Glass-ceramic and glass-ceramic article
1. Glass-ceramic, characterized in that its composition, expressed in weight percentages, contains: SiO 22：68～82％；Al2O3：2～15％；Li2O：7～15％；P2O5+ZrO2：1～10％。
2. The glass-ceramic according to claim 1, further comprising, in weight percent: ZnO + MgO: 0 to 5 percent; 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.
3. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, wherein: li2O/(ZnO + MgO) is 9.5 or more, and Li is preferable2O/(ZnO + MgO) is 10 to 50, and Li is more preferable2O/(ZnO + MgO) is 11 to 40, and Li is more preferable2O/(ZnO + MgO) is 13 to 30.
4. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, wherein: (SiO)2+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)/ZrO2Is 31 to 38.5.
5. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, wherein: (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3.
6. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, wherein: (SiO)2+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.
7. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, 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: 0.1-5%, preferably ZnO + MgO: 0.1 to 3%, more 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.
8. The glass-ceramic according to claim 1 or 2, characterized in that its composition is expressed in weight percentages, 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％。
9. The glass-ceramic according to claim 1 or 2, wherein the crystalline phase in the glass-ceramic comprises lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phase in the glass ceramic contains lithium disilicate and petalite, the total content of the lithium disilicate and the petalite 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% of the weight percent of the glass ceramic, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75% of the weight percent of the glass ceramic, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70% of the weight percent of the glass ceramic.
10. The glass-ceramic according to claim 1 or 2, wherein the lithium disilicate crystalline phase is 15 to 40% by weight of the glass-ceramic, preferably the lithium disilicate crystalline phase is 20 to 35% by weight of the glass-ceramic, more preferably the lithium disilicate crystalline phase is 25 to 35% by weight of the glass-ceramic; and/or the petalite crystal phase accounts for 30-55% of the glass ceramic by weight, preferably the petalite crystal phase accounts for 35-55% of the glass ceramic by weight, and more preferably the petalite crystal phase accounts for 35-50% of the glass ceramic by weight; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the glass ceramic by weight, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the glass ceramic by weight; and/or the lithium monosilicate crystal phase accounts for 0-10% of the glass ceramic by weight, preferably the lithium monosilicate crystal phase accounts for 0-7% of the glass ceramic by weight, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the glass ceramic by weight.
11. The glass-ceramic according to claim 1 or 2, wherein the glass-ceramic has a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the glass-ceramic has a crystal grain size of 40nm or less, preferably 30nm or less, preferably 25nm or less; and/or the ball falling height of the glass ceramic body is 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the glass-ceramic has a Vickers hardness of 650kgf/mm2Above, preferably 680kgf/mm2Above, more preferably 700kgf/mm2The above; and/or the coefficient of thermal expansion of the glass-ceramic is 65X 10-7/K～85×10-7K; and/or the refractive index of the glass ceramic is 1.5300 to 1.5420.
12. The glass-ceramic according to claim 1 or 2, wherein the glass-ceramic has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less, for a thickness of 1mm or less; and/or a glass ceramic 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 glass ceramic 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 glass ceramic having a thickness of 1mm or less, the average light | B | value of 400 to 800nm being 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less.
13. The glass-ceramic according to claim 12, wherein the glass-ceramic has a thickness of 0.2 to 1mm, preferably 0.3 to 0.9mm, more preferably 0.5 to 0.8mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.
14. The glass-ceramic of claim 1 or 2, 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％。
15. A glass-ceramic article made of the glass-ceramic according to any one of claims 1 to 14.
16. Glass-ceramic article, characterized in that it comprises, expressed in weight percent: SiO 22：68～82％；Al2O3：2～15％；Li2O：7～15％；P2O5+ZrO2：1～10％。
17. The glass-ceramic article according to claim 16,the composite material is characterized by also comprising the following components in percentage by weight: ZnO + MgO: 0 to 5 percent; 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.
18. The glass-ceramic article according to claim 16 or 17, wherein the composition is expressed in weight percent, wherein: li2O/(ZnO + MgO) is 9.5 or more, and Li is preferable2O/(ZnO + MgO) is 10 to 50, and Li is more preferable2O/(ZnO + MgO) is 11 to 40, and Li is more preferable2O/(ZnO + MgO) is 13 to 30.
19. The glass-ceramic article according to claim 16 or 17, wherein the composition is expressed in weight percent, wherein: (SiO)2+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)/ZrO2Is 31 to 38.5.
20. The glass-ceramic article according to claim 16 or 17, wherein the composition is expressed in weight percent, wherein: (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3.
21. The glass-ceramic article according to claim 16 or 17, wherein the composition is expressed in weight percent, wherein: (SiO)2+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.
22. The glass-ceramic article according to claim 16 or 17, wherein the composition is 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: 0.1-5%, preferably ZnO + MgO: 0.1 to 3%, more 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.
23. The glass-ceramic article of claim 16 or 17, wherein the components are present in weight percentIs shown, in which: 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％。
24. The glass-ceramic article of claim 16 or 17, wherein the glass-ceramic article comprises a crystalline phase comprising lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phases in the glass ceramic article comprise lithium disilicate and petalite, the combined content of lithium disilicate and petalite being in a higher weight percentage than the other crystalline phases, more preferably the combined content of lithium disilicate and petalite crystalline phases is 50-80% by weight of the glass ceramic article, even more preferably the combined content of lithium disilicate and petalite crystalline phases is 55-75% by weight of the glass ceramic article, even more preferably the combined content of lithium disilicate and petalite crystalline phases is 55-70% by weight of the glass ceramic article.
