Glass ceramic, glass ceramic product and manufacturing method thereof

Abstract

The invention provides a microcrystalline glass product with excellent mechanical properties. The microcrystalline glass product comprises the following components by mole percent: 50-68% of SiO2; 8 to 20 percent of Al2O3; li2O: 7 to 18%; na2O: 4%-15%; 0.1 to 10 percent of P2O5; and 0 to 10 percent of ZrO2. Through reasonable component design, the microcrystalline glass product disclosed by the invention has excellent mechanical properties and is suitable for electronic equipment or display equipment.

Description

[0001] This application is a divisional application of the invention patent application with the application number 201910773568.X, the application date of August 21, 2019, and the title of "Glass-ceramics, glass-ceramic products and manufacturing methods thereof". Technical Field

[0002] The present invention relates to a glass-ceramics, and particularly to a glass-ceramics, glass-ceramic products with excellent mechanical properties and manufacturing methods thereof. Background Art

[0003] Glass-ceramics is a material in which crystals precipitate inside the glass by heat-treating the base glass, and has higher mechanical properties than the base glass. And because microcrystals are formed in the glass, its toughness, wear resistance, etc. have obvious advantages compared with ordinary glass. Therefore, glass-ceramics are currently applied to display devices or electronic devices.

[0004] When glass-ceramics are applied to display devices or electronic devices, especially portable electronic devices or display devices, the requirements for anti-drop, anti-compression, and scratch resistance are relatively high. Chemical strengthening of glass-ceramics can improve the mechanical properties of glass-ceramics, but the existing glass-ceramics on the market are difficult to be chemically strengthened, or the mechanical properties are difficult to meet the requirements for application as cover plate materials after chemical strengthening. Therefore, developing a glass-ceramics and glass-ceramic products suitable for display devices or electronic devices with high requirements for anti-drop, anti-compression, and scratch resistance has become the goal pursued by researchers. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a glass-ceramic product with excellent mechanical properties.

[0006] The technical solution adopted by the present invention to solve the technical problem is as follows:

[0007] (1) A glass-ceramic product, the components of which are expressed in mole percentages and contain: SiO2: 50-70%; Al2O3: 8-20%; Li2O: 7-18%; Na2O: 4-15%; P2O5: 0.1-10%; ZrO2: 0-10%.

[0008] (2) The glass-ceramic product according to (1), the components of which are expressed in mole percentages and further contain: ZnO: 0-10%; and / or MgO: 0-10%; and / or K2O: 0-10%; and / or SrO: 0-5%; and / or BaO: 0-5%; and / or TiO2: 0-5%; and / or Y2O3: 0-5%; and / or B2O3: 0-6%; and / or clarifying agent: 0-2%.

[0009] (3) Glass-ceramic products, the components of which contain SiO2, Al2O3, Li2O and Na2O, and the components are expressed in mole percentages, where the value of (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, and the value of Li2O / Na2O is 0.55 to 4.2, and the grain size of the glass-ceramic products is below 70 nm.

[0010] (4) The glass-ceramic products according to (3), the components of which are expressed in mole percentages, contain: SiO2: 50 to 70%; Al2O3: 8 to 20%; Li2O: 7 to 18%; Na2O: 4 to 15%; P2O5: 0.1 to 10%; ZrO2: 0 to 10%; ZnO: 0 to 10%; MgO: 0 to 10%; K2O: 0 to 10%; SrO: 0 to 5%; BaO: 0 to 5%; TiO2: 0 to 5%; Y2O3: 0 to 5%; B2O3: 0 to 6%; fining agent: 0 to 2%.

[0011] (5) The glass-ceramic products according to any one of (1) to (4), the components of which are expressed in mole percentages, contain: SiO2: 52 to 68%; and / or Al2O3: 9 to 18%; and / or Li2O: 9 to 16%; and / or Na2O: 5 to 12%; and / or P2O5: 0.1 to 5%; and / or ZrO2: 0.1 to 6%; and / or ZnO: 0.1 to 8%; and / or MgO: 0.5 to 6%; and / or K2O: 0 to 7%; and / or SrO: 0 to 1%; and / or BaO: 0 to 1%; and / or TiO2: 0 to 1%; and / or Y2O3: 0 to 1%; and / or B2O3: 0.1 to 2%; and / or fining agent: 0 to 1%.

[0012] (6) The glass-ceramic products according to any one of (1) to (5), the components of which are expressed in mole percentages, contain: SiO2: 54 to 65%; and / or ZrO2: 0.1 to 3%; and / or P2O5: 0.3 to 2.5%.

[0013] (7) The glass-ceramic products according to any one of (1) to (6), the components of which are expressed in mole percentages, (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 to 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, and more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 to 0.4.

[0014] (8) The glass-ceramic article according to any one of (1) to (7), wherein the components are expressed in mole percentages, and (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 to 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 to 2.5.

[0015] (9) The glass-ceramic article according to any one of (1) to (8), wherein the components are expressed in mole percentages, and Li2O / Na2O is 0.55 to 4.2, preferably Li2O / Na2O is 0.7 to 3.5, more preferably Li2O / Na2O is 0.8 to 3.0.

[0016] (10) 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 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, and even more preferably 20 nm or less.

[0017] (11) The glass-ceramic article according to any one of (1) to (10), wherein the surface stress of the glass-ceramic article is 300 MPa or more, preferably 500 MPa or more, more preferably 700 MPa or more; and / or the depth of the ion exchange layer is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, further preferably 25 μm or more.

[0018] (12) The glass-ceramic article according to any one of (1) to (11), wherein the dropping ball test height of the glass-ceramic article is 1000 mm or more, preferably 1100 mm or more, more preferably 1200 mm or more; and / or the fracture toughness is 1 MPa·m 1 / 2 or more, preferably 1.3 MPa·m 1 / 2 or more, more preferably 1.5 MPa·m 1 / 2 or more; and / or the Vickers hardness (H v ) is 600 kgf / mm 2 or more, preferably 650 kgf / mm 2 or more, more preferably 700 kgf / mm 2 or more.

[0019] (13) The glass-ceramic article according to any one of (1) to (12), wherein the crystallinity of the glass-ceramic article is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more.

[0020] (14) The glass-ceramic article according to any one of (1) to (13), the haze of the glass-ceramic article with a thickness of 0.55 mm is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or for the glass-ceramic article with a thickness of 0.55 mm, the average transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or for the glass-ceramic article with a thickness of 0.55 mm, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more.

[0021] (15) The glass-ceramic article according to any one of (1) to (14), the crystalline phase of the glass-ceramic article contains lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

[0022] (16) The glass-ceramic article according to any one of (1) to (15), the glass-ceramic article further contains a colorant, which can make the glass-ceramic article present different colors.

[0023] (17) The glass-ceramic article according to any one of (1) to (16), the colorant is expressed in mole percentage and contains: NiO: 0 - 4%; and / or Ni₂O₃: 0 - 4%; and / or CoO: 0 - 2%; and / or Co₂O₃: 0 - 2%; and / or Fe₂O₃: 0 - 7%; and / or MnO₂: 0 - 4%; and / or Er₂O₃: 0 - 3%; and / or Nd₂O₃: 0 - 3%; and / or Cu₂O: 0 - 4%; and / or Pr₂O₅: 0 - 3%; and / or CeO₂: 0 - 4%.

[0024] (18) The glass-ceramic article according to any one of (1) to (17), the colorant is expressed in mole percentage and contains: NiO: 0.1 - 3%; and / or Ni₂O₃: 0.1 - 3%; and / or CoO: 0.05 - 1.8%; and / or Co₂O₃: 0.05 - 1.8%; and / or Fe₂O₃: 0.2 - 5%; and / or MnO₂: 0.1 - 3%; and / or Er₂O₃: 0.1 - 2%; and / or Nd₂O₃: 0.05 - 2%; and / or Cu₂O: 0.5 - 3%; and / or Pr₂O₅: 0.05 - 2.5%; and / or CeO₂: 0.5 - 3%.

[0025] (19) The glass-ceramic, its components are expressed in mole percentage and contain: SiO₂: 50 - 70%; Al₂O₃: 8 - 20%; Li₂O: 7 - 18%; Na₂O: 4 - 15%; P₂O₅: 0.1 - 10%; ZrO₂: 0 - 10%.

[0026] (20) The glass-ceramics according to (19), the components of which are expressed in mole percentages, further contain: ZnO: 0 to 10%; and / or MgO: 0 to 10%; and / or K2O: 0 to 10%; and / or SrO: 0 to 5%; and / or BaO: 0 to 5%; and / or TiO2: 0 to 5%; and / or Y2O3: 0 to 5%; and / or B2O3: 0 to 6%; and / or clarifying agent: 0 to 2%.

[0027] (21) Glass-ceramics, the components of which contain SiO2, Al2O3, Li2O and Na2O, the components of which are expressed in mole percentages, wherein the value of (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, and the value of Li2O / Na2O is 0.55 to 4.2, and the grain size of the glass-ceramics is below 70 nm.

[0028] (22) The glass-ceramics according to (21), the components of which are expressed in mole percentages, contain: SiO2: 52 to 68%; Al2O3: 9 to 18%; Li2O: 9 to 16%; Na2O: 5 to 12%; P2O5: 0.1 to 10%; ZrO2: 0 to 10%; ZnO: 0 to 10%; MgO: 0 to 10%; K2O: 0 to 10%; SrO: 0 to 5%; BaO: 0 to 5%; TiO2: 0 to 5%; Y2O3: 0 to 5%; B2O3: 0 to 6%; clarifying agent: 0 to 2%.

