3D curved glass-ceramics, chemically strengthened glass-ceramics, and methods of making and using the same

Abstract

The application belongs to the technical field of glass, and particularly relates to a 3D curved surface microcrystalline glass, a chemical strengthening microcrystalline glass and a preparation method and application thereof. In terms of molar percentage of oxides, the composition of the 3D curved surface microcrystalline glass satisfies: 0.180 <= 5*P2O5 / (Li2O+0.5*Al2O3) <= 0.250; 18.200 <= Li2O / P2O5 <= 25.500; 0.100 <= P2O5*(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3) <= 2.200; 1.500 <= 10*(ZrO2+P2O5) / Li2O <= 2.000; 4.000 <= (SiO2-7*Al2O3-Li2O) / (P2O5+ZrO2) <= 6.000. The application can guarantee the generation of main crystal phase, and meanwhile, the product as a whole presents a relatively uniform display effect.

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 202311801461.4, application date December 25, 2023, and invention title "3D curved surface microcrystalline glass, chemically strengthened microcrystalline glass and its preparation method and application". Technical Field

[0002] This application belongs to the field of glass technology, specifically relating to a 3D curved microcrystalline glass, a chemically strengthened microcrystalline glass, its manufacturing method and application. Background Technology

[0003] With the development of electronic display technology, glass has gradually replaced plastic materials in display devices as a protective cover material. Meanwhile, with the diversified applications of electronic products, 3D curved screens such as curved-screen phones and smartwatches are becoming increasingly popular. Among them, 3D curved microcrystalline glass, due to its superior strength compared to ordinary 3D curved glass, is gradually gaining industry attention.

[0004] Mass production of 3D curved microcrystalline glass for displays with high optical performance requirements is challenging. A major reason is the difficulty in ensuring uniformity of composition and temperature field during the production of large-size prefabricated microcrystalline glass for 3D curved glass. This leads to localized optical defects in the prefabricated microcrystalline glass products, and this problem persists even after the prefabricated microcrystalline glass undergoes heat bending. Consequently, the resulting 3D curved microcrystalline glass may exhibit undesirable colors in certain areas or exhibit an overall uneven display effect, and may even break during the heat bending process.

[0005] It should be noted that this part of the application only provides background technology related to this application, and does not necessarily constitute prior art or publicly known technology. Summary of the Invention

[0006] To increase output, when mass-producing 3D curved glass-ceramics with lithium feldspar and lithium disilicate crystalline phase structures, the production line typically first produces large-sized substrate glass bricks, such as substrate glass bricks with dimensions of (200mm-500mm)×(100mm-500mm)×(10mm-40mm). The substrate glass bricks are then heat-treated to obtain pre-fabricated glass-ceramics. Considering that the glass-ceramics in this system usually undergo a certain degree of crystallization during hot bending, the degree of crystallization of the pre-fabricated glass-ceramics is generally lower than that of the final 3D curved glass-ceramics. The pre-fabricated glass-ceramics are then cold-processed to produce multiple planar glass-ceramics of the required dimensions. Finally, the obtained planar glass-ceramics are hot-bent to obtain the 3D curved glass-ceramics.

[0007] Existing microcrystalline glass solutions with lithium feldspar and lithium disilicate as the main crystalline phases are prone to optical defects in the prefabricated microcrystalline glass bricks during industrial-scale mass production. These defects manifest primarily as significant variations in b-values ​​across different regions of the prefabricated microcrystalline glass bricks, resulting in undesirable localized colors and a tendency for chipping. These variations cannot be mitigated by subsequent hot bending processes, leading to similarly large b-value differences in different regions of the resulting 3D curved microcrystalline glass. This negatively impacts the overall display quality of the 3D curved microcrystalline glass, making it difficult to meet the application requirements of display screen covers. Furthermore, some prefabricated microcrystalline glass products may even break during the hot bending process, resulting in reduced yield.

[0008] The purpose of this application is to overcome the problems of low mass production yield, easy chipping and poor display of 3D curved microcrystalline glass products with lithium feldspar and lithium disilicate as the main crystal phases in the existing technology. This application provides a 3D curved microcrystalline glass, and provides its preparation method and application.

[0009] To achieve the above objectives, the following technical solution is provided:

[0010] 1. A 3D curved microcrystalline glass, wherein the 3D curved microcrystalline glass contains a lithium feldspar crystal phase and a lithium disilicate crystal phase, wherein the lithium feldspar crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the 3D curved microcrystalline glass.

[0011] The composition of the 3D curved glass-ceramic, based on the molar percentage of oxides, includes:

[0012] SiO2: 60.00mol%-71.00mol%, Al2O3: 1.50mol%-5.00mol%, P2O5: 0.80mol%-1.50mol%, ZrO2: 2.00mol%-4.00mol%, Na2O: 0.00m ol%-1.00mol%, K2O: 0.00mol%-0.50mol%, Li2O: 20.00mol%-30.00mol%, CaO: 0.00mol%-1.60mol%, B2O3: 0.00mol%-1.00mol%;

[0013] The composition of the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in its composition, satisfies the following:

[0014] 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250;

[0015] 18.200≤Li2O / P2O5≤25.500;

[0016] 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200;

[0017] 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000;

[0018] 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000. When the content of each oxide is within a suitable range and the oxide content ratio is determined under specific conditions, the formation of the main crystalline phase can be guaranteed during the mass production of 3D curved microcrystalline glass products. Simultaneously, the prepared 3D curved microcrystalline glass products exhibit a relatively uniform display effect, effectively avoiding the problem of large differences in b-values ​​and poor display effects in different areas of mass-produced 3D curved microcrystalline glass products.

[0019] It should be noted that in the above formulas of this application, the content percentage is substituted into each formula in molar terms, that is, the molar unit is not involved in the calculation of the formula. For example, if the molar content of P2O5 is 0.80%, then 0.80% is substituted into the formula for calculation.

[0020] 2. The 3D curved microcrystalline glass according to technical solution 1, wherein, based on the molar percentage of each oxide in the composition of the 3D curved microcrystalline glass, the composition of the 3D curved microcrystalline glass satisfies:

[0021] 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000;

[0022] 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000. Further adjustments to the content relationships between the components help ensure that the 3D curved glass-ceramic achieves excellent optical and mechanical strength properties.

[0023] 3. The 3D curved microcrystalline glass according to technical solution 1 or 2, wherein the 3D curved microcrystalline glass is transparent in the visible light range. By making the 3D curved microcrystalline glass transparent in the visible light range, it can meet the usage requirements of the display screen, which helps to broaden the application fields and application scenarios of 3D curved microcrystalline glass.

[0024] 4. The 3D curved surface microcrystalline glass according to any one of technical solutions 1-3, wherein, based on the molar percentage of oxides, the composition of the 3D curved surface microcrystalline glass comprises:

[0025] SiO2: 67.50 mol% - 71.00 mol%, Al2O3: 3.50 mol% - 5.00 mol%, P2O5: not less than 0.85 mol% and less than 1.50 mol%, ZrO2: 2.50 mol% - 3.50 mol%, Na2O: greater than 0.00 mol% and not greater than 1.00 mol%, K2O: greater than 0.00 mol% and not greater than 0.50 mol%, Li2O: 20.00 mol% - 25.00 mol%, CaO: greater than 0.50 mol% and not greater than 1.50 mol%, B2O3: 0.00 mol% - 1.00 mol%. Adjusting the content of the necessary oxides helps to further improve the network structure of 3D curved glass-ceramics, thereby ensuring the large-scale mass production of prefabricated glass-ceramics and ensuring the excellent optical and strength properties of mass-produced 3D curved glass-ceramic products.

[0026] 5. The 3D curved microcrystalline glass according to any one of technical solutions 1-4, wherein the 3D curved microcrystalline glass does not contain a quartz crystal phase. By avoiding the precipitation of a quartz crystal phase in the 3D curved microcrystalline glass whose main crystal phases are lithium feldspar and lithium disilicate, it is beneficial to ensure the optical performance and overall uniformity of the 3D curved microcrystalline glass.

[0027] 6. The 3D curved glass-ceramic according to any one of technical solutions 1-5, wherein the total content of the lithium feldspar crystal phase and the lithium disilicate crystal phase in the 3D curved glass-ceramic accounts for more than 60.00 wt% of the mass of the 3D curved glass-ceramic, preferably more than 70.00 wt%, and more preferably more than 80.00 wt%; the average crystal size in the 3D curved glass-ceramic does not exceed 100 nm. A higher content of the main crystalline phase is beneficial to improving the mechanical strength properties of the 3D curved glass-ceramic. A smaller average crystal size is beneficial to ensuring the excellent optical properties of the 3D curved glass-ceramic.

[0028] 7. The 3D curved microcrystalline glass according to any one of technical solutions 1-6, wherein, based on the molar percentage of each oxide in the composition of the 3D curved microcrystalline glass, the composition of the 3D curved microcrystalline glass satisfies:

[0029] 0.184≤5×P2O5 / (Li2O+0.5Al2O3)≤0.245; and / or

[0030] 18.200≤Li2O / P2O5≤25.000; and / or

[0031] 0.190≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.180; and / or

[0032] 1.500≤10×(ZrO2+P2O5) / Li2O≤1.900; and / or

[0033] 4.200≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤5.900; and / or

[0034] 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤4.950; and / or

[0035] 15.000≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000.

[0036] 8. The 3D curved microcrystalline glass according to any one of technical solutions 1-7, wherein, based on the molar percentage of each oxide in the composition of the 3D curved microcrystalline glass, the composition of the 3D curved microcrystalline glass satisfies:

[0037] 0.186≤5×P2O5 / (Li2O+0.5Al2O3)≤0.243; and / or

[0038] 18.500≤Li2O / P2O5≤24.700; and / or

[0039] 0.190≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.170; and / or

[0040] 1.550≤10×(ZrO2+P2O5) / Li2O≤1.850; and / or

[0041] 4.600≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤5.850; and / or

[0042] 2.680≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤4.930; and / or

[0043] 16.000≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000.

[0044] 9. The 3D curved microcrystalline glass according to any one of technical solutions 1-8, wherein, when the thickness is 0.6mm, the optical b-value of the 3D curved microcrystalline glass is ≤1.00, preferably ≤0.70, and more preferably ≤0.55. The smaller the b-value, the better the optical performance and the better the overall display effect of the 3D curved microcrystalline glass.

[0045] 10. The 3D curved microcrystalline glass according to any one of technical solutions 1-9, wherein, when the thickness is 0.6mm, the range of nine b-values ​​on the main surface of the 3D curved microcrystalline glass is ≤0.30, preferably ≤0.10, and more preferably ≤0.06. The smaller the range of nine b-values ​​on the main surface of the 3D curved microcrystalline glass sheet of this specification, the better the overall uniformity of the 3D curved microcrystalline glass sheet of this application, and the better the overall display effect.

[0046] Among them, the nine locations are: (1) the test locations of test circles I near the four corners of the main surface, a total of four locations; (2) the test locations of test circles II formed by taking the point closest to the middle of the long or short side of the main surface as the center of the line segment formed by the center of the above four test circles I, a total of four locations; (3) the location of test circle III formed by taking the center point of the main surface as the center.

[0047] 11. A substrate glass, said substrate glass being used to prepare 3D curved microcrystalline glass as described in any one of technical solutions 1-10, wherein, based on the molar percentage of oxides, the composition of said substrate glass comprises:

[0048] SiO2: 60.00mol%-71.00mol%, Al2O3: 1.50mol%-5.00mol%, P2O5: 0.80mol%-1.50mol%, ZrO2: 2.00mol%-4.00mol%, Na2O: 0.00m ol%-1.00mol%, K2O: 0.00mol%-0.50mol%, Li2O: 20.00mol%-30.00mol%, CaO: 0.00mol%-1.60mol%, B2O3: 0.00mol%-1.00mol%;

[0049] The composition of the substrate glass, expressed as the molar percentage of each oxide in the substrate glass composition, satisfies the following:

[0050] 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250;

[0051] 18.200≤Li2O / P2O5≤25.500;

[0052] 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200;

[0053] 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000;

[0054] 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000;

[0055] 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000;

[0056] 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000. By ensuring the substrate glass meets the above composition requirements, not only can good melting conditions be achieved in the substrate glass brick, but also prefabricated microcrystalline glass bricks with good overall uniformity, good display effect, excellent optical performance, and excellent mechanical properties, and whose main crystalline phases are lithium feldspar and lithium disilicate, can be prepared. This is beneficial for hot bending to obtain 3D curved surface microcrystalline glass products with excellent optical and mechanical properties.