25. The glass-ceramic article of claim 16 or 17, wherein the lithium disilicate crystalline phase comprises 15 to 40% by weight of the glass-ceramic article, preferably the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic article, and more preferably the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic article; and/or the petalite crystal phase accounts for 30-55 wt% of the glass ceramic product, preferably the petalite crystal phase accounts for 35-55 wt% of the glass ceramic product, and more preferably the petalite crystal phase accounts for 35-50 wt% of the glass ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the glass ceramic product by weight, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the glass ceramic product by weight; and/or the lithium monosilicate crystal phase is 0 to 10% by weight of the glass-ceramic article, preferably the lithium monosilicate crystal phase is 0 to 7% by weight of the glass-ceramic article, more preferably the lithium monosilicate crystal phase is 0 to 5% by weight of the glass-ceramic article.
26. The glass-ceramic article of claim 16 or 17, wherein the glass-ceramic article has a four-point bending strength of 600MPa or greater, preferably 650MPa or greater, more preferably 700MPa or greater; and/or the glass-ceramic article has an ion exchange layer depth of 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more; and/or the surface stress of the glass-ceramic article is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or the glass-ceramic article has a ball drop test height of 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more; and/or the fracture toughness of the glass ceramic article is 1MPa m1/2Above, preferably 1.1MPa · m1/2More preferably 1.2MPa · m or more1/2The above; and/or the glass-ceramic article has a Vickers hardness of 730kgf/mm2Above, preferably 750kgf/mm2Above, more preferably 780kgf/mm2The above; and/or the glass-ceramic article has a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the glass-ceramic article has a grain size of 40nm or less, preferably 30nm or less, more preferably 25nm or less.
27. The glass-ceramic article of claim 16 or 17, wherein the glass-ceramic article 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 glass-ceramic product 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 glass-ceramic article 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 the glass-ceramic article has a thickness of 1mm or less, and 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 falling 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 further preferably 2000mm or more.
28. The glass-ceramic article of claim 27, wherein the glass-ceramic article has a thickness of 0.2 mm to 1mm, preferably 0.3 mm to 0.9mm, more preferably 0.5 mm to 0.8mm, and even more preferably 0.55mm or 0.6mm or 0.68mm or 0.7mm or 0.75 mm.
29. The glass-ceramic article of claim 16 or 17, 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％。
30. Glass cover plate, characterized in that it is made of a glass-ceramic according to any one of claims 1 to 14 and/or a glass-ceramic according to any one of claims 15 to 29.
31. A glass component, characterized in that it is made of the glass-ceramic according to any one of claims 1 to 14 and/or made of the glass-ceramic according to any one of claims 15 to 29.
32. A display device comprising the glass-ceramic according to any one of claims 1 to 14, and/or comprising the glass-ceramic article according to any one of claims 15 to 29, and/or comprising the glass cover plate according to claim 30, and/or comprising the glass component according to claim 31.
33. An electronic device comprising the glass-ceramic according to any one of claims 1 to 14, and/or comprising the glass-ceramic product according to any one of claims 15 to 29, and/or comprising the glass cover plate according to claim 30, and/or comprising the glass component according to claim 31.
Background
In recent years, glass ceramics have a tendency to be processed into cover plates or protective housings for various consumer electronics products, such as mobile phones, music players, electronic book readers, notebook computers, tablet computers, automated teller machines, and other similar devices. In addition, the glass ceramic can be widely applied to equipment such as automobiles, monitoring security and the like. The glass ceramics used in the above fields are required to have excellent mechanical properties to meet the requirements of drop resistance, pressure resistance, scratch resistance, etc. during use. It is known that the glass ceramic in the prior art can be chemically strengthened to improve the mechanical properties of the glass ceramic, but the glass ceramic in the prior art has the problems that the chemical strengthening is not easy to occur, or the mechanical properties after the chemical strengthening are difficult to meet the requirements of being applied to cover plate materials. Therefore, the development of a glass ceramic suitable for display devices or electronic devices with high requirements on drop resistance, pressure resistance and scratch resistance is a goal pursued by science and technology personnel.
Disclosure of Invention
The invention aims to provide a glass ceramic and a glass ceramic product with excellent mechanical properties.
The technical scheme adopted by the invention for solving the technical problem is as follows:
glass-ceramic, the composition of which, expressed in weight percent, contains: SiO 22：68～82％；Al2O3：2～15％；Li2O：7～15％；P2O5+ZrO2：1～10％。
Further, the glass ceramic comprises the following components in percentage by weight: ZnO + MgO: 0 to 5 percent; 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.
Further, the glass ceramic comprises the following components in percentage by weight: li2O/(ZnO + MgO) is 9.5 or more, and Li is preferable2O/(ZnO + MgO) is 10 to 50, and Li is more preferable2O/(ZnO + MgO) is 11 to 40, and Li is more preferable2O/(ZnOAnd + MgO) is 13 to 30.
Further, the glass ceramic comprises the following components in percentage by weight: (SiO)2+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)/ZrO2Is 31 to 38.5.
Further, the glass ceramic comprises the following components in percentage by weight: (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3.
Further, the glass ceramic comprises the following components in percentage by weight: (SiO)2+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.
