微晶玻璃、微晶玻璃制品及其制造方法

Glass ceramics, glass ceramics product and manufacturing method thereof

文档序号：2175 发布日期：2021-09-17 浏览：46次中文

1. A microcrystalline glass product, characterized in that its composition, expressed in weight percent, contains: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

2. The glass-ceramic article according to claim 1, characterized in that it further comprises, in percentages by weight: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

3. Microcrystalline glass product, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0 to 2% of a compound of Li₂O/(ZnO + MgO) is 9.5 or more.

4. A crystallized glass product according to any one of claims 1 to 3, wherein the components thereof are expressed by weight percentage, and the components thereof satisfy one or more of the following 4 cases:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

2)(SiO₂+Al₂O₃+Li₂O)/ZrO₂is 26 or more, preferably (SiO)₂+Al₂O₃+Li₂O)/ZrO₂Is 28 to 50, more preferably (SiO)₂+Al₂O₃+Li₂O)/ZrO₂Is 30 to 45, and (SiO) is more preferable₂+Al₂O₃+Li₂O)/ZrO₂31 to 38.5;

3)(Al₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.1 to 0.8, preferably (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.2 to 0.62, more preferably (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.3 to 0.6, and more preferably (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.4 to 0.55;

4)(SiO₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂is 24 or more, preferably (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 25 to 50, more preferably (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂26 to 45, further onePreferred Step (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 27 to 40.

5. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition, expressed in weight percentages, is: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1-3%, preferably ZnO + MgO: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O: 0-2%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

6. A microcrystalline glass product according to any of claims 1-3, characterised in that its composition, expressed in weight percentages, is: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂: 0.5 to 7%, more preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

7. A crystallized glass product according to any one of claims 1 to 3, wherein the crystallized glass product contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass-ceramic product by weight percent, further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass-ceramic product by weight percent, and further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass-ceramic product by weight percent.

8. A glass-ceramic article according to any of claims 1 to 3, characterized in that the lithium disilicate crystalline phase represents 15 to 40% by weight of the glass-ceramic article, preferably the lithium disilicate crystalline phase represents 20 to 35% by weight of the glass-ceramic article, more preferably the lithium disilicate crystalline phase represents 25 to 35% by weight of the glass-ceramic article; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass-ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass-ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass-ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass product, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass product; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass product, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass product, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass product.

9. A crystallized glass product according to any one of claims 1 to 3, wherein the crystallized glass product has a four-point bending strength of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or moreAbove MPa; and/or the ion exchange layer depth of the glass-ceramic product is 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more; and/or the surface stress of the glass-ceramic product is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or the height of the microcrystalline glass product in a ball drop test is more than 1400mm, preferably more than 1500mm, and more preferably more than 1600 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 730kgf/mm²Above, preferably 750kgf/mm²Above, more preferably 780kgf/mm²The above; and/or the crystallinity of the glass-ceramic product is 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystallite glass product has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.

10. A crystallized glass product according to any one of claims 1 to 3, wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or a microcrystalline glass product having a thickness of 1mm or less, and having an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less; and/or the shatter resistance of the microcrystalline glass product having a thickness of 1mm or less is 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and further preferably 2000mm or more.

11. A crystallized glass product according to claim 10, wherein the crystallized glass product has a thickness of 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

12. A crystallized glass article according to any one of claims 1 or 2, wherein the crystallized glass article further comprises: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

13. The microcrystalline glass is characterized by comprising the following components in percentage by weight: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

14. The glass-ceramic according to claim 13, characterized in that it further comprises, in weight percent: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

15. Microcrystalline glass ofCharacterized in that the components are expressed in weight percent by SiO₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0 to 2% of a compound of Li₂O/(ZnO + MgO) is 9.5 or more.

16. The glass-ceramic according to any one of claims 13 to 15, characterized in that the composition thereof, expressed in weight percentage, satisfies one or more of the following 4 cases:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

4)(SiO₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂is 24 or more, preferably (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 25 to 50, more preferably (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 26 to 45, and (SiO) is more preferable₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 27 to 40.

17. A glass-ceramic according to any one of claims 13 to 15, characterized in that its composition, expressed in weight percentages, is such that: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1-3%, preferably ZnO + MgO: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O: 0-2%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

18. A glass-ceramic according to any one of claims 13 to 15, characterized in that its composition, expressed in weight percentages, is such that: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂：0.5～7％More preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

19. The glass-ceramic according to any one of claims 13 to 15, wherein the crystalline phase in the glass-ceramic contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass ceramics by weight percent, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass ceramics by weight percent, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass ceramics by weight percent.

20. A glass-ceramic according to any one of claims 13 to 15, wherein the lithium disilicate crystalline phase accounts for 15 to 40% by weight of the glass-ceramic, preferably the lithium disilicate crystalline phase accounts for 20 to 35% by weight of the glass-ceramic, and more preferably the lithium disilicate crystalline phase accounts for 25 to 35% by weight of the glass-ceramic; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramics, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramics, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramics; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass.

21. The glass-ceramic according to any one of claims 13 to 15, wherein the glass-ceramic has a crystallinity of 50% or more, preferably 60%Above, more preferably 70% or above; and/or the crystallite size of the glass ceramics is less than 40nm, preferably less than 30nm, preferably less than 25 nm; and/or the ball falling height of the microcrystalline glass body is 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the Vickers hardness of the glass-ceramic is 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or the coefficient of thermal expansion of the glass-ceramic is 65 x 10^-7/K～85×10^-7K; and/or the refractive index of the microcrystalline glass is 1.5300-1.5420.

22. The crystallized glass according to any one of claims 13 to 15, wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or microcrystalline glass having a thickness of 1mm or less, and having an average transmittance of 87% or more, preferably 88% or more, more preferably 89% or more at a wavelength of 400 to 800 nm; and/or a microcrystalline glass having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or microcrystalline glass having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less.

23. A glass-ceramic according to claim 22, wherein the thickness of the glass-ceramic is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

24. A glass-ceramic according to any one of claims 13 or 14, further comprising: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

25. Matrix glass, characterized in that its composition, expressed in weight percentages, contains: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

26. The matrix glass according to claim 25, further comprising, in weight percent: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

27. The matrix glass according to any one of claims 25 or 26, wherein the components thereof, expressed in weight percent, satisfy one or more of the following 4 conditions:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

28. The matrix glass according to any one of claims 25 or 26, wherein the components are expressed in weight percent, wherein: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1-3%, preferably ZnO + MgO: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O：0～2％(ii) a And/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

29. The matrix glass according to any one of claims 25 or 26, wherein the components are expressed in weight percent, wherein: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂: 0.5 to 7%, more preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

30. The matrix glass of any one of claims 25 or 26, wherein the matrix glass has a coefficient of thermal expansion of 50 x 10^-7/K～70×10^-7And/or a refractive index of 1.5200-1.5300.

31. The matrix glass according to any one of claims 25 or 26, further comprising: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

32. Glass cover plate, characterized in that it is made of a glass-ceramic product according to any of claims 1 to 12, and/or made of a glass-ceramic according to any of claims 13 to 24, and/or made of a matrix glass according to any of claims 25 to 31.

33. A glass component, characterized in that it is made of a glass-ceramic product as defined in any one of claims 1 to 12, and/or a glass-ceramic product as defined in any one of claims 13 to 24, and/or a matrix glass as defined in any one of claims 25 to 31.

34. A display device comprising the crystallized glass product according to any one of claims 1 to 12, and/or comprising the crystallized glass according to any one of claims 13 to 24, and/or comprising the matrix glass according to any one of claims 25 to 31, and/or comprising the glass cover plate according to claim 32, and/or comprising the glass component according to claim 33.