[0057] 12. According to the substrate glass described in technical solution 11, wherein: through simultaneous thermal analysis testing, under a nitrogen protective atmosphere, the substrate glass is heated from room temperature to 900℃ at a heating rate of 10℃ / min to obtain a heating DSC curve. In this heating DSC curve, there are at least two exothermic peaks, wherein the first exothermic peak temperature T1 is 600℃-730℃, and the second exothermic peak temperature T2 is 740℃-800℃, and T1 and T2 satisfy the relationship: 100℃≥T2-T1≥40℃, preferably 80℃≥T2-T1≥50℃. Large-size substrate glass bricks made using a substrate glass scheme that satisfies specific DSC curve characteristics, when heat-treated under the production line process conditions for mass production of microcrystalline glass, can produce prefabricated microcrystalline glass bricks whose optical performance and display effects meet the requirements for display screen use. This effectively solves the problems that easily occur in the mass production of prefabricated microcrystalline glass bricks in the prior art, such as large differences in b-values ​​in different areas of the glass brick, localized undesirable colors, mosaic patterns, and poor display.

[0058] 13. The substrate glass according to technical solution 12, wherein: in T g Within the temperature range of -T2, the upper limit temperature T for the precipitation of a lithium silicate crystalline phase in the substrate glass was tested. max Upper limit temperature T for precipitation of quartz phase in (Li2SiO3) and substrate glass max (SiO2), T max(Li2SiO3)≥T max (SiO2), where T g This refers to the glass transition temperature of the substrate glass. By ensuring that the upper limit temperature Tmax (SiO2) for the precipitation of the quartz crystal phase is lower than the upper limit temperature Tmax (Li2SiO3) for the precipitation of the lithium monosilicate crystal phase within a specific temperature range, it is possible to effectively prevent the precipitation of the quartz crystal phase in the substrate glass under specific heat treatment process conditions used to prepare pre-fabricated glass-ceramics with lithium feldspar and lithium disilicate as the main crystal phases. Combined with the subsequent hot bending process, the lithium monosilicate crystal phase can also be transformed into the desired lithium disilicate crystal phase, thereby avoiding the adverse effects of the quartz crystal phase and lithium monosilicate crystal phase on the optical effects of the glass-ceramics.

[0059] 14. The substrate glass according to any one of technical solutions 11-13, wherein, based on the molar percentage of oxides, the composition of the substrate glass comprises:

[0060] SiO2: 67.50 mol% - 71.00 mol%, Al2O3: 3.50 mol% - 5.00 mol%, P2O5: not less than 0.85 mol% and less than 1.50 mol%, ZrO2: 2.50 mol% - 3.50 mol%, Na2O: greater than 0.00 mol% and not greater than 1.00 mol%, K2O: greater than 0.00 mol% and not greater than 0.50 mol%, Li2O: 20.00 mol% - 25.00 mol%, CaO: greater than 0.50 mol% and not greater than 1.50 mol%, B2O3: 0.00 mol% - 1.00 mol%. Adjusting the content of the necessary oxides helps to further improve the network structure of the glass, thereby ensuring the production of large-size prefabricated microcrystalline glass with good overall uniformity, and ultimately ensuring the production of 3D curved microcrystalline glass with excellent optical and strength properties.

[0061] 15. A method for preparing 3D curved surface microcrystalline glass as described in any one of technical solutions 1-10, comprising the following steps:

[0062] (1) Heat-treat the substrate glass as described in any one of technical solutions 11-14 to obtain a pre-made microcrystalline glass product containing a lithium silicate crystalline phase, a lithium disilicate crystalline phase and a lithium feldspar crystalline phase, and having a crystallinity of not less than 60.00 wt%.

[0063] (2) The prefabricated microcrystalline glass product obtained in step (1) is processed into a planar microcrystalline glass sheet of the required size and specifications, and the obtained planar microcrystalline glass sheet is subjected to hot bending treatment to obtain 3D curved microcrystalline glass. The 3D curved microcrystalline glass contains lithium feldspar crystal phase and lithium disilicate crystal phase, and the lithium feldspar crystal phase and lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the 3D curved microcrystalline glass.

[0064] 16. The method for preparing 3D curved microcrystalline glass according to technical solution 15, wherein in step (1), the heat treatment includes nucleation treatment and crystallization treatment, wherein the temperature of nucleation treatment is (Tg-20℃) to (Tg+40℃), the time of nucleation treatment is 0min-6000min, the temperature of crystallization treatment is (T1-50℃) to T1, and the time of crystallization treatment is 30min-6000min; Tg is the glass transition temperature of the substrate glass; in step (1), the heating rate of the heat treatment process is 5℃ / min-15℃ / min.

[0065] 17. The method for preparing 3D curved microcrystalline glass according to technical solution 15 or 16, wherein, in step (2), the hot bending process includes at least 3 preheating stations, at least 3 hot pressing stations and at least 3 cooling stations; the temperature of the preheating station is 500℃-850℃, the temperature of the hot pressing station is 700℃-900℃, the pressure of the hot pressing station is 0MPa-1MPa, and the temperature of the cooling station is 500℃-800℃.

[0066] 18. The method for preparing 3D curved microcrystalline glass according to technical solution 17, wherein the working time of each preheating station is 90s-360s, the working time of each hot pressing station is 90s-360s, and the working time of each cooling station is 90s-360s.

[0067] 19. A chemically strengthened glass-ceramic, wherein the composition at the center of the chemically strengthened glass-ceramic is the same as that of the 3D curved glass-ceramic as described in any one of claims 1-10, the chemically strengthened glass-ceramic includes a compressive stress layer region extending from the surface of the chemically strengthened glass-ceramic to a compression depth, and has tensile stress within the chemically strengthened glass-ceramic. Forming a compressive stress layer on the surface of the 3D curved glass-ceramic is beneficial for further improving the mechanical properties of the 3D curved glass-ceramic.

[0068] 20. A glass device, wherein the glass device comprises a 3D curved microcrystalline glass as described in any one of technical solutions 1-10 or comprises a chemically strengthened microcrystalline glass as described in technical solution 19.

[0069] 21. An electronic device, wherein the electronic device comprises 3D curved microcrystalline glass as described in any one of technical solutions 1-10 or comprises chemically strengthened microcrystalline glass as described in technical solution 19.

[0070] One or more of the above technical solutions have at least the following advantages or

[0071] Beneficial effects:

[0072] This application, through the above-mentioned technical solution, especially by ensuring that the content of each oxide is within a suitable range and in combination with the oxide content ratio under specific conditions, can guarantee the formation of the main crystalline phase during the mass production of 3D curved microcrystalline glass products. At the same time, it ensures that the prepared 3D curved microcrystalline glass products exhibit a relatively uniform display effect, effectively avoiding the problem of large differences in b-values ​​in different areas and poor display effects in mass-produced 3D curved microcrystalline glass products.

[0073] The large-size substrate glass bricks prepared by the glass scheme of this application, when heat-treated to prepare pre-fabricated microcrystalline glass bricks, ensure that the overall b-value of the main surface of the pre-fabricated microcrystalline glass bricks is close to a certain value, thereby ensuring that the 3D curved microcrystalline glass produced from it also exhibits good display effects. Using the specific composition scheme of this application, it is possible to ensure the acquisition of 3D curved microcrystalline glass with good optical performance, which is conducive to the industrial-scale mass production of 3D curved microcrystalline glass and improves the yield of 3D curved microcrystalline glass products. At the same time, the microcrystalline glass prepared using the above-mentioned substrate glass formulation scheme can be chemically strengthened to obtain chemically strengthened microcrystalline glass with excellent strength properties, especially drop resistance.

[0074] Another or more of the above technical solutions have the following advantages or beneficial effects:

[0075] In the mass production of 3D curved microcrystalline glass with lithium feldspar and lithium disilicate as the main crystalline phases, products exhibiting optical display defects generally contain cristobalite (SiO2) impurities. This application, by adjusting the composition of the substrate glass, achieves an upper limit T for the precipitation of the quartz crystalline phase within a specific temperature range. max (SiO2) is below the upper limit temperature T for the precipitation of lithium silicate crystalline phase. max (Li2SiO3) can ensure that the precipitation of quartz crystal phase is effectively avoided in the substrate glass under specific heat treatment process conditions for preparing pre-fabricated microcrystalline glass with lithium feldspar and lithium disilicate as the main crystal phases. Combined with the subsequent hot bending process, the lithium monosilicate crystal phase can also be transformed into the desired lithium disilicate crystal phase, thereby avoiding the adverse effects of quartz crystal phase and lithium monosilicate crystal phase on the optical effect of glass. Attached Figure Description

[0076] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0077] Figure 1 The image shows the temperature rise DSC curve of the substrate glass in Example 1.

[0078] Figure 2 The image shows the temperature rise DSC curve of the substrate glass in Example 10.

[0079] Figure 3 The temperature rise DSC curve of the substrate glass in Comparative Example 1 is shown.

[0080] Figure 4 The temperature rise DSC curve of the substrate glass in Comparative Example 2 is shown.

[0081] Figure 5 A schematic diagram of a Li3PO4 crystal with lithium silicate crystals attached to it.

[0082] Figure 6 The standard XRD diffraction pattern of quartz appearing in glass-ceramics;

[0083] Figure 7 A schematic diagram of the nine test locations for conducting b-value tests on the main surface of the glass-ceramic.

[0084] Figure 8 The XRD diffraction pattern of the pre-fabricated microcrystalline glass obtained after heat treatment process C of the substrate glass in Example 2 is shown.

[0085] Figure 9 The XRD diffraction pattern of the pre-fabricated glass-ceramic obtained by heat treatment process C on the substrate glass of Comparative Example 2 is shown.

[0086] Figure 10 The XRD diffraction curves are shown at the positions of maximum and minimum b-value of the 3D curved glass-ceramic in Example 1.

[0087] Figure 11 The XRD diffraction curves are shown at the positions of maximum and minimum b-values ​​of the 3D curved glass-ceramic in Comparative Example 6.

[0088] Figure 12 The image shows the cracking of the prefabricated microcrystalline glass in Comparative Example 7 during the 3D hot bending process.

[0089] Figure 13 The transmittance curve of the 3D curved microcrystalline glass in Example 1 is shown. Detailed Implementation

[0090] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The terms "optional" and "discretionary" mean that they may or may not be included (or may or may not be present).

[0091] Definitions and testing methods:

[0092] Substrate glass: refers to glass that has not undergone nucleation, crystallization, or strengthening treatment.

[0093] Glass-ceramics, also known as glass-ceramics, are a type of solid composite material that contains both a glass phase and a crystalline phase (or microcrystalline phase, crystalline phase) through the targeted and controlled crystallization of a substrate glass.

[0094] 3D curved glass-ceramics: also known as 3D curved glass ceramics, are made by bending planar glass-ceramics through methods such as cold grinding, hot bending, and hot pressing, thereby forming curved surfaces on both main surfaces of the planar glass-ceramics.

[0095] Chemically strengthened glass-ceramics: These are solid composite materials obtained by chemically strengthening glass-ceramics. During high-temperature chemical strengthening, alkali metal ions with larger ionic radii (such as potassium and sodium ions) in the molten salt bath replace alkali metal ions with smaller ionic radii (such as sodium and lithium ions) in the glass-ceramics, thereby creating a volume difference in exchange ions and generating compressive stress on the surface of the glass-ceramics.

[0096] Main crystalline phase: refers to the crystalline phase that has a higher weight content than other crystalline phases present in glass-ceramics.

[0097] Main surface: refers to the surface with the largest surface area in a glass block or glass sheet, such as the upper and lower surfaces of a cover glass.

[0098] "Colored spots" refers to a condition where, when strong light shines on a glass slide from the side, the main surface of the glass slide exhibits localized coloration and / or uneven coloration throughout the glass slide. (See reference...) Figure 8 As shown. Products with defects such as scratches or blemishes are considered defective during the production process because they fail to meet the display requirements of the screen cover glass.

[0099] Glass transition temperature: T g The unit is °C, also known as the brittleness temperature of glass. It is the highest temperature at which glass becomes brittle, and the corresponding viscosity is 10. 12Pa·s, also known as the upper limit of annealing temperature, is the temperature at which internal stresses caused by uneven cooling in glass products can be eliminated. T g The glass transition temperature is obtained by analyzing the DSC curve of the substrate glass. The change in the baseline of the DSC curve is represented by a step-like change in the direction of heat absorption. Tangents are drawn between the extended baselines before and after the step and the inflection points of the curve. The average value of the temperatures corresponding to the two intersection points is the glass transition temperature.

[0100] CS_50: refers to the compressive stress value at a depth of 50μm, measured from the main surface of the chemically strengthened glass-ceramic.