Further, the glass ceramic 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: 0.1-5%, preferably ZnO + MgO: 0.1 to 3%, more 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.
Further, the glass ceramic 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％。
Further, the glass ceramic 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 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% of the weight percent of the glass ceramic, even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-75% of the weight percent of the glass ceramic, and even more preferably the total content of the lithium disilicate and the petalite crystalline phase accounts for 55-70% of the weight percent of the glass ceramic.
Furthermore, in the glass ceramic, the content of the lithium disilicate crystal phase in the glass ceramic is 15-40 wt%, preferably the content of the lithium disilicate crystal phase in the glass ceramic is 20-35 wt%, and more preferably the content of the lithium disilicate crystal phase in the glass ceramic is 25-35 wt%; and/or the petalite crystal phase accounts for 30-55% of the glass ceramic by weight, preferably the petalite crystal phase accounts for 35-55% of the glass ceramic by weight, and more preferably the petalite crystal phase accounts for 35-50% of the glass ceramic by weight; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the glass ceramic by weight, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the glass ceramic by weight; and/or the lithium monosilicate crystal phase accounts for 0-10% of the glass ceramic by weight, preferably the lithium monosilicate crystal phase accounts for 0-7% of the glass ceramic by weight, and more preferably the lithium monosilicate crystal phase accounts for 0-5% of the glass ceramic by weight.
Further, the glass ceramic has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more; and/or the glass-ceramic has a crystal grain size of 40nm or less, preferably 30nm or less, preferably 25nm or less; and/or the ball falling height of the glass ceramic body is 1700mm or more, preferably 1900mm or more, and more preferably 2000mm or more; and/or the glass-ceramic has a Vickers hardness of 650kgf/mm2Above, preferably 680kgf/mm2Above, more preferably 700kgf/mm2The above; and/or the coefficient of thermal expansion of the glass-ceramic is 65X 10-7/K～85×10-7K; and/or the refractive index of the glass ceramic is 1.5300 to 1.5420.
Further, the glass ceramic has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less, when the glass ceramic has a thickness of 1mm or less; and/or a glass ceramic 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 glass ceramic 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 glass ceramic having a thickness of 1mm or less, the average light | B | value of 400 to 800nm being 0.9 or less, preferably 0.8 or less, more preferably 0.7 or less.
Further, 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 further preferably 0.55mm, 0.6mm, 0.68mm, 0.7mm or 0.75 mm.
Further, the glass-ceramic 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％。
A glass-ceramic article made from any of the glass-ceramics described above.
A glass-ceramic article having a composition, expressed in weight percent, comprising: SiO 22：68～82％；Al2O3：2～15％；Li2O：7～15％；P2O5+ZrO2：1～10％。
Further, the glass-ceramic article comprises, in weight percent: ZnO + MgO: 0 to 5 percent; 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.
Further, the glass-ceramic article has a composition, expressed in weight percent, wherein: li2O/(ZnO + MgO) is 9.5 or more, and Li is preferable2O/(ZnO + MgO) is 10 to 50, and Li is more preferable2O/(ZnO + MgO) is 11 to 40, and Li is more preferable2O/(ZnO + MgO) is 13 to 30.
Further, the glass-ceramic article has a composition, expressed in weight percent, wherein: (SiO)2+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)/ZrO2Is 31 to 38.5.
Further, the glass-ceramic article has a composition, expressed in weight percent, wherein: (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3.
Further, the glass-ceramic article has a composition, expressed in weight percent, wherein: (SiO)2+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 ℃40。
Further, the glass-ceramic article has a composition, 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: 0.1-5%, preferably ZnO + MgO: 0.1 to 3%, more 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.
Further, the glass-ceramic article has a composition, 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％。
Further, the glass-ceramic article comprises a crystalline phase comprising lithium silicate; and/or quartz and quartz solid solutions; and/or petalite, preferably the crystalline phases in the glass ceramic article comprise lithium disilicate and petalite, the combined content of lithium disilicate and petalite being in a higher weight percentage than the other crystalline phases, more preferably the combined content of lithium disilicate and petalite crystalline phases is 50-80% by weight of the glass ceramic article, even more preferably the combined content of lithium disilicate and petalite crystalline phases is 55-75% by weight of the glass ceramic article, even more preferably the combined content of lithium disilicate and petalite crystalline phases is 55-70% by weight of the glass ceramic article.
Further, the glass ceramic product has a lithium disilicate crystal phase 15-40 wt%, preferably 20-35 wt%, and more preferably 25-35 wt%; and/or the petalite crystal phase accounts for 30-55 wt% of the glass ceramic product, preferably the petalite crystal phase accounts for 35-55 wt% of the glass ceramic product, and more preferably the petalite crystal phase accounts for 35-50 wt% of the glass ceramic product; and/or the quartz and quartz solid solution crystal phase accounts for 5-25% of the glass ceramic product by weight, preferably the quartz and quartz solid solution crystal phase accounts for 7-20% of the glass ceramic product by weight; and/or the lithium monosilicate crystal phase is 0 to 10% by weight of the glass-ceramic article, preferably the lithium monosilicate crystal phase is 0 to 7% by weight of the glass-ceramic article, more preferably the lithium monosilicate crystal phase is 0 to 5% by weight of the glass-ceramic article.
