Glass ceramic and glass ceramic product

Abstract

Provided are a glass ceramic and a glass ceramic product having excellent scratch resistance and break resistance. The microcrystalline glass product comprises the following components in percentage by weight: 41-50% of SiO2; al2O3: 27.5% to 35%; 8.5% to 12% of ZnO; 0.1 to 5 percent of Li2O; 2 to 7 percent of TiO2; 0.1 to 8 percent of Ln2O3; the ratio of (ZnO + MgO + SiO2) / Al2O3 is 1.5 to 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3 and Yb2O3. The invention also discloses a preparation method of the catalyst. Through reasonable component design, the obtained microcrystalline glass and microcrystalline glass products have excellent scratch resistance and break resistance.

Description

Technical Field

[0001] The present invention relates to a glass-ceramics, and particularly to a glass-ceramics and glass-ceramics products having excellent scratch resistance and drop resistance. Background Art

[0002] Glass-ceramics is a material that crystallizes inside the glass by heat-treating the glass, and has better mechanical properties than conventional glass. With the continuous rise and development of consumer electronics products, glass-ceramics are widely used in such electronic devices, such as LED and LCD displays, computer monitors, and portable electronic products (such as mobile phones, tablet computers, and personal media terminals). Compared with high-aluminum glass, the glass-ceramics in the prior art have poor scratch resistance and are difficult to meet the requirements for use as a cover plate material. On the other hand, during the use of portable electronic products, there will inevitably be situations where they are dropped. If the protective cover glass applied to them has poor drop resistance, the electronic device is easily damaged due to dropping, resulting in a reduced service life of the electronic product. Therefore, developing a glass-ceramics with excellent scratch resistance and drop resistance has become the goal pursued by technical personnel. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a glass-ceramics and glass-ceramics products having excellent scratch resistance and drop resistance.

[0004] The technical solution adopted by the present invention to solve the technical problem is as follows:

[0005] (1) A glass-ceramics product, the components of which are expressed in weight percentages and contain: SiO2: 41-50%; Al2O3: 27.5-35%; ZnO: 8.5-12%; Li2O: 0.1-5%; TiO2: 2-7%; Ln2O3: 0.1-8%; MgO: 0-6%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0006] (2) The glass-ceramics product according to (1), the components of which are expressed in weight percentages and further contain: Na2O: 0-8%; and / or ZrO2: 0-5%; and / or K2O: 0-3%; and / or B2O3: 0-4%; and / or CaO + BaO + SrO: 0-5%; and / or P2O5: 0-5%; and / or a clarifying agent: 0-2%.

[0007] (3) A glass-ceramics product, the components of which contain SiO2, Al2O3, ZnO, Li2O, and TiO2, and the glass-ceramics product contains a spinel crystal phase.

[0008] (4) A glass-ceramic product containing a spinel crystal phase, wherein the grain size of the glass-ceramic product is 70 nm or less.

[0009] (5) A glass-ceramic product containing a spinel crystal phase, wherein the drop resistance of the glass-ceramic product is 800 mm or more.

[0010] (6) A glass-ceramic product, the components of which contain SiO2, Al2O3, ZnO, Li2O, Ln2O3 and TiO2. For a glass-ceramic product with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0011] (7) A glass-ceramic product, the components of which contain SiO2, Al2O3, ZnO, and the surface stress of the glass-ceramic product is 40 MPa or more.

[0012] (8) The glass-ceramic product according to any one of (3) - (7), the components of which are expressed in weight percentages and contain: SiO2: 41 - 50%; and / or Al2O3: 27.5 - 35%; and / or ZnO: 8.5 - 12%; and / or Li2O: 0.1 - 5%; and / or TiO2: 2 - 7%; and / or Ln2O3: 0.1 - 8%; and / or MgO: 0 - 6%; and / or Na2O: 0 - 8%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or P2O5: 0 - 5%; and / or fining agent: 0 - 2%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0013] (9) A glass-ceramic product, the components of which are expressed in weight percentages and are composed of SiO2: 41 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 7%; Ln2O3: 0.1 - 8%; MgO: 0 - 6%; Na2O: 0 - 8%; ZrO2: 0 - 5%; K2O: 0 - 3%; B2O3: 0 - 4%; CaO + BaO + SrO: 0 - 5%; P2O5: 0 - 5%; fining agent: 0 - 2%, wherein (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0014] (10) The glass-ceramic article according to any one of (1) to (9), wherein the components are expressed in weight percentages, and: (ZnO + MgO + SiO2) / Al2O3 is 1.5 to 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.6 to 2.15, more preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 to 2.1; and / or Al2O3 / Li2O is 11.0 to 60.0, preferably Al2O3 / Li2O is 12.0 to 40.0, more preferably Al2O3 / Li2O is 13.0 to 20.0; and / or (ZnO + MgO) / (Li2O + Na2O) is 1.5 to 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 to 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 to 4.0; and / or (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5; and / or SiO2 / Al2O3 is 1.2 to 1.8, preferably SiO2 / Al2O3 is 1.3 to 1.7, more preferably SiO2 / Al2O3 is 1.4 to 1.67; and / or Ln2O3 / Li2O is 0.1 to 3.0, preferably Ln2O3 / Li2O is 0.3 to 2.2, more preferably Ln2O3 / Li2O is 0.5 to 2.1, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0015] (11) The glass-ceramic article according to any one of (1) to (9), wherein the components are expressed by weight percentage, where: SiO2: 42 to 50%, preferably SiO2: 43 to 50%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2.1 to 6%, preferably TiO2: 2.3 to 5%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 5%, preferably Ln2O3: 1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 7%, preferably Na2O: 1 to 5%; and / or MgO: 0 to 5%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or P2O5: 0 to 4%, preferably P2O5: 0 to 3%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0016] (12) The glass-ceramic article according to any one of (1) to (8), wherein the components are expressed by weight percentage, containing: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, and further preferably not containing Nb2O5, and / or not containing WO3, and / or not containing Bi2O3, and / or not containing Ta2O5, and / or not containing TeO2.

[0017] (13) The glass-ceramic article according to any one of (1) to (9), wherein the glass-ceramic article does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

[0018] (14) The glass-ceramic article according to any one of (1) to (9), wherein the glass-ceramic article contains a spinel crystal phase, preferably the spinel crystal phase has a higher weight percentage than other crystal phases, more preferably the spinel crystal phase accounts for 20 to 50% of the weight of the glass-ceramic article, further preferably the spinel crystal phase accounts for 30 to 50% of the weight of the glass-ceramic article, and even more preferably the spinel crystal phase accounts for 30 to 45% of the weight of the glass-ceramic article.

[0019] (15) The glass-ceramic article according to (14), wherein the spinel crystal phase is ZnAl2O4.

[0020] (16) The glass-ceramic article according to any one of (1) to (9), wherein the glass-ceramic article does not contain spodumene crystal phase, and / or does not contain zirconia crystal phase, and / or does not contain quartz crystal phase, and / or does not contain quartz solid solution crystal phase, and / or does not contain Zn2SiO4 crystal phase.

[0021] (17) The glass-ceramic article according to any one of (1) to (9), wherein the grain size of the glass-ceramic article is 70 nm or less, preferably 60 nm or less, more preferably 50 nm or less; and / or the surface stress is 40 MPa or more, preferably 80 - 200 MPa, more preferably 100 - 200 MPa; and / or the ball-drop test height is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the drop resistance is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the extrusion resistance strength is 200 N or more, preferably 250 N or more, more preferably 300 N or more; and / or the Young's modulus E is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or the scratch width is less than 30 μm, preferably 25 μm or less, more preferably 20 μm or less; and / or the Vickers hardness is 600 kgf / mm 2 or more, preferably 650 - 800 kgf / mm 2 , more preferably 680 - 800 kgf / mm 2 ; and / or for a glass-ceramic article with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

[0022] (18) The glass-ceramic, in terms of weight percentage of components, contains: SiO2: 41 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 7%; Ln2O3: 0.1 - 8%; MgO: 0 - 6%, wherein (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0023] (19) The glass-ceramics according to (18), in terms of weight percentage of its components, further contains: Na2O: 0 - 8%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or P2O5: 0 - 5%; and / or clarifying agent: 0 - 2%.

[0024] (20) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, Li2O and TiO2, and the glass-ceramics contain a spinel crystal phase.

[0025] (21) Glass-ceramics, containing a spinel crystal phase, and the grain size of the glass-ceramics is below 70 nm.

[0026] (22) Glass-ceramics, containing a spinel crystal phase, and the Young's modulus of the glass-ceramics is 80 - 105 GPa.