[0101] DOL_0: Compressive stress layer depth, also known as compressive stress layer depth, refers to the distance from any surface of the glass to a position close to zero compressive stress in the glass thickness direction.

[0102] |CT_AV|: The absolute value of the average tensile stress in the tensile stress layer, specifically the absolute value of the average value of all tensile stresses in the tensile stress layer.

[0103] Test conditions for CS_50, |CT_AV|, and DOL_0: The test was conducted using an Orihara SLP-2000 from Japan, with a light source wavelength of 518nm, SOC = 25.5 (nm / cm) / MPa, refractive index = 1.54, and exposure time of 300µsc.

[0104] When testing surfaces CS_50, |CT_AV|, and DOL_0, a conductive liquid needs to be applied to the stress meter first. Then, the chemically strengthened glass-ceramic sample to be tested should be wiped clean and placed on the test path to measure its stress value. The stress meter used is an SLP-2000, and the conductive liquid used has a refractive index of 1.51.

[0105] Transmittance: The ratio of the radiant energy projected onto and transmitted through an object to the total radiant energy projected onto the object during the process of incident light flux from the incident surface or medium to the other side.

[0106] b-value: A color model belonging to the Lab color model, a color mode developed by the International Commission on Illumination. Positive and negative b-values ​​represent yellow and blue.

[0107] Haze: Haze is the percentage of transmitted light intensity that deviates from the incident light by more than 2.5° from the total transmitted light intensity.

[0108] Precursor: A form of existence that exists before the target is obtained.

[0109] Residual glass phase: refers to the amorphous phase portion in glass-ceramics.

[0110] Simultaneous thermal analysis test: The Mettler Toledo TGA / DSC3+ simultaneous thermal analyzer is used to perform tests according to the required process. The obtained curves are called DSC curves, including temperature-rising DSC curves.

[0111] Test conditions for the temperature-rising DSC curve: After grinding the substrate glass and passing it through a 200-mesh sieve, the sample to be tested was obtained. Approximately 20 mg of the sample was weighed and heated from room temperature to 900℃ at a heating rate of 10℃ / min under a nitrogen protective atmosphere to obtain the temperature-rising DSC curve of the sample. The differential thermal analysis instrument used in this application for testing the temperature-rising DSC curve was a Mettler Toledo TGA / DSC3+ simultaneous thermal analyzer. The standard used for testing was α-Al2O3 powder, the container for placing the sample was a platinum crucible, and the ambient temperature and humidity of the instrument were 24℃ and 40%, respectively.

[0112] Glass thickness: obtained by laser thickness gauge.

[0113] Optical performance testing of microcrystalline glass with a thickness of less than 2 mm: This application uses a Konica Minolta CM-3600A spectrophotometer in transmission mode to test the haze, L, a, and b values ​​of the microcrystalline glass. The CM-3600A spectrophotometer has a test aperture of 25.6 mm. This application uses a Shimadzu UV-2000 ultraviolet-visible spectrophotometer to test the transmittance and its curve. To ensure accuracy, this test method is applicable to testing glass sheets with a thickness of less than 2 mm.

[0114] Determination of crystal phase: The crystal phase in the glass-ceramic sample can be determined by importing the XRD test results (RAW format) into the Rietveld X-ray diffraction data refinement software JADE Standard 8.6 for fitting and analysis.

[0115] In this application, crystal content refers to the percentage of crystals or crystalline phases in the mass of the glass-ceramic, expressed as a weight percentage.

[0116] Determination of crystal content: The crystal content in the glass-ceramic sample can be obtained by importing the XRD test results (RAW format) into the Rietveld X-ray diffraction data refinement software JADE Standard 8.6 for fitting and calculation. Specifically, the ratio of the fitted crystalline phase peak area to the fitted total peak area is the crystal content.

[0117] Average Crystal Size Measurement: Using the XRD test results, the average crystal size of the sample can be calculated according to the Scherrer formula D = Kλ / (βcosθ). Here, λ is the X-ray wavelength (λ = 0.154056 nm), β is the full width at half maximum (FWHM) of the diffraction peak (K = 0.89), and θ is the Bragg diffraction angle. Specifically, the RAW file (diffraction pattern) output from the XRD instrument is curve-fitted in JADE Standard 8.6 software. Jade outputs a fitting report. Based on the angle 2θ and Peak FWHM value (full width at half maximum) corresponding to each diffraction peak in the fitting report, and converting the Peak FWHM value to radians: β = (FWHM / 180 × 3.14), the grain size of each diffraction peak is calculated using the Scherrer formula D = Kλ / (βcosθ), and then averaged to obtain the average crystal size.

[0118] The method for testing the upper limit temperature of crystal phase precipitation is as follows: The substrate glass is heated at a heating rate of 10℃ / min to Tg, Tg+5℃, Tg+10℃, and Tg+15℃ respectively, and then heat-treated at an increase of 5℃ until T2. The heat treatment time at each temperature is 30-240 min (the corresponding heat treatment time at each temperature in the embodiments and comparative examples of this application is 240 min). The crystal phase composition of the samples obtained by treating the substrate glass under the above-mentioned different heat treatment temperature conditions is tested to obtain the upper limit temperature of precipitation of lithium silicate (Li2SiO3) crystal phase and quartz (SiO2) crystal phase.

[0119] The "upper limit temperature for precipitation of lithium silicate phase" here specifically refers to the temperature at T... g - Within the T2 temperature range, this is the highest temperature at which a lithium silicate crystalline phase precipitates in the substrate glass. Above this temperature, no lithium silicate will precipitate in the substrate glass.

[0120] The "upper limit temperature for precipitation of quartz phase" here specifically refers to the temperature at T... g Within the -T2 temperature range, this is the highest temperature at which quartz crystals precipitate in the substrate glass. Above this temperature, quartz will not precipitate in the substrate glass. The standard XRD diffraction pattern for quartz in glass-ceramics is shown below. Figure 6 As shown.

[0121] The T here g T1 is the glass transition temperature of the substrate glass, and T2 is the temperature of the second exothermic peak in the DSC curve obtained when the substrate glass is subjected to DSC testing.

[0122] If a certain crystalline phase persists at temperature T2, it indicates that its upper limit of precipitation temperature is greater than T2.

[0123] Fixed-point height drop test:

[0124] (1) Attach 120-grit sandpaper to the lower surface of the 187g model and place the model on the Wonder Inno drop tester;

[0125] (2) Place a microcrystalline glass sample with dimensions of 50mm×50mm×0.6mm on a smooth marble slab directly below the model machine, with the microcrystalline glass sample facing the sandpaper.

[0126] (3) Drop the model machine from a fixed height of 1.0m onto the microcrystalline glass sample located directly below it. If the microcrystalline glass sample does not break, replace the sandpaper on the lower surface of the model machine and repeat the drop impact process until the microcrystalline glass breaks. Record the number of drops when it breaks.

[0127] At least 10 identical microcrystalline glass samples from each batch were taken for a fixed-point drop test, and the average value of the test results of the 10 microcrystalline glass samples was calculated to characterize the drop resistance of the microcrystalline glass.

[0128] Surface Na2O concentration test: The surface Na2O concentration equals the surface Na2O mass divided by the total surface oxide mass. The total surface oxide mass includes oxides that can be accurately measured by XRF, such as SiO2, Al2O3, P2O5, ZrO2, Na2O, K2O, and CaO, but excludes oxides that cannot be accurately measured by XRF, such as Li2O and B2O3. In this application, the surface Na2O concentration of the chemically strengthened microcrystalline glass was measured using X-ray fluorescence spectrometry (XRF) on a Thermo Scientific ARL instrument. TM PERFORM'X. The target material was Rh (rhodium), the photodiode voltage was 40 kW, the current was 60 mA, the collimator was 0.15, the crystal was LiF200, the detector was FPC, the test range was a 29 mm circle, and the analysis software was UniQuant standard-free analysis. Standard-free XRF testing was used, and the concentration of elements with atomic numbers 6 and below, or their oxides, in the glass was not tested. That is, in this application, when the surface Na2O concentration is tested by XRF, the total mass of surface oxides does not include the mass of elements with atomic numbers 6 and below, or their oxides, in the glass.

[0129] As described above, this application provides a 3D curved microcrystalline glass, wherein the 3D curved microcrystalline glass contains lithium feldspar (LiAlSi4O3). 10 The crystalline phases are lithium disilicate (Li2Si2O5) and lithium lithium feldspar, wherein the lithium disilicate and lithium lithium feldspar crystal phases have a higher weight percentage than other crystal phases present in 3D curved glass-ceramics.

[0130] The 3D curved microcrystalline glass of this application is made by heat treatment and hot bending of the substrate glass. Therefore, it can be understood that, in terms of oxides, the composition of the substrate glass is the same as that of the 3D curved microcrystalline glass.

[0131] In this application, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, based on the molar percentage of oxides, includes:

[0132] SiO2: 60.00mol%-71.00mol%, Al2O3: 1.50mol%-5.00mol%, P2O5: 0.80mol%-1.50mol%, ZrO2: 2.00mol%-4.00mol%, Na2O: 0.00m ol%-1.00mol%, K2O: 0.00mol%-0.50mol%, Li2O: 20.00mol%-30.00mol%, CaO: 0.00mol%-1.60mol%, B2O3: 0.00mol%-1.00mol%;

[0133] The composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following:

[0134] 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250;

[0135] 18.200≤Li2O / P2O5≤25.500;

[0136] 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200;

[0137] 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000;

[0138] 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000;

[0139] 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000;

[0140] 12.200≤(5.6B₂O₃+10Al₂O₃+6.5CaO) / ZrO₂≤20.000. When the content of each oxide is within a suitable range and the oxide content ratio is determined under specific conditions, the formation of the main crystalline phase can be guaranteed during the mass production of 3D curved microcrystalline glass products. Simultaneously, the prepared 3D curved microcrystalline glass products exhibit a relatively uniform display effect, effectively avoiding the problem of large differences in b-values ​​and poor display effects in different areas of mass-produced 3D curved microcrystalline glass products.

[0141] In the glass system of this application, SiO2 is an oxide that forms the glass network framework, used to stabilize the network structure of the substrate glass and the 3D curved glass-ceramic. It is an important component constituting crystalline phases such as lithium silicate, pyrite, β-spodumene, and quartz. When the substrate glass is heat-treated to form glass-ceramics, the SiO2 content should be high enough to form a sufficient amount of pyrite and lithium silicate crystals. If the SiO2 content is too low, the glass tends to have a higher coefficient of thermal expansion and reduced thermal shock resistance; if the SiO2 content is too high, it will lead to poorer glass meltability or increased viscosity of the molten glass, making it difficult to clarify the glass, increasing the difficulty of glass forming, reducing productivity, and also prolonging the crystallization heat treatment time of the substrate glass. In some embodiments, the glass-ceramic or substrate glass of this application contains 60.00 mol%-71.00 mol% SiO2. In some embodiments, the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic may contain 60.00 mol%-71.00 mol%, 60.90 mol%-70.00 mol%, 60.90 mol%-69.00 mol%, 60.90 mol%-68.00 mol%, 62.00 mol%-65.00 mol%, 63.00 mol%-70.00 mol%, 64.00 mol%-68.00 mol%, 65.00 mol%-67.00 mol%, or 67.50 mol%-71.00 mol% of SiO2. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 60.00 mol%, 61.00 mol%, 62.00 mol%, 63.00 mol%, 64.00 mol%, 65.00 mol%, 66.00 mol%, 67.00 mol%, 67.50 mol%, 68.00 mol%, 69.00 mol%, 70.00 mol%, or 71.00 mol% of SiO2, or SiO2 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0142] In the glass system of this application, Al2O3 can be used to construct the glass framework and is an indispensable component for the formation of lithium feldspar. Al2O3 is coordinated around the crystal nucleus, forming a "center-shell" structure. This structure makes it difficult for the crystal nucleus components to be supplied from the outer shell, making it difficult for the crystal nucleus to grow and easily forming multiple tiny grains. An appropriate amount of Al2O3 can stabilize the glass network structure, improve mechanical and chemical durability, suppress phase separation of the glass, reduce the coefficient of thermal expansion, and increase the strain point. When the Al2O3 content is too low, the glass tends to have a higher coefficient of thermal expansion, its chemical durability decreases, and the crystal nucleus becomes larger, making the glass prone to turbidity. When the Al2O3 content is too high, the glass meltability deteriorates, production becomes difficult, and mullite crystals are easily precipitated, causing the glass to devitrify. In some embodiments, the 3D curved glass-ceramic of this application or the substrate glass used to prepare the 3D curved glass-ceramic contains 1.50 mol% to 5.00 mol% Al2O3. In some embodiments, the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic may contain 1.50 mol%-5.00 mol%, 3.00 mol%-5.00 mol%, 3.00 mol%-4.00 mol%, 3.00 mol%-4.50 mol%, 3.50 mol%-4.50 mol%, or 4.50 mol%-5.00 mol% of Al2O3. In some embodiments, the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic may contain 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.20 mol%, 3.80 mol%, 4.00 mol%, 4.40 mol%, 4.80 mol%, or 5.00 mol% of Al2O3, or Al2O3 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges, as long as the 3D curved microcrystalline glass or substrate glass with the performance required by this application can be obtained.