Further, the glass-ceramic article has a four-point bending strength of 600MPa or more, preferably 650MPa or more, and more preferably 700MPa or more; and/or the glass-ceramic article has an ion exchange layer depth of 80 μm or more, preferably 100 μm or more, more preferably 120 μm or more; and/or the surface stress of the glass-ceramic article is 100MPa or more, preferably 150MPa or more, more preferably 200MPa or more; and/or the glass-ceramic article has a ball drop test height of 1400mm or more, preferably 1500mm or more, more preferably 1600mm or more; and/or the fracture toughness of the glass ceramic article is 1MPa m1/2Above, preferably 1.1MPa · m1/2More preferably 1.2MPa · m or more1/2The above; and/or the glass-ceramic article has a Vickers hardness of 730kgf/mm2Above, preferably 750kgf/mm2Above, more preferably 780kgf/mm2The above; and/or the glass-ceramic article has a crystallinity of 50% or more, preferably 60% or more, more preferably 70% or more; and/or the glass-ceramic article has a grain size of 40nm or less, preferably 30nm or less, more preferably 25nm or less.
Further, the glass ceramic article has a haze of 0.2% or less, preferably 0.15% or less, more preferably 0.12% or less, for a thickness of 1mm or less; and/or a glass-ceramic product 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 glass-ceramic article 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 the glass-ceramic article has a thickness of 1mm or less, and 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 falling 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 further preferably 2000mm or more.
Further, 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.
Further, the glass-ceramic 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％。
A matrix glass, the composition of which, expressed in weight percent, comprises: SiO 22：68～82％；Al2O3：2～15％；Li2O：7～15％；P2O5+ZrO2：1～10％。
Further, the matrix glass comprises the following components in percentage by weight: ZnO + MgO: 0 to 5 percent; 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.
Further, the matrix glass comprises the following components in percentage by weight: li2O/(ZnO + MgO) is 9.5 or more, and Li is preferable2O/(ZnO + MgO) is 10 to 50, and Li is more preferable2O/(ZnO + MgO) is 11 to 40, and Li is more preferable2O/(ZnO + MgO) is 13 to 30.
Further, the matrix glass comprises the following components in percentage by weight: (SiO)2+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)/ZrO2Is 31 to 38.5.
Further, the matrix glass comprises the following components in percentage by weight: (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3.
Further, the matrix glass comprises the following components in percentage by weight: (SiO)2+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.
Further, the matrix glass 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: 0.1-5%, preferably ZnO + MgO: 0.1 to 3%, more 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.
Further, the matrix glass is composed ofExpressed 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％。
Further, the matrix glass has a thermal expansion coefficient of 50X 10-7/K～70×10-7And/or a refractive index of 1.5200-1.5300.
Further, the matrix glass further contains: 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％。
A glass cover plate made of any one of the glass-ceramics described above, and/or made of any one of the glass-ceramic articles described above, and/or made of any one of the matrix glasses described above.
A glass component made of any one of the above-described glass ceramics, and/or made of any one of the above-described glass ceramic articles, and/or made of any one of the above-described matrix glasses.
A display device comprising a glass-ceramic according to any of the preceding claims and/or comprising a glass-ceramic product according to any of the preceding claims and/or comprising a matrix glass according to any of the preceding claims and/or comprising a glass cover plate according to any of the preceding claims and/or comprising a glass component according to any of the preceding claims.
An electronic device comprising the glass-ceramic according to any of the above, and/or comprising the matrix glass according to any of the above, and/or comprising the glass cover plate according to any of the above, and/or comprising the above glass component.
A method of making a glass-ceramic, the method comprising the steps of: generating matrix glass, and then forming the glass ceramic by the crystallization process of the matrix glass.
Furthermore, the manufacturing method of the glass ceramic comprises the steps of manufacturing the matrix glass into a glass forming body, and then forming the glass ceramic by the glass forming body through a crystallization process.
Further, the method for manufacturing the glass ceramic comprises the following steps: 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.
Further, the method for manufacturing the glass ceramic comprises the following steps: 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.
Further, the method for manufacturing the glass ceramic comprises the following steps: 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.
A method of making a glass-ceramic article, the method comprising the steps of: generating matrix glass, then forming glass ceramic by a crystallization process on the matrix glass, and then forming the glass ceramic into a glass ceramic product by a chemical strengthening process on the glass ceramic.
Further, the manufacturing method of the glass ceramic product comprises the steps of manufacturing matrix glass into a glass forming body, then forming glass ceramic by the glass forming body through a crystallization process, and then forming the glass ceramic into the glass ceramic through a chemical strengthening process, or manufacturing the glass ceramic into the glass ceramic forming body, and then forming the glass ceramic into the glass ceramic through the chemical strengthening process.
Further, the method for manufacturing the glass-ceramic product comprises the following steps: 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.
Further, the method for manufacturing the glass-ceramic product comprises the following steps: 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.
Further, the method for manufacturing the glass-ceramic product comprises the following steps: 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.
Further, the method for manufacturing the glass-ceramic product comprises the following steps: immersing the glass ceramic 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 glass ceramic 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 glass ceramic 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.
The invention has the beneficial effects that: through reasonable component design, the glass ceramic and the glass ceramic product obtained by the invention have excellent mechanical properties; in some embodiments, the obtained glass-ceramic article has excellent drop resistance, and meets the requirements of high drop resistance, high pressure resistance and high scratch resistance of display equipment or electronic equipment.