35. An electronic device comprising the glass-ceramic product according to any one of claims 1 to 12, and/or comprising the glass-ceramic according to any one of claims 13 to 24, and/or comprising the matrix glass according to any one of claims 25 to 31, and/or comprising the glass cover plate according to claim 32, and/or comprising the glass component according to claim 33.

36. A method for producing a crystallized glass product according to any one of claims 1 to 12, characterized by comprising the steps of: generating matrix glass, then forming microcrystalline glass by the matrix glass through a crystallization process, and then forming a microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.

37. The method for producing a crystallized glass product according to claim 36, wherein the base glass is formed into a glass shaped body, the glass shaped body is crystallized to form a crystallized glass, and the crystallized glass is chemically strengthened to form a crystallized glass product, or the crystallized glass is formed into a crystallized glass shaped body, and the crystallized glass product is chemically strengthened to form a crystallized glass product.

38. The method of manufacturing a crystallized glass article according to claim 36, wherein the crystallization process comprises the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

39. The method of manufacturing a crystallized glass article according to claim 36, wherein the crystallization process comprises the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

40. The method of manufacturing a crystallized glass article according to claim 36, wherein the crystallization process comprises the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

41. The method for manufacturing a crystallized glass product according to claim 36, wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 320-470 ℃ for 6-20 hours, wherein the preferred temperature range is 360-460 ℃, and the preferred time range is 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours; and/or immersing the microcrystalline glass in a salt bath of a molten K salt and a molten Na salt at the temperature of 340-500 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

42. A method for producing a glass ceramic according to any one of claims 13 to 24, characterized by comprising: generating matrix glass, and then forming microcrystalline glass on the matrix glass through a crystallization process.

43. The method for producing glass ceramics according to claim 42, wherein the glass ceramics is formed by producing a glass shaped body from a matrix glass and then subjecting the glass shaped body to a crystallization process.

44. The method for producing glass-ceramic according to claim 42, wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

45. The method for producing glass-ceramic according to claim 42, wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

46. The method for producing glass-ceramic according to claim 42, wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

Background

In recent years, with the rise and development of consumer electronics (such as display devices or electronic devices), microcrystalline glass is used as a transparent and good-performance material, and tends to be applied to such electronic devices. When the glass ceramics is used as a front cover plate of a display surface of an electronic product (such as a mobile phone, a watch, a PAD, a portable media player, a personal computer, a camera and the like), the glass ceramics is required to have excellent optical performance so as to meet the requirement of good display definition of the electronic product. The microcrystalline glass in the prior art has the problems of high haze, low light transmittance and the like, and is difficult to be applied to display equipment or electronic equipment with higher requirements.

Disclosure of Invention

The invention aims to provide microcrystalline glass with excellent optical performance and a microcrystalline glass product.

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 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

(2) The glass-ceramic product according to (1), which comprises the following components in percentage by weight: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(3) Microcrystalline glass product, the composition of which is expressed in weight percentage by SiO₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0 to 2% of a component (B), whereinLi₂O/(ZnO + MgO) is 9.5 or more.

(4) A microcrystalline glass article having the composition, expressed in weight percent, comprising: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％。

(5) The glass-ceramic article according to (4), which comprises the following components in percentage by weight: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(6) A microcrystalline glass article having the composition, expressed in weight percent, comprising: SiO 2₂：68～82％，Al₂O₃：2～15％，Li₂O: 7-15%, wherein the crystalline phase of the microcrystalline glass product contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(7) A microcrystalline glass article having the composition, expressed in weight percent, comprising: SiO 2₂：68～82％，Al₂O₃：2～15％，Li₂O: 7-15%, the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases in percentage by weight, and the haze of the glass-ceramic product with the thickness of less than 1mm is less than 0.2%.

(8) The glass-ceramic article according to any one of (6) and (7), which further comprises, in terms of weight percent: ZnO + MgO: 0 to 5 percent; and/or P₂O₅+ZrO₂: 1-10%; and/or Na₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(9) The crystallized glass product according to any one of (1) to (8), wherein the components thereof are expressed by weight percentage, and the components satisfy one or more of the following 4 cases:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

(10) The crystallized glass product according to any one of (1) to (8), wherein the components are expressed by weight percentage: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1 to 3 percentZnO + MgO is preferable: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O: 0-2%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

(11) The crystallized glass product according to any one of (1) to (8), wherein the components are expressed by weight percentage: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂: 0.5 to 7%, more preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

(12) The crystallized glass product according to any one of (1) to (8), wherein the crystallized glass product contains lithium silicate in a crystal phase; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass-ceramic product contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass-ceramic product by weight percent, further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass-ceramic product by weight percent, and further preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass-ceramic product by weight percent.

(13) The microcrystalline glass product according to any one of (1) to (8), wherein the lithium disilicate crystal phase accounts for 15 to 40% by weight of the microcrystalline glass product, preferably the lithium disilicate crystal phase accounts for 20 to 35% by weight of the microcrystalline glass product, and more preferably the lithium disilicate crystal phase accounts for 25 to 35% by weight of the microcrystalline glass product; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass-ceramic product, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass-ceramic product, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass-ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass product, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass product; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass product, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass product, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass product.

(14) The crystallized glass product according to any one of (1) to (8), wherein the crystallized glass product has a four-point bending strength of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more; and/or the ion exchange layer depth of the glass-ceramic product is 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more; and/or the surface stress of the glass-ceramic product is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or the height of the microcrystalline glass product in a ball drop test is more than 1400mm, preferably more than 1500mm, and more preferably more than 1600 mm; and/or the fracture toughness of the glass-ceramic product is 1 MPa.m^1/2Above, preferably 1.1MPa · m^1/2More preferably 1.2MPa · m or more^1/2The above; and/or the Vickers hardness of the glass-ceramic article is 730kgf/mm²Above, preferably 750kgf/mm²Above, more preferably 780kgf/mm²The above; and/or the crystallinity of the glass-ceramic product is 50% or more, preferably 60% or more, more preferably 70% or more; and/or the crystallite glass product has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.

(15) The crystallized glass product according to any one of (1) to (8), wherein the crystallized glass product having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less; and/or a microcrystalline glass product having a thickness of 1mm or less, and having an average transmittance at a wavelength of 400 to 800nm of 87% or more, preferably 88% or more, more preferably 89% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or a microcrystalline glass product having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less; and/or the shatter resistance of the microcrystalline glass product having a thickness of 1mm or less is 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and further preferably 2000mm or more.

(16) The glass-ceramic product according to (15), wherein the thickness of the glass-ceramic product is 0.2-1 mm, preferably 0.3-0.9 mm, more preferably 0.5-0.8 mm, and further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(17) The crystallized glass product according to any one of (1) to (8), further comprising: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(18) The microcrystalline glass comprises the following components in percentage by weight: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

(19) The glass-ceramic according to (18), which comprises the following components in percentage by weight: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(20) Microcrystalline glass, the composition of which is expressed in weight percent by SiO₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0 to 2% of a compound of Li₂O/(ZnO + MgO) is 9.5 or more.

(21) The microcrystalline glass comprises the following components in percentage by weight: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂：1～10％。

(22) The glass-ceramic according to (21), which comprises the following components in percentage by weight: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(23) The microcrystalline glass comprises the following components in percentage by weight: SiO 2₂：68～82％，Al₂O₃：2～15％，Li₂O：7～15Percent, the crystalline phase in the microcrystalline glass contains lithium silicate, and/or quartz and quartz solid solution, and/or petalite.