[0143] In the glass system of this application, Li₂O is the main component of the lithium feldspar crystalline phase and the lithium silicate crystalline phase, and is also a necessary component for chemical strengthening. An appropriate amount of Li₂O is beneficial in ensuring that the transparency, melt-forming effect, crystallization ability, and chemical strengthening performance of the 3D curved microcrystalline glass meet the requirements. When the Li₂O content is too low, the glass is prone to precipitating crystalline phases, such as mullite, causing devitrification, reduced meltability, or increased viscosity, making it difficult to clarify and form. When the Li₂O content is too high, the crystallization heat treatment temperature of the substrate glass decreases accordingly, the crystallization ability of the glass becomes too strong, the glass has a tendency to devitrify, and the crystallized glass becomes easily broken. In some embodiments, the 3D curved microcrystalline glass of this application or the substrate glass used to prepare the 3D curved microcrystalline glass contains 20.00 mol%-30.00 mol% Li₂O. In some embodiments, the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic may contain 20.00 mol%-30.00 mol%, 22.00 mol%-28.00 mol%, 24.00 mol%-26.00 mol%, 20.00 mol%-24.00 mol%, 24.00 mol%-30.00 mol%, 20.00 mol%-22.00 mol%, 28.00 mol%-30.00 mol%, or 21.00 mol%-28.00 mol% of Li₂O. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 20.50 mol%, 21.50 mol%, 22.50 mol%, 23.50 mol%, 24.50 mol%, 25.50 mol%, 26.50 mol%, 27.50 mol%, 28.50 mol%, 29.50 mol%, or 30.00 mol% of Li₂O, or Li₂O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0144] In the glass system of this application, P2O5 is the glass-forming oxide, existing as phosphorus-oxygen tetrahedra [PO4] in the network structure. P2O5 preferentially appears during heat treatment, initially causing phase separation and agglomeration in the glass, forming the amorphous precursor phase Li3PO4. Then, Li3PO4 acts as a non-uniform nucleation site, allowing crystalline phases such as lithium silicate to grow attached to the amorphous Li3PO4. With increasing P2O5 content, the number of non-uniform nucleation sites increases, effectively refining the grains nucleated by Li3PO4. This is beneficial for improving the overall transmittance of the glass-ceramic, the uniformity of the glass, and reducing the b-value. Within a certain P2O5 range, the gain effect reaches its optimal level. However, when the P2O5 content is too high, the upper limit of crystallization temperature increases, making it easier to generate more Li3PO4 crystals. This results in insufficient Li2O content for the formation of lithium silicate and lithium feldspar, which in turn leads to the precipitation of quartz crystals in the substrate glass, causing a decrease in the transmittance of the glass-ceramic and a decrease in the overall optical uniformity of the glass-ceramic. In severe cases, it can even cause crystallization of the substrate glass during melting and molding. Conversely, when the P2O5 content is too low, coarse ZrO2 crystals are easily precipitated, causing the glass to become devitrified.

[0145] In some embodiments, the 3D curved microcrystalline glass of this application, or the substrate glass used to prepare the 3D curved microcrystalline glass, contains 0.80 mol%-1.50 mol% of P2O5. This range of P2O5 content is beneficial in ensuring high transmittance, good optical uniformity, significantly reduced b-value, and optimal gain effect of the 3D curved microcrystalline glass. In some embodiments, the 3D curved microcrystalline glass, or the substrate glass used to prepare the 3D curved microcrystalline glass, may contain 0.80 mol%-1.50 mol%, 0.80 mol%-1.30 mol%, 1.30 mol%-1.50 mol%, 0.80 mol%-1.00 mol%, 1.00 mol%-1.30 mol%, or 1.10 mol%-1.50 mol% of P2O5. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.85 mol%, 0.95 mol%, 1.00 mol%, 1.10 mol%, 1.20 mol%, 1.35 mol%, 1.40 mol%, or 1.50 mol% of P2O5, or P2O5 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application is obtained.

[0146] In the glass system of this application, P2O5 preferentially forms amorphous Li3PO4 during heat treatment. The increase in P2O5 inevitably competes for more Li2O, thus reducing the formation of lithium silicate and lithium feldspar. Therefore, a certain amount of Li2O needs to be added. To address this, in the system of this application, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare it, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 18.200 ≤ Li2O / P2O5 ≤ 25.500. The chemical formulas in this formula represent the molar percentage of oxides, which helps ensure the formation of the main crystalline phase and improves the strength properties of the glass. In some implementations, the value of Li2O / P2O5 can be, for example, 18.200, 18.500, 19.000, 19.500, 20.000, 20.500, 21.000, 21.500, 22.000, 22.500, 23.000, 23.500, 24.000, 24.500, 25.000, or 25.500, or it can be a value within a range of values ​​defined by any two of the above specific values ​​as endpoints.

[0147] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 0.180 ≤ 5 × P₂O₅ / (Li₂O + 0.5Al₂O₃) ≤ 0.250, where the chemical formula represents the molar percentage of the oxide, thereby facilitating the formation of the main crystalline phases of lithium feldspar and lithium disilicate. In some embodiments, the value of 5 × P₂O₅ / (Li₂O + 0.5Al₂O₃) can be, for example, 0.180, 0.184, 0.190, 0.200, 0.210, 0.220, 0.230, 0.240, 0.245, or 0.250, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0148] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 4.000 ≤ (SiO2-7Al2O3-Li2O) / (P2O5+ZrO2) ≤ 6.000, where the chemical formula represents the molar percentage of the oxides. This is beneficial for ensuring the optical performance of the 3D curved microcrystalline glass. In some embodiments, the value of (SiO2-7Al2O3-Li2O) / (P2O5+ZrO2) can be, for example, 4.000, 4.200, 4.500, 5.000, 5.500, or 6.000, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0149] In the glass system of this application, an appropriate amount of ZrO2 can improve the viscosity, hardness, elastic modulus, refractive index, chemical stability, and reduce the coefficient of thermal expansion of the glass. ZrO2 does not act as a nucleating agent in the lithium feldspar and lithium silicate-structured glass-ceramics; rather, it exists in the residual glass phase after heat treatment, effectively improving the mechanical properties of the residual glass phase. However, excessive ZrO2 increases the difficulty of melting the substrate glass and produces white zirconium precipitate during discharge, which is detrimental to the production of transparent glass-ceramics. In some embodiments, the 3D curved glass-ceramics of this application, or the substrate glass used to prepare the 3D curved glass-ceramics, contain 2.00 mol%-4.00 mol% ZrO2. ZrO2 content within this range is beneficial for the production of transparent 3D curved glass-ceramics and for improving the mechanical properties of the 3D curved glass-ceramics. In some embodiments, the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic may contain 2.00 mol%-4.00 mol%, 2.50 mol%-3.50 mol%, 2.70 mol%-3.30 mol%, 2.90 mol%-3.10 mol%, 2.50 mol%-3.00 mol%, 2.50 mol%-2.80 mol%, 2.80 mol%-3.50 mol%, 2.80 mol%-3.40 mol%, 2.80 mol%-3.30 mol%, or 2.80 mol%-3.10 mol% of ZrO2. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 2.00 mol%, 2.50 mol%, 2.75 mol%, 2.95 mol%, 3.15 mol%, 3.25 mol%, 3.35 mol%, 3.50 mol%, or 4.00 mol% ZrO2, or ZrO2 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0150] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 1.500 ≤ 10 × (ZrO2 + P2O5) / Li2O ≤ 2.000, where the chemical formula represents the molar percentage of the oxides. This is beneficial for ensuring the strength performance of the 3D curved microcrystalline glass. In some embodiments, the value of 10 × (ZrO2 + P2O5) / Li2O can be, for example, 1.500, 1.550, 1.600, 1.700, 1.800, 1.900, 1.95, or 2.000, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0151] In the glass system of this application, B2O3 helps to lower the melting temperature of the substrate glass. B2O3 uses boron-oxygen trigonal [BO3] and boron-oxygen tetrahedron [BO4] as structural units. As the B2O3 content increases, the relative content of boron-oxygen trigonal and boron-oxygen tetrahedrons changes, leading to a reversal of the structure and properties. An appropriate amount of B2O3 helps to lower the melting temperature of the substrate glass and improve the transmittance and overall uniformity of the 3D curved microcrystalline glass. However, when too much B2O3 is added, on the one hand, the three-dimensional framework structure of boron-oxygen tetrahedra [BO4] transforms into a two-dimensional layered structure of boron-oxygen trigonal [BO3]. Since the tricoordinated boron-oxygen trigonal [BO3] is not as strong as the boron-oxygen tetrahedra [BO4], it can open up the network structure. Simultaneously, the increased B2O3 content in the residual glass phase reduces its viscosity, promoting the growth of crystals such as lithium monosilicate. On the other hand, it lowers the second exothermic peak temperature of the DSC curve of the substrate glass, increasing the precipitation of SiO2 crystal phases (e.g., cristobalite), affecting glass transmittance and worsening the overall uniformity of the glass brick. In some embodiments, the 3D curved microcrystalline glass of this application or the substrate glass used to prepare the 3D curved microcrystalline glass contains 0.00 mol%-1.00 mol% B2O3. In some embodiments, the microcrystalline glass or the substrate glass may contain 0.00 mol%-1.00 mol%, 0.10 mol%-0.90 mol%, 0.30 mol%-0.80 mol%, 0.50 mol%-0.70 mol%, 0.00 mol%-0.60 mol%, 0.00 mol%-0.50 mol%, 0.60 mol%-1.00 mol%, 0.50 mol%-1.00 mol%, or 0.30 mol%-0.50 mol% of B2O3. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol%, 0.55 mol%, 0.75 mol%, 0.95 mol%, or 1.00 mol% of B2O3, or B2O3 within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0152] In the glass system of this application, Na₂O is an external oxide of the glass network, which can provide free oxygen to increase the oxygen-silicon ratio in the glass structure, thereby regulating grain size. The presence of an appropriate amount of Na₂O is beneficial to promoting the precipitation of lithium disilicate phase, reducing the tendency of glass to crystallize, increasing the transmittance of the glass, and improving the thermal stability, chemical stability, mechanical strength, and weather resistance of the glass. In some embodiments, the 3D curved microcrystalline glass of this application or the substrate glass used to prepare the 3D curved microcrystalline glass contains 0.00 mol%-1.00 mol% Na₂O. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%-1.00 mol%, 0.20 mol%-0.90 mol%, 0.40 mol%-0.80 mol%, 0.00 mol%-0.40 mol%, 0.00 mol%-0.50 mol%, 0.00 mol%-0.40 mol%, 0.40 mol%-1.00 mol%, 0.30 mol%-0.50 mol%, or 0.40 mol%-0.60 mol% of Na2O. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%, 0.15 mol%, 0.35 mol%, 0.55 mol%, 0.75 mol%, 0.95 mol%, or 1.00 mol% Na₂O, or Na₂O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application is obtained.