Detailed Description
The glass-ceramic and glass-ceramic articles of the present invention are materials having a crystalline phase and a glass phase, as distinguished from amorphous solids. The crystalline phases of the glass-ceramic and glass-ceramic articles can be identified by the angle of the peaks 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 the glass-ceramic or glass-ceramic article of the present invention at a low cost by specifying the content and content ratio of specific components constituting the glass-ceramic or glass-ceramic article to specific values and precipitating specific crystal phases.
The ranges of the respective components (components) of the matrix glass, glass ceramic and glass ceramic article 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 matrix glass, or glass ceramic article material converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the composition components of the matrix glass, glass ceramic, or glass ceramic article of the present invention are decomposed at melting and converted into oxides, the total amount of the oxides is 100%. In the present specification, the term "glass" refers to a matrix glass before crystallization, the term "glass ceramic" refers to a glass ceramic after crystallization, and the term "glass ceramic" refers to a glass ceramic after chemical strengthening.
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 glass-ceramic or glass-ceramic article of the present invention, the crystalline 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 glass-ceramic or glass-ceramic article comprise lithium disilicate, which is present in an amount having a higher weight percent than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic articles of the present invention.
In some embodiments of the invention, the crystalline phase in the glass-ceramic or glass-ceramic article comprises 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 invention.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article comprise lithium monosilicate in an amount having a higher weight percent than 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 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 percent than other crystalline phases, resulting in excellent properties of the glass-ceramic or glass-ceramic article of the present invention.
In some embodiments of the present invention, the crystalline phases in the glass-ceramic or glass-ceramic article 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 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 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 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 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 glass-ceramic or glass-ceramic article. In some embodiments, the lithium disilicate crystalline phase comprises 20 to 35% by weight of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium disilicate crystalline phase comprises 25 to 35% by weight of the glass-ceramic or glass-ceramic article.
In some embodiments, the quartz and quartz solid solution crystalline phases comprise 5 to 25 weight percent of the glass-ceramic or glass-ceramic article. In some embodiments, the quartz and quartz solid solution crystalline phases comprise 7 to 20 weight percent of the glass-ceramic or glass-ceramic article.
In some embodiments, the petalite crystalline phase comprises 30 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 glass-ceramic or glass-ceramic article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 7% by weight of the glass-ceramic or glass-ceramic article. In some embodiments, the lithium monosilicate crystal phase comprises 0 to 5% 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 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 glass-ceramic or glass-ceramic 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 the basic component of the matrix glass, glass-ceramic and glass-ceramic articles of the inventionAs one of the main constituents of the crystalline phase of the glass-ceramic and glass-ceramic article, if SiO2Less than 68%, the formation of crystals in the glass-ceramic and glass-ceramic articles is reduced and the crystals are easily coarsened, which affects the ball drop test height and haze of the glass-ceramic and glass-ceramic articles. 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 a component forming a network structure of glass and is one of components forming a crystal phase of petalite, which is advantageous for chemical strengthening of glass and increase of ball drop test height of glass ceramic articles, but if the content thereof is less than 2%, the above 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 the glass ceramic and glass of the present inventionThe component necessary for the formation of crystals in the ceramic product is also an essential component for participating in chemical strengthening and improving the mechanical properties of the glass-ceramic product, if Li is used2When the O content is less than 7%, the crystal content in the glass ceramic and the glass ceramic product is insufficient, and the strength of the glass ceramic and the glass ceramic 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 glass-ceramic and glass-ceramic articles 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 ceramic, and when the total content of ZnO + MgO is too high, the haze of the glass ceramic and the glass ceramic article increases. Therefore, ZnO + MgO is limited to 5% or less. If ZnO + MgO is too low, the glass ceramic and the glass ceramic product do not form quartz or quartz solid solution under the condition of low haze, which is not favorable for realizing the excellent mechanical properties of the glass ceramic and the glass ceramic 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 + MgO2The O/(ZnO + MgO) is controlled to be more than 9.5, the haze and the | B | value of the glass ceramic and the glass ceramic product can be reduced, and the light transmittance of the glass ceramic and the glass ceramic 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 glass ceramic and the glass ceramic product can be further improved, the chemical strengthening performance of the glass ceramic can be improved, the depth and the surface stress of an ion exchange layer of the glass ceramic product can be improved, and the falling resistance of the glass ceramic 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 embodiments, 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%, the formation of the desired crystals of the present invention is facilitated to achieve the excellent mechanical and optical properties of the glass-ceramic and glass-ceramic articles of the present invention. If the total content P thereof is2O5+ZrO2If the content exceeds 10%, the crystal grain size in the glass ceramic or glass ceramic article becomes large, the haze and transmittance of the glass ceramic or glass ceramic article increases, 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%.
P2O5Can form crystal nucleus in glass, promote crystal formation, raise the strength of glass ceramic and glass ceramic product and reduce the haze of glass ceramic and glass ceramic product. 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 crystal precipitation to form crystal nucleus, can refine crystal grains and reduce the haze of glass ceramics and glass ceramic products. On the other hand, if ZrO is contained excessively2The haze of the glass-ceramic and glass-ceramic products 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), (C2+Al2O3+Li2O)/ZrO2Control over 26 can improve glass ceramicAnd four-point bending strength and fracture toughness of the glass-ceramic article. 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 is 30-45, the Vickers hardness and the falling ball test height of the glass ceramic and the glass ceramic product can be further improved, and the ion exchange layer depth and the surface stress of the glass ceramic 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 be 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, 40, 40.5, 41, 41.5, 42, 42.5, 43, 43.5, 44, 44.5, 45, 45.5, 46, 46.5, 47, 47.5, 48, 48.5, 49, 49.5, 50.