(24) The microcrystalline glass comprises the following components in percentage by weight: SiO 2₂：68～82％，Al₂O₃：2～15％，Li₂O: 7-15%, the crystalline phase in the glass ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, and the haze of the glass ceramics with the thickness of less than 1mm is less than 0.2%.

(25) The glass-ceramic according to any one of (23) and (24), which further comprises, in terms of weight percent: ZnO + MgO: 0 to 5 percent; and/or P₂O₅+ZrO₂: 1-10%; and/or Na₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(26) The crystallized glass according to any one of (18) to (25), which has a composition, expressed in terms of weight percentage, satisfying one or more of the following 4 cases:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

(27) The crystallized glass according to any one of (18) to (25), which comprises the following components in percentage by weight: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1-3%, preferably ZnO + MgO: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O: 0-2%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

(28) The crystallized glass according to any one of (18) to (25), which comprises the following components in percentage by weight: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂: 0.5 to 7%, more preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

(29) The crystallized glass of any one of (18) to (25), wherein the crystallized glass contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass ceramics contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite is higher than that of other crystalline phases by weight percent, more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 50-80 percent of the glass ceramics by weight percent, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75 percent of the glass ceramics by weight percent, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70 percent of the glass ceramics by weight percent.

(30) The microcrystalline glass according to any one of (18) to (25), wherein the content of the lithium disilicate crystal phase in the microcrystalline glass is 15 to 40% by weight, preferably the content of the lithium disilicate crystal phase in the microcrystalline glass is 20 to 35% by weight, and more preferably the content of the lithium disilicate crystal phase in the microcrystalline glass is 25 to 35% by weight; and/or the petalite crystal phase accounts for 30-55% of the weight of the glass ceramics, preferably the petalite crystal phase accounts for 35-55% of the weight of the glass ceramics, and more preferably the petalite crystal phase accounts for 35-50% of the weight of the glass ceramics; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the weight of the microcrystalline glass, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the weight of the microcrystalline glass; and/or the lithium monosilicate crystal phase accounts for 0-10% of the weight of the microcrystalline glass, preferably the lithium monosilicate crystal phase accounts for 0-7% of the weight of the microcrystalline glass, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the weight of the microcrystalline glass.

(31) The crystallized glass of any one of (18) to (25)The crystallinity of the glass ceramics is 50% or more, preferably 60% or more, and more preferably 70% or more; and/or the crystallite size of the glass ceramics is less than 40nm, preferably less than 30nm, preferably less than 25 nm; and/or the ball falling height of the microcrystalline glass body is 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the Vickers hardness of the glass-ceramic is 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above; and/or the coefficient of thermal expansion of the glass-ceramic is 65 x 10^-7/K～85×10^-7K; and/or the refractive index of the microcrystalline glass is 1.5300-1.5420.

(32) The crystallized glass according to any one of (18) to (25), wherein the crystallized glass having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less; and/or microcrystalline glass having a thickness of 1mm or less, and having an average transmittance of 87% or more, preferably 88% or more, more preferably 89% or more at a wavelength of 400 to 800 nm; and/or a microcrystalline glass having a thickness of 1mm or less, and having a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, more preferably 91% or more; and/or microcrystalline glass having a thickness of 1mm or less, wherein the average light | B | value of 400 to 800nm is 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less.

(33) The microcrystalline glass according to (32), wherein the microcrystalline glass has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm, or 0.75 mm.

(34) The crystallized glass according to any one of (18) to (25), further comprising: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/or Fe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(35) A matrix glass, the composition of which, expressed in weight percent, comprises: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0.1～5％；P₂O₅+ZrO₂: 1 to 10% of Li₂O/(ZnO + MgO) is 9.5 or more.

(36) The base glass according to (35), which further comprises, in terms of weight percent: na (Na)₂O: 0 to 4 percent; and/or B₂O₃: 0 to 4 percent; and/or K₂O: 0 to 4 percent; and/or SrO: 0 to 5 percent; and/or BaO: 0 to 5 percent; and/or CaO: 0 to 5 percent; and/or TiO₂: 0 to 5 percent; and/or a clarifying agent: 0 to 2 percent.

(37) A matrix glass, the composition of which, expressed in weight percent, comprises: SiO 2₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0 to 2 percent.

(38) A matrix glass, the composition of which is expressed in weight percentage by SiO₂：68～82％；Al₂O₃：2～15％；Li₂O：7～15％；ZnO+MgO：0～5％；P₂O₅+ZrO₂：1～10％；Na₂O：0～4％；B₂O₃：0～4％；K₂O：0～4％；SrO：0～5％；BaO：0～5％；CaO：0～5％；TiO₂: 0 to 5 percent; a clarifying agent: 0-2% of the composition.

(39) The matrix glass according to any one of (35) to (38), whose composition, expressed in terms of weight percentage, satisfies one or more of the following 4 cases:

1)Li₂O/(ZnO + MgO) is 10 to 50, and Li is preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13-30;

(40) The matrix glass according to any one of (35) to (38), which comprises, in terms of weight percent: SiO 2₂: 70-80%, preferably SiO₂: 71-76%; and/or Al₂O₃: 4-12%, preferably Al₂O₃: 6-11%; and/or Li₂O: 8 to 14%, preferably Li₂O: 9-13%; and/or ZnO + MgO: 0.1-3%, preferably ZnO + MgO: 0.2-1.5%; and/or P₂O₅+ZrO₂: 2-8%, preferably P₂O₅+ZrO₂: 3-7%; and/or Na₂O: 0.5 to 3%, preferably Na₂O: 0.5-2.5%; and/or B₂O₃: 0.5 to 3%, preferably B₂O₃: 0.5-2.5%; and/or K₂O: 0 to 3%, preferably K₂O: 0-2%; and/or SrO: 0 to 3%, preferably SrO: 0 to 1 percent; and/or BaO: 0-3%, preferably BaO: 0 to 1 percent; and/or CaO: 0-3%, preferably CaO: 0 to 1 percent; and/or TiO₂: 0 to 3%, preferably TiO₂: 0 to 1 percent; and/or a clarifying agent: 0-1%, preferably clarifying agent: 0 to 0.5 percent.

(41) The matrix glass according to any one of (35) to (38), which comprises, in terms of weight percent: ZnO: 0-3%, preferably ZnO: 0 to 2%, more preferably ZnO: 0 to 1 percent; and/or MgO: 0-3%, preferably MgO: 0 to 2%, more preferably MgO: 0 to 1 percent; and/or P₂O₅: 0 to 5%, preferably P₂O₅: 0.5 to 5%, more preferably P₂O₅: 1 to 3%, and preferably P₂O₅: 1.5-2.5%; and/or ZrO₂: 0 to 7%, preferably ZrO₂: 0.5 to 7%, more preferably ZrO₂: 1 to 6%, and more preferably ZrO₂：1.5～5％。

(42) The base glass according to any one of (35) to (38), wherein the base glass has a thermal expansion coefficient of 50X 10^-7/K～70×10^-7And/or a refractive index of 1.5200-1.5300.