[0153] In the glass system of this application, K2O is the outer oxide of the glass network. An appropriate amount of K2O can reduce the glass's crystallization tendency and increase its transparency and gloss. However, when the K2O content is too high, the glass's crystallization ability becomes stronger, making it prone to devitrification and causing the crystallized glass to break easily. + The ionic radius is larger than that of Li, which is the main crystalline phase. + It is not easy to enter the crystal, therefore the crystallized K +K₂O remains in the glass phase. Therefore, in some embodiments, the 3D curved microcrystalline glass of this application or the substrate glass used to prepare the 3D curved microcrystalline glass contains 0.00 mol%-0.50 mol% of K₂O. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%-0.50 mol%, 0.10 mol%-0.40 mol%, 0.20 mol%-0.30 mol%, 0.00 mol%-0.20 mol%, 0.30 mol%-0.50 mol%, 0.10 mol%-0.20 mol%, or 0.20 mol%-0.40 mol% of K₂O. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol%, or 0.50 mol% K₂O, or K₂O within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0154] In the glass system of this application, CaO is beneficial for increasing the chemical stability and mechanical strength of the glass. CaO reduces the viscosity of the glass, enhances its meltability and formability, and also helps to adjust the coefficient of thermal expansion and refractive index of the glass-ceramic. However, when the CaO content is too high, the glass is prone to devitrification after crystallization treatment. Excessive CaO residue in the glass phase creates a refractive index difference with the main crystalline phase, leading to a decrease in the transmittance and an increase in haze of the glass-ceramic. In some embodiments, the 3D curved glass-ceramic of this application or the substrate glass used to prepare the 3D curved glass-ceramic contains 0.00 mol% to 1.60 mol% CaO. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%-1.60 mol%, 0.50 mol%-1.60 mol%, 0.60 mol%-1.50 mol%, 0.80 mol%-1.30 mol%, 1.00 mol%-1.20 mol%, 0.50 mol%-1.00 mol%, 0.50 mol%-0.85 mol%, 0.85 mol%-1.40 mol%, 1.40 mol%-1.60 mol%, 0.85 mol%-1.20 mol%, 1.20 mol%-1.60 mol%, 0.85 mol%-1.00 mol%, 0.85 mol%-0.90 mol%, or 1.00 mol%-1.30 mol% of CaO. In some embodiments, the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass may contain 0.00 mol%, 0.50 mol%, 0.70 mol%, 0.85 mol%, 1.10 mol%, 1.25 mol%, 1.35 mol%, 1.45 mol%, or 1.60 mol% CaO, or CaO within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass or substrate glass with the desired performance of this application can be obtained.

[0155] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200, where the chemical formula represents the molar percentage of the oxide. This is beneficial for forming 3D curved microcrystalline glass with excellent performance (especially the forming performance, optical performance, and strength performance) that meets specific structural requirements. In some embodiments, the value of P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3) can be, for example, 0.100, 0.150, 0.190, 0.200, 0.205, 0.210, 0.250, 0.300, 0.350, 0.380, 0.400, 0.600, 0.800, 1.000, 1.200, 1.400, 1.600, 1.800, 2.000, or 2.200, or a value within a range of values ​​defined by any two of the above specific values ​​as endpoints.

[0156] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 2.600 ≤ 99 × (CaO + ZrO2) / (Li2O + Na2O + 1000 × K2O) ≤ 5.000, where the chemical formula represents the molar percentage of the oxide. This facilitates the formation of 3D curved microcrystalline glass with excellent performance (especially the strength performance) that meets specific structural requirements. In some embodiments, the value of 99 × (CaO + ZrO2) / (Li2O + Na2O + 1000 × K2O) can be 2.600, 2.800, 3.000, 3.500, 4.000, or 5.000, or a value within a range defined by any two of the above specific values ​​as endpoints.

[0157] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following condition: 12.200≤(5.6×B2O3+10×Al2O3+6.5×CaO) / ZrO2≤20.000, where the chemical formula represents the molar percentage of the oxide. This is beneficial for forming a 3D curved microcrystalline glass with excellent performance (especially the optical and mechanical properties) that meets specific structural requirements. In some implementations, the value of (5.6×B2O3+10×Al2O3+6.5×CaO) / ZrO2 can be 12.200, 13.000, 14.000, 15.000, 16.000, 17.000, 18.000, 19.000 or 20.000, or it can be a value within a range of values ​​defined by any two of the above specific values ​​as endpoints.

[0158] In some embodiments, the 3D curved microcrystalline glass is transparent in the visible light range, where visible light refers to light in the wavelength range of 360nm-780nm. "Transparent in the visible light range" means that the transmittance under light in the 360nm-780nm wavelength range is greater than 80%, which meets the optical performance requirements for the front cover display effect. In some embodiments, the 0.6mm thick 3D curved microcrystalline glass has a transmittance of not less than 90% in the visible light range.

[0159] In some embodiments, the composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, based on the molar percentage of oxides, includes: SiO2: 67.50 mol%-71.00 mol%, Al2O3: 3.50 mol%-5.00 mol%, P2O5: not less than 0.85 mol% and less than 1.50 mol%, ZrO2: 2.50 mol%-3.50 mol%, Na2O: greater than 0.00 mol% and not greater than 1.00 mol%, K2O: greater than 0.00 mol% and not greater than 0.50 mol%, Li2O: 20.00 mol%-25.00 mol%, CaO: greater than 0.50 mol% and not greater than 1.50 mol%, B2O3: 0.00 mol%-1.00 mol%.

[0160] In some embodiments, the 3D curved glass-ceramic does not contain a quartz crystalline phase. The standard XRD diffraction pattern of quartz appearing in the glass-ceramic is as follows: Figure 6As shown. In glass-ceramics with lithium feldspar and lithium disilicate as the main crystalline phases, the precipitation of quartz phase can adversely affect the optical properties of the glass-ceramics, leading to reduced transmittance and poor overall uniformity, resulting in significant differences in b-values ​​across different regions. The oxide formulations of this application enable the mass production of quartz-free 3D curved glass-ceramics from the substrate glass under specific heat treatment conditions.

[0161] In some embodiments, the total content of the lithium feldspar and lithium disilicate crystal phases in the 3D curved glass-ceramic is 60.00 wt% or more, preferably 70.00 wt% or more, and more preferably 80.00 wt% or more by weight of the 3D curved glass-ceramic. A higher content of lithium feldspar and lithium disilicate crystal phases is beneficial for improving the mechanical strength of the 3D curved glass-ceramic. The total content of the lithium feldspar and lithium disilicate crystal phases as a percentage of the weight of the glass-ceramic can be, for example, 60.00 wt%, 65.00 wt%, 68.00 wt%, 70.00 wt%, 75.00 wt%, 80.00 wt%, 85.00 wt%, 90.00 wt%, 93.00 wt%, 95.00 wt%, 98.00 wt%, or 100.00 wt%, or a crystallinity within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges, as long as the 3D curved microcrystalline glass with the performance required by this application can be obtained.

[0162] In some embodiments, in the 3D curved glass-ceramic, the lithium feldspar crystal phase accounts for 35.00 wt%-50.00 wt% of the mass of the transparent glass-ceramic, and the lithium disilicate crystal phase accounts for 35.00 wt%-50.00 wt% of the mass of the transparent glass-ceramic. In some embodiments, the percentage of the lithium disilicate crystal phase or the lithium feldspar crystal phase in the mass of the transparent glass-ceramic can be 35.00 wt%-50.00 wt%, 35.00 wt%-45.00 wt%, 35.00 wt%-40.00 wt%, or 40.00 wt%-50.00 wt%. In some embodiments, the glass-ceramic may contain 35.00 wt%, 40.00 wt%, 45.00 wt%, or 50.00 wt% of the lithium disilicate crystal phase or the lithium feldspar crystal phase, or the lithium disilicate crystal phase or the lithium feldspar crystal phase within the numerical range formed by any two of the above specific values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges, as long as the microcrystalline glass with the desired performance of this application can be obtained.

[0163] In some embodiments, the glass-ceramic contains one or more of the following as secondary crystalline phases: lithium silicate (Li₂SiO₃), lithium phosphate (Li₃PO₄), and spodumene. In some embodiments, the secondary crystalline phase accounts for less than 20.00 wt% of the transparent glass-ceramic mass. The low content of secondary crystalline phases in the glass-ceramic of this application is more conducive to ensuring a high content of the main crystalline phase, thereby ensuring the excellent mechanical strength properties of the glass-ceramic. In some embodiments, the lithium phosphate (Li₃PO₄) crystalline phase is usually accompanied by the growth of secondary phases such as lithium silicate (Li₂SiO₃), for example... Figure 5 As shown.

[0164] In some embodiments, in the transparent glass-ceramic, a lithium silicate phase accounts for less than 8.00 wt% of the mass of the transparent glass-ceramic, and the total amount of lithium phosphate phase and spodumene phase accounts for less than 8.00 wt% of the mass of the transparent glass-ceramic.

[0165] In some embodiments, the average crystal size in the 3D curved glass-ceramic does not exceed 100 nm, for example, it can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm, or the average crystal size within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as a transparent 3D curved glass-ceramic with the performance required by this application can be obtained.

[0166] In some embodiments, the crystallinity of the 3D curved glass-ceramic is ≥70.00 wt%, preferably ≥80.00 wt%, which is beneficial for improving the mechanical strength properties of the glass-ceramic. Here, "crystallization" refers to the percentage of the content of all crystalline phases / crystals in the 3D curved glass-ceramic by its mass, for example, it can be 70.00 wt%, 80.00 wt%, 85.00 wt%, 90.00 wt%, 93.00 wt%, 95.00 wt%, 98.00 wt%, or 100.00 wt%, or a crystallinity within a range defined by any two of the above specific values ​​as endpoints. It should be understood that in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved glass-ceramic with the desired properties of this application is obtained.

[0167] In some embodiments, when the thickness is 0.6 mm, the optical b-value of the 3D curved microcrystalline glass is ≤1.00, preferably ≤0.70, and more preferably ≤0.55. In some embodiments, the optical b-value of the 3D curved microcrystalline glass at this thickness can be 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, or 1.00, or a value within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass with the performance required by this application can be obtained.

[0168] Among them, the nine locations are as follows Figure 7 As shown, the test locations are: (1) four test circles (I) located near the four corners of the main surface; (2) four test circles (II) located at the points on the line segments formed by the centers of the four test circles (I) that are closest to the midpoint of the long or short side of the main surface; and (3) one test circle (III) located at the center point of the main surface. The diameter of the test circle depends on the size of the instrument's test window (which is a circle).

[0169] In some embodiments, when the thickness is 0.6 mm, the range of nine b-values ​​on the main surface of the 3D curved microcrystalline glass is ≤0.30, preferably ≤0.10, and more preferably ≤0.06. In some embodiments, the range of nine b-values ​​on the main surface of the 3D curved microcrystalline glass at this thickness can be 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.25, or 0.30, or a range within a numerical range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the 3D curved microcrystalline glass with the desired performance of this application can be obtained.

[0170] In some embodiments, when the thickness of the 3D curved glass-ceramic is 0.6 mm, the haze is ≤0.20%, and the transmittance of the glass-ceramic is ≥90.00% under 550 nm wavelength light. Here, the b-value refers to the b-value at any location of the glass-ceramic. In some embodiments, the transmittance of the 0.6 mm thick glass-ceramic under 550 nm wavelength light can be 90.00%, 90.50%, 91.00%, 92.00%, 93.00%, 94.00%, 95.00%, 96.00%, 97.00%, 98.00%, 99.00%, 100.00%, or a transmittance within a range defined by any two of the above specific values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the glass-ceramic with the performance required by this application can be obtained.

[0171] As described above, the range of b-values ​​at nine locations on the main surface of the 3D curved microcrystalline glass mass-produced in this application is small, meaning that the b-values ​​in different regions of the 3D curved microcrystalline glass are close. Moreover, the 3D curved microcrystalline glass of this application has high transmittance, low b-value, and low haze. This indicates that the 3D curved microcrystalline glass mass-produced in this application has superior optical performance and good display uniformity, which can meet the application requirements of display cover plates.

[0172] This application also provides a substrate glass that can be used to prepare the aforementioned 3D curved microcrystalline glass, wherein the composition of the substrate glass is the same as that of the aforementioned 3D curved microcrystalline glass, based on the molar percentage of oxides.

[0173] In some embodiments, during simultaneous thermal analysis testing, under a nitrogen protective atmosphere, the substrate glass is heated from room temperature to 900°C at a heating rate of 10°C / min to obtain a heating DSC curve. In this heating DSC curve, there are at least two exothermic peaks, where the first exothermic peak temperature T1 is 600°C-730°C and the second exothermic peak temperature T2 is 740°C-800°C. T1 and T2 satisfy the relationship: 100°C ≥ T2 - T1 ≥ 40°C, preferably 80°C ≥ T2 - T1 ≥ 50°C.

[0174] In some implementations, in T g Within the temperature range of -T2, the upper limit temperature T for the precipitation of a lithium silicate crystalline phase in the substrate glass was tested. max Upper limit temperature T for precipitation of quartz phase in (Li2SiO3) and substrate glass max (SiO2), T max (Li2SiO3)≥T max (SiO2), where T gT2 is the glass transition temperature of the substrate glass. Here, T2 is the temperature of the second exothermic peak in the above-mentioned heating DSC curve.