Na2O can reduce the haze of the glass ceramic and the glass ceramic product, increase the glass phase in the glass ceramic, and facilitate the hot bending of the glass ceramic, but if Na is contained excessively, the content of Na is increased2O, can lead to coarsening of the crystals in the glass-ceramic and glass-ceramic articles, and conversely, to a deterioration in the haze and transmittance of the glass-ceramic and glass-ceramic articles. 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。
B2O3Does not participate in the formation of crystals in the glass, can increase the glass phase in the glass ceramic, is beneficial to the hot bending forming of the glass ceramic,but if too much B is contained2O3Therefore, 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, by controlling (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is above 1.25, which is beneficial to improving the crystallinity and four-point bending strength of the glass ceramic and the glass ceramic product. Therefore, (B) is preferred2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.25 or more, more preferably (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 10. Further, by controlling (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is within 1.3-5, which is also beneficial to reducing the grain size and haze of the glass ceramic and glass ceramic products and improving the height of the ball drop test. Therefore, (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.3 to 5, and (B) is more preferable2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) is 1.4 to 3. In some embodiments, (B)2O3+Na2O+Li2O)/(Al2O3+ ZnO + MgO) may have a value of 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10.
In some embodiments, (SiO)2+Al2O3+Na2O+B2O3)/ZrO2And controlling the grain size of the glass ceramic and the glass ceramic product to be more than 24, reducing the | B | value and the haze and improving the light transmission rate. 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 glass ceramic and the glass ceramic 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, (SiO)2+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 excessively2O, which easily causes coarsening of glass crystals, and reduces the transmittance and ball drop test height of the glass ceramic and the glass ceramic product. 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, glass-ceramic or glass-ceramic article may further comprise 0-2% of a fining agent to enhance the defoaming capability of the glass, glass-ceramic or glass-ceramic article. Such clarifying agents include, but are not limited toSb2O3、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 achieve the desired excellent properties of mechanical, optical, production and chemical strengthening of the glass, glass-ceramic or glass-ceramic articles of the present invention, it is preferred that F is not present in some embodiments of the present invention; 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, a colored matrix glass, glass-ceramic, or glass-ceramic article can be prepared by including a colorant, the colorant comprising: 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:
the brown or green matrix glass, glass ceramic or glass ceramic product prepared by the invention uses NiO and Ni2O3Or Pr2O5Is a colorant. NiO and Ni2O3For coloringAgent for the preparation of brown or green matrix glass, glass ceramic or glass ceramic articles, the two components being used individually or in mixtures and generally in amounts of less than 4%, preferably less than 3%, respectively, and if the amount exceeds 4%, the colorant is not very soluble in the matrix glass, glass ceramic or glass ceramic article, respectively, in amounts of above 0.1%, e.g. below 0.1%, and the matrix glass, glass ceramic or glass ceramic article is not noticeably colored. 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%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of NiO and Ni may be included2O3. Using Pr2O5As a colorant for green matrix glass, glass ceramic or glass ceramic articles, it is used alone, generally in an amount of 8% or less, preferably 6% or less, with the lower limit of the amount being 0.4% or more, e.g., less than 0.4%, and the matrix glass, glass ceramic or glass ceramic article being inconspicuous 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% Pr2O5。
Blue matrix glasses, glass-ceramics or glass-ceramic articles prepared according to the invention, using CoO or Co2O3The two colorant components can be used alone or in combination as a colorant, and are each present in an amount of generally 2% or less, preferably 1.8% or less, and if the amount exceeds 2%, the colorant is not well soluble in the matrix glass, glass-ceramic or glass-ceramic article, and the lower limit of the amount is 0.05% or more, e.g., less than 0.05%, respectively, and the matrix glass, glass-ceramic or glass-ceramic article 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%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% of CoO and Co may be included2O3。
The yellow matrix glass, glass-ceramic or glass-ceramic article prepared by the invention uses Cu2O or CeO2The two colorant components are used alone or in combination as a colorant, and have a lower limit of 0.5% or more, e.g., less than 0.5%, a non-noticeable color of the matrix glass, glass-ceramic or glass-ceramic, 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% Cu2And O. Using CeO alone2The content is usually 4% or less, preferably 3% or less, for example, the content exceeds 4%, and the gloss of the matrix glass, glass ceramic or glass ceramic article is not good. 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, 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 included2And Cu2O。
The black or smoky grey matrix glass, glass-ceramic or glass-ceramic articles prepared according to the invention are based on Fe alone2O3Is 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 grayish matrix glasses, glass ceramics or glass ceramic articles, essentially Fe2O3Coloring, in an amount of 7% or less, preferably 5% or less, with a lower limit of 0.2% or more, and in some embodiments, may comprise about 0.2%, 0.3%, 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% Fe2O3. CoO and Co2O3Absorbing in visible light, and increasing the coloration of the substrate glass, glass-ceramic or glass-ceramic article, typically 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, glass ceramic or glass ceramic article prepared by the invention uses MnO2As colorants, use is generally made of less than 4%, preferably less than 3%, with a lower limit of more than 0.1%, for example less than 0.1%, and with no noticeable color of the matrix glass, glass-ceramic or glass-ceramic article. 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。