(43) The base glass according to any one of (35) to (37), further comprising: NiO: 0-4%, preferably NiO: 0.1-3%; and/or Ni₂O₃: 0 to 4%, preferably Ni₂O₃: 0.1-3%; and/or a CoO: 0-2%, preferably CoO: 0.05-1.8%; and/or Co₂O₃: 0 to 2%, preferably Co₂O₃: 0.05-1.8%; and/orFe₂O₃: 0 to 7%, preferably Fe₂O₃: 0.2-5%; and/or MnO₂: 0 to 4%, preferably MnO₂: 0.1-3%; and/or Er₂O₃: 0 to 8%, preferably Er₂O₃: 0.4-6%; and/or Nd₂O₃: 0 to 8%, preferably Nd₂O₃: 0.4-6%; and/or Cu₂O: 0 to 4%, preferably Cu₂O: 0.5-3%; and/or Pr₂O₅: 0 to 8%, preferably Pr₂O₅: 0.4-6%; and/or CeO₂: 0 to 4%, preferably CeO₂：0.5～3％。

(44) A glass cover plate made of the crystallized glass product according to any one of (1) to (17), and/or made of the crystallized glass according to any one of (18) to (34), and/or made of the matrix glass according to any one of (35) to (43).

(45) A glass component produced from the glass-ceramic product according to any one of (1) to (17), and/or produced from the glass-ceramic according to any one of (18) to (34), and/or produced from the base glass according to any one of (35) to (43).

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

(47) An electronic device comprising the glass-ceramic article according to any one of (1) to (17), and/or comprising the glass-ceramic according to any one of (18) to (34), and/or comprising the matrix glass according to any one of (35) to (43), and/or comprising the glass cover plate according to (44), and/or comprising the glass component according to (45).

(48) The method for producing a crystallized glass product according to any one of (1) to (17), comprising the steps of: generating matrix glass, then forming microcrystalline glass by the matrix glass through a crystallization process, and then forming a microcrystalline glass product by the microcrystalline glass through a chemical strengthening process.

(49) According to the method for producing a glass-ceramic product described in (48), the matrix glass is formed into a glass-ceramic shaped body, the glass-ceramic shaped body is crystallized to form the glass-ceramic, and the glass-ceramic is chemically strengthened to form the glass-ceramic product, or the glass-ceramic is formed into a glass-ceramic shaped body, and the glass-ceramic shaped body is chemically strengthened to form the glass-ceramic product.

(50) The method for producing a crystallized glass article according to (48), said crystallization process comprising the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(51) The method for producing a crystallized glass article according to (48), said crystallization process comprising the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

(52) The method for producing a crystallized glass article according to (48), said crystallization process comprising the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

(53) The method for manufacturing a crystallized glass article according to (48), wherein the chemical strengthening process comprises: immersing the microcrystalline glass in a salt bath of molten Na salt at the temperature of 320-470 ℃ for 6-20 hours, wherein the preferred temperature range is 360-460 ℃, and the preferred time range is 8-13 hours; and/or immersing the microcrystalline glass in a salt bath for melting K salt at the temperature of 340-450 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours; and/or immersing the microcrystalline glass in a salt bath of a molten K salt and a molten Na salt at the temperature of 340-500 ℃ for 1-24 hours, wherein the preferable time range is 2-10 hours.

(54) The method for producing a crystallized glass according to any one of (18) to (34), the method comprising the steps of: generating matrix glass, and then forming microcrystalline glass on the matrix glass through a crystallization process.

(55) According to the method for producing a glass ceramic in (54), the glass ceramic is formed by forming a glass-shaped body from a matrix glass and then subjecting the glass-shaped body to a crystallization process.

(56) The method for producing a crystallized glass according to (54), wherein the crystallization process includes the steps of: raising the temperature to a specified crystallization treatment temperature, keeping the temperature for a certain time after reaching the crystallization treatment temperature, and then reducing the temperature, wherein the crystallization treatment temperature is 600-750 ℃, preferably 650-720 ℃, and the keeping time at the crystallization treatment temperature is 0-8 hours, preferably 1-6 hours.

(57) The method for producing a crystallized glass according to (54), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd, wherein the temperature of 1 st is 470-600 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 600-750 ℃, and the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours.

(58) The method for producing a crystallized glass according to (54), wherein the crystallization process includes the steps of: the method comprises the steps of carrying out nucleation process treatment at the temperature of 1 st, and then carrying out crystal growth process treatment at the temperature of 2 nd and the temperature of 3 rd, wherein the temperature of 1 st is 470-550 ℃, the holding time at the temperature of 1 st is 0-24 hours, preferably 2-15 hours, the temperature of 2 nd is 570-630 ℃, the holding time at the temperature of 2 nd is 0-10 hours, preferably 0.5-6 hours, the temperature of 3 rd is 650-750 ℃, and the holding time at the temperature of 3 rd is 0-10 hours, preferably 0.5-6 hours.

The invention has the beneficial effects that: through reasonable component design, the microcrystalline glass and the microcrystalline glass product obtained by the invention have lower haze and excellent optical performance, and are suitable for electronic equipment or display equipment with higher requirements.

Detailed Description

The 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, the contents of the respective components are all expressed in weight percent (wt%) with respect to the total amount of the substance of the matrix glass, or the glass ceramics product converted into the composition of the oxide, if not specifically stated. Here, the "composition 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 end-point values, as well as all integers and fractions within the range, and are not limited to the specific values recited in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.

In the crystallized glass or crystallized glass article of the present invention, the crystal phase contains lithium silicate; and/or quartz and quartz solid solutions; and/or petalite. The lithium silicate crystalline phase of the present invention comprises lithium monosilicate and/or lithium disilicate. The crystalline phase is sometimes referred to as crystalline in the present invention.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium disilicate, which is present in an amount having a higher weight percent than other crystalline phases, resulting in superior properties of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phase in the glass-ceramic or glass-ceramic article contains petalite, which is present in an amount having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium monosilicate, with the lithium monosilicate being present in an amount having a higher weight percent than the other crystalline phases, resulting in superior performance of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise quartz and quartz solid solutions, the quartz and quartz solid solutions being present in an amount having a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium disilicate and petalite, the combined content of lithium disilicate and petalite having a higher weight percentage than the other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium monosilicate and petalite, the combined content of lithium monosilicate and petalite having a higher weight percentage than the other crystalline phases, resulting in the glass-ceramic or glass-ceramic article of the present invention having superior properties.

In some embodiments of the present invention, the crystalline phases in the microcrystalline glass or microcrystalline glass article comprise lithium disilicate and quartz solid solutions, and the combined content of lithium disilicate and quartz solid solutions has a higher weight percentage than other crystalline phases, resulting in excellent properties of the microcrystalline glass or microcrystalline glass article of the present invention.

In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise petalite and quartz solid solutions, and the combined content of petalite and quartz solid solutions has a higher weight percentage than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.

In some embodiments, the lithium disilicate crystalline phase comprises 15 to 40% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium disilicate crystalline phase comprises 20 to 35% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium disilicate crystalline phase comprises 25 to 35% by weight of the microcrystalline glass or microcrystalline glass article.

In some embodiments, the crystalline quartz and quartz solid solution phases comprise 5 to 25 weight percent of the microcrystalline glass or microcrystalline glass article. In some embodiments, the crystalline quartz and quartz solid solution phases constitute 7-20% by weight of the glass-ceramic or glass-ceramic article.

In some embodiments, the petalite crystalline phase comprises 30 to 55% by weight of the glass ceramic or glass ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 55% by weight of the glass ceramic or glass ceramic article. In some embodiments, the petalite crystalline phase comprises 35 to 50% by weight of the glass ceramic or glass ceramic article.

In some embodiments, the lithium monosilicate crystal phase comprises 0 to 10% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 7% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 5% by weight of the microcrystalline glass or microcrystalline glass article.

In some embodiments, the lithium disilicate and petalite crystalline phases are present in a combined amount of 50 to 80% by weight of the glass ceramic or glass ceramic article. In some embodiments, the combined content of the lithium disilicate and petalite crystalline phases is 55 to 75% by weight of the microcrystalline glass or microcrystalline glass article. In some embodiments, the combined content of the lithium disilicate and petalite crystalline phases is 55 to 70% by weight of the glass ceramic or glass ceramic article.