[0027] (23) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, and for the glass-ceramics with a thickness below 2.0 mm, the average light transmittance at a wavelength of 400 - 800 nm is above 85%.

[0028] (24) Glass-ceramics, whose components contain SiO2, Al2O3, ZnO, and the Vickers hardness of the glass-ceramics is 500 kgf / mm 2 or more.

[0029] (25) The glass-ceramics according to any one of (20) - (24), in terms of weight percentage of its components, contains: SiO2: 41 - 50%; and / or Al2O3: 27.5 - 35%; and / or ZnO: 8.5 - 12%; and / or Li2O: 0.1 - 5%; and / or TiO2: 2 - 7%; and / or Ln2O3: 0.1 - 8%; and / or MgO: 0 - 6%; and / or Na2O: 0 - 8%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or P2O5: 0 - 5%; and / or clarifying agent: 0 - 2%, where the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

[0030] (26) Glass-ceramics, the components of which are expressed in weight percentages, are composed of: SiO2: 41 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 7%; Ln2O3: 0.1 - 8%; MgO: 0 - 6%; Na2O: 0 - 8%; ZrO2: 0 - 5%; K2O: 0 - 3%; B2O3: 0 - 4%; CaO + BaO + SrO: 0 - 5%; P2O5: 0 - 5%; clarifying agent: 0 - 2%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0031] (27) The glass-ceramics according to any one of (18) - (26), the components of which are expressed in weight percentages, wherein: (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.6 - 2.15, more preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 - 2.1; and / or Al2O3 / Li2O is 11.0 - 60.0, preferably Al2O3 / Li2O is 12.0 - 40.0, more preferably Al2O3 / Li2O is 13.0 - 20.0; and / or (ZnO + MgO) / (Li2O + Na2O) is 1.5 - 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 - 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 - 4.0; and / or (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 - 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 - 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 - 1.5; and / or SiO2 / Al2O3 is 1.2 - 1.8, preferably SiO2 / Al2O3 is 1.3 - 1.7, more preferably SiO2 / Al2O3 is 1.4 - 1.67; and / or Ln2O3 / Li2O is 0.1 - 3.0, preferably Ln2O3 / Li2O is 0.3 - 2.2, more preferably Ln2O3 / Li2O is 0.5 - 2.1, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0032] (28) The glass-ceramics according to any one of (18) to (26), wherein the components are expressed in weight percentages, and: SiO2: 42 to 50%, preferably SiO2: 43 to 50%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2.1 to 6%, preferably TiO2: 2.3 to 5%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 5%, preferably Ln2O3: 1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 7%, preferably Na2O: 1 to 5%; and / or MgO: 0 to 5%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or P2O5: 0 to 4%, preferably P2O5: 0 to 3%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

[0033] (29) The glass-ceramics according to any one of (18) to (25), wherein the components are expressed in weight percentages, containing: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, and further preferably not containing Nb2O5, and / or not containing WO3, and / or not containing Bi2O3, and / or not containing Ta2O5, and / or not containing TeO2.

[0034] (30) The glass-ceramics according to any one of (18) to (26), wherein the glass-ceramics do not contain B2O3, and / or do not contain SnO2, and / or do not contain SnO.

[0035] (31) The glass-ceramics according to any one of (18) to (26), wherein the glass-ceramics contain a spinel crystal phase, preferably the spinel crystal phase has a higher weight percentage than other crystal phases, more preferably the spinel crystal phase accounts for 20 to 50% of the weight of the glass-ceramics, further preferably the spinel crystal phase accounts for 30 to 50% of the weight of the glass-ceramics, and even more preferably the spinel crystal phase accounts for 30 to 45% of the weight of the glass-ceramics.

[0036] (32) The glass-ceramics according to (31), wherein the spinel crystal phase is ZnAl2O4.

[0037] (33) The glass-ceramics according to any one of (18) to (26), wherein the glass-ceramics do not contain spodumene crystal phase, and / or do not contain zirconia crystal phase, and / or do not contain quartz crystal phase, and / or do not contain quartz solid solution crystal phase, and / or do not contain Zn2SiO4 crystal phase.

[0038] (34) The glass-ceramics according to any one of (18) to (26), wherein the grain size of the glass-ceramics is 70 nm or less, preferably 60 nm or less, more preferably 50 nm or less; and / or the Vickers hardness is 500 kgf / mm 2 or more, preferably 600 - 750 kgf / mm 2 , more preferably 650 - 750 kgf / mm 2 ; and / or the Young's modulus is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or for the glass-ceramics with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

[0039] (35) A glass cover plate, containing the glass-ceramics product according to any one of (1) to (17), and / or the glass-ceramics according to any one of (18) to (34).

[0040] (36) A glass component, containing the glass-ceramics product according to any one of (1) to (17), and / or the glass-ceramics according to any one of (18) to (34).

[0041] (37) An electronic device, containing the glass-ceramics product according to any one of (1) to (17), and / or the glass-ceramics according to any one of (18) to (34), and / or the glass cover plate according to (35), and / or the glass component according to (36).

[0042] (38) A display device, containing the glass-ceramics product according to any one of (1) to (17), and / or the glass-ceramics according to any one of (18) to (34), and / or the glass cover plate according to (35), and / or the glass component according to (36).

[0043] (39) A manufacturing method of the glass-ceramics product according to any one of (1) to (17), the method comprising the following steps: forming a base glass, forming glass-ceramics from the base glass through a crystallization process, and then forming a glass-ceramics product from the glass-ceramics through a chemical strengthening process.

[0044] (40) The manufacturing method of the glass-ceramic product according to (39), wherein the formation of the matrix glass comprises the following steps: mixing the raw materials evenly according to the component ratio, then putting them into a crucible, and melting them in an electric furnace or a gas furnace within a temperature range of 1500 to 1700 °C for 5 to 24 hours, preferably the melting temperature is 1500 to 1600 °C, and then obtaining the matrix glass through clarification, homogenization, forming, and annealing. The clarification temperature is 1550 to 1650 °C, and the annealing temperature is 550 to 650 °C.

[0045] (41) The manufacturing method of the glass-ceramic product according to (39), wherein the crystallization process comprises the following steps: heating to the specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining its temperature for a certain period of time, and then cooling down. The crystallization treatment temperature is 600 to 800 °C, preferably 650 to 750 °C, and the holding time at the crystallization treatment temperature is 1 to 10 hours, preferably 3 to 6 hours.

[0046] (42) The manufacturing method of the glass-ceramic product according to (39), wherein the crystallization process comprises the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

[0047] (43) The manufacturing method of the glass-ceramic product according to (42), wherein the crystallization process comprises: the first temperature is 600 to 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 to 6 hours, and the holding time at the second temperature is 2 to 5 hours.

[0048] (44) The manufacturing method of the glass-ceramic product according to (39), wherein the chemical strengthening process comprises: immersing the glass-ceramic in a molten Na salt bath at 350 to 470 °C for 1 to 36 hours, preferably the temperature range is 400 to 460 °C, preferably the time range is 2 to 15 hours; and / or immersing the glass-ceramic in a mixed salt bath of molten K salt and Na salt at 360 to 460 °C for 1 to 36 hours, preferably the time range is 2 to 24 hours.

[0049] (45) The manufacturing method of the glass-ceramic according to any one of (18) to (34), the method comprising the following steps: forming a matrix glass, and then forming the matrix glass into a glass-ceramic through a crystallization process.

[0050] (46) The manufacturing method of the glass-ceramics according to (45), wherein the formation of the base glass comprises the following steps: mixing the raw materials evenly according to the component ratio, then putting them into a crucible, and melting them in an electric furnace or a gas furnace within a temperature range of 1500 to 1700 °C for 5 to 24 hours. Preferably, the melting temperature is 1500 to 1600 °C. Then, after clarification, homogenization, forming, and annealing, the base glass is obtained. The clarification temperature is 1550 to 1650 °C, and the annealing temperature is 550 to 650 °C.

[0051] (47) The manufacturing method of the glass-ceramics according to (45), wherein the crystallization process comprises the following steps: heating to the specified crystallization treatment temperature, and after reaching the crystallization treatment temperature, maintaining its temperature for a certain period of time, and then cooling down. The crystallization treatment temperature is 600 to 800 °C, preferably 650 to 750 °C, and the holding time at the crystallization treatment temperature is 1 to 10 hours, preferably 3 to 6 hours.