The pink matrix glass, glass ceramic or glass ceramic product prepared by the invention uses Er2O3The content of the colorant used is generally 8% or less, preferably 6% or less. Due to rarenessEr element of soil2O3The coloring efficiency is low, and when the content exceeds 8%, the color of the base glass, glass ceramic or glass ceramic article cannot be further deepened, but the cost is increased, and the lower limit thereof is more than 0.4%, such as less than 0.4%, and the color of the base glass, glass ceramic or glass ceramic article is not conspicuous. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Er may be included2O3。
The mauve substrate glass, glass ceramic or glass ceramic 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%, the color of the matrix glass, glass ceramic or glass ceramic article cannot be further deepened, and the cost is increased, the lower limit of the content is more than 0.4%, such as less than 0.4%, and the color of the matrix glass, glass ceramic or glass ceramic article is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd may be included2O3。
The red matrix glass, glass ceramic or glass ceramic product prepared by the invention uses Er2O3、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 be used for preparing the glassPreparation of Red matrix glass, glass-ceramic or glass-ceramic articles, due to Er2O3And 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%" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the matrix glass, glass ceramic or glass ceramic article of the present invention; it is within the scope of the present disclosure that certain impurities or components may be present as starting materials and/or equipment for producing the matrix glass, glass-ceramic or glass-ceramic articles that are not intentionally added, and may be present in small or trace amounts in the final matrix glass, glass-ceramic or glass-ceramic 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, the glass-ceramic and glass-ceramic articles having high fracture toughness; the ball drop test height and four-point bending strength of the glass ceramic and the glass ceramic product are increased; the haze is reduced and the light transmittance is increased. The glass ceramic has excellent chemical strengthening performance, and can obtain more excellent mechanical strength through chemical strengthening. Through reasonable component design, the glass ceramic and the glass ceramic product can obtain proper grain size, and the glass ceramic product have high strength. The glass ceramics and glass ceramic products of the invention have good crystallinity, so that the glass ceramics and glass ceramic products of the invention 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 glass-ceramic article or glass-ceramic 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 glass ceramic or the glass ceramic product can influence the haze and the transmittance of the glass ceramic or the glass ceramic product, and the smaller the crystal grain, the higher the transmittance; the smaller the haze, the higher the transmittance. In some embodiments, the glass-ceramic article or glass-ceramic having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. In some embodiments, the glass-ceramic article or glass-ceramic has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.
In some embodiments, the glass-ceramic or glass-ceramic article of the present invention exhibits a high transmittance in the visible light range, and in some embodiments the glass-ceramic or glass-ceramic article having a thickness of 1mm or less preferably has an average light transmittance of 89% or more at 400 to 800 nm. In some preferred embodiments, the glass-ceramic article or glass-ceramic having a thickness of 1mm or less preferably has a light transmittance of 91% or more at 550 nm.
In some embodiments, an antimicrobial component can be added to the matrix glass, glass-ceramic, or glass-ceramic article. The glass-ceramic or glass-ceramic articles described herein may be used in applications such as kitchens or countertops where exposure to harmful bacteria is likely. Antimicrobial components that can 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, glass-ceramic and glass-ceramic articles of the present invention may be produced and manufactured by the following method:
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 the 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 glass or glass-ceramic described herein may 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 glass ceramic 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 substrate glass or glass ceramic molded body 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 glasses, glass-ceramics and glass-ceramic articles described herein can be of any thickness that is reasonably useful.
The glass ceramic of the present invention can be produced into a glass ceramic article 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 processed into sheets, and/or shaped (e.g., punched, hot bent, etc.), shaped, polished and/or swept, and chemically strengthened by a chemical strengthening process.
The chemical strengthening method is an ion exchange method. In the ion exchange process, smaller metal ions in the matrix glass or glass-ceramic are replaced or "exchanged" by larger metal ions having the same valence state that are closer to the matrix glass or glass-ceramic. Replacing the smaller ions with larger ions creates a compressive stress in the matrix glass or glass-ceramic, forming 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 that are used to displace 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 immersing a molten Na salt (e.g., NaNO) 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 glass ceramic, thereby forming a surface compression layer and exhibiting high mechanical properties. In some embodiments, the matrix glass or glass-ceramic may be formed by melting a K salt (e.g., KNO) by immersion at a temperature of about 340 ℃ to 450 ℃3) 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 the matrix glass or glass ceramic, and a thermal strengthening method of heating the matrix glass or glass ceramic and then rapidly cooling it.
The glass ceramic and/or glass ceramic product and/or matrix glass of the invention are tested by the following methods:
[ 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 glass ceramic in HF (hydrofluoric acid), carrying out gold spraying on the surface of the glass ceramic, and carrying out surface scanning under the SEM, so as to determine the size of crystal grains of the glass ceramic.
[ 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 ]
A150 mm X57 mm X0.7 mm glass ceramic product sample was placed on a glass carrier jig, and 132g of a steel ball was dropped from a predetermined height to a maximum ball drop test height at which the sample could withstand an impact without breaking. Specifically, the test was conducted from a ball drop test height of 800mm, and the height was changed in the order of 850mm, 900mm, 950mm, 1000mm and more without breaking. For the examples having the "ball drop test height", glass-ceramic articles were used as test objects. The test data recorded as 1000mm in the examples shows that the steel ball was dropped from the height of 1000mm without breaking and receiving impact. The drop test height is sometimes referred to herein as the drop height.