SiO₂Is a basic component of the matrix glass, the glass-ceramic and the glass-ceramic product of the present invention, and is one of the main components forming the crystal phase of the glass-ceramic and the glass-ceramic product if SiO₂The content of (b) is less than 68%, crystal formation in the microcrystalline glass and the microcrystalline glass article becomes less and the crystal becomes coarse easily, which affects the falling ball test height and haze of the microcrystalline glass and the microcrystalline glass article. Thus, SiO₂The lower limit of the content is 68%, preferably 70%, more preferably 71%. On the other hand, if SiO₂If the content exceeds 82%, the glass has high melting temperature, difficult melting and difficult molding in the manufacturing process, and the uniformity of the glass is affected. Thus, SiO₂The upper limit of the content is 82%, preferably 80%, more preferably 76%. In some embodiments, about 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, 80.5%, 81%, 81.5%, 82% SiO may be included₂。

Al₂O₃Is formed byThe glass network structure component, which is one of the components forming the petalite crystal phase, is beneficial to the chemical strengthening of the glass and the increase of the ball drop test height of the glass ceramic product, but if the content of the glass ceramic product is less than 2 percent, the effect is not good. Thus, Al₂O₃The lower limit of the content is 2%, preferably 4%, more preferably 6%. On the other hand, if Al₂O₃When the content of (b) exceeds 15%, the glass tends to have a low melting property and a low devitrification resistance, and crystals tend to grow during crystallization of the glass, thereby lowering the strength of the glass-ceramic product and the glass-ceramic. Thus, Al₂O₃The upper limit of the content is 15%, preferably 12%, more preferably 11%. In some embodiments, about 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Al may be included₂O₃。

Li₂O is an essential component for forming crystals of the microcrystalline glass and the microcrystalline glass product in the invention, and is also an essential component participating in chemical strengthening and improving the mechanical property of the microcrystalline glass product, if Li is used₂When the content of O is less than 7 percent, the content of crystals in the microcrystalline glass and the microcrystalline glass product is insufficient, and the strength of the microcrystalline glass and the microcrystalline glass product is reduced. Thus, Li₂The lower limit of the O content is 7%, preferably 8%, more preferably 9%. On the other hand, if Li is contained excessively₂O, the haze of the crystallized glass and the crystallized glass article increases. Thus, Li₂The upper limit of the O content is 15%, preferably 14%, more preferably 13%. In some embodiments, about 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Li may be included₂O。

ZnO and MgO promote the formation of quartz and quartz solid solutions in the glass ceramics, and if the total content of ZnO + MgO is too high, the haze of the glass ceramics and glass ceramics products increases. Therefore, ZnO + MgO is limited to 5% or less. If ZnO + MgO is too low, the microcrystalline glass and the microcrystalline glass product can not form quartz or quartz solid solution under the condition of low haze, which is not beneficial to realizing the excellent mechanical properties of the microcrystalline glass and the microcrystalline glass product. Therefore, ZnO + MgO is preferably 0.1 to 5%, ZnO + MgO is more preferably 0.1 to 3%, and ZnO + MgO is still more preferably 0.2 to 1.5%. In some embodiments, the content of ZnO is preferably 0 to 3%, more preferably 0 to 2%, and further preferably 0 to 1%. In some embodiments, the content of MgO is preferably 0 to 3%, more preferably 0 to 2%, and still more preferably 0 to 1%. In some embodiments, the ZnO + MgO value may be 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% ZnO may be included. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% MgO may be included.

The inventors have found, through extensive experimental studies, that in some embodiments of the invention, Li is incorporated₂Li being the ratio of O to the sum of ZnO and MgO, ZnO + MgO₂And the O/(ZnO + MgO) is controlled to be more than 9.5, so that the haze and the | B | of the microcrystalline glass and the microcrystalline glass product can be reduced, and the light transmittance of the microcrystalline glass and the microcrystalline glass product can be improved. Therefore, Li is preferable₂O/(ZnO + MgO) is 9.5 or more, and Li is more preferable₂O/(ZnO + MgO) is 10 to 50. Further, by controlling Li₂The content of O/(ZnO + MgO) is within the range of 11-40, the Vickers hardness of the microcrystalline glass and the microcrystalline glass product can be further improved, the chemical strengthening performance of the microcrystalline glass can be improved, the depth and the surface stress of an ion exchange layer of the microcrystalline glass product can be improved, and the falling resistance of the microcrystalline glass product can be improved. Therefore, Li is more preferable₂O/(ZnO + MgO) is 11 to 40, and Li is more preferable₂O/(ZnO + MgO) is 13 to 30. In some embodimentsIn, Li₂The value of O/(ZnO + MgO) may be 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50.

P₂O₅And ZrO₂Has a nucleating effect when its total content P is₂O₅+ZrO₂Above 1%, formation of the desired crystals of the present invention is facilitated to achieve excellent mechanical and optical properties of the crystallized glass and crystallized glass article of the present invention. If the total content P thereof is₂O₅+ZrO₂If the content exceeds 10%, the crystallite size in the glass ceramics or the glass ceramics product becomes large, the haze and transmittance of the glass ceramics or the glass ceramics product increase, and the mechanical properties deteriorate. Thus, P₂O₅+ZrO₂1 to 10%, preferably P₂O₅+ZrO₂2 to 8%, more preferably P₂O₅+ZrO₂3 to 7 percent. In some embodiments, P₂O₅+ZrO₂Values of (a) may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%.

P₂O₅The crystal nucleus can be formed in the glass, the crystal formation is promoted, the strength of the microcrystalline glass and the microcrystalline glass product is improved, and the haze of the microcrystalline glass and the microcrystalline glass product is favorably reduced. On the other hand, if P is contained excessively₂O₅Therefore, devitrification is easily generated in the production process of the matrix glass, and the forming difficulty of the glass is increased. Thus, P₂O₅The content range of (b) is preferably 0 to 5%, more preferably 0.5 to 5%, further preferably 1 to 3%, and further preferably 1.5 to 2.5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% P may be included₂O₅。

ZrO₂Has the function of forming crystal nucleus by crystallization precipitation, can refine crystal grains and reduce the haze of the microcrystalline glass and the microcrystalline glass product. On the other hand, if ZrO is contained excessively₂The haze of the crystallized glass and the crystallized glass product is rather increased. Thus, ZrO₂The content of (b) is preferably 0 to 7%, more preferably 0.5 to 7%, further preferably 1 to 6%, and further preferably 1.5 to 5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7% ZrO may be included₂。

In some embodiments, the SiO is₂、Al₂O₃And Li₂Total content of O SiO₂+Al₂O₃+Li₂O and ZrO₂Ratio between contents of (A), (B), (C) and C)₂+Al₂O₃+Li₂O)/ZrO₂The control of the content of the carbon fiber is more than 26, so that the four-point bending strength and the fracture toughness of the microcrystalline glass and the microcrystalline glass product can be improved. Therefore, (SiO) is preferable₂+Al₂O₃+Li₂O)/ZrO₂Is 26 or more, more preferably (SiO)₂+Al₂O₃+Li₂O)/ZrO₂Is 28 to 50. Further, by controlling (SiO)₂+Al₂O₃+Li₂O)/ZrO₂The hardness of the microcrystalline glass is 30-45, the Vickers hardness and the falling ball test height of the microcrystalline glass and the microcrystalline glass product can be further improved, and the ion exchange layer depth and the surface stress of the microcrystalline glass product can be improved. Therefore, (SiO) is more preferable₂+Al₂O₃+Li₂O)/ZrO₂Is 30 to 45, and (SiO) is more preferable₂+Al₂O₃+Li₂O)/ZrO₂Is 31 to 38.5. In some embodiments, (SiO)₂+Al₂O₃+Li₂O)/ZrO₂May have a value of 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 30,37.5、38、38.5、39、39.5、40、40.5、41、41.5、42、42.5、43、43.5、44、44.5、45、45.5、46、46.5、47、47.5、48、48.5、49、49.5、50。