[0052] (48) The manufacturing method of the glass-ceramics according to (45), wherein the crystallization process comprises the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

[0053] (49) The manufacturing method of the glass-ceramics according to (48), wherein the crystallization process comprises: the first temperature is 600 to 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 to 6 hours, and the holding time at the second temperature is 2 to 5 hours.

[0054] The beneficial effects of the present invention are as follows: Through reasonable component design, the glass-ceramics and glass-ceramic products obtained by the present invention have excellent scratch resistance and drop resistance. Detailed Embodiments

[0055] The glass-ceramics and glass-ceramic products of the present invention are materials having a crystalline phase (sometimes also referred to as crystals) and a glass phase, which are different from amorphous solids. The crystalline phase of the glass-ceramics and glass-ceramic products can be identified by the peak angles appearing in the X-ray diffraction pattern analyzed by X-ray diffraction.

[0056] The inventors of the present invention have conducted repeated experiments and research. For the specific components constituting the glass-ceramics and glass-ceramic products, by specifying their contents and content ratios as specific values and precipitating specific crystalline phases, the glass-ceramics and glass-ceramic products of the present invention are obtained.

[0057] Next, the ranges of the components (constituents) of the base glass, glass-ceramics, and glass-ceramic products of the present invention will be described. In this specification, unless otherwise specified, the contents, total contents, and total amounts of the components are all expressed as weight percentages (wt%) relative to the total amount of the base glass, or glass-ceramics, or glass-ceramic product substances in terms of the composition converted to oxides. Here, the "composition converted to oxides" means that when oxides, double salts, hydroxides, etc., used as raw materials for the composition of the base glass, glass-ceramics, or glass-ceramic products of the present invention decompose and transform into oxides during melting, the total amount of the oxides is taken as 100%. In addition, in this specification, when only referred to as glass, it is the base glass before crystallization (i.e., crystallization process treatment), and after the base glass is crystallized (i.e., crystallization process treatment), it is called glass-ceramics. A glass-ceramic product refers to a product obtained by chemically strengthening the glass-ceramics.

[0058] Unless otherwise indicated in specific cases, the numerical ranges listed herein include upper and lower limit values, "above" and "below" include the endpoint values, and all integers and fractions within the range, and are not limited to the specific values listed when defining the range. As used herein, "and / or" is inclusive. For example, "A; and / or B" means only A, or only B, or both A and B.

[0059] In some embodiments of the present invention, the crystal phase in the glass-ceramics or glass-ceramic products contains a spinel crystal phase. Preferably, the spinel crystal phase includes a zinc aluminate spinel crystal phase (ZnAl2O4). In some embodiments, it is preferably free of the Zn2SiO4 crystal phase to prevent the scratch resistance and the height of the ball drop test of the glass-ceramics and glass-ceramic products of the present invention from deteriorating.

[0060] In some embodiments, the spinel crystal phase has a higher weight percentage than other crystal phases in the glass-ceramics or glass-ceramic products, preferably the zinc aluminate spinel crystal phase (ZnAl2O4). In some embodiments, the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic products is 20 - 50%, preferably the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic products is 30 - 50%, and more preferably the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic products is 30 - 45%. In some embodiments, the weight percentage of the spinel crystal phase in the glass-ceramics or glass-ceramic products is 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%.

[0061] In some embodiments, the glass-ceramics or glass-ceramic articles of the present invention preferably do not contain spodumene crystal phase and / or zirconia crystal phase. The glass-ceramics or glass-ceramic articles of the present invention can obtain relatively high light transmittance, excellent extrusion resistance and scratch resistance, and can be used to manufacture cover glass for electronic devices or display devices with relatively high transparency requirements.

[0062] In some embodiments, the glass-ceramics or glass-ceramic articles of the present invention preferably do not contain quartz crystal phase and / or quartz solid solution phase to prevent the deterioration of the light transmittance of the glass-ceramics or glass-ceramic articles of the present invention.

[0063] SiO2 is a network-forming component of the glass-ceramics and glass-ceramic articles of the present invention, which can improve the chemical stability of the matrix glass, glass-ceramics and glass-ceramic articles. If the content of SiO2 is too low, it is difficult to form glass, and the chemical stability of the glass-ceramics and glass-ceramic articles deteriorates. If the content of SiO2 is too high, the viscosity of the glass increases, it is difficult to precipitate crystals during the manufacture of the glass-ceramics and glass-ceramic articles, and the crystal phase content of the glass-ceramics and glass-ceramic articles decreases. Therefore, the content of SiO2 in the present invention is 41-50%, preferably 42-50%, more preferably 43-50%. In some embodiments, it may contain 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% of SiO2.

[0064] Al2O3 can improve the scratch resistance of the glass-ceramics and glass-ceramic articles. The inventors found through a large number of experimental studies that when the content of Al2O3 exceeds a certain threshold, the high-coordination aluminum ions are connected to three oxygen atoms through covalent bonds. Compared with the two-coordination bridging oxygen, this bond type has stronger ionic property, weaker bond energy and greater flexibility. During energy loading and unloading, these bonds experience an easier bond breaking-closing process, which locally dissipates mechanical energy and there is not enough energy to break the O-Si or O-Al bonds. Therefore, the scratch resistance of the glass-ceramics and glass-ceramic articles can be improved. In addition, Al2O3 is also a necessary component for forming the crystal phase of the present invention, which can improve the mechanical properties of the glass-ceramics and glass-ceramic articles. However, if the content of Al2O3 is too high, glass melting is difficult and the melting temperature is high. Therefore, the content of Al2O3 in the present invention is 27.5-35%, preferably 28-34%, more preferably 28-33%. In some embodiments, it may contain 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, 32%, 32.5%, 33%, 33.5%, 34%, 34.5%, 35% of Al2O3.

[0065] The inventors found through a large number of experimental studies that, in some embodiments, by controlling the ratio SiO2 / Al2O3 between the content of SiO2 and the content of Al2O3 within the range of 1.2 to 1.8, the drop resistance of the glass-ceramics and glass-ceramic products can be improved. Therefore, in the present invention, SiO2 / Al2O3 is preferably 1.2 to 1.8, more preferably 1.3 to 1.7, and further preferably 1.4 to 1.67. In some embodiments, the value of SiO2 / Al2O3 is 1.2, 1.21, 1.23, 1.25, 1.27, 1.3, 1.31, 1.35, 1.37, 1.4, 1.41, 1.43, 1.45, 1.47, 1.5, 1.51, 1.53, 1.55, 1.57, 1.6, 1.61, 1.63, 1.65, 1.67, 1.7, 1.71, 1.73, 1.75, 1.77, 1.8.

[0066] ZnO can improve the properties such as the Young's modulus, Vickers hardness, and extrusion resistance of the glass-ceramics and glass-ceramic products. If the content of ZnO is too low, the viscosity of the glass is relatively large, which is not conducive to the forming of the glass; if the content of ZnO is higher than 12%, the glass structure is loose, and a large amount of Al2O3 enters the crystal, resulting in poor scratch resistance of the glass-ceramics and glass-ceramic products, the scratch width of the glass-ceramic products is more than 30 μm, and at the same time, crystals are likely to precipitate on the surface during the forming of the glass, and white spots are generated inside. Therefore, in the present invention, the content of ZnO is 8.5 to 12%, preferably 9 to 12%, and more preferably 9 to 11%. In some embodiments, ZnO with contents of 8.5%, 8.7%, 9%, 9.3%, 9.5%, 9.7%, 10%, 10.3%, 10.5%, 10.7%, 11%, 11.3%, 11.5%, 11.7%, 12% can be included.

[0067] MgO helps to reduce the viscosity of the glass. During crystallization, it can refine the crystal grains and improve the transmittance of the glass-ceramics and glass-ceramic products. If the content of MgO is too high, serious surface crystallization will occur during the glass crystallization, and the transmittance of the glass-ceramics and glass-ceramic products will instead decrease. Therefore, in the present invention, the content of MgO is 0-6%, preferably 0-5%, and more preferably 1-3%. In some embodiments, it may contain 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%, 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%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6% of MgO.

[0068] The inventors found through a large number of experimental studies that in some embodiments, by controlling the ratio (ZnO + MgO + SiO2) / Al2O3 between the total content of ZnO, MgO, and SiO2 (ZnO + MgO + SiO2) and the content of Al2O3 within the range of 1.5-2.15, it is beneficial to improve the scratch resistance of the glass-ceramics and glass-ceramic products. Therefore, it is preferred that (ZnO + MgO + SiO2) / Al2O3 is 1.5-2.15, more preferably (ZnO + MgO + SiO2) / Al2O3 is 1.6-2.15, and further preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8-2.1. In some embodiments, the value of (ZnO + MgO + SiO2) / Al2O3 is 1.5, 1.53, 1.55, 1.57, 1.6, 1.63, 1.65, 1.67, 1.7, 1.73, 1.75, 1.77, 1.8, 1.83, 1.85, 1.87, 1.9, 1.93, 1.95, 1.97, 2.0, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, 2.09, 2.1, 2.11, 2.12, 2.13, 2.14, 2.15.