[0175] Large-size substrate glass bricks made using a specific substrate glass scheme that meets specific thermal properties can be heat-treated under the production line process conditions for mass production of 3D curved microcrystalline glass to obtain prefabricated microcrystalline glass bricks with uniform b-value distribution. Flat microcrystalline glass products made from slices of these prefabricated microcrystalline glass bricks can then be hot-bent to obtain 3D curved microcrystalline glass with better display effects. Furthermore, by ensuring that the upper limit temperature Tmax (SiO2) of the quartz crystal phase is lower than the upper limit temperature Tmax (Li2SiO3) of the lithium monosilicate crystal phase within a specific temperature range, it is possible to effectively avoid the precipitation of the quartz crystal phase under specific heat treatment process conditions used to prepare prefabricated microcrystalline glass with lithium feldspar and lithium disilicate as the main crystal phases. Combined with the subsequent hot bending process, the lithium monosilicate crystal phase can also be transformed into the desired lithium disilicate crystal phase, thereby avoiding the adverse effects of the quartz crystal phase and lithium monosilicate crystal phase on the optical effects of the microcrystalline glass.

[0176] Before preparing large-size prefabricated microcrystalline glass bricks, a small sample of the substrate glass can be made according to the glass formula. By obtaining the above-mentioned characteristics, it can be verified whether the glass scheme is suitable for mass production of qualified 3D curved microcrystalline glass products on the production line. If it does not meet the requirements, it can be adjusted in time, which can greatly save time and cost and effectively avoid waste of resources.

[0177] In some embodiments, the composition of the 3D curved glass-ceramic or the substrate glass used to prepare the 3D curved glass-ceramic, based on the molar percentage of oxides, includes:

[0178] SiO2: 67.50 mol% - 71.00 mol%, Al2O3: 3.50 mol% - 5.00 mol%, P2O5: not less than 0.85 mol% and less than 1.50 mol%, ZrO2: 2.50 mol% - 3.50 mol%, Na2O: greater than 0.00 mol% and not greater than 1.00 mol%, K2O: greater than 0.00 mol% and not greater than 0.50 mol%, Li2O: 20.00 mol% - 25.00 mol%, CaO: greater than 0.50 mol% and not greater than 1.50 mol%, B2O3: 0.00 mol% - 1.00 mol%.

[0179] The composition of the 3D curved microcrystalline glass or the substrate glass used to prepare the 3D curved microcrystalline glass, expressed as the molar percentage of each oxide in the composition, satisfies the following:

[0180] 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250;

[0181] 18.200≤Li2O / P2O5≤25.500;

[0182] 0.190≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200;

[0183] 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000;

[0184] 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000;

[0185] 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000;

[0186] 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000.

[0187] This application also provides a method for preparing 3D curved surface microcrystalline glass, which includes the following steps:

[0188] (1) The aforementioned substrate glass is heat-treated to obtain a pre-made microcrystalline glass product containing lithium monosilicate crystal phase, lithium disilicate crystal phase and lithium feldspar crystal phase, and with a crystallinity of not less than 60.00 wt%.

[0189] (2) The prefabricated microcrystalline glass product obtained in step (1) is processed into a planar microcrystalline glass sheet of the required size and specifications, and the obtained planar microcrystalline glass sheet is subjected to hot bending treatment to obtain 3D curved microcrystalline glass. The 3D curved microcrystalline glass contains lithium feldspar crystal phase and lithium disilicate crystal phase, and the lithium feldspar crystal phase and lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the microcrystalline glass.

[0190] In some embodiments, the process of preparing 3D curved microcrystalline glass according to this application may also include a conventional cold working process on the pre-fabricated microcrystalline glass product (such as a brick) obtained by heat treatment of the substrate glass to obtain a planar microcrystalline glass with the required dimensions (e.g., a thickness of 0.2 mm to 2.0 mm), and then performing the aforementioned step (2) hot bending process. The cold working processes here include commonly used shaping processes, slicing processes, CNC machining processes, grinding processes, polishing processes, etc., according to the art. Those skilled in the art can select one or more of the above methods to perform cold working processes on the microcrystalline glass according to actual needs.

[0191] In this application, the hot bending process may be accompanied by further crystallization of the pre-made microcrystalline glass product, resulting in the crystallinity of the final 3D curved microcrystalline glass being no less than that of the pre-made microcrystalline glass product.

[0192] In this application, the crystallinity of the pre-fabricated microcrystalline glass product obtained by heat treatment of the substrate glass is 60wt%-90wt%, preferably 65wt%-90wt%; the crystallinity of the 3D curved microcrystalline glass obtained by hot bending of the pre-fabricated microcrystalline glass product is 70wt%-99wt%, preferably 80wt%-99wt%.

[0193] In this application, the heat treatment conditions in step (1) above have a wide range of selectable options, and those skilled in the art can select from existing technologies according to actual needs. In some embodiments, in step (1), the heat treatment includes nucleation treatment and crystallization treatment, wherein the temperature of nucleation treatment is (Tg-20℃) to (Tg+40℃), the time of nucleation treatment is 0min-6000min, the temperature of crystallization treatment is (T1-50℃) to T1, and the time of crystallization treatment is 30min-6000min; Tg is the glass transition temperature of the substrate glass, and T1 is the first exothermic peak temperature in the DSC curve of the substrate glass; in step (1), the heating rate of the heat treatment process is 5℃ / min-15℃ / min. It should be understood that in this application, the nucleation treatment is heating to the specified nucleation treatment temperature (also called nucleation temperature), and after reaching the nucleation treatment temperature, holding it at that temperature for a certain time, which is the nucleation treatment time (also called nucleation time). The crystallization process involves heating to a predetermined crystallization temperature (also known as the crystallization temperature) and holding the temperature for a certain period of time, which is the crystallization time. Using these heat treatment conditions facilitates the production of pre-fabricated 3D curved glass-ceramics with specific and uniform microstructures. These pre-fabricated glass-ceramics can be heat-bent to produce glass-ceramics with excellent optical and mechanical properties, primarily composed of lithium feldspar and lithium disilicate crystal phases.

[0194] In some embodiments, step (1) includes nucleation and crystallization treatments. The nucleation temperature is between (Tg-20℃) and (Tg+40℃), for example, it can be (Tg-20℃), (Tg-15℃), (Tg-10℃), (Tg-5℃), (Tg-2℃), Tg, (Tg+2℃), (Tg+5℃), (Tg+10℃), (Tg+15℃), or (Tg+40℃), or any value between these adjacent points. Here, Tg is the glass transition temperature of the substrate glass.

[0195] In some implementations, the nucleation process in step (1) takes 30 min to 360 min, for example, 30 min, 50 min, 70 min, 100 min, 130 min, 150 min, 180 min, 200 min, 250 min, 280 min, 300 min, 330 min, 360 min, 600 min, 1000 min, 2000 min, 3000 min, 4000 min, 5000 min, or 6000 min, or any value between these adjacent values.

[0196] In some embodiments, in step (1), the temperature of the crystallization treatment is ((T1-50℃) to T1, for example, (T1-50℃), (T1-45℃), (T1-40℃), (T1-35℃), (T1-30℃), (T1-25℃), (T1-20℃), (T1-15℃), (T1-10℃), (T1-5℃) or T1, or any value between these adjacent point values.

[0197] In some implementations, the crystallization time in step (1) is 30 min to 600 min, for example, it can be 30 min, 50 min, 70 min, 100 min, 130 min, 150 min, 180 min, 200 min, 250 min, 280 min, 300 min, 330 min, 360 min, 400 min, 450 min, 500 min, 550 min, 600 min, 1000 min, 2000 min, 3000 min, 4000 min, 5000 min or 6000 min, or any value between these adjacent point values.

[0198] In some embodiments, in step (1), the heating rate of the heat treatment process is 5°C / min to 15°C / min, for example, it can be 5°C / min, 8°C / min, 10°C / min, 12°C / min, 14°C / min, or 15°C / min, or any value between these adjacent points. Here, "heating rate" includes the heating rate of the entire heat treatment process, that is, it includes the heating rate of the nucleation process and the heating rate of the crystallization process.

[0199] In some embodiments, in step (2) above, the hot bending process includes at least three preheating stations, at least three hot pressing stations, and at least three cooling stations; the temperature of the preheating stations is 500℃-850℃, the temperature of the hot pressing stations is 700℃-900℃, the pressure of the hot pressing stations is 0MPa-1MPa, and the temperature of the cooling stations is 500℃-800℃. The conditions (such as temperature and pressure) of each preheating station, each hot pressing station, or each cooling station described in this application may be the same or different; for example, the temperatures of each preheating station may be the same or different.

[0200] In some implementations, the temperature of the preheating station is 500°C-850°C, for example, it can be 500°C, 600°C, 700°C, 800°C or 850°C, or any value between these adjacent points.

[0201] In some embodiments, the temperature of the hot press station is 700°C-900°C, for example, it can be 700°C, 750°C, 800°C, 850°C or 900°C, or any value between these adjacent points.

[0202] In some embodiments, the pressure of the hot press station is 0MPa-1MPa, for example, it can be 0MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa or 1MPa, or any value between these adjacent points.

[0203] In some embodiments, the temperature of the cooling station is 500°C-800°C, for example, it can be 500°C, 600°C, 700°C, 800°C or 850°C, or any value between these adjacent points.

[0204] In some embodiments, the operating time of the preheating station is 90s-360s, the operating time of the hot pressing station is 90s-360s, and the operating time of the cooling station is 90s-360s. The operating time of each station is 90s-360s, and can be, for example, 90s, 100s, 110s, 150s, 200s, 250s, 300s, 350s, or 360s, or any value between these adjacent values.

[0205] This application also provides a chemically strengthened glass crystal, wherein the composition at the center of the chemically strengthened glass crystal is substantially the same as that of the 3D curved glass crystal, the chemically strengthened glass crystal includes a compressive stress layer region extending from the surface of the chemically strengthened glass crystal to the compression depth, and has tensile stress inside the chemically strengthened glass crystal.

[0206] It should be understood that the composition of the glass-ceramic surface after chemical strengthening may differ from that of freshly formed glass-ceramics (i.e., glass-ceramics that have not undergone ion exchange before chemical strengthening). This is because ion exchange occurs on the surface of the glass-ceramic during chemical strengthening, and a certain type of alkali metal ion (e.g., Li) in the freshly formed glass-ceramic changes. + Or Na + ) are respectively subjected to larger alkali metal ions (e.g., Na) + or K + Replaced by, for example, Na in glass-ceramics + With K in molten salt bath + To exchange, K + The Li replaced, and / or, in the glass-ceramic + Na in molten salt bath + To exchange, by Na + Instead. However, in embodiments, the composition of the glass-ceramic at or near the center of the depth of the glass article will still have the composition of the newly formed glass-ceramic. That is, in the chemically strengthened glass-ceramic of this application, the composition of the compressive stress layer formed on the surface by ion exchange may be different from the composition of the unstrengthened 3D curved glass-ceramic, while the composition at the center of the chemically strengthened glass-ceramic with internal tensile stress (also known as tensile stress) will still have the composition of the unstrengthened glass-ceramic.

[0207] In this application, the conditions for chemical strengthening treatment used in the preparation of chemically strengthened 3D curved glass-ceramics have a wide range of selectable options, which can be chosen by those skilled in the art according to actual needs. For example, in some embodiments, the salt bath for chemical strengthening treatment is a mixed molten salt, the composition of which includes: 0 < NaNO3 < 100 wt%, 0 < KNO3 < 100 wt%, and 0 < LiNO3 ≤ 0.2 wt%. In some embodiments, the temperature of the salt bath for chemical strengthening treatment is 430℃-530℃, and the chemical strengthening treatment time is 0.5 h-15.0 h.

[0208] In some embodiments, the chemically strengthened glass-ceramic has a CS_50 of 110-200 MPa, where CS_50 refers to the compressive stress value at a depth of 50 μm measured from the main surface of the chemically strengthened glass-ceramic. The fact that the CS_50 of the chemically strengthened glass-ceramic falls within this range indicates a high compressive stress at a depth of 50 μm from the surface, suggesting a higher level of surface stress. A higher level of surface compressive stress can offset more residual energy from drop impacts, thus ensuring excellent damage resistance.

[0209] In some embodiments, the compressive stress layer depth DOL_0 of the chemically strengthened glass-ceramic is 0.18t-0.25t, where t is the thickness of the chemically strengthened glass-ceramic. The fact that the DOL_0 of the chemically strengthened glass-ceramic is within this range indicates that it has a high compressive stress layer depth, which is more conducive to offsetting the energy driving crack propagation, thereby ensuring its excellent damage resistance.

[0210] In some embodiments, the chemically strengthened glass-ceramic has a |CT_AV| of 84-140 MPa, where |CT_AV| refers to the absolute value of the average tensile stress. For example, the chemically strengthened glass-ceramic has a |CT_AV| of 84-140 MPa, 85-140 MPa, 85-120 MPa, 85-100 MPa, 90-140 MPa, 100-140 MPa, or 120-140 MPa. The fact that the |CT_AV| of the chemically strengthened glass-ceramic falls within these ranges indicates that the glass-ceramic has a high level of tensile stress, reflecting a high level of surface stress. A higher level of surface compressive stress can offset more residual energy from drop impacts, thus ensuring excellent damage resistance.