[0029] (23) The glass-ceramics according to any one of (19) to (22), the components of which are expressed in mole percentages, contain: SiO2: 52 to 68%; and / or Al2O3: 9 to 18%; and / or Li2O: 9 to 16%; and / or Na2O: 5 to 12%; and / or P2O5: 0.1 to 5%; and / or ZrO2: 0.1 to 6%; and / or ZnO: 0.1 to 8%; and / or MgO: 0.5 to 6%; and / or K2O: 0 to 7%; and / or SrO: 0 to 1%; and / or BaO: 0 to 1%; and / or TiO2: 0 to 1%; and / or Y2O3: 0 to 1%; and / or B2O3: 0.1 to 2%; and / or clarifying agent: 0 to 1%.

[0030] (24) The glass-ceramics according to any one of (19) to (23), the components of which are expressed in mole percentages, contain: SiO2: 54 to 65%; and / or ZrO2: 0.1 to 3%; and / or P2O5: 0.3 to 2.5%.

[0031] (25) The glass-ceramics according to any one of (19) to (24), wherein the components are expressed in mole percentages, and (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 to 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, and more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 to 0.4.

[0032] (26) The glass-ceramics according to any one of (19) to (25), wherein the components are expressed in mole percentages, and (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 to 3.0, and more preferably (Li2O + Na2O) / Al2O3 is 1.0 to 2.5.

[0033] (27) The glass-ceramics according to any one of (19) to (26), wherein the components are expressed in mole percentages, and Li2O / Na2O is 0.55 to 4.2, preferably Li2O / Na2O is 0.7 to 3.5, and more preferably Li2O / Na2O is 0.8 to 3.0.

[0034] (28) The glass-ceramics according to any one of (19) to (27), wherein the grain size of the glass-ceramics is 70 nm or less, preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, and even more preferably 20 nm or less.

[0035] (29) The glass-ceramics according to any one of (19) to (28), wherein the crystallinity of the glass-ceramics is 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.

[0036] (30) The glass-ceramics according to any one of (19) to (29), wherein the refractive index (nd) of the glass-ceramics is 1.500 to 1.540, preferably 1.510 to 1.530; and / or the thermal expansion coefficient (α 20℃-120℃ ) is 70 to 120×10 -7 / K, preferably 86 to 100×10 -7 / K.

[0037] (31) The microcrystalline glass according to any one of (19) to (30), the haze of the microcrystalline glass with a thickness of 0.55 mm is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or for the microcrystalline glass with a thickness of 0.55 mm, the average transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or for the microcrystalline glass with a thickness of 0.55 mm, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more.

[0038] (32) The microcrystalline glass according to any one of (19) to (31), the crystal phase of the microcrystalline glass contains lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

[0039] (33) The microcrystalline glass according to any one of (19) to (32), the microcrystalline glass further contains a colorant, which can make the microcrystalline glass present different colors.

[0040] (34) The microcrystalline glass according to any one of (19) to (33), the colorant is expressed in mole percentage and contains: NiO: 0 - 4%; and / or Ni2O3: 0 - 4%; and / or CoO: 0 - 2%; and / or Co2O3: 0 - 2%; and / or Fe2O3: 0 - 7%; and / or MnO2: 0 - 4%; and / or Er2O3: 0 - 3%; and / or Nd2O3: 0 - 3%; and / or Cu2O: 0 - 4%; and / or Pr2O5: 0 - 3%; and / or CeO2: 0 - 4%.

[0041] (35) The microcrystalline glass according to any one of (19) to (34), the colorant is expressed in mole percentage and contains: NiO: 0.1 - 3%; and / or Ni2O3: 0.1 - 3%; and / or CoO: 0.05 - 1.8%; and / or Co2O3: 0.05 - 1.8%; and / or Fe2O3: 0.2 - 5%; and / or MnO2: 0.1 - 3%; and / or Er2O3: 0.1 - 2%; and / or Nd2O3: 0.05 - 2%; and / or Cu2O: 0.5 - 3%; and / or Pr2O5: 0.05 - 2.5%; and / or CeO2: 0.5 - 3%.

[0042] (36) The base glass, its components are expressed in mole percentage and contain: SiO2: 50 - 70%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%.

[0043] (37) The base glass according to (36), wherein the components are expressed in mole percentages and further contain: ZnO: 0 to 10%; and / or MgO: 0 to 10%; and / or K2O: 0 to 10%; and / or SrO: 0 to 5%; and / or BaO: 0 to 5%; and / or TiO2: 0 to 5%; and / or Y2O3: 0 to 5%; and / or B2O3: 0 to 6%; and / or fining agent: 0 to 2%.

[0044] (38) The base glass according to any one of (36) or (37), wherein the components are expressed in mole percentages and contain: SiO2: 52 to 68%; and / or Al2O3: 9 to 18%; and / or Li2O: 9 to 16%; and / or Na2O: 5 to 12%; and / or P2O5: 0.1 to 5%; and / or ZrO2: 0.1 to 6%; and / or ZnO: 0.1 to 8%; and / or MgO: 0.5 to 6%; and / or K2O: 0 to 7%; and / or SrO: 0 to 1%; and / or BaO: 0 to 1%; and / or TiO2: 0 to 1%; and / or Y2O3: 0 to 1%; and / or B2O3: 0.1 to 2%; and / or fining agent: 0 to 1%.

[0045] (39) The base glass according to any one of (36) to (38), wherein the components are expressed in mole percentages and contain: SiO2: 54 to 65%; and / or ZrO2: 0.1 to 3%; and / or P2O5: 0.3 to 2.5%.

[0046] (40) The base glass according to any one of (36) to (39), wherein the components are expressed in mole percentages, and (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 to 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, and more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 to 0.4.

[0047] (41) The base glass according to any one of (36) to (40), wherein the components are expressed in mole percentages, and (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 to 3.0, and more preferably (Li2O + Na2O) / Al2O3 is 1.0 to 2.5.

[0048] (42) The base glass according to any one of (36) to (41), wherein the components are expressed in mole percentages, and Li2O / Na2O is 0.55 to 4.2, preferably Li2O / Na2O is 0.7 to 3.5, and more preferably Li2O / Na2O is 0.8 to 3.0.

[0049] (43) The base glass according to any one of (36) to (42), the refractive index (nd) of the base glass is 1.500 to 1.530, preferably 1.505 to 1.525; and / or the coefficient of thermal expansion (α 20℃-120℃ ) is 60 to 85×10 -7 / K, preferably 70 to 85×10 -7 / K.

[0050] (44) The base glass according to any one of (36) to (42), the base glass further contains a colorant, which can make the glass-ceramic product present different colors.

[0051] (45) The base glass according to any one of (36) to (44), the colorant is expressed in mole percentage and contains: NiO: 0 to 4%; and / or Ni2O3: 0 to 4%; and / or CoO: 0 to 2%; and / or Co2O3: 0 to 2%; and / or Fe2O3: 0 to 7%; and / or MnO2: 0 to 4%; and / or Er2O3: 0 to 3%; and / or Nd2O3: 0 to 3%; and / or Cu2O: 0 to 4%; and / or Pr2O5: 0 to 3%; and / or CeO2: 0 to 4%.

[0052] (46) The base glass according to any one of (36) to (45), the colorant is expressed in mole percentage and contains: NiO: 0.1 to 3%; and / or Ni2O3: 0.1 to 3%; and / or CoO: 0.05 to 1.8%; and / or Co2O3: 0.05 to 1.8%; and / or Fe2O3: 0.2 to 5%; and / or MnO2: 0.1 to 3%; and / or Er2O3: 0.1 to 2%; and / or Nd2O3: 0.05 to 2%; and / or Cu2O: 0.5 to 3%; and / or Pr2O5: 0.05 to 2.5%; and / or CeO2: 0.5 to 3%.

[0053] (47) The glass cover plate is made of the glass-ceramic product according to any one of (1) to (18), and / or made of the glass-ceramic according to any one of (19) to (35), and / or made of the base glass according to any one of (36) to (46).

[0054] (48) The glass component is made of the glass-ceramic product according to any one of (1) to (18), and / or made of the glass-ceramic according to any one of (19) to (35), and / or made of the base glass according to any one of (36) to (46).

[0055] (49) Display device, comprising the glass-ceramic article according to any one of (1) to (18), and / or comprising the glass-ceramics according to any one of (19) to (35), and / or comprising the base glass according to any one of (36) to (46), and / or comprising the glass cover plate according to (47).

[0056] (50) Electronic device, comprising the glass-ceramic article according to any one of (1) to (18), and / or comprising the glass-ceramics according to any one of (19) to (35), and / or comprising the base glass according to any one of (36) to (46), and / or comprising the glass cover plate according to (47), and / or comprising the glass component according to (48).

[0057] (51) Manufacturing method of glass-ceramic article, the method comprising the following steps:

[0058] Form a base glass, the components of which are expressed in mole percentage and contain: SiO2: 50 - 70%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%; ZnO: 0 - 10%; MgO: 0 - 10%; K2O: 0 - 10%; SrO: 0 - 5%; BaO: 0 - 5%; TiO2: 0 - 5%; Y2O3: 0 - 5%; B2O3: 0 - 6%; fining agent: 0 - 2%.

[0059] Form glass-ceramics from the base glass through a crystallization process, and then form a glass-ceramic article from the glass-ceramics through a chemical strengthening process.