[0069] Li2O can reduce the viscosity of the glass, lower the melting temperature of the glass, and also participate in chemical strengthening, increasing the surface stress of the glass-ceramic products and raising the height of the ball-drop test of the glass-ceramic products. If the content of Li2O is too high, it is easy to form a quartz solid solution crystal phase, reducing the transmittance of the glass-ceramic and the glass-ceramic products. Therefore, in the present invention, the content of Li2O is 0.1-5%, preferably 1-5%, and more preferably 1-4%. In some embodiments, the Li2O may include 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

[0070] In some embodiments, controlling the ratio Al2O3 / Li2O between the content of Al2O3 and the content of Li2O within the range of 11.0-60.0 is beneficial to increasing the height of the ball-drop test of the glass-ceramic and the glass-ceramic products and enhancing the extrusion resistance. Therefore, preferably, Al2O3 / Li2O is 11.0-60.0, more preferably Al2O3 / Li2O is 12.0-40.0, and further preferably Al2O3 / Li2O is 13.0-20.0. In some embodiments, the value of Al2O3 / Li2O is 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0, 56.0, 57.0, 58.0, 59.0, 60.0.

[0071] The function of Na2O is to promote glass melting and improve the chemical strengthening performance of glass. However, if there is too much Na2O, it is easy to cause more broken bonds in the glass, resulting in a decrease in the strength of the matrix glass, which is instead unfavorable to the strength of the glass-ceramics and glass-ceramic products. Therefore, in the present invention, the content of Na2O is 0-8%, preferably 1-7%, and more preferably 1-5%. In some embodiments, it may contain 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.5%, 7%, 7.5%, 8% of Na2O.

[0072] In some embodiments, by controlling the ratio (ZnO + MgO) / (Li2O + Na2O) between the total content of ZnO and MgO, ZnO + MgO, and the total content of Li2O and Na2O, Li2O + Na2O, within the range of 1.5-5.0, it is beneficial to improve the extrusion resistance strength and the height of the ball-drop test of the glass-ceramics and glass-ceramic products of the present invention. Therefore, it is preferred that (ZnO + MgO) / (Li2O + Na2O) is 1.5-5.0, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7-4.5, and further preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8-4.0. In some embodiments, the value of (ZnO + MgO) / (Li2O + Na2O) is 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, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.

[0073] TiO2 and ZrO2 are nucleating agents for the glass-ceramics and glass-ceramic products of the present invention. The simultaneous use of these two nucleating agents can maximize the number of crystal nuclei in the glass-ceramics and glass-ceramic products. With a relatively large number of crystal nuclei, the growth of crystal phases is stable and the sizes are uniform. If the content of TiO2 is too high, it will cause serious coloring (brownish-yellow) of the glass-ceramics and glass-ceramic products, reducing the transmittance in the visible light region. If the content of ZrO2 is too high, it will increase the difficulty of glass melting. Therefore, in the present invention, the content of TiO2 is 2-7%, preferably 2.1-6%, more preferably 2.3-5%. The content of ZrO2 is 0-5%, preferably 0.5-4%, more preferably 1-3%. In some embodiments, TiO2 with contents of 2%, 2.1%, 2.3%, 2.5%, 2.7%, 3%, 3.3%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 4.7%, 5%, 5.3%, 5.5%, 5.7%, 6%, 6.3%, 6.5%, 6.7%, 7% can be included. In some embodiments, ZrO2 with contents of 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% can be included.

[0074] In some embodiments, by controlling the ratio (TiO2 + ZrO2) / (Li2O + Na2O) of the total content of TiO2 and ZrO2, TiO2+ZrO2, to the total content of Li2O and Na2O, Li2O+Na2O, within the range of 0.5 to 5.0, it is beneficial to improve the light transmittance of the glass-ceramics and glass-ceramic products. Therefore, it is preferred that (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, and further preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5. In some embodiments, the value of (TiO2 + ZrO2) / (Li2O + Na2O) is 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, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.

[0075] Ln2O3 (Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3) can improve the structural compactness of glass-ceramics and glass-ceramic products, and improve the scratch resistance of glass-ceramics and glass-ceramic products. When the content is excessive, it will cause difficulties in forming crystals during the crystallization of glass-ceramics and glass-ceramic products, resulting in a decrease in the crystal phase content of glass-ceramics and glass-ceramic products, and a decrease in the height of the ball-drop test of glass-ceramics and glass-ceramic products. Therefore, in the present invention, the content of Ln2O3 is 0.1 to 8%, preferably 0.1 to 5%, and more preferably 1 to 3%. In some embodiments, it may contain 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8% of Ln2O3.

[0076] In some embodiments, controlling the ratio Ln2O3 / Li2O between the content of Ln2O3 and the content of Li2O within the range of 0.1 to 3.0 is beneficial to improving the scratch resistance of glass-ceramics and glass-ceramic products. Therefore, in the present invention, Ln2O3 / Li2O is preferably 0.1 to 3.0, more preferably Ln2O3 / Li2O is 0.3 to 2.2, and further preferably Ln2O3 / Li2O is 0.5 to 2.1. In some embodiments, the value of Ln2O3 / Li2O is 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.

[0077] K2O helps to reduce the melting temperature of the glass, is beneficial to chemical strengthening, and can increase the depth of the ion exchange layer of the glass-ceramics and glass-ceramic products. However, if it contains too much K2O, it is very easy to cause a decrease in the chemical stability of the glass and a decline in mechanical strength. Therefore, in the present invention, the content of K2O is 0-3%, preferably 0-2%, and more preferably 0-1%. In some embodiments, it may contain 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% of K2O.

[0078] P2O5 can be used as a composite nucleating agent for glass-ceramics and glass-ceramic products together with TiO2 and ZrO2, which can refine the crystal grains and increase the transmittance of glass-ceramics and glass-ceramic products. However, if it contains too much P2O5, phase separation is likely to occur during glass forming, resulting in a decrease in the chemical stability of glass-ceramics and glass-ceramic products. Therefore, in the present invention, the content of P2O5 is 0-5%, preferably 0-4%, and more preferably 0-3%. In some embodiments, it may contain 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% of P2O5.

[0079] B2O3 is used as a flux, which helps with the melting of the glass. However, if the content of B2O3 is too high, the chemical stability of the glass-ceramics and glass-ceramic products will deteriorate. In addition, boron volatilization easily forms streaks, resulting in non-uniformity inside the glass-ceramics and glass-ceramic products. Therefore, the content of B2O3 is 0 to 4%, preferably 0 to 2%, more preferably 0 to 1%. In some embodiments, it is further preferably that B2O3 is not contained. In some embodiments, it may contain about 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4% of B2O3.

[0080] CaO, BaO, and SrO do not participate in the formation of the crystal phase and are retained in the residual glass phase of the glass-ceramics and glass-ceramic products, which is beneficial to reducing the melting temperature and processing temperature. However, too high a content will damage the nucleation and crystallization during the process of the matrix glass transforming into glass-ceramics, and have an adverse effect on the chemical stability of the glass-ceramics and glass-ceramic products. Therefore, the total content of CaO, BaO, and SrO, CaO + BaO + SrO, is 0 to 5%, preferably 0 to 4%, more preferably 0 to 2%. In some embodiments, CaO + BaO + SrO is 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%.

[0081] In some embodiments, the base glass, glass-ceramics or glass-ceramic article may further contain 0 to 2% of a clarifying agent to improve the defoaming ability of the base glass, glass-ceramics or glass-ceramic article. Such clarifying agents include, but are not limited to, one or more of Sb2O3, SnO2, SnO, CeO2, F (fluorine) compounds, Cl (chlorine) compounds and Br (bromine) compounds, and Sb2O3 is preferably used as the clarifying agent. In some embodiments, it is preferred not to contain SnO2 and / or not to contain SnO, which is beneficial to the precipitation of spinel crystal phases in the glass-ceramics and glass-ceramic articles of the present invention, especially the formation of ZnAl2O4 crystal phase, ensuring the desired crystal phase types are obtained, preventing the formation of spodumene crystal phase and zirconia crystal phase, and being beneficial to improving the properties such as extrusion resistance and scratch resistance of the glass-ceramics and glass-ceramic articles. When the above-mentioned clarifying agents are present alone or in combination, the upper limit of their content is preferably 2%, more preferably the upper limit is 1%, and further preferably the upper limit is 0.5%. In some embodiments, the content of one or more of the clarifying agents is 0%, greater than 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.