[0211] By meeting specific stress characteristics, chemically strengthened glass-ceramics can be ensured to have excellent mechanical strength properties, especially excellent drop resistance.

[0212] In some embodiments, the chemically strengthened microcrystalline glass with a thickness of 0.6 mm is subjected to multiple drop tests from a fixed height of 1.0 m using 120-grit sandpaper. The chemically strengthened microcrystalline glass breaks after being dropped ≥30 times, preferably ≥50 times. This indicates that the chemically strengthened microcrystalline glass of this application has excellent drop resistance.

[0213] In some embodiments, the surface Na2O concentration of the chemically strengthened glass-ceramic is 5.0 wt% to 20.0 wt%. For example, the surface Na2O concentration of the chemically strengthened glass-ceramic can be 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10.0 wt%, 11.0 wt%, 12.0 wt%, 13.0 wt%, 14.0 wt%, 15.0 wt%, 16.0 wt%, 17.0 wt%, 18.0 wt%, 19.0 wt%, or 20.0 wt%, or a value within a range defined by any two of the above specific values ​​as endpoints. By satisfying the above range of surface Na2O concentration, not only can the chemically strengthened glass-ceramic have a superior surface stress level, but it can also ensure that the chemically strengthened glass-ceramic has good weather resistance and chemical durability.

[0214] The 3D curved surface microcrystalline glass or chemically strengthened microcrystalline glass with excellent optical and mechanical properties provided in this application can be used in any desired microcrystalline glass device and can be used in many applications.

[0215] This application also provides a glass device, wherein the glass device comprises the 3D curved microcrystalline glass or the chemically strengthened microcrystalline glass.

[0216] This application also provides an electronic device, wherein the electronic device comprises the 3D curved microcrystalline glass or comprises the chemically strengthened microcrystalline glass.

[0217] The embodiments of this application are described in detail below. They are exemplary and are only used to explain this application, and should not be construed as limiting this application. In the example numbers in the following tables, S refers to an embodiment, such as S1 referring to embodiment 1; D refers to a comparative example, such as D1 referring to comparative example 1.

[0218] Example 1

[0219] (1) Preparation of substrate glass: The raw materials were prepared according to the proportions of each oxide in S1 of Table 1, and the substrate glass was produced by continuous melting method to obtain substrate glass (brick) with a forming size of 360mm (length) × 180mm (width) × 30mm (thickness). Table 2 shows the calculation results of the content relationship of each oxide in Table 1.

[0220] The following are the test results for the substrate glass obtained from S1:

[0221] I. Through observation, the substrate glass prepared in S1 is clear and transparent overall.

[0222] II. Measure the Tg of the substrate glass in S1 and the heating DSC curve. Record the first exothermic peak temperature T1, the second exothermic peak temperature T2, and their difference in the heating DSC curve, as shown in Table 3. Figure 1 As shown, no exothermic or endothermic peaks were observed under the temperature conditions not covered.

[0223] III. In T g Within the temperature range of -T2, the upper limit temperature T for the precipitation of lithium silicate crystalline phase in the substrate glass obtained by testing. max Upper limit temperature T for precipitation of quartz phase in (Li2SiO3) and substrate glass max (SiO2), T max (Li2SiO3), T max (SiO2) are shown in Table 3, where T g This refers to the glass transition temperature of the substrate glass.

[0224] (2) Preparation of pre-fabricated microcrystalline glass: Pre-fabricated microcrystalline glass bricks are produced by heat treatment of the substrate glass using a heat treatment roller kiln line. The heat treatment process is shown in Table 4, which includes nucleation and crystallization treatments performed sequentially (denoted as heat treatment process C). The heating rate during the heat treatment process is 10℃ / min. Pre-fabricated microcrystalline glass bricks are obtained after exiting the furnace.

[0225] The following tests were conducted on the precast microcrystalline glass bricks obtained from S1:

[0226] I. Through observation, the microcrystalline glass bricks prepared in S1 are clear and transparent as a whole.

[0227] II. The crystal phase composition, crystal phase content and crystallinity of the prefabricated microcrystalline glass were tested, and the results are shown in Table 4.

[0228] III. The range of b-values ​​at nine locations on the main surface of a prefabricated microcrystalline glass with dimensions of 360mm (length) × 180mm (width) × 30mm (thickness) was tested. The results are shown in Table 4.

[0229] (3) Cold processing of prefabricated microcrystalline glass bricks: The prefabricated microcrystalline glass bricks are subjected to cold processing, which includes shaping, slicing, CNC processing, grinding and polishing in sequence to obtain a planar microcrystalline glass sheet with dimensions of 170mm (length) × 80mm (width) × 0.6mm (thickness). The range of nine b values ​​and the average value of nine b values ​​on the main surface of the obtained planar microcrystalline glass sheet are tested. The results are shown in Table 4.

[0230] (4) Preparation of 3D curved microcrystalline glass: The obtained planar microcrystalline glass sheet is placed on a 3D hot bending machine for hot bending treatment to form 3D curved microcrystalline glass. The hot bending machine used in this process is divided into three temperature zones: a preheating zone, a hot pressing zone, and a slow cooling zone. The hot bending process (denoted as hot bending process C1) includes 3 preheating stations, 3 hot pressing stations, and 3 cooling stations. The temperatures of the 3 preheating stations are 590℃, 680℃, and 790℃, respectively. The temperatures and pressures of the 3 hot pressing stations are 790℃ / 0.4MPa, 790℃ / 0.4MPa, and 790℃ / 0.2MPa, respectively. The temperatures of the 3 cooling stations are 790℃, 650℃, and 600℃, respectively. The dwell time of each station is 90s.

[0231] The following are the test results of the 3D curved glass-ceramic obtained by S1:

[0232] I. The optical properties of the 3D curved microcrystalline glass were tested, including the range and average of the b-values ​​at nine locations on the main surface of the 3D curved microcrystalline glass sample. The test results are shown in Table 4.

[0233] II. The crystal phase composition of the 3D curved glass-ceramic was tested, and the results are shown in Table 4. The average crystal size in the 3D curved glass-ceramic was calculated to be 19 nm.

[0234] III. The XRD diffraction curves of the 3D curved microcrystalline glass slide at the locations of maximum and minimum b-values ​​were tested at nine different b-value locations. The comparison results are as follows: Figure 10 As shown. From Figure 10 It can be seen that the crystal phase structure at the position with the maximum b-value and the position with the minimum b-value on the main surface of the microcrystalline glass sheet is basically the same or very similar. This indicates that the 3D curved microcrystalline glass sheet is relatively uniform overall and the optical display effect tends to be consistent.

[0235] IV. Test the transmittance of the 3D curved microcrystalline glass, such as... Figure 13 As shown, the 3D curved microcrystalline glass of this application has high transmittance and excellent light transmission in the visible light band.

[0236] (5) Preparation of chemically strengthened glass-ceramics: The 3D curved glass-ceramics with dimensions of 170mm (length) × 80mm (width) × 0.6mm (thickness) obtained in step (4) were placed in a mixed nitrate salt bath at 470℃ containing 70.00wt% KNO3 + 30.00wt% NaNO3 + 0.03wt% LiNO3 (here, the mixed molten salt contains 0.03wt% LiNO3 based on the total amount of NaNO3 and KNO3 in the mixed molten salt) for 7.0h to obtain chemically strengthened glass-ceramics with t = 0.6mm.

[0237] Testing of the chemically strengthened glass-ceramic obtained from S1: The CS_50, |CT_AV|, and DOL_0 of the chemically strengthened glass-ceramic were tested using a stress tester. The chemically strengthened glass-ceramic underwent a drop test at a fixed height of 1.0m using 120-grit sandpaper; the test data are shown in Table 5.

[0238] Examples 2 to 13

[0239] Each of these examples was carried out in accordance with Example 1. The hot bending process was the same as in Example 1. The difference was that the raw material composition and the corresponding test results of each example were shown in Tables 1-5.

[0240] The 3D curved glass-ceramics of Examples 2 to 13 all meet the following requirements: They are generally clear and transparent in appearance; the main crystalline phases of the 3D curved glass-ceramics are Li₂Si₂O₅ and LiAlSi₄O₅. 10 There is no quartz crystal phase. Calculations show that the average crystal size in the 3D curved glass-ceramics of Examples 2 to 13 is 10-50 nm.

[0241] The XRD diffraction pattern of the substrate glass in Example 2 after heat treatment process C before hot bending is shown in the figure. Figure 8 As shown. The DSC curve of the substrate glass in Example 10, measured at temperature, is shown below. Figure 2 As shown.

[0242] Comparative Examples 1-13

[0243] The procedures were carried out in accordance with Example 1, and the hot bending process was the same as in Example 1. The difference was that the raw material composition and the corresponding test results of each comparative example were shown in Tables 6 to 11.

[0244] Among them, the heating DSC curve of Comparative Example 1 is as follows: Figure 3 As shown. The heating DSC curve for Comparative Example 2 is shown below. Figure 4 As shown, the XRD diffraction pattern of the substrate glass in Comparative Example 2 after heat treatment process C is as follows. Figure 9 As shown. The XRD diffraction curves of the microcrystalline glass slide in Comparative Example 6 at the locations of maximum and minimum b-values ​​in nine b-value tests are compared as follows: Figure 11 As shown in the figure, there is a significant difference in the crystal structure between the locations with the maximum and minimum b-values ​​on the main surface of the 3D curved microcrystalline glass sheet. This indicates that the microstructure of different regions of the 3D curved microcrystalline glass sheet is inconsistent, which leads to differences in its overall display effect, resulting in localized color rendering and / or uneven overall color rendering on the main surface. The pre-fabricated microcrystalline glass in Comparative Example 7 cracked during the 3D hot bending process, such as... Figure 12 As shown.

[0245] Calculations show that the average crystal size in the 3D curved glass-ceramics of Comparative Examples 1-12 is greater than 20 nm.

[0246] Table 1

[0247] Composition (mol%) <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[P2O5]]> <![CDATA[ZrO2]]> <![CDATA[Na2O]]> <![CDATA[K2O]]> <![CDATA[Li2O]]> CaO <![CDATA[B2O3]]> S1 68.48 4.26 0.95 2.66 0.84 0.08 21.53 0.85 0.35 S2 70.35 4.17 1.02 2.67 0.33 0.05 20.28 0.84 0.29 S3 68.01 4.03 1.00 2.58 0.29 0.08 23.10 0.77 0.14 S4 69.20 4.15 1.15 2.50 0.30 0.09 21.60 0.82 0.19 S5 69.08 4.08 1.00 2.60 0.68 0.10 21.35 0.80 0.31 S6 68.86 4.05 1.03 2.65 0.28 0.09 21.35 0.80 0.89 S7 69.35 3.72 1.01 2.67 0.25 0.10 21.81 0.80 0.29 S8 69.20 4.05 1.05 2.85 0.15 0.10 21.53 0.77 0.30 S9 69.50 4.11 1.02 2.64 0.00 0.08 21.55 0.79 0.31 S10 69.05 4.08 0.89 2.65 0.29 0.08 21.89 0.79 0.28 S11 68.86 4.08 1.01 2.82 0.03 0.08 22.22 0.87 0.03 S12 69.19 4.09 1.01 2.61 0.29 0.11 21.45 0.96 0.29 S13 68.80 4.05 1.00 2.60 0.32 0.10 21.34 1.50 0.29

[0248] Table 2

[0249]

[0250] Table 3

[0251]

[0252]

[0253] Note: In Table 3, " / " indicates that the SiO2 crystalline phase does not appear, so there is no quartz disappearance temperature; the same interpretation applies to the comparative examples in the corresponding table.