[0060] (52) The manufacturing method of the glass-ceramics product according to (51), characterized in that the base glass, with its components expressed in mole percentages, contains: SiO2: 52 - 68%, preferably SiO2: 54 - 65%; and / or Al2O3: 9 - 18%; and / or Li2O: 9 - 16%; and / or Na2O: 5 - 12%; and / or P2O5: 0.1 - 5%, preferably P2O5: 0.3 - 2.5%; and / or ZrO2: 0.1 - 6%, preferably ZrO2: 0.1 - 3%; and / or ZnO: 0.1 - 8%; and / or MgO: 0.5 - 6%; and / or K2O: 0 - 7%; and / or SrO: 0 - 1%; and / or BaO: 0 - 1%; and / or TiO2: 0 - 1%; and / or Y2O3: 0 - 1%; and / or B2O3: 0.1 - 2%; and / or clarifying agent: 0 - 1%; and / or (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 - 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 - 0.45, more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 - 0.4; and / or (Li2O + Na2O) / Al2O3 is 0.6 - 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 - 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 - 2.5; and / or Li2O / Na2O is 0.55 - 4.2, preferably Li2O / Na2O is 0.7 - 3.5, more preferably Li2O / Na2O is 0.8 - 3.0.

[0061] (53) The manufacturing method of the glass-ceramics product according to any one of (51) or (52), characterized in that the base glass, with its components expressed in mole percentages, contains: NiO: 0 - 4%; and / or Ni2O3: 0 - 4%; and / or CoO: 0 - 2%; and / or Co2O3: 0 - 2%; and / or Fe2O3: 0 - 7%; and / or MnO2: 0 - 4%; and / or Er2O3: 0 - 3%; and / or Nd2O3: 0 - 3%; and / or Cu2O: 0 - 4%; and / or Pr2O5: 0 - 3%; and / or CeO2: 0 - 4%.

[0062] (54) The manufacturing method of the glass-ceramic article according to any one of (51) to (53), characterized in that the base glass, with its components expressed in mole percentages, contains: NiO: 0.1 to 3%; and / or Ni₂O₃: 0.1 to 3%; and / or CoO: 0.05 to 1.8%; and / or Co₂O₃: 0.05 to 1.8%; and / or Fe₂O₃: 0.2 to 5%; and / or MnO₂: 0.1 to 3%; and / or Er₂O₃: 0.1 to 2%; and / or Nd₂O₃: 0.05 to 2%; and / or Cu₂O: 0.5 to 3%; and / or Pr₂O₅: 0.05 to 2.5%; and / or CeO₂: 0.5 to 3%.

[0063] (55) The manufacturing method of the glass-ceramic article according to any one of (51) to (54), wherein the crystallization process includes the following steps: heating to a specified crystallization temperature, after reaching the heat treatment temperature, maintaining the temperature for a certain period of time, and then cooling. The crystallization temperature is 480 to 700 °C, preferably 520 to 600 °C, and the holding time at the crystallization temperature is 0 to 8 hours, preferably 1 to 6 hours.

[0064] (56) The manufacturing method of the glass-ceramic article according to any one of (51) to (54), wherein 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 higher than the nucleation process temperature.

[0065] (57) The manufacturing method of the glass-ceramic article according to (56), wherein the crystallization process includes the following steps: the first temperature is 480 to 550 °C, the second temperature is 550 to 700 °C; the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

[0066] (58) The manufacturing method of the glass-ceramic article according to any one of (51) to (57), wherein the chemical strengthening process includes: immersing the glass-ceramic in a molten Na salt bath at a temperature of 430 °C to 470 °C for 6 to 20 hours, preferably in the temperature range of 435 °C to 460 °C, preferably in the time range of 8 to 13 hours; and / or immersing the glass-ceramic in a molten K salt bath at a temperature of 400 °C to 450 °C for 1 to 8 hours, preferably in the time range of 2 to 4 hours.

[0067] (59) The manufacturing method of the glass-ceramic article according to any one of (51) to (58), wherein the crystal phase of the glass-ceramic article contains lithium metasilicate; and / or aluminum phosphate; and / or meta-aluminum phosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

[0068] (60) According to the manufacturing method of the glass-ceramics article described in any one of (51) to (59), the haze of the glass-ceramics article with a thickness of 0.55 mm is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or for the glass-ceramics article with a thickness of 0.55 mm, the average transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or for the glass-ceramics article with a thickness of 0.55 mm, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more; and / or the surface stress of the glass-ceramics article is 300 MPa or more, preferably 500 MPa or more, more preferably 700 MPa or more; and / or the depth of the ion-exchange layer of the glass-ceramics article is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, further preferably 25 μm or more; and / or the height of the ball-drop test of the glass-ceramics article is 1000 mm or more, preferably 1100 mm or more, more preferably 1200 mm or more; and / or the fracture toughness of the glass-ceramics article is 1 MPa·m 1 / 2 or more, preferably 1.3 MPa·m 1 / 2 or more, more preferably 1.5 MPa·m 1 / 2 or more; and / or the Vickers hardness (H v ) of the glass-ceramics article is 600 kgf / mm 2 or more, preferably 650 kgf / mm 2 or more, more preferably 700 kgf / mm 2 or more; and / or the grain size of the glass-ceramics article is 70 nm or less, preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, even more preferably 20 nm or less.

[0069] (61) According to the manufacturing method of the glass-ceramics article described in any one of (51) to (60), the crystallinity of the glass-ceramics article is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more

[0070] (62) A manufacturing method of glass-ceramics, the method comprising the following steps:

[0071] Forming a base glass, the components of which are expressed in mole percentages and contain: SiO2: 50 - 70%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%; ZnO: 0 - 10%; MgO: 0 - 10%; K2O: 0 - 10%; SrO: 0 - 5%; BaO: 0 - 5%; TiO2: 0 - 5%; Y2O3: 0 - 5%; B2O3: 0 - 6%; clarifying agent: 0 - 2%.

[0072] The matrix glass is formed into glass-ceramics by a crystallization process.

[0073] (63) According to the method for manufacturing glass-ceramics described in (62), the matrix glass, with its components expressed in mole percentages, contains: SiO2: 52 to 68%, preferably SiO2: 54 to 65%; and / or Al2O3: 9 to 18%; and / or Li2O: 9 to 16%; and / or Na2O: 5 to 12%; and / or P2O5: 0.1 to 5%, preferably P2O5: 0.3 to 2.5%; and / or ZrO2: 0.1 to 6%, preferably ZrO2: 0.1 to 3%; and / or ZnO: 0.1 to 8%; and / or MgO: 0.5 to 6%; and / or K2O: 0 to 7%; and / or SrO: 0 to 1%; and / or BaO: 0 to 1%; and / or TiO2: 0 to 1%; and / or Y2O3: 0 to 1%; and / or B2O3: 0.1 to 2%; and / or fining agent: 0 to 1%; and / or (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 to 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 to 0.4; and / or (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 to 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 to 2.5; and / or Li2O / Na2O is 0.55 to 4.2, preferably Li2O / Na2O is 0.7 to 3.5, more preferably Li2O / Na2O is 0.8 to 3.0.

[0074] (64) According to the method for manufacturing glass-ceramics described in either (62) or (63), the matrix glass, with its components expressed in mole percentages, contains: NiO: 0 to 4%; and / or Ni2O3: 0 to 4%; and / or CoO: 0 to 2%; and / or Co2O3: 0 to 2%; and / or Fe2O3: 0 to 7%; and / or MnO2: 0 to 4%; and / or Er2O3: 0 to 3%; and / or Nd2O3: 0 to 3%; and / or Cu2O: 0 to 4%; and / or Pr2O5: 0 to 3%; and / or CeO2: 0 to 4%.

[0075] (65) According to the method for manufacturing a glass-ceramic according to any one of (62) to (64), the base glass, in terms of molar percentage of its components, contains: NiO: 0.1 to 3%; and / or Ni₂O₃: 0.1 to 3%; and / or CoO: 0.05 to 1.8%; and / or Co₂O₃: 0.05 to 1.8%; and / or Fe₂O₃: 0.2 to 5%; and / or MnO₂: 0.1 to 3%; and / or Er₂O₃: 0.1 to 2%; and / or Nd₂O₃: 0.05 to 2%; and / or Cu₂O: 0.5 to 3%; and / or Pr₂O₅: 0.05 to 2.5%; and / or CeO₂: 0.5 to 3%.

[0076] (66) According to the method for manufacturing a glass-ceramic according to any one of (62) to (65), the crystallization process includes the following steps: heating to a specified crystallization treatment temperature, after reaching the heat treatment temperature, maintaining its temperature for a certain period of time, and then cooling. The temperature of this crystallization treatment is 480 to 700 °C, preferably 520 to 600 °C, and the holding time at the crystallization treatment temperature is 0 to 8 hours, preferably 1 to 6 hours.

[0077] (67) According to the method for manufacturing a glass-ceramic according to any one of (62) to (65), 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 higher than the nucleation process temperature.

[0078] (68) According to the method for manufacturing a glass-ceramic according to (67), the crystallization process includes the following steps: the first temperature is 480 to 550 °C, the second temperature is 550 to 700 °C; the holding time at the first temperature is 0 to 24 hours, preferably 2 to 15 hours; the holding time at the second temperature is 0 to 10 hours, preferably 0.5 to 6 hours.

[0079] (69) According to the method for manufacturing a glass-ceramic according to any one of (62) to (68), the crystal phase of the glass-ceramic contains lithium metasilicate; and / or aluminum phosphate; and / or meta-aluminum phosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

[0080] (70) According to the method for manufacturing the glass-ceramics described in any one of (62) to (69), the haze of the glass-ceramics with a thickness of 0.55 mm is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or for the glass-ceramics product with a thickness of 0.55 mm, the average transmittance at a wavelength of 400 to 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or for the glass-ceramics product with a thickness of 0.55 mm, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more; and / or the grain size of the glass-ceramics is 70 nm or less, preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, and even more preferably 20 nm or less; and / or the coefficient of thermal expansion (α 20℃-120℃ ) of the glass-ceramics is 70 to 120×10 -7 / K, preferably 86 to 100×10 -7 / K.