[0082] Without affecting the properties of the base glass, glass-ceramics or glass-ceramic article of the present invention, other components not mentioned above, such as Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, etc., may be appropriately contained. However, to maintain the excellent properties of the base glass, glass-ceramics or glass-ceramic article of the present invention, the respective content or the total content of Nb2O5, WO3, Bi2O3, Ta2O5, TeO2 is preferably 5% or less, more preferably 2% or less, further preferably 1% or less, and even more preferably not contained.

[0083] PbO and As2O3 are toxic substances, and even a small amount of their content does not meet the environmental protection requirements. Therefore, in some embodiments of the present invention, it is preferred not to contain PbO and / or As2O3.

[0084] The "not containing" and "0%" described herein mean that the compound, molecule or element, etc. is not intentionally added as a raw material to the base glass, glass-ceramics or glass-ceramic article of the present invention; however, as raw materials and / or equipment for producing the base glass, glass-ceramics or glass-ceramic article, there will be certain impurities or components that are not intentionally added, and they will be contained in small amounts or traces in the final base glass, glass-ceramics or glass-ceramic article. Such a situation is also within the protection scope of this invention patent.

[0085] In the microcrystalline glass or microcrystalline glass products of the present invention, the grain size and crystal phase type will affect the light transmittance of the microcrystalline glass or microcrystalline glass products. The smaller the grain size, the higher the light transmittance. In some embodiments, the microcrystalline glass or microcrystalline glass products of the present invention exhibit high transparency in the visible light range. The microcrystalline glass or microcrystalline glass products exhibit high transmittance in the visible light range. In some embodiments, for microcrystalline glass products or microcrystalline glass with a thickness of less than 2.0 mm, the average light transmittance in the range of 400-800 nm is preferably 85% or more, more preferably 87% or more, and further preferably 88% or more.

[0086] The base glass, microcrystalline glass and microcrystalline glass products of the present invention can be produced and manufactured by the following methods:

[0087] Generating the base glass: Mix the raw materials (oxides, hydroxides, double salts, boric acid, etc.) evenly according to the component ratio. Put the evenly mixed raw materials into a crucible (such as a platinum or quartz crucible), and according to the melting difficulty of the glass composition, melt in an electric furnace or gas furnace within the temperature range of 1500-1700 °C for 5-24 hours. The preferred melting temperature is 1500-1600 °C; then obtain the base glass after clarification, homogenization, forming and annealing. The preferred clarification temperature is 1550-1650 °C, and the preferred annealing temperature is 550-650 °C.

[0088] The base glass of the present invention can be formed by well-known methods.

[0089] The base glass of the present invention is subjected to a crystallization treatment through a crystallization process after forming or forming and processing, and crystals are precipitated uniformly inside the glass to make microcrystalline glass. This crystallization treatment can be carried out in one stage or in two stages. It is preferably carried out in two stages. The crystallization treatment in two stages is to carry out a nucleation process treatment at the first temperature, and then carry out a crystal growth process treatment at the second temperature. The crystallization treatment carried out at the first temperature is called the first crystallization treatment, and the crystallization treatment carried out at the second temperature is called the second crystallization treatment.

[0090] In order to endow the microcrystalline glass with the desired physical and chemical properties, the preferred crystallization process is:

[0091] The above-mentioned crystallization treatment in one stage can continuously carry out the nucleation process and the crystal growth process. That is, heat up to the specified crystallization treatment temperature, and after reaching the crystallization treatment temperature, keep the temperature for a certain time, and then cool down. The preferred crystallization treatment temperature is 600-800 °C. In order to be able to precipitate the desired crystal phase, it is more preferably 650-750 °C. The holding time at the crystallization treatment temperature is preferably 1-10 hours, and more preferably 3-6 hours.

[0092] When the crystallization treatment is carried out in the above two stages, the first temperature is preferably 600 to 700 °C, the second temperature is preferably greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is preferably 1 to 6 hours, and the holding time at the second temperature is preferably 2 to 5 hours.

[0093] In some embodiments, the vitreous matrix or glass-ceramics described herein can be made into a shaped body by various processes, and the shaped body includes but is not limited to sheets, and the processes include but are not limited to slot drawing, the float process, roll pressing, and other processes for forming sheets known in the art. Alternatively, the vitreous matrix or glass-ceramics can be formed by the float process or roll pressing method well known in the art. The shaped bodies of the present invention also include lenses, prisms, etc.

[0094] For the vitreous matrix or glass-ceramics of the present invention, methods such as grinding or polishing can be used to manufacture a glass shaped body or a glass-ceramic shaped body of a sheet, but the methods for manufacturing a glass shaped body or a glass-ceramic shaped body are not limited to these methods.

[0095] For the vitreous matrix or glass-ceramics of the present invention, glass shaped bodies or glass-ceramic shaped bodies of various shapes can be prepared by methods such as hot bending process or pressing process at a certain temperature, but are not limited to these methods.

[0096] In some embodiments, a glass shaped body or a glass-ceramic shaped body can be made by a hot bending process. The hot bending process is a process of placing 2D or 2.5D glass or glass-ceramics in a mold and sequentially performing steps including heating and preheating, pressure forming, and pressure holding and cooling in a hot bending machine to obtain a 3D curved glass shaped body or glass-ceramic shaped body.

[0097] In some embodiments, the glass-ceramic shaped body has a 2.5D or 3D structure, that is, the glass-ceramic shaped body has a non-planar structure. The "non-planar structure" described herein means that in a 2.5D or 3D shape, at least a part of the glass-ceramic shaped body extends outward or extends along an angle with the plane defined by the original layout configuration of the 2D vitreous matrix. The 2.5D or 3D glass-ceramic shaped body formed from the vitreous matrix can have one or more convex or curved parts.

[0098] The vitreous matrix, glass-ceramics, and glass-ceramic products of the present invention can have any thickness that is reasonably useful.

[0099] In addition to improving the mechanical properties by precipitating crystals, the glass-ceramics of the present invention can also obtain more excellent mechanical properties by forming a compressive stress layer, thereby making glass-ceramic products.

[0100] In some embodiments, the substrate glass or glass-ceramics can be processed into sheets and / or shaped (such as drilling, hot bending, etc.), polished and / or buffed after shaping, and then chemically strengthened through a chemical strengthening process.

[0101] The chemical strengthening described in the present invention includes the ion exchange method. During the ion exchange process, smaller metal ions in the substrate glass or glass-ceramics are replaced or "exchanged" by larger metal ions with the same valence state near the substrate glass or glass-ceramics. Replacing smaller ions with larger ions builds compressive stress in the substrate glass or glass-ceramics, forming a compressive stress layer.

[0102] In some embodiments, the metal ions are monovalent alkali metal ions (such as Na + , K + , Rb + , Cs + , etc.). The ion exchange is carried out by immersing the substrate glass or glass-ceramics in a salt bath containing at least one molten salt of the larger metal ion, which is used to replace the smaller metal ions in the substrate glass. One or more ion exchange processes for chemically strengthening the substrate glass or glass-ceramics can include, but are not limited to: immersing it in a single salt bath, or immersing it in multiple salt baths with the same or different compositions, with washing and / or annealing steps between immersions.

[0103] In some embodiments, the substrate glass or glass-ceramics can be ion-exchanged by immersing it in a salt bath of molten Na salt (such as NaNO3) at a temperature of about 350 - 470 °C for about 1 - 36 hours, preferably in the temperature range of 400 - 460 °C, and preferably in the time range of 2 - 15 hours. In this embodiment, Na ions replace some Li ions in the substrate glass or glass-ceramics, thereby forming a surface compressive layer and exhibiting high mechanical properties. In some embodiments, the substrate glass or glass-ceramics can be ion-exchanged by immersing it in a mixed salt bath of molten K salt and Na salt at a temperature of about 360 - 460 °C for 1 - 36 hours, preferably in the time range of 2 - 24 hours.