Na₂O can reduce the haze of the glass ceramics and the glass ceramics products, increase the glass phase in the glass ceramics, and is beneficial to the hot bending forming of the glass ceramics, but if the content of Na is excessive, the content of Na₂O, in turn, causes coarsening of crystals in the crystallized glass and the crystallized glass article, and in turn causes deterioration of haze and transmittance of the crystallized glass and the crystallized glass article. Thus, Na₂The content of O is 0 to 4%, preferably 0.5 to 3%, more preferably 0.5 to 2.5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% Na may be included₂O。

In some embodiments, (Al) is₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) The control range is 0.1-0.8, which is beneficial to forming a crystalline phase of lithium disilicate and petalite in the crystallization process of matrix glass, and improves the crystallinity and the Vickers hardness of the microcrystalline glass and the microcrystalline glass product. Therefore, (Al) is preferable₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.1 to 0.8, more preferably (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.2 to 0.62. Further, by controlling (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) In the range of 0.3-0.6, the crystal grains can be refined, the falling resistance of the microcrystalline glass and the microcrystalline glass product is improved, and the falling ball test height of the microcrystalline glass product and the microcrystalline glass is improved. Therefore, (Al) is more preferable₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.3 to 0.6, and more preferably (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) 0.4 to 0.55. In some embodiments, (Al)₂O₃+ZnO)/(Li₂O+Na₂O+ZrO₂) May have a value of 0.1, 0.15, 0.2, 0.25、0.3、0.35、0.4、0.45、0.5、0.55、0.6、0.65、0.7、0.75、0.8。

B₂O₃The glass does not participate in the formation of crystals, the glass phase in the glass ceramics can be increased, and the glass ceramics is beneficial to the hot bending forming of the glass ceramics, but if the glass contains B excessively₂O₃Therefore, the crystal grains are promoted to grow rapidly, and the crystallization treatment is not easy to control. Thus B₂O₃The content is in the range of 0 to 4%, preferably 0.5 to 3%, more preferably 0.5 to 2.5%. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% B may be included₂O₃。

In some embodiments, (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂And controlling the grain size of the microcrystalline glass and the microcrystalline glass product to be more than 24, reducing the | B | value and the haze, and improving the light transmittance. Therefore, (SiO) is preferable₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 24 or more, more preferably (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 25 to 50. Further, mixing (SiO)₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂The control is within the range of 26-45, and the crystallinity and the falling resistance of the microcrystalline glass and the microcrystalline glass product can be improved. Therefore, (SiO) is more preferable₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 26 to 45, and (SiO) is more preferable₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂Is 27 to 40. In some embodiments of the present invention, the substrate is,

(SiO₂+Al₂O₃+Na₂O+B₂O₃)/ZrO₂may be 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5、32、32.5、33、33.5、34、34.5、35、35.5、36、36.5、37、37.5、38、38.5、39、39.5、40、40.5、41、41.5、42、42.5、43、43.5、44、44.5、45、45.5、46、46.5、47、47.5、48、48.5、49、49.5、50。

K₂O lowers the viscosity of the glass, promotes the formation of crystals during heat treatment, but if K is contained excessively₂And O, the glass crystal is easy to coarsen, and the transmittance and the falling ball test height of the microcrystalline glass and the microcrystalline glass product are reduced. Thus, K₂The content of O is 4% or less, preferably 3% or less, and more preferably 2% or less. In some embodiments, K may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%₂O。

SrO is an optional component for improving the low-temperature melting property of the glass and suppressing devitrification at the time of glass forming, but is not favorable for glass forming when the content is too large. Therefore, in the present invention, the SrO content is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no SrO is contained. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% SrO may be included.

BaO is an optional component which contributes to the improvement of glass forming properties of the glass, and when the content is too large, glass forming is not facilitated. Therefore, the content of BaO in the present invention is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably contains no BaO. In some embodiments, BaO may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

CaO can increase the hardness of the glass, and when the content is too large, the glass is easy to be milky during forming. Therefore, in the present invention, the content of CaO is in the range of 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%, and further preferably no CaO is contained. In some embodiments, CaO may be included at about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

TiO₂Is an optional component which is helpful for reducing the melting temperature of the glass and improving the chemical stability, and the content of TiO is less than 5 percent in the invention₂The crystallization process of the glass can be easily controlled, and TiO is preferred₂The content of (b) is 3% or less, more preferably 1% or less. In some embodiments, it is further preferred that no TiO is present₂. In some embodiments, about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% TiO may be included₂。

In some embodiments, the glass, microcrystalline glass or microcrystalline glass product can further comprise 0-2% of a fining agent to improve the defoaming capability of the glass, microcrystalline glass or microcrystalline glass product. Such fining agents include, but are not limited to, Sb₂O₃、SnO₂SnO and CeO₂Preferably Sb₂O₃As a clarifying agent. The upper limit of the content of the above-mentioned clarifying agent, when it is present alone or in combination, is preferably 1%, more preferably 0.5%. In some embodiments, one or more of the above 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%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.

In order to obtain the desired excellent properties of the glass, glass-ceramic or glass-ceramic article of the present invention, such as mechanical properties, optical properties, productivity and chemical strengthening properties, it is preferred in some embodiments of the present invention that F is not included; and/or does not contain Ta₂O₅。

PbO and As₂O₃Are 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 embodiments₂O₃。

In some embodiments of the present invention, by including a colorant, a colored matrix glass can be producedThe glass, the microcrystalline glass or the microcrystalline glass product can make the matrix glass, the microcrystalline glass or the microcrystalline glass product show different colors, and the colorant comprises: NiO: 0 to 4 percent; and/or Ni₂O₃: 0 to 4 percent; and/or a CoO: 0-2%; and/or Co₂O₃: 0-2%; and/or Fe₂O₃: 0 to 7 percent; and/or MnO₂: 0 to 4 percent; and/or Er₂O₃: 0-8%; and/or Nd₂O₃: 0-8%; and/or Cu₂O: 0 to 4 percent; and/or Pr₂O₅: 0-8%; and/or CeO₂: 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 product₂O₃Or Pr₂O₅Is a colorant. NiO and Ni₂O₃For 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 included₂O₃. NiO and Ni, if used in admixture₂O₃The 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% may be included1.8%, 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 Ni₂O₃. Using Pr₂O₅The colorant for green matrix glass, glass ceramics or glass ceramics is used alone, and is generally contained in an amount of 8% or less, preferably 6% or less, and the lower limit of the content is 0.4% or more, for example, less than 0.4%, and the matrix glass, glass ceramics or glass ceramics product is not conspicuous in color. 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 included₂O₅。

The blue matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses CoO or Co₂O₃The 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 included₂O₃. CoO and Co, if used in admixture₂O₃The 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%, or,1.6%, 1.7%, 1.8%, 1.9%, 2.0% of CoO and Co₂O₃。