[0081] (71) According to the method for manufacturing the glass-ceramics described in any one of (62) to (70), the crystallinity of the glass-ceramics is 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.

[0082] The present invention also provides a method for manufacturing a parent glass.

[0083] (72) The method for manufacturing a parent glass, the method comprising the following steps:

[0084] Mix the raw materials evenly according to the component content of the parent glass. The components of the parent glass are expressed in mole percentages and contain: SiO2: 50 to 70%; Al2O3: 8 to 20%; Li2O: 7 to 18%; Na2O: 4 to 15%; P2O5: 0.1 to 10%; ZrO2: 0 to 10%; ZnO: 0 to 10%; MgO: 0 to 10%; K2O: 0 to 10%; SrO: 0 to 5%; BaO: 0 to 5%; TiO2: 0 to 5%; Y2O3: 0 to 5%; B2O3: 0 to 6%; fining agent: 0 to 2%.

[0085] Then put the evenly mixed raw materials into a crucible, melt, homogenize and then form.

[0086] (73) The manufacturing method of the substrate glass according to (72), the component content of the substrate glass is expressed in mole percentage and contains: SiO2: 52 - 68%, preferably SiO2: 54 - 65%; and / or Al2O3: 9 - 18%; and / or Li2O: 9 - 16%; and / or Na2O: 5 - 12%; and / or P2O5: 0.1 - 5%, preferably P2O5: 0.3 - 2.5%; and / or ZrO2: 0.1 - 6%, preferably ZrO2: 0.1 - 3%; and / or ZnO: 0.1 - 8%; and / or MgO: 0.5 - 6%; and / or K2O: 0 - 7%; and / or SrO: 0 - 1%; and / or BaO: 0 - 1%; and / or TiO2: 0 - 1%; and / or Y2O3: 0 - 1%; and / or B2O3: 0.1 - 2%; and / or clarifying agent: 0 - 1%; and / or (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 - 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 - 0.45, more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 - 0.4; and / or (Li2O + Na2O) / Al2O3 is 0.6 - 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 - 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 - 2.5; and / or Li2O / Na2O is 0.55 - 4.2, preferably Li2O / Na2O is 0.7 - 3.5, more preferably Li2O / Na2O is 0.8 - 3.0.

[0087] (74) The manufacturing method of the substrate glass according to any one of (72) or (73), the substrate glass, its components are expressed in mole percentage and contain: NiO: 0 - 4%; and / or Ni2O3: 0 - 4%; and / or CoO: 0 - 2%; and / or Co2O3: 0 - 2%; and / or Fe2O3: 0 - 7%; and / or MnO2: 0 - 4%; and / or Er2O3: 0 - 3%; and / or Nd2O3: 0 - 3%; and / or Cu2O: 0 - 4%; and / or Pr2O5: 0 - 3%; and / or CeO2: 0 - 4%.

[0088] (75) The manufacturing method of the substrate glass according to any one of (72) or (73), the substrate glass, in terms of mole percentage of its components, contains: NiO: 0.1 - 3%; and / or Ni₂O₃: 0.1 - 3%; and / or CoO: 0.05 - 1.8%; and / or Co₂O₃: 0.05 - 1.8%; and / or Fe₂O₃: 0.2 - 5%; and / or MnO₂: 0.1 - 3%; and / or Er₂O₃: 0.1 - 2%; and / or Nd₂O₃: 0.05 - 2%; and / or Cu₂O: 0.5 - 3%; and / or Pr₂O₅: 0.05 - 2.5%; and / or CeO₂: 0.5 - 3%.

[0089] (76) The manufacturing method of the substrate glass according to any one of (72) or (73), the refractive index (nd) of the substrate glass is 1.500 - 1.530, preferably 1.505 - 1.525; and / or the coefficient of thermal expansion (α 20℃-120℃ ) is 60 - 85×10 -7 / K, preferably 70 - 85×10 -7 / K.

[0090] The beneficial effects of the present invention are: Through reasonable component design, the glass-ceramics and glass-ceramic products of the present invention have excellent mechanical properties and are suitable for electronic devices or display devices. Detailed implementation manners

[0091] The glass-ceramics and glass-ceramic products of the present invention are materials having a crystalline phase 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 of X-ray diffraction analysis and / or measured by TEM-EDX.

[0092] The inventors of the present invention through 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 causing specific crystalline phases to precipitate, obtained the glass-ceramics or glass-ceramic products of the present invention at a lower cost.

[0093] Next, the ranges of the components (constituents) of the base glass, glass-ceramics, and glass-ceramic articles of the present invention will be described. In this specification, unless otherwise specified, the contents of all components are expressed as mole percentages relative to the total amount of the base glass, or glass-ceramics, or glass-ceramic article substance in terms of the composition converted into oxides. Here, the "composition converted into oxides" means that when oxides, double salts, hydroxides, etc. used as the constituent components of the base glass, glass-ceramics, or glass-ceramic article of the present invention decompose and transform into oxides during melting, the total molar 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, and after the base glass is crystallized, it is called glass-ceramics. A glass-ceramic article refers to glass-ceramics after chemical strengthening.

[0094] Unless otherwise indicated in specific cases, the numerical ranges listed herein include upper and lower limit values, "above" and "below" include the endpoint values, 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 simultaneously.

[0095] The crystal phases in the glass-ceramics or glass-ceramic articles of the present invention include lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystals; and / or zirconium silicate crystals, etc.

[0096] In the present invention, the mole percentage range of the crystal phase in the glass-ceramics or glass-ceramic articles reaches 20 - 80%; in some embodiments, the mole percentage range reaches 25 - 70%; in some embodiments, the mole percentage range reaches 30 - 70%.

[0097] SiO2 is an essential component of the glass of the present invention. It is one of the components that form crystals after heat treatment. If the content of SiO2 is below 50%, the glass-forming property of the glass deteriorates and it is not easy to form glass. Therefore, the lower limit of the SiO2 content is 50%, preferably 52%, more preferably 54%. If the SiO2 content is above 70%, it is not conducive to the chemical strengthening of the glass and will reduce the ball-drop test height of the glass-ceramic article and the glass-ceramics. Therefore, the upper limit of the SiO2 content is 70%, preferably 68%, more preferably 65%.

[0098] Al2O3 is an essential component for forming the glass network structure. It can reduce the expansion coefficient of the matrix glass and glass-ceramics, refine the crystal grains, reduce the haze of glass-ceramics and glass-ceramic products, and is beneficial to the chemical strengthening of glass-ceramics to improve the ion exchange ability. However, if its content is less than 8%, the above effects are not good. Therefore, the lower limit of the Al2O3 content is 8%, and the preferred lower limit is 9%. On the other hand, if the content of Al2O3 exceeds 20%, the difficulty of glass melting increases, the formation of crystals is hindered, and the fracture toughness and ball-drop test height of glass-ceramics and glass-ceramic products are reduced. Therefore, the upper limit of the Al2O3 content is 20%, and the preferred upper limit is 18%.

[0099] Li2O can reduce the viscosity of the glass and promote crystal formation. It is an essential component of the crystal phase composition and is also the main component that replaces sodium and potassium ions during the ion exchange process. It can increase the surface stress after chemical strengthening. However, if its content is less than 7%, the effect is not good. Therefore, the lower limit of the Li2O content is 7%, and the preferred lower limit is 9%. On the other hand, if Li2O is contained too much, it will instead affect the ion exchange layer depth and surface stress of glass-ceramic products, resulting in a decrease in the strength of glass-ceramic products. Therefore, the upper limit of the Li2O content is 18%, and the preferred upper limit is 16%.

[0100] Na2O can reduce the melting temperature of glass raw materials, reduce the low-temperature viscosity of the glass in the solid state, effectively promote the precipitation of crystals during the heat treatment of the glass, and is beneficial to the chemical strengthening of glass-ceramics. However, if the glass contains too much Na2O, the moisture resistance stability of the matrix glass and glass-ceramics is reduced, and the crystallization rate of glass-ceramics is too fast, reducing the strength of glass-ceramics. Therefore, the upper limit of the Na2O content is 15%, and the preferred upper limit is 12%. On the other hand, if the glass contains too little Na2O, the matrix glass and glass-ceramics cannot obtain the expected thermal expansion coefficient, which is not conducive to subsequent processing, reduces the exchange content of Na ions and K ions in glass-ceramics, and reduces the surface stress of glass-ceramic products, thereby reducing the strength of glass-ceramic products. Therefore, the lower limit of the Na2O content is 4%, and the preferred lower limit is 5%.

[0101] Through a large number of experimental studies, the present inventor has found that by introducing SiO2, Al2O3, Na2O, and Li2O in certain proportions, the thermal expansion coefficients of the base glass and the glass-ceramics, the hardness, flexural strength, and fracture toughness of the glass-ceramics and glass-ceramic products can be affected. In particular, when (Li2O + Na2O) / (SiO2 + Al2O3) is in the range of 0.13 to 0.5, the base glass or the glass-ceramics can have appropriate thermal expansion coefficients, and after crystallization, more grains can be obtained, improving the hardness and fracture toughness of the glass-ceramics and glass-ceramic products. In some embodiments, it is preferred that (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, more preferably 0.2 to 0.4, and a high flexural strength can also be obtained. In some embodiments, the four-point flexural strength is above 600 MPa, preferably above 650 MPa, more preferably above 700 MPa.

[0102] In the present invention, by controlling the value of (Li2O + Na2O) / Al2O3 within the range of 0.6 to 3.5, the chemical strengthening performance of the glass-ceramics can be optimized, and the ion exchange layer depth and surface stress of the glass-ceramic products can be improved. In particular, when the value of (Li2O + Na2O) / Al2O3 is preferably within the range of 0.8 to 3.0, the ball-drop test height of the glass-ceramic products can also be increased. More preferably, the value of (Li2O + Na2O) / Al2O3 is 1.0 to 2.5.