[0104] The glass-ceramics involved in the present invention have efficient low-temperature ion exchange performance. In some embodiments, at lower ion exchange temperatures and shorter exchange times, the surface stress of the glass-ceramics products can reach more than 40 Mpa. After ion exchange, the hardness of the glass-ceramics products is significantly improved. The main reason is that ion exchange forms a relatively high compressive stress on the surface of the glass-ceramics products through the "jamming effect", increasing the anti-deformation performance and hardness of the glass-ceramics products. In some embodiments, after chemical strengthening of the glass-ceramics of the present invention, the Vickers hardness of the obtained glass-ceramics products can reach 600 kgf / mm 2 or more.

[0105] The glass-ceramic products of the present invention have excellent scratch resistance. In some embodiments, after chemical strengthening of the glass-ceramics of the present invention, the scratch width of the obtained glass-ceramic products is less than 30 μm.

[0106] The performance indexes of the glass-ceramics and / or glass-ceramic products of the present invention are tested by the following methods:

[0107] [Grain size]

[0108] It is measured by using a SEM scanning electron microscope. The sample is surface-treated in HF acid, then the surface of the sample is sputtered with gold, and surface scanning is carried out under the SEM scanning electron microscope to determine the size of its grains.

[0109] [Light transmittance]

[0110] The light transmittance described herein is all external transmittance, sometimes simply referred to as transmittance.

[0111] The sample is processed into a thickness of less than 2 mm and the opposite surfaces are polished parallel, and the average light transmittance at 400-800 nm is measured by using a Hitachi U-41000 spectrophotometer.

[0112] [Surface stress (CS)]

[0113] The surface stress is measured by using a glass surface stress meter SLP-2000.

[0114] As the measurement conditions, it is calculated with the refractive index of the sample being 1.57 and the photoelastic constant being 28 [(nm / cm) / Mpa].

[0115] [Scratch resistance]

[0116] A Knoop micro-indentation hardness tester is used, and the indenter is a conical Knoop indenter. A sample of 145 mm × 67 mm × 0.7 mm is placed on the stage to fix the sample to be tested. A fixed load of 8 (N) is applied to the indenter, and a preset distance track is scratched on the surface of the sample to be tested at a preset speed by the indenter. The scratch width is observed under a microscope. The scratch resistance of the sample is judged according to the scratch width. The wider the scratch, the worse the scratch resistance of the sample.

[0117] [Drop resistance]

[0118] The drop test machine WH-2101 is used for the drop resistance test. By loading glass products of the same specification (each weighing 20 g, with 2 pieces loaded) on the 2D sample, and laying 80-mesh sandpaper on the base, the sample of 145 mm × 67 mm × 0.7 mm is directly dropped on the sandpaper from a specified height. The height at which the sample can withstand the impact without breaking is the drop resistance. Specifically, the test starts from a height of 600 mm. Without breaking, the height is successively changed to 700 mm, 800 mm, 900 mm, 1000 mm and above. For the embodiments with "drop resistance", the glass-ceramic products are used as the test objects. The test data recorded as 1000 mm in the embodiments indicates that even when the glass-ceramic products with load are dropped from a height of 1000 mm, they do not break and withstand the impact. The maximum test height of the drop test machine WH-2101 is 2000 mm.

[0119] [Falling ball test height]

[0120] Place the sample of 145 mm × 67 mm × 0.7 mm on the glass carrier fixture, and let a 132-g steel ball drop from a specified height. The landing point is the center point of the sample. The maximum falling ball test height at which the sample can withstand the impact without breaking. Specifically, the falling ball test height starts from 400 mm, and the ball drops once at each height. If the sample does not break, the height is successively increased by 100 mm for continuous testing until the sample breaks. For the embodiments with "falling ball test height", the glass-ceramic products are used as the test objects. The test data recorded as 1700 mm in the embodiments indicates that even when the steel ball is dropped from a height of 1700 mm onto the glass-ceramic products, they do not break and withstand the impact. In the present invention, the falling ball test height is sometimes abbreviated as the falling ball height.

[0121] [Vickers hardness]

[0122] It is represented by the value obtained by dividing the load (N) when a diamond square pyramid indenter with a relative face angle of 136° presses into a pyramid-shaped depression on the test surface by the surface area (mm 2 ) calculated through the length of the depression. The test load is 100 (N) and the holding time is 15 (seconds). In the present invention, the Vickers hardness is sometimes abbreviated as hardness.

[0123] [Crushing strength]

[0124] Using a microcomputer-controlled electronic universal testing machine CMT6502, place a sample of 145 mm × 67 mm × 0.7 mm on a glass bearing fixture. The extrusion rod is designed with a mushroom head, with a diameter of ￠10 mm and a downward pressing speed of 5 mm / min until the sample is damaged. It needs to be calibrated with a jig before testing, and the test point is at the center position. Click the test button until the sample is crushed by extrusion, and record the pressure (N) when the sample is broken. For the embodiments with "crushing strength", the glass-ceramic products are used as the test objects. The test data recorded as 500 N in the embodiments indicates that the maximum extrusion force that the glass-ceramic products can withstand before breaking is 500 N.

[0125] [Young's modulus]

[0126] The Young's modulus (E) is measured by ultrasonic testing of the longitudinal wave velocity and transverse wave velocity, and then calculated according to the following formula.

[0127]

[0128] G = V S 2 ρ

[0129] In the formula: E is the Young's modulus, Pa;

[0130] G is the shear modulus, Pa;

[0131] V T is the transverse wave velocity, m / s;

[0132] V S is the longitudinal wave velocity, m / s;

[0133] ρ is the glass density, g / cm 3 .

[0134] The glass-ceramic products of the present invention have the following properties:

[0135] 1) In some embodiments, the grain size of the glass-ceramic products is below 70 nm, preferably below 60 nm, and more preferably below 50 nm.

[0136] 2) In some embodiments, the surface stress (CS) of the glass-ceramic products is 40 MPa or more, preferably 80 - 200 MPa, and more preferably 100 - 200 MPa.

[0137] 3) In some embodiments, the drop ball test height of the glass-ceramic products is 800 mm or more, preferably 1000 mm or more, and more preferably 1200 mm or more.

[0138] 4) In some embodiments, the drop resistance of the glass-ceramic product is 800 mm or more, preferably 1000 mm or more, and more preferably 1200 mm or more.

[0139] 5) In some embodiments, the extrusion resistance strength of the glass-ceramic product is 200 N or more, preferably 250 N or more, and more preferably 300 N or more.

[0140] 6) In some embodiments, the Young's modulus (E) of the glass-ceramic product is 80 - 105 GPa, preferably 85 - 105 GPa, and more preferably 90 - 105 GPa.

[0141] 7) In some embodiments, the scratch width of the glass-ceramic product is less than 30 μm, preferably 25 μm or less, and more preferably 20 μm or less.

[0142] 8) In some embodiments, the Vickers hardness (H v ) of the glass-ceramic product is 600 kgf / mm 2 or more, preferably 650 - 800 kgf / mm 2 , and more preferably 680 - 800 kgf / mm 2 .

[0143] 9) In some embodiments, for a glass-ceramic product with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, and more preferably 88% or more. The thickness is preferably 0.2 - 2.0 mm, more preferably 0.3 - 1.0 mm, and further preferably 0.5 - 1.0 mm.

[0144] The glass-ceramic of the present invention has the following properties:

[0145] 1) In some embodiments, the grain size of the glass-ceramic is 70 nm or less, preferably 60 nm or less, and more preferably 50 nm or less.

[0146] 2) In some embodiments, for a glass-ceramic with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, and more preferably 88% or more. The thickness is preferably 0.2 - 2.0 mm, more preferably 0.3 - 1.0 mm, and further preferably 0.5 - 1.0 mm.

[0147] 3) In some embodiments, the Vickers hardness (H v ) of the glass-ceramic is 500 kgf / mm 2 or more, preferably 600 - 750 kgf / mm 2 , and more preferably 630 - 750 kgf / mm 2 .

[0148] 4) In some embodiments, the Young's modulus (E) of the glass-ceramics is 80 to 105 GPa, preferably 85 to 105 GPa, and more preferably 90 to 105 GPa.

[0149] Due to the above excellent properties, the glass-ceramics, glass-ceramic products, parent glasses, glass preforms, and glass-ceramic preforms of the present invention can be widely fabricated into glass covers or glass components; at the same time, the glass-ceramics, glass-ceramic products, parent glasses, glass preforms, and glass-ceramic preforms of the present invention can be applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc., for manufacturing protective glasses for mobile phones, smart phones, tablet computers, laptop computers, PDAs, televisions, personal computers, MTA machines, or industrial displays, or for manufacturing touch screens, protective windows, automobile windows, train windows, aviation machinery windows, touch screen protective glasses, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white household appliances, such as for manufacturing refrigerator components or kitchen utensils.