The yellow matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Cu₂O or CeO₂The 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%, no apparent color of the matrix glass, microcrystalline glass or microcrystalline glass product, and Cu alone₂O 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 included₂And O. Using CeO alone₂The 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 included₂. At the same time, a small amount of CeO₂Added to glass with a defoaming effect, CeO₂Can 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, 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 percent and 4.0 percent of CeO₂And Cu₂O。

The black or smoke gray matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention independently uses Fe₂O₃Is a colorant; or using Fe₂O₃And CoO; or using Fe₂O₃And Co₂O₃Two colorants used in combination; or using Fe₂O₃Three colorants mixed together, CoO and NiO; or using Fe₂O₃、Co₂O₃And NiO. Colorants for the production of black and smoky grey matrix glass, glass ceramics or glass ceramic articles using predominantly Fe₂O₃Coloration, 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 included₂O₃. CoO and Co₂O₃Can absorb visible light to increase the coloring degree of matrix glass, microcrystalline glass or microcrystalline glass products, and is generally combined with Fe₂O₃The 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 included₂O₃. 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 and the microcrystalline glass prepared by the inventionGlass or glass-ceramic articles, using MnO₂As 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, MnO of 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% may be included₂。

Er is used in the pink substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃The content of the colorant used is generally 8% or less, preferably 6% or less. Because of rare earth element Er₂O₃The 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 included₂O₃。

The mauve substrate glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention uses Nd₂O₃The content of the colorant used is generally 8% or less, preferably 6% or less. Due to rare earth element Nd₂O₃The coloring efficiency is low, the use content exceeds 8 percent, the color of the matrix glass, the microcrystalline glass or the microcrystalline glass product cannot be further deepened, but the cost is increased, and the lower limit of the content is 0.4% or more, e.g., less than 0.4%, the color of the matrix glass, microcrystalline glass or microcrystalline glass article is not apparent. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd may be included₂O₃。

Er is used for the red matrix glass, the microcrystalline glass or the microcrystalline glass product prepared by the invention₂O₃、Nd₂O₃And MnO₂The 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 product₂O₃And Nd₂O₃Coloring rare earth, relatively weak coloring ability, Er₂O₃The usage amount is less than 6 percent, Nd₂O₃The usage amount is less than 4 percent, MnO₂The 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.

"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the matrix glass, the glass ceramic or the glass ceramic product of the present invention; it is within the scope of the present invention that certain impurities or components, 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 glass-ceramic and glass-ceramic articles comprises lithium disilicate and petalite, and/or quartz and quartz solid solution, providing high strength to the glass-ceramic and glass-ceramic articles of the present invention, and the glass-ceramic and glass-ceramic articles have high fracture toughness; the height of the ball drop test and the four-point bending strength of the microcrystalline glass and the microcrystalline glass product are increased; the haze is reduced and the light transmittance is increased. The microcrystalline glass has excellent chemical strengthening performance, and can obtain more excellent mechanical strength through chemical strengthening. Through reasonable component design, the microcrystalline glass and the microcrystalline glass product can obtain proper grain size, and the microcrystalline glass product have high strength. The microcrystalline glass and the microcrystalline glass product have good crystallinity, so that the microcrystalline glass and the microcrystalline glass product have excellent mechanical properties. The crystallinity is the complete degree of crystallization, the arrangement of mass points in the complete crystal is regular, the diffraction line is strong, sharp and symmetrical, and the half-height width of a diffraction peak is close to the width measured by an instrument; the crystals with poor crystallinity have defects such as dislocation and the like, so that diffraction line peaks are wide and diffuse. The poorer the crystallinity, the weaker the diffraction power, the wider the diffraction peak until it disappears in the background. In some embodiments, the microcrystalline glass article or microcrystalline glass has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

The size and the type of crystal grains in the microcrystalline glass or the microcrystalline glass product can influence the haze and the transmittance of the microcrystalline glass or the microcrystalline glass product, and the smaller the crystal grain is, the higher the transmittance is; the smaller the haze, the higher the transmittance. In some embodiments, the haze of the microcrystalline glass article or microcrystalline glass having a thickness of 1mm or less is 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. In some embodiments, the crystallite glass article or crystallite glass has a grain size of 40nm or less, preferably 30nm or less, more preferably 25nm or less.

In some embodiments, the microcrystalline glass or the microcrystalline glass product of the present invention exhibits a high transmittance in the visible light range, and in some embodiments, an average light transmittance of 400 to 800nm of a microcrystalline glass product or a microcrystalline glass having a thickness of 1mm or less is preferably 89% or more. In some preferred embodiments, the microcrystalline glass product or microcrystalline glass having a thickness of 1mm or less preferably has a light transmittance of 91% or more at 550 nm.

At one endIn some embodiments, an antimicrobial component may be added to the matrix glass, microcrystalline glass, or microcrystalline glass article. The crystallized glass or crystallized glass article described herein may be used in applications such as kitchens or countertops where exposure to harmful bacteria is likely. Antimicrobial components that may be added to the matrix glass, glass-ceramic, or glass-ceramic article include, but are not limited to, Ag, AgO, Cu, CuO, Cu₂O, and the like. In some embodiments, the antimicrobial components described above are present at 2% or less, preferably 1% or less, alone or in combination.

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

and (3) generation of matrix glass: the raw materials are uniformly mixed according to the component proportion, the uniform mixture is put into a crucible made of platinum or quartz, and the melting is carried out for 5 to 24 hours in an electric furnace or a gas furnace within the temperature range of 1400 to 1650 ℃ according to the melting difficulty of the glass composition. Melting, stirring to make it uniform, cooling to proper temperature, casting into mould, and slowly cooling.

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

The matrix glass of the invention is crystallized by a crystallization process after molding or after molding processing, and crystals are uniformly precipitated in the glass. The crystallization may be performed in 1 stage, 2 stages, or 3 stages. In order to obtain desired physical properties of the glass-ceramic, the preferred crystallization process is:

the above-mentioned crystallization treatment is performed in 1 stage, and the nucleus formation process and the crystal growth process can be continuously performed. That is, the temperature is raised to a predetermined crystallization temperature, and after reaching the crystallization temperature, the temperature is maintained for a predetermined time, and then the temperature is lowered. The crystallization temperature is preferably 600 to 750 ℃, and more preferably 650 to 720 ℃, in order to precipitate a desired crystal phase, the holding time at the crystallization temperature is preferably 0 to 8 hours, and more preferably 1 to 6 hours.

In the case of performing the crystallization process through 2 stages as described above, the process of the nucleation process is performed at the 1 st temperature, and then the process of the crystal growth process is performed at the 2 nd temperature. The 1 st temperature is preferably 470-600 ℃, and the 2 nd temperature is preferably 600-750 ℃. 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.

When the crystallization is performed through 3 stages, the nucleation process is performed at the 1 st temperature, and then the crystal growth process is performed at the 2 nd and 3 rd temperatures, wherein the 1 st temperature is preferably 470-550 ℃, the 2 nd temperature is preferably 570-630 ℃, and the 3 rd temperature is preferably 650-750 ℃. 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 holding time at the 3 rd temperature is preferably 0 to 10 hours, more preferably 0.5 to 6 hours.

The above-mentioned holding time of 0 hour means that the temperature is lowered or raised less than 1 minute after the temperature is reached.

In some embodiments, the matrix or 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. 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 the smaller ions with the larger ions to build a compressive stress in the matrix glass or the microcrystalline glass to form a compressive stress layer.

In some embodiments, the metal ion is a monovalent alkali metal ion (e.g., Na)⁺、K⁺、Rb⁺、Cs⁺Etc.), ion exchange is performed by immersing the matrix glass or glass-ceramic in a salt bath of at least one molten salt containing larger metal ions for replacing the smaller metal ions in the matrix glass. Alternatively, other monovalent metal ions such as Ag⁺、Tl⁺、Cu⁺Etc. may also be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or glass-ceramic may include, but are not limited to: it is immersed in a single salt bath or in a plurality of salt baths of the same or different composition with washing and/or annealing steps between the immersions.