[0103] In the present invention, when the ratio of the introduction amounts of Li2O and Na2O, Li2O / Na2O, is controlled within the range of 0.55 to 4.2, the crystallization performance of the base glass can be optimized, and the glass-ceramics and glass-ceramic products can have appropriate grain sizes, so that the glass-ceramics and glass-ceramic products have excellent properties. It is preferred that Li2O / Na2O is 0.7 to 3.5, more preferably 0.8 to 3.0, and the ball-drop test height of the glass-ceramics and glass-ceramic products becomes larger. In some embodiments, the ball-drop test height of the glass-ceramic products is preferably above 1000 mm, more preferably above 1100 mm, further preferably above 1200 mm, and even more preferably above 1500 mm.

[0104] K2O is an optional component that helps to improve the melting performance and forming performance of the base glass. However, if too much K2O is contained, it is easy to cause a decrease in the chemical stability of the base glass or the glass-ceramics and an increase in the thermal expansion coefficient. Therefore, the content of K2O is 0 to 10%, preferably 0 to 7%.

[0105] ZrO2 is an optional component in the present invention. It has the function of crystallizing and forming crystal nuclei, and at the same time helps to improve the chemical stability of the matrix glass and the glass-ceramics. It has been found that ZrO2 can also significantly reduce the risk of glass devitrification during the formation of the matrix glass. The lower limit of the ZrO2 content in the present invention is preferably 0.1%; however, if too much ZrO2 is contained, the devitrification resistance of the matrix glass is liable to decrease, and at the same time, the difficulty of controlling the crystallization process of the matrix glass increases. Therefore, the upper limit of the ZrO2 content is 10%, preferably the upper limit is 6%, and more preferably the upper limit is 3%.

[0106] P2O5 is a component that helps to improve the melting performance of the matrix glass. It can form crystal nuclei in the matrix glass and improve the thermal expansion stability of the matrix glass during crystallization. The lower limit of the P2O5 content is preferably 0.1%, more preferably 0.3%; however, if too much P2O5 is contained, it is very easy to cause a decrease in the devitrification resistance of the matrix glass, and there is a tendency for the mechanical properties of the glass-ceramics and the glass-ceramic products to deteriorate. Therefore, the upper limit of the P2O5 content is 10%, preferably the upper limit is 5%, and more preferably the upper limit is 2.5%.

[0107] MgO helps to reduce the viscosity of the glass, inhibits glass crystallization during forming, and refines the crystal grains during crystallization. It also has the effect of improving the melting performance. MgO is an optional component in the present invention, and the lower limit is preferably 0.5%; however, if the MgO content is too high, it will cause a decrease in the devitrification resistance, and after crystallization, an unsatisfactory crystal will be obtained, resulting in a decrease in the performance of the glass-ceramics and the glass-ceramic products. Therefore, the upper limit of the MgO content is 10%, preferably the upper limit is 6%.

[0108] ZnO can improve the melting performance of the matrix glass, improve the chemical stability of the matrix glass, and refine the crystal grains during crystallization. ZnO is an optional component in the present invention, and the preferred content is above 0.1%; controlling the upper limit of the ZnO content below 10% can prevent the crystal grains of the matrix glass from being too large during the crystallization process. Therefore, the upper limit of the ZnO content is 10%, preferably the upper limit is 8%.

[0109] SrO is an optional component for improving the melting performance of the matrix glass and inhibiting the crystallization of the matrix glass during forming. In the present invention, it is preferably controlled that SrO is below 5%, which can make it easier for the glass-ceramics and the glass-ceramic products to obtain excellent crystal grain sizes, and more preferably its content is below 1%. In some embodiments, it is preferred not to introduce SrO.

[0110] BaO is an optional component that helps to improve the glass-forming performance of the matrix glass. When its content exceeds 5%, the devitrification resistance of the matrix glass decreases. Therefore, in the present invention, the BaO content is preferably controlled below 5%, more preferably below 1%. In some embodiments, it is preferred not to introduce BaO.

[0111] TiO2 is an optional component that helps reduce the melting temperature of the base glass and improve its chemical stability. Introducing TiO2 below 5% in the present invention can make the crystallization process of the base glass easier to control, preferably below 1%. In some embodiments, it is preferred not to introduce TiO2.

[0112] Y2O3 is an optional component that improves the hardness and chemical stability of the base glass. However, if its content is too high, it is likely to cause crystallization during the forming of the base glass. Its content is below 5%, preferably below 1%. In some embodiments, it is preferred not to introduce Y2O3.

[0113] B2O3 helps optimize the melting performance of the base glass. When its content is too high, the chemical stability of the base glass decreases. Therefore, the content of B2O3 is below 6%, preferably the content of B2O3 is 0.1 - 2%.

[0114] One or several components among Sb2O3, SnO2, SnO, and CeO2 are added as clarifying agents. The upper limit of the content of Sb2O3 is 2%, preferably 1%, more preferably 0.5%. The upper limit of the content of SnO2, SnO, and CeO2 is 2% respectively, preferably 1%, more preferably 0.5%. In some embodiments, the content of one or more of the above 4 clarifying agents is 0 - 2%, preferably 0 - 1%.

[0115] In some embodiments, As2O3, compounds of Cl, compounds of Br, etc. can also be used as clarifying agents, and their contents are below 2% respectively, preferably below 1%, more preferably below 0.5%.

[0116] In the present invention, in order to obtain appropriate grain sizes and crystal phase types, in some embodiments, components such as La2O3, Cs2O, Tb2O3, GeO2, and CaO can be introduced, but their individual or total content is preferably below 2%. PbO and As2O3 are toxic substances, and even a small amount of addition does not meet the environmental protection requirements. Therefore, in some embodiments of the present invention, it is preferred not to contain PbO and As2O3.

[0117] In some embodiments of the present invention, by adding colorants to the raw materials, colored base glass, glass-ceramics, or glass-ceramic products are prepared, which can make the base glass, glass-ceramics, or glass-ceramic products present different colors. The colorants include: NiO: 0 - 4%; and / or Ni2O3: 0 - 4%; and / or CoO: 0 - 2%; and / or Co2O3: 0 - 2%; and / or Fe2O3: 0 - 7%; and / or MnO2: 0 - 4%; and / or Er2O3: 0 - 3%; and / or Nd2O3: 0 - 3%; and / or Cu2O: 0 - 4%; and / or Pr2O5: 0 - 3%; and / or CeO2: 0 - 4%. The molar percentage content of the colorants and their functions are described in detail as follows:

[0118] The brown or green matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use NiO, Ni2O3 or Pr2O5 as colorants. NiO and Ni2O3 are used as colorants for preparing brown or green matrix glass, glass-ceramics or glass-ceramic products. The two components can be used alone or in combination. Their respective contents are generally below 4%, preferably below 3%. If the content exceeds 4%, the colorants cannot be well dissolved in the matrix glass, glass-ceramics or glass-ceramic products. The lower limit of their respective contents is above 0.1%. If it is below 0.1%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious. When used in combination, the total amount of NiO and Ni2O3 is generally below 4%, and the lower limit of the total amount is above 0.1%. Using Pr2O5 as the colorant for green matrix glass, glass-ceramics or glass-ceramic products, used alone, the content is generally below 3%, preferably below 2.5%. The lower limit of its content is above 0.05%. If it is below 0.05%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious.

[0119] The blue matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use CoO or Co2O3 as colorants. The two colorant components can be used alone or in combination. Their respective contents are generally below 2%, preferably below 1.8%. If the content exceeds 2%, the colorants cannot be well dissolved in the matrix glass, glass-ceramics or glass-ceramic products. The lower limit of their respective contents is above 0.05%. If it is below 0.05%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious. When used in combination, the total amount of CoO and Co2O3 does not exceed 2%, and the lower limit of the total amount is above 0.05%.

[0120] The yellow matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use Cu2O or CeO2 as colorants. The two colorant components are used alone or in combination. The lower limit of their respective contents is above 0.5%. If it is below 0.5%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious. When using Cu2O alone, it is below 4%, preferably below 3%. If the content exceeds 4%, it is easy to cause the glass to crystallize. When using CeO2 alone, the content is generally below 4%, preferably below 3%. If the content exceeds 4%, the luster of the matrix glass, glass-ceramics or glass-ceramic products is not good. At the same time, adding a small amount of CeO2 to the glass has a defoaming effect, and CeO2 can also be used as a fining agent in the glass. If the two colorants are used in combination, the total amount is generally below 4%, and the lower limit of the total amount is above 0.5%.

[0121] The black or smoky gray matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use Fe2O3 alone as a colorant; or use a combination of Fe2O3 and CoO as colorants; or use a combination of Fe2O3 and Co2O3 as colorants; or use a combination of Fe2O3, CoO and NiO as colorants; or use a combination of Fe2O3, Co2O3 and NiO as colorants. The colorant for preparing black and smoky gray matrix glass, glass-ceramics or glass-ceramic products mainly uses Fe2O3 for coloring, with a content of less than 7%, preferably less than 5%, and the lower limit of its content is above 0.2%. CoO and Co2O3 have absorption in visible light and can deepen the coloring degree of the matrix glass, glass-ceramics or glass-ceramic products. Generally, when used in combination with Fe2O3, their respective contents are below 0.3%, and the lower limit is above 0.05%. NiO has absorption in visible light and can deepen the coloring degree of the matrix glass, glass-ceramics or glass-ceramic products. Generally, when used in combination, its content is below 1%, and the lower limit of the total content is above 0.1%.

[0122] The purple matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use MnO2 as a colorant, and the usage amount is generally below 4%, preferably below 3%, and the lower limit of its content is above 0.1%. If it is lower than 0.1%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious.