[0150] Examples

[0151] To further clearly illustrate and explain the technical solutions of the present invention, the following non-limiting examples are provided. In the examples of the present invention, numerous efforts have been made to ensure the accuracy of the numerical values, but it must be taken into account that there are some errors and deviations. The compositions themselves are given in weight % based on oxides and have been normalized to 100%.

[0152] <Examples of Glass-Ceramics>

[0153] In this example, glass-ceramics having the compositions shown in Tables 1 to 3 were obtained by using the above-described method for manufacturing glass-ceramics. In addition, the properties of each glass-ceramic were measured by the testing method described in the present invention, and the measurement results are shown in Tables 1 to 3. In the following examples, the thickness of the test sample for the average light transmittance at wavelengths of 400 to 800 nm was 1 mm.

[0154] Table 1.

[0155]

[0156]

[0157] Table 2.

[0158]

[0159] Table 3.

[0160]

[0161] <Examples of Glass-Ceramic Products>

[0162] In this embodiment, the glass-ceramic articles with the compositions shown in Tables 4 to 6 are obtained by using the above manufacturing method of glass-ceramic articles. In addition, the properties of each glass-ceramic article are measured by the testing method described in the present invention, and the measurement results are shown in Tables 4 to 6. In the following embodiments, the thickness of the test sample for the average light transmittance at a wavelength of 400 to 800 nm is 1.0 mm.

[0163] Table 4.

[0164]

[0165] Table 5.

[0166]

[0167]

[0168] Table 6.

[0169]

[0170]

Claims

1. Glass-ceramic product, characterized in that, Its components are expressed by weight percentage and contain: SiO2: 41 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 7%; Ln2O3: 0.1 - 8%; MgO: 0 - 6%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

2. The glass-ceramic article according to claim 1, wherein Its components are expressed by weight percentage and also contain: Na2O: 0 - 8%; and / or ZrO2: 0 - 5%; and / or K2O: 0 - 3%; and / or B2O3: 0 - 4%; and / or CaO + BaO + SrO: 0 - 5%; and / or P2O5: 0 - 5%; and / or clarifying agent: 0 - 2%.

3. Glass-ceramic product, characterized in that, Its components are expressed by weight percentage and consist of: SiO2: 41 - 50%; Al2O3: 27.5 - 35%; ZnO: 8.5 - 12%; Li2O: 0.1 - 5%; TiO2: 2 - 7%; Ln2O3: 0.1 - 8%; MgO: 0 - 6%; Na2O: 0 - 8%; ZrO2: 0 - 5%; K2O: 0 - 3%; B2O3: 0 - 4%; CaO + BaO + SrO: 0 - 5%; P2O5: 0 - 5%; clarifying agent: 0 - 2%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 - 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

4. The glass-ceramic article according to any one of claims 1 to 3, characterized in that, Its components are expressed in weight percentages, wherein: (ZnO + MgO + SiO2) / Al2O3 is 1.6 to 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 to 2.1; and / or Al2O3 / Li2O is 11.0 to 60.0, preferably Al2O3 / Li2O is 12.0 to 40.0, more preferably Al2O3 / Li2O is 13.0 to 20.0; and / or (ZnO + MgO) / (Li2O + Na2O) is 1.5 to 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 to 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 to 4.0; and / or (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5; and / or SiO2 / Al2O3 is 1.2 to 1.8, preferably SiO2 / Al2O3 is 1.3 to 1.7, more preferably SiO2 / Al2O3 is 1.4 to 1.67; and / or Ln2O3 / Li2O is 0.1 to 3.0, preferably Ln2O3 / Li2O is 0.3 to 2.2, more preferably Ln2O3 / Li2O is 0.5 to 2.1, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

5. The glass-ceramic article according to any one of claims 1 to 3, characterized in that, Its components are expressed in weight percentages, wherein: SiO2: 42 to 50%, preferably SiO2: 43 to 50%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2.1 to 6%, preferably TiO2: 2.3 to 5%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 5%, preferably Ln2O3: 1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 7%, preferably Na2O: 1 to 5%; and / or MgO: 0 to 5%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or P2O5: 0 to 4%, preferably P2O5: 0 to 3%; and / or clarifying agent: 0 to 1%, preferably clarifying agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

6. The glass-ceramic article according to claim 1 or 2, wherein, Its components are expressed in weight percentages and contain: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably without Nb2O5, and / or without WO3, and / or without Bi2O3, and / or without Ta2O5, and / or without TeO2.

7. The glass-ceramic article according to any one of claims 1 to 3, characterized in that, The glass-ceramic article does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

8. The glass-ceramic article according to any one of claims 1 to 3, characterized in that, The glass-ceramic article contains a spinel crystal phase. Preferably, the spinel crystal phase has a higher weight percentage than other crystal phases. More preferably, the weight percentage of the spinel crystal phase in the glass-ceramic article is 20 to 50%. Further preferably, the weight percentage of the spinel crystal phase in the glass-ceramic article is 30 to 50%. Even more preferably, the weight percentage of the spinel crystal phase in the glass-ceramic article is 30 to 45%.

9. The glass-ceramic article according to claim 8, wherein, The spinel crystal phase is ZnAl2O4.

10. The glass-ceramic article according to any one of claims 1 to 3, characterized in that, The glass-ceramic article does not contain a spodumene crystal phase, and / or does not contain a zirconia crystal phase, and / or does not contain a quartz crystal phase, and / or does not contain a quartz solid solution crystal phase, and / or does not contain a Zn2SiO4 crystal phase.

11. The glass-ceramics product according to any one of claims 1 to 3, characterized in that, The grain size of the glass-ceramics product is below 70 nm, preferably below 60 nm, more preferably below 50 nm; and / or the surface stress is 40 MPa or more, preferably 80 - 200 MPa, more preferably 100 - 200 MPa; and / or the height of the ball-drop test is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the drop resistance is 800 mm or more, preferably 1000 mm or more, more preferably 1200 mm or more; and / or the extrusion resistance strength is 200 N or more, preferably 250 N or more, more preferably 300 N or more; and / or the Young's modulus E is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or the scratch width is less than 30 μm, preferably 25 μm or less, more preferably 20 μm or less; and / or the Vickers hardness is 600 kgf / mm 2 or more, preferably 650 - 800 kgf / mm 2 , more preferably 680 - 800 kgf / mm 2 ; and / or for the glass-ceramics product with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

12. Glass-ceramics, characterized in that, Its components are expressed in weight percentages and contain: SiO2: 41 to 50%; Al2O3: 27.5 to 35%; ZnO: 8.5 to 12%; Li2O: 0.1 to 5%; TiO2: 2 to 7%; Ln2O3: 0.1 to 8%; MgO: 0 to 6%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 to 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

13. The glass-ceramics according to claim 12, wherein, Its components are expressed in weight percentages and further contain: Na2O: 0 to 8%; and / or ZrO2: 0 to 5%; and / or K2O: 0 to 3%; and / or B2O3: 0 to 4%; and / or CaO + BaO + SrO: 0 to 5%; and / or P2O5: 0 to 5%; and / or a clarifying agent: 0 to 2%.

14. Glass-ceramics, characterized in that, Its components are expressed in weight percentages and consist of SiO2: 41 to 50%; Al2O3: 27.5 to 35%; ZnO: 8.5 to 12%; Li2O: 0.1 to 5%; TiO2: 2 to 7%; Ln2O3: 0.1 to 8%; MgO: 0 to 6%; Na2O: 0 to 8%; ZrO2: 0 to 5%; K2O: 0 to 3%; B2O3: 0 to 4%; CaO + BaO + SrO: 0 to 5%; P2O5: 0 to 5%; Clarifying agent: 0 to 2%, where (ZnO + MgO + SiO2) / Al2O3 is 1.5 to 2.15, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, and Yb2O3.