[ height of falling ball of body ]
A150 mm x 57mm x 0.7mm glass ceramic sample is placed on a glass bearing clamp, 32g of steel ball is 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 a "body ball drop height", glass ceramics were used as test objects. The test data recorded as 1000mm in the examples shows that the glass ceramic did not break and received impact even when the steel ball was dropped from a height of 1000 mm.
[ fracture toughness ]
The method for directly measuring the size of the indentation propagation crack is used, the specification of a sample is 2mm multiplied by 4mm multiplied by 20mm, after the sample is chamfered, ground and polished, a Vickers hardness indenter is used for applying 49N force on the sample and maintaining the force for 30s, after the indentation is made, the fracture strength is measured by a three-point bending method.
[ four-point bending Strength ]
A microcomputer-controlled electronic universal tester CMT6502 is adopted, the sample specification is below 1mm in thickness, and the test is carried out by taking ASTM C158-2002 as a standard.
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)) The process is carried out. 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 pieces), 60-80 meshes of sand paper is laid on a base, the sand paper freely falls from the specified height, a sample is directly hit 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", glass-ceramic articles were used as test subjects. The test data recorded as 2000mm in the examples indicate that even a loaded glass-ceramic article does not break and withstand impact from a height of 2000mm, the maximum test height of the drop tester WH-2101 is 2000 mm.
The glass-ceramic article of the present invention has the following properties:
1) in some embodiments, the glass-ceramic article has a four-point bending strength of 600MPa or greater, preferably 650MPa or greater, and more preferably 700MPa or greater.
2) In some embodiments, the glass-ceramic article has an ion exchange layer depth of 80 μm or more, preferably 100 μm or more, and more preferably 120 μm or more.
3) In some embodiments, the glass-ceramic article has a surface stress of 100MPa or greater, preferably 150MPa or greater, and more preferably 200MPa or greater.
4) In some embodiments, the glass-ceramic article has a ball drop test height of 1400mm or more, preferably 1500mm or more, and more preferably 1600mm or more.
5) In some embodiments, the glass-ceramic article has a fracture toughness of 1 MPa-m1/2Above, preferably 1.1MPa · m1/2More preferably 1.2MPa · m or more1/2The above.
6) In some embodiments, the glass-ceramic article has a Vickers hardness of 730kgf/mm2Above, preferably 750kgf/mm2Above, more preferably 780kgf/mm2The above.
7) In some embodiments, the glass-ceramic article has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.
8) In some embodiments, the glass-ceramic article has a grain size of 40nm or less, preferably 30nm or less, and more preferably 25nm or less.
9) In some embodiments, the glass-ceramic article having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.
10) In some embodiments, the glass-ceramic article 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 glass-ceramic article 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 glass-ceramic article has a thickness of 1mm or less and an average light | B | value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, and more preferably 0.7 or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.
13) In some embodiments, the glass-ceramic article having a thickness of 1mm or less has a drop resistance of 1500mm or more, preferably 1600mm or more, more preferably 1800mm or more, and even more preferably 2000mm or more. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.
The glass ceramic of the invention has the following properties:
1) in some embodiments, the glass-ceramic has a crystallinity of 50% or more, preferably 60% or more, and more preferably 70% or more.
2) In some embodiments, the glass-ceramic has a grain size of 40nm or less, preferably 30nm or less, preferably 25nm or less.
3) In some embodiments, the glass-ceramic having a thickness of 1mm or less has a haze of 0.2% or less, preferably 0.15% or less, and more preferably 0.12% or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.
4) In some embodiments, the glass-ceramic 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 glass-ceramic having a thickness of 1mm or less has a transmittance of 88% or more, preferably 90% or more, and more preferably 91% or more at a wavelength of 550 nm. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, and still more preferably 0.55mm, or 0.6mm, or 0.68mm, or 0.7mm, or 0.75 mm.
6) In some embodiments, the glass-ceramic article has a thickness of 1mm or less and an average light | B | value of 400 to 800nm of 0.9 or less, preferably 0.8 or less, and more preferably 0.7 or less. The thickness is preferably 0.2 to 1mm, more preferably 0.3 to 0.9mm, still more preferably 0.5 to 0.8mm, 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, more preferably 2000mm or more.
8) In some embodiments, the glass-ceramic has a Vickers hardness of 650kgf/mm2Above, preferably 680kgf/mm2Above, more preferably 700kgf/mm2The above.
9) In some embodiments, the glass-ceramic 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-ceramicd) 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 glassd) Is 1.5200 to 1.5300.
The glass ceramic, the glass ceramic product and the matrix glass have the excellent performances, so that the glass ceramic, the glass ceramic product and the matrix glass can be widely made into glass cover plates or glass components; meanwhile, the glass ceramics, glass ceramic products and 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 cover glass for mobile phones, smart phones, tablet computers, notebook computers, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, cover windows, automobile windows, train windows, aircraft windows, touch screen cover 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.
< glass ceramic 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 ceramic 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 ceramic in the examples was 0.7 mm.
Table 3.
Table 4.
< glass-ceramic article example >
In this example, glass-ceramic articles having compositions shown in tables 5 to 6 were obtained by the above-mentioned method for producing glass-ceramic articles. Further, the characteristics of each glass-ceramic article were measured by the test method described in the present invention, and the measurement results are shown in tables 5 to 6, and the test thickness of the sample of the glass-ceramic article in the example was 0.7 mm.
Table 5.
Table 6.
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