[0123] The pink matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use Er2O3 as a colorant, and the usage amount is generally below 3%, preferably below 2%. Due to the low coloring efficiency of the rare earth element Er2O3, when the usage amount exceeds 3%, it cannot further deepen the color of the matrix glass, glass-ceramics or glass-ceramic products, but instead increases the cost. The lower limit of its content is above 0.1%. If it is lower than 0.1%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious.

[0124] The magenta matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use Nd2O3 as a colorant, and the usage amount is generally below 3%, preferably below 2%. Due to the low coloring efficiency of the rare earth element Nd2O3, when the usage amount exceeds 3%, it cannot further deepen the color of the matrix glass, glass-ceramics or glass-ceramic products, but instead increases the cost. The lower limit of its content is above 0.05%. If it is lower than 0.05%, the color of the matrix glass, glass-ceramics or glass-ceramic products is not obvious.

[0125] The red matrix glass, glass-ceramics or glass-ceramic products prepared by the present invention use a mixed colorant of Er2O3, Nd2O3 and MnO2. Er ions in the glass have absorption at 400 - 500 nm, Mn ions mainly have absorption at 500 nm, and Nd ions mainly have strong absorption at 580 nm. The mixture of these three substances can be used to prepare red matrix glass, glass-ceramics or glass-ceramic products. Since Er2O3 and Nd2O3 are rare earth colorants with relatively weak coloring ability, the usage amount of Er2O3 is within 3%, the usage amount of Nd2O3 is within 3%, and MnO2 has strong coloring ability with a usage amount within 2%. The lower limit of the total amount of the mixed colorant used is above 0.9%.

[0126] "Not introducing", "not containing", and "0%" as described herein mean that the compound, molecule, element, etc. are not intentionally added as raw materials to the matrix glass, glass-ceramics or glass-ceramic products of the present invention; however, as raw materials and / or equipment for producing matrix glass, glass-ceramics or glass-ceramic products, there may be certain impurities or components that are not intentionally added and will be contained in trace amounts or in small amounts in the final matrix glass, glass-ceramics or glass-ceramic products. Such a situation is also within the protection scope of this invention patent.

[0127] In some embodiments of the present invention, the crystal phase in the glass-ceramics and glass-ceramic products contains lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal, etc., which provide high strength for the glass-ceramics and glass-ceramic products of the present invention, and the fracture toughness of the glass-ceramics and glass-ceramic products becomes higher; the ball-drop test height and four-point bending strength of the glass-ceramics and glass-ceramic products become larger. The glass-ceramics of the present invention can also be ion-exchanged to obtain additional mechanical strength. Through reasonable component design, the present invention can make the glass-ceramics and glass-ceramic products of the present invention obtain appropriate grain sizes and have high strength.

[0128] The glass-ceramics or glass-ceramic products of the present invention can be transparent, translucent and opaque. The grain size and haze of the glass-ceramics or glass-ceramic products will affect the transmittance of the glass-ceramics or glass-ceramic products, that is, affect the light passing rate. The smaller the grain size, the higher the transmittance; the smaller the haze, the higher the transmittance. In some embodiments, the haze of the glass-ceramic products or glass-ceramics with a thickness of 0.55 mm is below 0.3%, preferably below 0.25%, more preferably below 0.2%. In some embodiments, the grain size of the glass-ceramic products or glass-ceramics is below 70 nm, preferably below 50 nm, more preferably below 40 nm, further preferably below 30 nm, and even more preferably below 20 nm. On the other hand, through research, it is found that the smaller the refractive index difference between the crystal phase and the glass phase in the glass-ceramics, the higher the transmittance of the glass-ceramics or glass-ceramic products.

[0129] In some embodiments of the present invention, the glass-ceramics or glass-ceramic articles exhibit high transmittance in the visible light range. In some embodiments, the average light transmittance of the glass-ceramic articles or glass-ceramics with a thickness of 0.55 mm in the range of 400-800 nm is more than 85%, preferably more than 88%, and more preferably more than 90%. In some preferred embodiments, the light transmittance of the glass-ceramic articles or glass-ceramics with a thickness of 0.55 mm at 550 nm is more than 80%, preferably more than 85%, more preferably more than 89%, and further preferably more than 91%.

[0130] In some embodiments, an antimicrobial component can be added to the base glass, glass-ceramics or glass-ceramic articles.

[0131] The base glass, glass-ceramics and glass-ceramic articles of the present invention can be produced and manufactured by the following methods:

[0132] Generating the base glass: Mix the raw materials evenly according to the component ratio, put the homogeneous mixture into a platinum or quartz crucible, and melt it in an electric furnace or gas furnace at a temperature range of 1250-1650 °C for 5-24 hours according to the melting difficulty of the glass composition. After stirring to make it uniform, cool it to an appropriate temperature and cast it into a mold, and then slowly cool it to form.

[0133] The base glass of the present invention can be formed by well-known methods. In some embodiments, the refractive index (nd) of the base glass of the present invention is 1.500-1.530, preferably 1.505-1.525.

[0134] 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. This crystallization treatment can be carried out in one stage or in two stages, and it is preferably carried out in two stages for crystallization treatment. The nucleation process is carried out at the first temperature, and then the crystal growth process is carried out at the second temperature higher than the nucleation process 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.

[0135] In order to endow the glass-ceramics with the desired physical properties, the preferred crystallization process is:

[0136] The above crystallization treatment through one stage can continuously carry out the nucleation process and the crystal growth process. That is, it is heated to a specified crystallization treatment temperature, and after reaching the heat treatment temperature, the temperature is maintained for a certain period of time and then cooled. The temperature of this crystallization treatment is preferably 480 - 700 °C, and more preferably 520 - 600 °C in order to precipitate the desired crystal phase. The holding time at the crystallization treatment temperature is preferably 0 - 8 hours, and more preferably 1 - 6 hours.

[0137] When the above crystallization treatment is carried out through two stages, the first temperature is preferably 480 - 550 °C, and the second temperature is preferably 550 - 700 °C. The holding time at the first temperature is preferably 0 - 24 hours, and more preferably 2 - 15 hours. The holding time at the second temperature is preferably 0 - 10 hours, and more preferably 0.5 - 6 hours.

[0138] The above holding time of 0 hours means that after reaching the temperature, it starts to cool or heat up again in less than 1 minute.

[0139] In some embodiments, the refractive index (nd) of the glass-ceramics obtained by the crystallization process of the present invention is 1.500 - 1.540, preferably 1.510 - 1.530.

[0140] In some embodiments, the base glass 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 a sheet. The processes include but are not limited to slot drawing, the float process, roll pressing, and other processes for forming sheets well-known in the art. Alternatively, the base glass or glass-ceramics can be formed by the float process or roll pressing method well-known in the art.

[0141] The base glass or glass-ceramics of the present invention can be used to manufacture a glass shaped body of a sheet by methods such as grinding or polishing, etc., but the methods for manufacturing the glass shaped body are not limited to these methods.

[0142] The base glass or glass-ceramics shaped body of the present invention can be prepared into various shapes by methods such as hot bending or pressing at a certain temperature, and is not limited to these methods.

[0143] The base glass, glass-ceramics, and glass-ceramics products described in the present invention can have any thickness that is reasonably useful.

[0144] In addition to improving the mechanical properties by precipitating crystals, the glass-ceramics of the present invention can also obtain higher strength by forming a compressive stress layer, thereby making glass-ceramics products.

[0145] In some embodiments, the base glass or glass-ceramics can be processed into a sheet, and / or shaped (such as punching, hot bending, etc.), polished and / or buffed after shaping, and then chemically strengthened by a chemical strengthening process.

[0146] The chemical strengthening described in the present invention is the ion exchange method. The substrate glass and the glass-ceramics of the present invention can both be subjected to ion exchange by methods well-known in the art. During the ion exchange process, smaller metal ions in the substrate glass or glass-ceramics are replaced or "exchanged" by larger metal ions of the same valence state that are close to 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.

[0147] 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 a larger metal ion, which is used to replace the smaller metal ions in the substrate glass. Alternatively, other monovalent metal ions such as Ag + , Tl + , Cu + , etc. can also be used for the exchange of monovalent ions. One or more ion exchange processes for chemically strengthening the substrate glass or glass-ceramics may 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.

[0148] In some embodiments, the substrate glass or glass-ceramics can be subjected to ion exchange by immersing them in a salt bath of molten Na salt (such as NaNO3) at a temperature of about 430 °C to 470 °C for about 6 to 20 hours, preferably in the temperature range of 435 °C to 460 °C and preferably in the time range of 8 to 13 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 subjected to ion exchange by immersing them in a salt bath of molten K salt (such as KNO3) at a temperature of about 400 °C to 450 °C for 1 to 8 hours, preferably in the time range of 2 to 4 hours.

[0149] In some preferred embodiments, by immersing in a salt bath of molten Na salt (such as NaNO3) at 450 °C for about 8 hours, the depth of the ion exchange layer reaches more than 20 μm, preferably more than 25 μm.

[0150] In some embodiments, there are also the ion implantation method of injecting ions into the surface layer of the substrate glass or glass-ceramics, and the thermal tempering method of heating the substrate glass or glass-ceramics and then rapidly cooling them.

[0151] The performance indexes of the matrix glass, glass-ceramics and / or glass-ceramic products of the present invention are tested by the following methods:

[0152] [Refractive index]

[0153] The refractive index (nd) is tested according to the method specified in GB / T7962.1-2010.

[0154] [Haze]

[0155] Using a haze meter EEL57D, preparing with a 0.55mm thick glass sample, and testing according to the standard of GB2410-80.