15. The glass-ceramics according to any one of claims 12 to 14, characterized in that, Its components are expressed in weight percentages, where: (ZnO + MgO + SiO2) / Al2O3 is 1.6 to 2.15, preferably (ZnO + MgO + SiO2) / Al2O3 is 1.8 to 2.1; and / or Al2O3 / Li2O is 11.0 to 60.0, preferably Al2O3 / Li2O is 12.0 to 40.0, more preferably Al2O3 / Li2O is 13.0 to 20.0; and / or (ZnO + MgO) / (Li2O + Na2O) is 1.5 to 5.0, preferably (ZnO + MgO) / (Li2O + Na2O) is 1.7 to 4.5, more preferably (ZnO + MgO) / (Li2O + Na2O) is 1.8 to 4.0; and / or (TiO2 + ZrO2) / (Li2O + Na2O) is 0.5 to 5.0, preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 3.0, more preferably (TiO2 + ZrO2) / (Li2O + Na2O) is 0.7 to 1.5; and / or SiO2 / Al2O3 is 1.2 to 1.8, preferably SiO2 / Al2O3 is 1.3 to 1.7, more preferably SiO2 / Al2O3 is 1.4 to 1.67; and / or Ln2O3 / Li2O is 0.1 to 3.0, preferably Ln2O3 / Li2O is 0.3 to 2.2, more preferably Ln2O3 / Li2O is 0.5 to 2.1, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

16. The glass-ceramics according to any one of claims 12 to 14, characterized in that, Its components are expressed in weight percentages, where: SiO2: 42 to 50%, preferably SiO2: 43 to 50%; and / or Al2O3: 28 to 34%, preferably Al2O3: 28 to 33%; and / or Li2O: 1 to 5%, preferably Li2O: 1 to 4%; and / or ZnO: 9 to 12%, preferably ZnO: 9 to 11%; and / or TiO2: 2.1 to 6%, preferably TiO2: 2.3 to 5%; and / or K2O: 0 to 2%, preferably K2O: 0 to 1%; and / or Ln2O3: 0.1 to 5%, preferably Ln2O3: 1 to 3%; and / or ZrO2: 0.5 to 4%, preferably ZrO2: 1 to 3%; and / or Na2O: 1 to 7%, preferably Na2O: 1 to 5%; and / or MgO: 0 to 5%, preferably MgO: 1 to 3%; and / or B2O3: 0 to 2%, preferably B2O3: 0 to 1%; and / or CaO + BaO + SrO: 0 to 4%, preferably CaO + BaO + SrO: 0 to 2%; and / or P2O5: 0 to 4%, preferably P2O5: 0 to 3%; and / or fining agent: 0 to 1%, preferably fining agent: 0 to 0.5%, and the Ln2O3 is one or more of La2O3, Gd2O3, Y2O3, Yb2O3.

17. The glass-ceramics according to claim 12 or 13, characterized in that, Its components are expressed by weight percentage and contain: Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 5%, preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 2%, more preferably Nb2O5 + WO3 + Bi2O3 + Ta2O5 + TeO2: 0 to 1%, further preferably does not contain Nb2O5, and / or does not contain WO3, and / or does not contain Bi2O3, and / or does not contain Ta2O5, and / or does not contain TeO2.

18. The glass-ceramics according to any one of claims 12 to 14, characterized in that, The glass-ceramics does not contain B2O3, and / or does not contain SnO2, and / or does not contain SnO.

19. The glass-ceramics according to any one of claims 12 to 14, characterized in that, The glass-ceramics contains a spinel crystal phase. Preferably, the spinel crystal phase has a higher weight percentage than other crystal phases. More preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 20 to 50%. Further preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 30 to 50%. Even more preferably, the weight percentage of the spinel crystal phase in the glass-ceramics is 30 to 45%.

20. The glass-ceramics according to claim 19, characterized in that, The spinel crystal phase is ZnAl2O4.

21. The glass-ceramics according to any one of claims 12 to 14, characterized in that, The glass-ceramics does not contain a spodumene crystal phase, and / or does not contain a zirconia crystal phase, and / or does not contain a quartz crystal phase, and / or does not contain a quartz solid solution crystal phase, and / or does not contain a Zn2SiO4 crystal phase.

22. The glass-ceramics according to any one of claims 12 to 14, characterized in that, The grain size of the glass-ceramics is below 70 nm, preferably below 60 nm, more preferably below 50 nm; and / or the Vickers hardness is 500 kgf / mm 2 or more, preferably 600 - 750 kgf / mm 2 , more preferably 650 - 750 kgf / mm 2 ; and / or the Young's modulus is 80 - 105 GPa, preferably 85 - 105 GPa, more preferably 90 - 105 GPa; and / or for the glass-ceramics with a thickness of 2.0 mm or less, the average light transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 87% or more, more preferably 88% or more.

23. Glass cover plate, characterized in that, Contains the glass-ceramics product according to any one of claims 1 to 11, and / or the glass-ceramics according to any one of claims 12 to 22.

24. Glass component, characterized in that, Contains the glass-ceramics product according to any one of claims 1 to 11, and / or the glass-ceramics according to any one of claims 12 to 22.

25. An electronic device, characterized in that, Contains the glass-ceramics product according to any one of claims 1 to 11, and / or the glass-ceramics according to any one of claims 12 to 22, and / or the glass cover plate according to claim 23, and / or the glass component according to claim 24.

26. A display device, characterized in that, Contains the glass-ceramics product according to any one of claims 1 to 11, and / or the glass-ceramics according to any one of claims 12 to 22, and / or the glass cover plate according to claim 23, and / or the glass component according to claim 24.

27. The manufacturing method of the glass-ceramic article according to any one of claims 1 to 11, characterized in that, The method includes the following steps: forming a base glass, forming glass-ceramics from the base glass through a crystallization process, and then forming a glass-ceramics product from the glass-ceramics through a chemical strengthening process.

28. The manufacturing method of the glass-ceramic article according to claim 27, characterized in that, The forming of the base glass includes the following steps: Mix the raw materials evenly according to the component ratio, then put them into a crucible, and melt them in an electric furnace or a gas furnace within the temperature range of 1500 to 1700 °C for 5 to 24 hours. Preferably, the melting temperature is 1500 to 1600 °C. Then, after clarification, homogenization, forming, and annealing, the base glass is obtained. The clarification temperature is 1550 to 1650 °C, and the annealing temperature is 550 to 650 °C.

29. The manufacturing method of the glass-ceramics product according to claim 27, characterized in that, The crystallization process includes the following steps: heating to the specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining its temperature for a certain period of time, and then cooling down. The crystallization treatment temperature is 600 to 800 °C, preferably 650 to 750 °C, and the holding time at the crystallization treatment temperature is 1 to 10 hours, preferably 3 to 6 hours.

30. The manufacturing method of the glass-ceramics product according to claim 27, characterized in that, The crystallization process includes the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

31. The manufacturing method of the glass-ceramic article according to claim 30, characterized in that, The crystallization process includes: the first temperature is 600 - 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 - 6 hours, and the holding time at the second temperature is 2 - 5 hours.

32. The manufacturing method of the glass-ceramics product according to claim 27, characterized in that, The chemical strengthening process includes: immersing the glass-ceramics in a molten Na salt bath at 350 - 470 °C for 1 - 36 hours, preferably in the temperature range of 400 - 460 °C and preferably in the time range of 2 - 15 hours; and / or immersing the glass-ceramics in a molten mixed salt bath of K salt and Na salt at 360 - 460 °C for 1 - 36 hours, preferably in the time range of 2 - 24 hours.

33. The manufacturing method of the glass-ceramics according to any one of claims 12 to 22, characterized in that, The method includes the following steps: forming a base glass, and then forming glass-ceramics from the base glass through a crystallization process.

34. The manufacturing method of the glass-ceramics according to claim 33, characterized in that, The forming of the base glass includes the following steps: Mix the raw materials evenly according to the component ratio, then put them into a crucible, melt them in an electric furnace or a gas furnace within the temperature range of 1500 - 1700 °C for 5 - 24 hours, preferably the melting temperature is 1500 - 1600 °C, and then obtain the base glass after clarification, homogenization, forming, and annealing. The clarification temperature is 1550 - 1650 °C, and the annealing temperature is 550 - 650 °C.

35. The manufacturing method of the glass-ceramics according to claim 33, characterized in that, The crystallization process includes the following steps: heating up to a specified crystallization treatment temperature, after reaching the crystallization treatment temperature, maintaining its temperature for a certain period of time, and then cooling down. The crystallization treatment temperature is 600 - 800 °C, preferably 650 - 750 °C, and the holding time at the crystallization treatment temperature is 1 - 10 hours, preferably 3 - 6 hours.

36. The manufacturing method of the glass-ceramics according to claim 33, characterized in that, The crystallization process includes the following steps: performing a nucleation process treatment at a first temperature, and then performing a crystal growth process treatment at a second temperature.

37. The manufacturing method of the glass-ceramics according to claim 36, characterized in that, The crystallization process includes: the first temperature is 600 - 700 °C, the second temperature is greater than 750 °C but less than or equal to 900 °C, the holding time at the first temperature is 1 - 6 hours, and the holding time at the second temperature is 2 - 5 hours.

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