, wherein the crystallization process includes the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 0-24 hours; the holding time at the 2 nd temperature is 0 to 10 hours.
116. A method of manufacturing glass ceramics according to claim 114, wherein the crystallization process comprises the steps of: the temperature of the No. 1 is 480-550 ℃, and the temperature of the No. 2 is 550-700 ℃; the holding time at the temperature of 1 st is 2-15 hours; the holding time at the 2 nd temperature is 0.5 to 6 hours.
117. The method for producing a crystallized glass according to claim 106 or 107, wherein the haze of the crystallized glass having a thickness of 0.55mm is 0.3% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 85%; and/or a microcrystalline glass product with a thickness of 0.55mm, wherein the transmittance at a wavelength of 550nm is more than 85%; and/or the crystallite size of the glass ceramics is less than 70 nm; and/or the coefficient of thermal expansion alpha of the glass-ceramic 20℃-120℃ 70 to 120 x 10 -7 /K。
118. The method for producing a crystallized glass according to claim 106 or 107, wherein the haze of the crystallized glass having a thickness of 0.55mm is 0.25% or less; and/or the microcrystalline glass product with the thickness of 0.55mm, the average transmittance of 400-800 nm wavelength is more than 88%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 89% or more; and/or the crystallite size of the glass ceramics is less than 50 nm; and/or the coefficient of thermal expansion alpha of the glass-ceramic 20℃-120℃ Is 86 to 100 x 10 -7 /K。
119. The method for producing a crystallized glass according to claim 106 or 107, wherein the haze of the crystallized glass having a thickness of 0.55mm is 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the crystallite size of the glass ceramics is less than 40 nm; and/or the coefficient of thermal expansion alpha of the glass-ceramic 20℃-120℃ Is 86-100 x 10 -7 /K。
120. The method for producing a crystallized glass according to claim 106 or 107, wherein the crystallized glass having a thickness of 0.55mm has a haze of 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the crystallite size of the glass ceramics is less than 30 nm; and/or the coefficient of thermal expansion alpha of the glass-ceramic 20℃-120℃ Is 86 to 100 x 10 -7 /K。
121. The method for producing a crystallized glass according to claim 106 or 107, wherein the haze of the crystallized glass having a thickness of 0.55mm is 0.2% or less; and/or a microcrystalline glass product with the thickness of 0.55mm, wherein the average transmittance of the microcrystalline glass product at the wavelength of 400-800 nm is more than 90%; and/or a microcrystalline glass product having a thickness of 0.55mm, and having a transmittance at a wavelength of 550nm of 91% or more; and/or the crystallite size of the glass ceramics isBelow 20 nm; and/or the coefficient of thermal expansion alpha of the glass-ceramic 20℃-120℃ Is 86 to 100 x 10 -7 /K。
122. A method for producing a glass ceramic according to claim 106 or 107, wherein a crystallinity of the glass ceramic is 20% or more.
123. A method for producing a glass ceramic according to claim 106 or 107, wherein a crystallinity of the glass ceramic is 30% or more.
124. A method for producing a glass ceramic according to claim 106 or 107, wherein a crystallinity of the glass ceramic is 40% or more.
125. A method for producing a glass ceramic according to claim 106 or 107, wherein a crystallinity of the glass ceramic is 50% or more.
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