[0156] [Grain size]

[0157] It is measured by using a SEM scanning electron microscope. The glass-ceramics are surface-treated in HF acid, then gold-sprayed on the surface of the glass-ceramics, and surface-scanned under the SEM scanning electron microscope to determine the grain size.

[0158] [Light transmittance]

[0159] The light transmittance described in this article is all external transmittance, sometimes simply referred to as transmittance.

[0160] The sample is processed into a thickness of 0.55mm and polished parallel on the opposite sides, and the average light transmittance at 400-800nm is measured by using a Hitachi U-41000 spectrophotometer.

[0161] The sample is processed into a thickness of 0.55mm and polished parallel on the opposite sides, and the light transmittance at 550nm is measured by using a Hitachi U-41000 spectrophotometer.

[0162] [Crystallinity]

[0163] The XRD diffraction peaks are compared with the database spectra. The crystallinity is obtained by calculating the proportion of the diffraction intensity of the crystalline phase in the overall spectrum intensity, and is internally calibrated by using a pure quartz crystal.

[0164] [Surface stress] and [Ion exchange layer depth]

[0165] The surface stress is measured by using a glass surface stress meter FSM-6000LEUV.

[0166] The ion exchange layer depth is measured by using a glass surface stress meter SLP-2000.

[0167] As the measurement conditions, calculations are carried out with the refractive index of the sample being 1.54 and the photoelastic constant being 25.3 [(nm / cm) / Mpa].

[0168] [Falling ball test height]

[0169] Place a sample of 150×57×0.55 mm on a glass carrier fixture, and let a 132 g steel ball fall from a specified height. The maximum drop ball test height of the impact that the sample can withstand without breaking. Specifically, the test starts from a drop ball test height of 800 mm. Without breaking, the height is sequentially changed through 850 mm, 900 mm, 950 mm, 1000 mm and above. For the examples with "drop ball test height", the glass-ceramic products are used as the test objects. The test data recorded as 1000 mm in the examples indicates that even when the steel ball falls from a height of 1000 mm, the glass-ceramic products do not break and withstand the impact.

[0170] [Fracture toughness]

[0171] Using the method of directly measuring the size of the indentation-induced crack, the sample size is 2 mm×4 mm×20 mm. After chamfering, grinding and polishing, after the sample preparation is completed, apply a force of 49 N on the sample with a Vickers hardness indenter and maintain it for 30 s. After making the indentation, measure its fracture strength by the three-point bending method.

[0172] [Four-point bending strength]

[0173] Adopt a computer-controlled electronic universal testing machine CMT6502, the glass size is 150×57×0.55 mm, and the test is carried out according to the standard of ASTM C158-2002.

[0174] [Vickers hardness]

[0175] The value represented by dividing the load (N) when pressing a diamond square pyramid indenter with a relative face angle of 136° 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) for the test.

[0176] [Coefficient of expansion]

[0177] Coefficient of thermal expansion (α 20℃-120℃ ) is tested according to the method specified in GB / T 7962.16-2010.

[0178] The matrix glass of the present invention has the following properties:

[0179] 1) In some embodiments, the refractive index (nd) is 1.500 to 1.530, preferably 1.505 to 1.525.

[0180] 2) In some embodiments, the coefficient of thermal expansion (α 20℃-120℃ ) is 60 to 85×10 -7 / K, preferably 70 to 85×10 -7 / K.

[0181] The glass-ceramics of the present invention have the following properties:

[0182] 1) In some embodiments, the crystallinity of the glass-ceramics is 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.

[0183] 2) In some embodiments, the grain size of the glass-ceramics is 70 nm or less, preferably 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and further preferably 20 nm or less.

[0184] 3) In some embodiments, the haze of the glass-ceramics with a thickness of 0.55 mm is 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less.

[0185] 4) In some embodiments, for the glass-ceramics with a thickness of 0.55 mm, the average transmittance at a wavelength of 400 - 800 nm is 85% or more, preferably 88% or more, and more preferably 90% or more.

[0186] 5) In some embodiments, for the glass-ceramics with a thickness of 0.55 mm, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, and more preferably 91% or more.

[0187] 6) In some embodiments, the refractive index (nd) of the glass-ceramics is 1.500 - 1.540, preferably 1.510 - 1.530.

[0188] 7) In some embodiments, the coefficient of thermal expansion (α 20℃-120℃ ) of the glass-ceramics is 70 - 120×10 -7 / K, preferably 86 - 100×10 -7 / K.

[0189] The glass-ceramics products of the present invention have the following properties:

[0190] 1) In some embodiments, the surface stress of the glass-ceramics products is 300 MPa or more, preferably 500 MPa or more, and more preferably 700 MPa or more.

[0191] 2) In some embodiments, the four-point bending strength of the glass-ceramics products is 600 MPa or more, preferably 650 MPa or more, and more preferably 700 MPa or more;

[0192] 3) In some embodiments, the depth of the ion-exchanged layer of the glass-ceramic article is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more.

[0193] 4) In some embodiments, the height of the ball-drop test of the glass-ceramic article is 1000 mm or more, preferably 1100 mm or more, and more preferably 1200 mm or more;

[0194] 5) In some embodiments, the fracture toughness of the glass-ceramic article is 1 MPa·m 1 / 2 or more, preferably 1.3 MPa·m 1 / 2 or more, and more preferably 1.5 MPa·m 1 / 2 or more.

[0195] 6) In some embodiments, the Vickers hardness (H v ) of the glass-ceramic article is 600 kgf / mm 2 or more, preferably 650 kgf / mm 2 or more, and more preferably 700 kgf / mm 2 or more.

[0196] 7) In some embodiments, the crystallinity of the glass-ceramic article is 20% or more, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.

[0197] 8) In some embodiments, the grain size of the glass-ceramic article is 70 nm or less, preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, and even more preferably 20 nm or less.

[0198] 9) In some embodiments, the haze of the 0.55-mm thick glass-ceramic article is 0.3% or less, preferably 0.25% or less, and more preferably 0.2% or less.

[0199] 10) In some embodiments, for the 0.55-mm thick glass-ceramic article, the average transmittance at wavelengths of 400 - 800 nm is 85% or more, preferably 88% or more, and more preferably 90% or more.

[0200] 11) In some embodiments, for the 0.55-mm thick glass-ceramic article, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, and more preferably 91% or more.

[0201] 12) In some embodiments, the refractive index (nd) of the glass-ceramic article is 1.500 - 1.540, preferably 1.510 - 1.530.

[0202] 13) In some embodiments, the coefficient of thermal expansion (α 20℃-120℃ ) of the glass-ceramic article is 70 to 120×10 -7 / K, preferably 86 to 100×10 -7 / K.

[0203] Due to the above excellent properties, the glass-ceramics, glass-ceramic articles and substrate glasses of the present invention can be widely fabricated into glass covers or glass components; meanwhile, the glass-ceramics, glass-ceramic articles and substrate glasses of the present invention are applied to electronic devices or display devices, such as mobile phones, watches, computers, touch display screens, etc.

[0204] Examples

[0205] 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 numerical values (such as quantities, temperatures, etc.), but some errors and deviations must be taken into account. The compositions themselves are given in mole% based on oxides and have been normalized to 100%.

[0206] The following Table 1 to 2 shows the examples of substrate glasses.

[0207] Table 1.

[0208]

[0209]

[0210] Table 2.

[0211]

[0212]

[0213] The following Table 3 to 4 shows the examples of glass-ceramics.

[0214] Table 3.

[0215]

[0216]

[0217] Table 4.

[0218]

[0219]

[0220]

[0221] The following Table 5 to 6 shows the examples of glass-ceramic articles.

[0222] Table 5.

[0223]

[0224]

[0225] Table 6.

[0226]

[0227] Examples of colored glass-ceramics are shown in Tables 7 to 9 below.

[0228] Table 7.

[0229]

[0230]

[0231] Table 8.

[0232]

[0233]

[0234] Table 9.

[0235]

[0236]

Claims

1. Glass-ceramic product, characterized in that, Its components are expressed in mole percentages and contain: SiO2: 50 - 68%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%.

2. The glass-ceramic article according to claim 1, wherein Its components are expressed in mole percentages and also contain: ZnO: 0 - 10%; and / or MgO: 0 - 10%; and / or K2O: 0 - 10%; and / or SrO: 0 - 5%; and / or BaO: 0 - 5%; and / or TiO2: 0 - 5%; and / or Y2O3: 0 - 5%; and / or B2O3: 0 - 6%; and / or clarifying agent: 0 - 2%.

3. Glass-ceramic product, characterized in that, Its components contain SiO2, Al2O3, Li2O and Na2O. Its components are expressed in mole percentages, wherein the value of (Li2O + Na2O) / Al2O3 is 0.6 - 3.5, and the value of Li2O / Na2O is 0.55 - 4.

2. The grain size of the glass-ceramics product is below 70 nm.

4. The glass-ceramic article according to claim 3, wherein, Its components are expressed in mole percentages and contain: SiO2: 50 - 68%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%; ZnO: 0 - 10%. BaO: 0 - 5%. TiO2: 0 - 5%; Y2O3: 0 - 5%; B2O3: 0 - 6%. Clarifying agent: 0 - 2%.

5. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed in mole percentages and contain: SiO2: 52 - 68%, preferably SiO2: 54 - 65%; and / or Al2O3: 9 - 18%; and / or Li2O: 9 - 16%; and / or Na2O: 5 - 12%; and / or P2O5: 0.1 - 5%, preferably P2O5: 0.3 - 2.5%; and / or ZrO2: 0.1 - 6%, preferably ZrO2: 0.1 - 3%; and / or ZnO: 0.1 - 8%; and / or MgO: 0.5 - 6%; and / or K2O: 0 - 7%; and / or SrO: 0 - 1%; and / or BaO: 0 - 1%; and / or TiO2: 0 - 1%; and / or Y2O3: 0 - 1%; and / or B2O3: 0.1 - 2%; and / or clarifying agent: 0 - 1%.

6. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed in mole percentages, where: (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 to 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 to 0.45, more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 to 0.4; and / or (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 to 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 to 2.5; and / or Li2O / Na2O is 0.55 to 4.2, preferably Li2O / Na2O is 0.7 to 3.5, more preferably Li2O / Na2O is 0.8 to 3.

0.

7. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The grain size of the glass-ceramic product is below 70 nm, preferably below 50 nm, more preferably below 40 nm, further preferably below 30 nm, and even more preferably below 20 nm; and / or the surface stress is 300 MPa or more, preferably 500 MPa or more, more preferably 700 MPa or more; and / or the depth of the ion exchange layer is 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, further preferably 25 μm or more; and / or the height of the ball-drop test is 1000 mm or more, preferably 1100 mm or more, more preferably 1200 mm or more; and / or the fracture toughness is 1 MPa·m 1 / 2 or more, preferably 1.3 MPa·m 1 / 2 or more, more preferably 1.5 MPa·m 1 / 2 or more; and / or the Vickers hardness H v is 600 kgf / mm 2 or more, preferably 650 kgf / mm 2 or more, more preferably 700 kgf / mm 2 or more; and / or the crystallinity is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more; and / or the haze of the 0.55-mm-thick glass-ceramic product is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or the average transmittance of the 0.55-mm-thick glass-ceramic product at wavelengths of 400 - 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or the transmittance of the 0.55-mm-thick glass-ceramic product at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more.

8. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The crystal phase of the glass-ceramic product contains lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

9. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, The crystal phase of the glass-ceramic product accounts for 20 to 80% in mole percentage of the glass-ceramic product, preferably 25 to 70%, more preferably 30 to 70%.

10. The glass-ceramic article according to any one of claims 1 to 4, characterized in that, Its components are expressed in mole percentages and also contain: NiO: 0 to 4%, preferably NiO: 0.1 to 3%; and / or Ni2O3: 0 to 4%, preferably Ni2O3: 0.1 to 3%; and / or CoO: 0 to 2%, preferably CoO: 0.05 to 1.8%; and / or Co2O3: 0 to 2%, preferably Co2O3: 0.05 to 1.8%; and / or Fe2O3: 0 to 7%, preferably Fe2O3: 0.2 to 5%; and / or MnO2: 0 to 4%, preferably MnO2: 0.1 to 3%; and / or Er2O3: 0 to 3%, preferably Er2O3: 0.1 to 2%; and / or Nd2O3: 0 to 3%, preferably Nd2O3: 0.05 to 2%; and / or Cu2O: 0 to 4%, preferably Cu2O: 0.5 to 3%; and / or Pr2O5: 0 to 3%, preferably Pr2O5: 0.05 to 2.5%; and / or CeO2: 0 to 4%, preferably CeO2: 0.5 to 3%.

11. Glass-ceramics, characterized in that, Its components are expressed in mole percentages and contain: SiO2: 50 to 68%; Al2O3: 8 to 20%; Li2O: 7 to 18%; Na2O: 4 to 15%; P2O5: 0.1 to 10%; ZrO2: 0 to 10%.

12. The glass-ceramics according to claim 11, wherein Its components are expressed in mole percentages and also contain: ZnO: 0 to 10%; and / or MgO: 0 to 10%; and / or K2O: 0 to 10%; and / or SrO: 0 to 5%; and / or BaO: 0 to 5%; and / or TiO2: 0 to 5%; and / or Y2O3: 0 to 5%; and / or B2O3: 0 to 6%; and / or fining agent: 0 to 2%.

13. Glass-ceramics, characterized in that, Its components include SiO2, Al2O3, Li2O and Na2O, and the components are expressed in mole percentages. Among them, the value of (Li2O + Na2O) / Al2O3 is 0.6 to 3.5, and the value of Li2O / Na2O is 0.55 to 4.

2. The crystal grain size of the glass-ceramics is below 70 nm.

14. The glass-ceramics according to claim 13, characterized in that, Its components are expressed in mole percentages and contain: SiO2: 50 - 68%; Al2O3: 8 - 20%; Li2O: 7 - 18%; Na2O: 4 - 15%; P2O5: 0.1 - 10%; ZrO2: 0 - 10%; ZnO: 0 - 10%; MgO: 0 - 10%; K2O: 0 - 10%; SrO: 0 - 5%; BaO: 0 - 5%; TiO2: 0 - 5%; Y2O3: 0 - 5%; B2O3: 0 - 6%; Clarifying agent: 0 - 2%.

15. The glass-ceramics according to any one of claims 11 to 14, characterized in that, Its components are expressed in mole percentages and contain: SiO2: 52 - 68%, preferably SiO2: 54 - 65%; and / or Al2O3: 9 - 18%; and / or Li2O: 9 - 16%; and / or Na2O: 5 - 12%; and / or P2O5: 0.1 - 5%, preferably P2O5: 0.3 - 2.5%; and / or ZrO2: 0.1 - 6%, preferably ZrO2: 0.1 - 3%; and / or ZnO: 0.1 - 8%; and / or MgO: 0.5 - 6%; and / or K2O: 0 - 7%; and / or SrO: 0 - 1%; and / or BaO: 0 - 1%; and / or TiO2: 0 - 1%; and / or Y2O3: 0 - 1%; and / or B2O3: 0.1 - 2%; and / or clarifying agent: 0 - 1%.

16. The glass-ceramics according to any one of claims 11 to 14, characterized in that, Its components are expressed in mole percentages, where: (Li2O + Na2O) / (SiO2 + Al2O3) is 0.13 - 0.5, preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.16 - 0.45, more preferably (Li2O + Na2O) / (SiO2 + Al2O3) is 0.2 - 0.4; and / or (Li2O + Na2O) / Al2O3 is 0.6 - 3.5, preferably (Li2O + Na2O) / Al2O3 is 0.8 - 3.0, more preferably (Li2O + Na2O) / Al2O3 is 1.0 - 2.5; and / or Li2O / Na2O is 0.55 - 4.2, preferably Li2O / Na2O is 0.7 - 3.5, more preferably Li2O / Na2O is 0.8 - 3.

0.

17. The glass-ceramics according to any one of claims 11 to 14, characterized in that, The grain size of the glass-ceramics is below 70 nm, preferably below 50 nm, more preferably below 40 nm, further preferably below 30 nm, and even more preferably below 20 nm; and / or the crystallinity is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more; and / or the refractive index nd is 1.500 to 1.540, preferably 1.510 to 1.530; and / or the thermal expansion coefficient α 20℃-120℃ is 70 to 120×10 -7 / K, preferably 86 to 100×10 -7 / K; and / or the haze of the 0.55 mm thick glass-ceramics is 0.3% or less, preferably 0.25% or less, more preferably 0.2% or less; and / or for the 0.55 mm thick glass-ceramics, the average transmittance at a wavelength of 400 to 800 nm is 85% or more, preferably 88% or more, more preferably 90% or more; and / or for the 0.55 mm thick glass-ceramics, the transmittance at a wavelength of 550 nm is 85% or more, preferably 89% or more, more preferably 91% or more.

18. The glass-ceramics according to any one of claims 11 to 14, characterized in that, The crystal phase of the glass-ceramics contains lithium metasilicate; and / or aluminum phosphate; and / or aluminum metaphosphate; and / or lithium phosphate; and / or quartz crystal; and / or zirconium silicate crystal.

19. The glass-ceramics according to any one of claims 11 to 14, characterized in that, The crystal phase of the glass-ceramics accounts for 20 - 80% of the glass-ceramics in mole percentage, preferably 25 - 70%, more preferably 30 - 70%.

20. The glass-ceramics according to any one of claims 11 to 14, characterized in that, The components are expressed in mole percentage and further contain: NiO: 0 to 4%, preferably NiO: 0.1 to 3%; and / or Ni2O3: 0 to 4%, preferably Ni2O3: 0.1 to 3%; and / or CoO: 0 to 2%, preferably CoO: 0.05 to 1.8%; and / or Co2O3: 0 to 2%, preferably Co2O3: 0.05 to 1.8%; and / or Fe2O3: 0 to 7%, preferably Fe2O3: 0.2 to 5%; and / or MnO2: 0 to 4%, preferably MnO2: 0.1 to 3%; and / or Er2O3: 0 to 3%, preferably Er2O3: 0.1 to 2%; and / or Nd2O3: 0 to 3%, preferably Nd2O3: 0.05 to 2%; and / or Cu2O: 0 to 4%, preferably Cu2O: 0.5 to 3%; and / or Pr2O5: 0 to 3%, preferably Pr2O5: 0.05 to 2.5%; and / or CeO2: 0 to 4%, preferably CeO2: 0.5 to 3%.

21. Glass cover plate, characterized in that, Made of the glass-ceramic product according to any one of claims 1 to 10, and / or made of the glass-ceramics according to any one of claims 11 to 20.

22. A glass component, characterized in that, Made of the glass-ceramic product according to any one of claims 1 to 10, and / or made of the glass-ceramics according to any one of claims 11 to 20.

23. Display device, characterized in that, Comprising the glass-ceramic product according to any one of claims 1 to 10, and / or comprising the glass-ceramics according to any one of claims 11 to 20, and / or comprising the glass cover plate according to claim 21; and / or comprising the glass component according to claim 22.

24. An electronic device, characterized in that, Comprising the glass-ceramic product according to any one of claims 1 to 10, and / or comprising the glass-ceramics according to any one of claims 11 to 20, and / or comprising the glass cover plate according to claim 21, and / or comprising the glass component according to claim 22.

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