In some embodiments, the matrix glass or glass-ceramic may be formed by melting a Na salt (e.g., NaNO) by immersion at a temperature of about 320 ℃ to 470 ℃₃) The salt bath is subjected to ion exchange for about 6 to 20 hours, the preferred temperature range is 360 to 460 ℃, and the preferred time range is 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 immersionMelting K salt (e.g. KNO) at a temperature of about 340 deg.C to 450 deg.C₃) The salt bath is subjected to ion exchange for 1 to 24 hours, and the preferable time range is 2 to 10 hours. 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 340 ℃ to 500 ℃₃) And molten Na salts (e.g., NaNO)₃) And carrying out ion exchange in the mixed salt bath for 1-24 hours, wherein the preferable time range is 2-10 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 heat strengthening method of heating a base glass or a glass ceramics and then rapidly cooling it.

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

[ haze ]

A haze tester EEL57D was used, and samples of 1mm or less were prepared 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 to be less than 1mm, 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 1mm or less and the opposed faces were polished in parallel, and the light transmittance at 550nm was measured by Hitachi U-41000 spectrophotometer.

[ degree of crystallinity ]

The XRD diffraction peaks were compared with the database 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 ]

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

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 ]

A microcrystalline glass product sample of 150mm × 57mm × 0.7mm 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. The drop test height is sometimes referred to herein as the drop height.

[ height of falling ball of body ]

A microcrystalline glass sample of 150mm multiplied by 57mm multiplied by 0.7mm is placed on a glass bearing clamp, 32g of steel balls are dropped from a specified height, and the maximum ball drop test height of the sample which can bear the impact without breaking is the body ball drop height. Specifically, the test was conducted from a ball drop test height of 500mm, and the height was changed in the order of 550mm, 600mm, 650mm, 700mm and more without breaking. For the examples having the "body ball drop height", glass ceramics were used as the test subjects. The test data recorded as 1000mm in the examples shows that the glass ceramics were not broken and received impact even when the steel ball was dropped from 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, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.

[ four-point bending Strength ]

A microcomputer-controlled electronic universal tester CMT6502 is adopted, the sample specification is below 1mm in thickness, and the test is carried out by taking ASTM C158-2002 as a standard.

The sample thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.

[ 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 depression²) The values of (b) indicate (a). The test load was set to 100(N) and the holding time was set to 15 (sec). In the present invention, Vickers hardness is sometimes referred to simply as hardness.

[ coefficient of thermal expansion ]

Coefficient of thermal expansion (alpha)_20℃-300℃) The test was carried out according to the test method GB/T7962.16-2010.

[ refractive index ]

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

[ | B | value ]

B value detection was performed using Mentenda CM-700 d. And (3) performing zero calibration and white board calibration of the instrument by using the matched long correction cylinder and the matched short correction cylinder respectively, performing an empty test by using the long cylinder after calibration, judging the stability and calibration reliability (B is less than or equal to 0.05) of the instrument, and placing a product on the zero long cylinder for testing after the instrument is qualified for calibration.

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

[ shatter resistance ]

The drop resistance test was carried out using a directional drop tester WH-2101. The 2D glass ceramic product is loaded with glass products with the same specification (each glass product is 20g in weight and is loaded with 2 glass sheets), 60-80 meshes of sand paper is laid on a base, the sand paper freely falls from the specified height, a sample is directly hammered on the sand paper, and the height which can bear the impact without breaking is the falling resistance. Specifically, the test was conducted from a height of 600mm, and the height was changed in the order of 700mm, 800mm, 900mm, 1000mm and more without breaking. For the examples having "drop-resistance", a glass ceramic product was used as a test object. The test data recorded as 2000mm in the examples indicates that even a loaded glass-ceramic article withstood impact without breaking from a height of 2000mm, the maximum test height of the drop tester WH-2101 was 2000 mm.

The microcrystalline glass product has the following properties:

1) 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.

2) In some embodiments, the ion exchange layer depth of the crystallized glass product is 80 μm or more, preferably 100 μm or more, and more preferably 120 μm or more.

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

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

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

6) In some embodiments, the microcrystalline glass article has a Vickers hardness of 730kgf/mm²Above, preferably 750kgf/mm²Above, more preferably 780kgf/mm²The above.

7) In some embodiments, the microcrystalline glass article has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

8) In some embodiments, the crystallite glass article has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.

9) In some embodiments, the microcrystalline glass article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

10) In some embodiments, the microcrystalline glass product having a thickness of 1mm or less has an average transmittance of 87% or more, preferably 88% or more, and more preferably 89% or more at a wavelength of 400 to 800 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

11) In some embodiments, the microcrystalline glass product having a thickness of 1mm or less has a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

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

13) In some embodiments, the shatter resistance of the glass-ceramic article having a thickness of 1mm or less is 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and still more preferably 2000mm or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

The microcrystalline glass has the following properties:

1) in some embodiments, the microcrystalline glass has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.

2) In some embodiments, the crystallite glass has a grain size of 40nm or less, preferably 30nm or less, preferably 25nm or less.

3) In some embodiments, the haze of the microcrystalline glass having a thickness of 1mm or less is 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

4) In some embodiments, the microcrystalline glass having a thickness of 1mm or less has an average transmittance of 87% or more, preferably 88% or more, and more preferably 89% or more at a wavelength of 400 to 800 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

5) In some embodiments, the microcrystalline glass having a thickness of 1mm or less has a transmittance at a wavelength of 550nm of 88% or more, preferably 90% or more, and more preferably 91% or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.

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

7) In some embodiments, the glass-ceramic body has a ball drop height of 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more.

8) In some embodiments, the microcrystalline glass has a Vickers hardness of 650kgf/mm²Above, preferably 680kgf/mm²Above, more preferably 700kgf/mm²The above.

9) In some embodiments, the microcrystalline glass has a coefficient of thermal expansion (α)_20℃-120℃) Is 65X 10^-7/K～85×10^-7/K。

10) In some embodiments, the refractive index (n) of the glass-ceramic_d) Is 1.5300 to 1.5420.

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

1) in some embodiments, the matrix glass has a coefficient of thermal expansion (α)_20℃-120℃) Is 50X 10^-7/K～70×10^-7/K。

2) In some embodiments, the refractive index (n) of the matrix glass_d) Is 1.5200 to 1.5300.

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 of the present invention are applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc., for manufacturing protective glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, automobile windows, train windows, aircraft windows, touch screen protective glass, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white home appliances, such as for manufacturing refrigerator parts or kitchen ware.

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%.

< example of matrix glass >

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

Table 1.

Table 2.

< microcrystalline glass example >

In this example, glass ceramics having compositions shown in tables 3 to 4 were obtained by the above-mentioned method for producing glass ceramics. The characteristics of each glass ceramics were measured by the test method described in the present invention, and the measurement results are shown in tables 3 to 4, and the test thickness of the sample of the glass ceramics in the examples was 0.7 mm.

Table 3.

Table 4.

< microcrystalline glass article example >

In this example, glass ceramics having compositions shown in tables 5 to 6 were obtained by the above-mentioned method for producing glass ceramics. The characteristics of each of the microcrystalline glass products were measured by the test method according to the present invention, and the measurement results are shown in tables 5 to 6, and the test thickness of the sample of the microcrystalline glass product in the example was 0.7 mm.

Table 5.

Table 6.

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