[0254]

[0255]

[0256]

[0257] Table 6

[0258] Composition (mol%) <![CDATA[SiO2]]> <![CDATA[Al2O3]]> <![CDATA[P2O5]]> <![CDATA[ZrO2]]> <![CDATA[Na2O]]> <![CDATA[K2O]]> <![CDATA[Li2O]]> CaO <![CDATA[B2O3 <!-- 27 -->]]> D1 71.46 4.24 1.05 2.72 0.30 0.08 19.03 0.82 0.30 D2 66.73 3.80 0.92 2.50 0.20 0.08 25.00 0.77 0.00 D3 69.43 4.13 0.80 2.64 0.29 0.08 21.53 0.80 0.30 D4 68.94 4.09 1.80 2.62 0.29 0.08 21.09 0.79 0.30 D5 68.43 4.06 1.00 2.60 0.29 0.08 21.22 0.78 1.54 D6 68.66 4.07 1.01 3.60 0.20 0.08 21.29 0.79 0.30 D7 69.77 4.22 1.24 2.71 0.32 0.08 20.47 0.83 0.36 D8 68.65 4.07 1.01 2.61 0.29 0.99 21.29 0.79 0.30 D9 68.90 4.15 1.00 2.60 0.25 0.10 21.00 1.80 0.20 D10 68.76 4.06 2.00 2.58 0.29 0.08 21.19 0.78 0.26 D11 70.10 4.27 0.83 1.75 1.48 0.00 21.42 0.00 0.15 D12 71.00 4.00 1.00 2.00 0.00 0.00 22.00 0.00 0.00 D13 69.11 5.00 1.00 2.45 0.29 0.08 21.17 0.60 0.30

[0259] Table 7

[0260]

[0261]

[0262] Table 8

[0263]

[0264] Table 9

[0265]

[0266]

[0267] Table 10

[0268]

[0269]

[0270] Table 11

[0271]

[0272] As can be seen from the examples in Tables 1-5 and the comparative examples in Tables 6-11 above, compared with the comparative examples, the embodiments of this application, while satisfying the range of oxide content, also satisfy the following: 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250, 18.200≤Li2O / P2O5≤25.500, 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200, 1.500 The large-size substrate glass bricks prepared with the compositional characteristics of ≤10×(ZrO2+P2O5) / Li2O≤2.000, 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000, 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000, and 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000 exhibit a clear and transparent appearance, and T max (Li2SiO3)≥Tmax (SiO2) facilitates the 3D curved surface microcrystalline glass with good and uniform optical properties. The heating DSC curve of the substrate glass tested by synchronous thermal analysis shows at least two exothermic peaks at a suitable temperature.

[0273] The pre-fabricated microcrystalline glass bricks obtained by heat treatment of the large-size substrate glass bricks prepared using the embodiments of this application are all transparent and clear in appearance. The b-value differences in different regions of the main surface of the pre-fabricated microcrystalline glass bricks are small, and the uniformity is good. Moreover, the pre-fabricated microcrystalline glass does not contain any quartz crystal phase. In the 3D curved microcrystalline glass prepared by hot bending treatment using the pre-fabricated microcrystalline glass, the range of b-values ​​at nine locations on the main surface is low, and the average b-value is also low. This indicates that the 3D curved microcrystalline glass has excellent optical properties and good display effects. At the same time, chemical strengthening of the prepared 3D curved microcrystalline glass can obtain chemically strengthened microcrystalline glass with high CS_50, |CT_AV|, and DOL_0.

[0274] In Comparative Examples 1-8 and Comparative Example 12, the formulations of the substrate glass do not simultaneously satisfy the following: the content ranges of each oxide in this application, and 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250, 18.200≤Li2O / P2O5≤25.500, 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200, 1 The following parameters are used to prepare large-size prefabricated microcrystalline glass bricks: 0.500≤10×(ZrO2+P2O5) / Li2O≤2.000, 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.000, 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000, and 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000. When these methods are used to prepare large-size substrate glass bricks for heat treatment to produce large-size prefabricated microcrystalline glass bricks, the b-values ​​of different regions on the main surface of the prefabricated microcrystalline glass bricks vary significantly. This large difference continues in the 3D curved microcrystalline glass obtained by hot bending, resulting in poor optical performance. Consequently, the display effect of the 3D curved microcrystalline glass does not meet the requirements for use, and cracking may even occur.

[0275] In Comparative Examples 9 and 10, after preparing large-size substrate glass bricks, milky white precipitates appeared directly in the substrate glass bricks, resulting in deteriorated optical properties and reduced transmittance. In Comparative Examples 11 and 12, the mass-produced microcrystalline glass, after chemical strengthening treatment, failed to achieve the desired superior mechanical properties, and its drop resistance was significantly worse than the product of this application. In Comparative Example 13, milky white precipitates and undissolved matter appeared in the prepared large-size substrate glass bricks.

[0276] The preferred embodiments of this application have been described in detail above; however, this application is not limited thereto. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in this application and are all within the protection scope of this application.

Claims

1. A chemically strengthened microcrystalline glass, characterized in that, It includes a first region, which contains a tensile stress layer region, the composition of which includes: Based on the molar percentage of oxides, SiO2: 60.00 mol% - 71.00 mol%, Al2O3: 1.50 mol% - 5.00 mol%, P2O5: 0.80 mol% - 1.50 mol%, ZrO2: 2.00 mol% - 4.00 mol%, Na2O: 0.00 mol% - 1.00 mol%, K2O: 0.00 mol% - 0.50 mol%, Li2O: 20.00 mol% - 30.00 mol%, CaO: 0.00 mol% - 1.60 mol%, B2O3: 0.00 mol% - 1.00 mol%. Furthermore, based on the molar percentage of each oxide, the composition of the tensile stress layer region satisfies: 18.200≤Li2O / P2O5≤25.500; 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000; 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000; 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.000; The chemically strengthened glass-ceramic further includes a compressive stress layer region extending from the surface of the chemically strengthened glass-ceramic to the compression depth, wherein the compressive stress layer depth DOL_0 of the chemically strengthened glass-ceramic is 0.18t-0.25t, where t is the thickness of the chemically strengthened glass-ceramic. The chemically strengthened glass-ceramic has a CS_50 of 110-200 MPa, where CS_50 refers to the compressive stress value at a depth of 50 μm measured from the main surface of the chemically strengthened glass-ceramic.

2. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The composition of the tensile stress layer region, based on the molar percentage of oxides, includes: SiO2: 67.50 mol% - 71.00 mol% Al2O3: 3.50 mol% - 5.00 mol%. P2O5: not less than 0.85 mol% and less than 1.50 mol%. ZrO2: 2.50 mol% - 3.50 mol% Na₂O: greater than 0.00 mol% and not greater than 1.00 mol%. K2O: greater than 0.00 mol% and not greater than 0.50 mol%. Li₂O: 20.00 mol% - 25.00 mol% CaO: greater than 0.50 mol% and not greater than 1.50 mol%. B2O3: 0.00 mol% - 1.00 mol%.

3. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 60.90 mol%-70.00 mol% SiO2; Composition 2: The tensile stress layer region contains 3.00 mol%-5.00 mol% Al2O3; Component 3: The tensile stress layer region contains 22.00 mol%-28.00 mol% of Li₂O; Composition 4: The tensile stress layer region contains 0.80 mol%-1.30 mol% of P2O5; Component 5: The tensile stress layer region contains 2.50 mol%-3.50 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.10 mol%-0.90 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.20 mol%-0.90 mol% Na2O; Component 8: The tensile stress layer region contains 0.10 mol%-0.40 mol% K2O; Component Nine: The tensile stress layer region contains 0.50 mol%-1.60 mol% CaO.

4. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 60.90 mol%-69.00 mol% SiO2; Composition 2: The tensile stress layer region contains 3.00 mol%-4.00 mol% Al2O3; Component 3: The tensile stress layer region contains 24.00 mol%-26.00 mol% of Li₂O; Composition 4: The tensile stress layer region contains 1.30 mol%-1.50 mol% of P2O5; Component 5: The tensile stress layer region contains 2.70 mol%-3.30 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.30 mol%-0.80 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.40 mol%-0.80 mol% Na2O; composition 8. The tensile stress layer region contains 0.20 mol%-0.30 mol% K2O; Component Nine: The tensile stress layer region contains 0.60 mol%-1.50 mol% CaO.

5. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 60.90 mol%-68.00 mol% SiO2; Composition 2: The tensile stress layer region contains 3.00 mol%-4.50 mol% of Al2O3; Component 3: The tensile stress layer region contains 20.00 mol%-24.00 mol% of Li₂O; Composition 4: The tensile stress layer region contains 0.80 mol%-1.00 mol% of P2O5; Component 5: The tensile stress layer region contains 2.90 mol%-3.10 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.50 mol%-0.70 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.00 mol%-0.40 mol% Na2O; Composition 8: The tensile stress layer region contains 0.00 mol%-0.20 mol% K2O; Component Nine: The tensile stress layer region contains 0.80 mol%-1.30 mol% CaO.

6. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 62.00 mol%-65.00 mol% SiO2; Composition 2: The tensile stress layer region contains 3.50 mol%-4.50 mol% of Al2O3; Component 3: The tensile stress layer region contains 24.00 mol%-30.00 mol% Li2O; Composition 4: The tensile stress layer region contains 1.00 mol%-1.30 mol% of P2O5; Component 5: The tensile stress layer region contains 2.50 mol%-3.00 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.00 mol%-0.60 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.00 mol%-0.50 mol% Na2O; Composition 8: The tensile stress layer region contains 0.30 mol%-0.50 mol% K2O; Component Nine: The tensile stress layer region contains 1.00 mol%-1.20 mol% CaO.

7. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 63.00 mol%-70.00 mol% SiO2; Composition 2: The tensile stress layer region contains 4.50 mol%-5.00 mol% of Al2O3; Component 3: The tensile stress layer region contains 20.00 mol%-22.00 mol% of Li₂O; Composition 4: The tensile stress layer region contains 1.10 mol%-1.50 mol% of P2O5; Component 5: The tensile stress layer region contains 2.50 mol%-2.80 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.00 mol%-0.50 mol% of B2O3; Component 8: The tensile stress layer region contains 0.10 mol%-0.20 mol% K2O; Component Nine: The tensile stress layer region contains 0.50 mol%-1.00 mol% CaO.

8. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 64.00 mol%-68.00 mol% SiO2; Component 3: The tensile stress layer region contains 28.00 mol%-30.00 mol% Li₂O; Component 5: The tensile stress layer region contains 2.80 mol%-3.50 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.60 mol%-1.00 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.40 mol%-1.00 mol% Na2O; Composition 8: The tensile stress layer region contains 0.20 mol%-0.40 mol% K2O; Component Nine: The tensile stress layer region contains 0.50 mol%-0.85 mol% CaO.

9. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 65.00 mol%-67.00 mol% SiO2; Component 3: The tensile stress layer region contains 21.00 mol%-28.00 mol% of Li₂O; Component 5: The tensile stress layer region contains 2.80 mol%-3.40 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.50 mol%-1.00 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.30 mol%-0.50 mol% Na2O; Composition 9: The tensile stress layer region contains 0.85 mol%-1.40 mol% CaO.

10. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 67.50 mol%-71.00 mol% SiO2; Component 5: The tensile stress layer region contains 2.80 mol%-3.30 mol% ZrO2; Composition 6: The tensile stress layer region contains 0.30 mol%-0.50 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.40 mol%-0.60 mol% Na2O; Composition 9: The tensile stress layer region contains 1.40 mol%-1.60 mol% CaO.

11. The chemically strengthened glass-ceramic according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Component 5: The tensile stress layer region contains 2.80 mol%-3.10 mol% ZrO2; Composition 9: The tensile stress layer region contains 0.85 mol%-1.20 mol% CaO.

12. The chemically strengthened glass-ceramic according to claim 1, characterized in that, The tensile stress layer region satisfies the following composition: based on the molar percentage of oxides, Composition 9: The tensile stress layer region contains 0.85 mol%-1.00 mol% CaO.

13. The chemically strengthened glass-ceramic according to claim 1, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: based on the molar percentage of oxides, Composition 1: The tensile stress layer region contains 60.00 mol%, 61.00 mol%, 62.00 mol%, 63.00 mol%, 64.00 mol%, 65.00 mol%, 66.00 mol%, 67.00 mol%, 67.50 mol%, 68.00 mol%, 69.00 mol%, 70.00 mol%, or 71.00 mol% of SiO2; Composition 2: The tensile stress layer region contains 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.20 mol%, 3.80 mol%, 4.00 mol%, 4.40 mol%, 4.80 mol%, or 5.00 mol% of Al2O3; Composition 3: The tensile stress layer region contains 20.50 mol%, 21.50 mol%, 22.50 mol%, 23.50 mol%, 24.50 mol%, 25.50 mol%, 26.50 mol%, 27.50 mol%, 28.50 mol%, 29.50 mol%, or 30.00 mol% of Li₂O; Composition 4: The tensile stress layer region contains 0.85 mol%, 0.95 mol%, 1.00 mol%, 1.10 mol%, 1.20 mol%, 1.35 mol%, 1.40 mol%, or 1.50 mol% of P2O5; Composition 5: The tensile stress layer region contains 2.00 mol%, 2.50 mol%, 2.75 mol%, 2.95 mol%, 3.15 mol%, 3.25 mol%, 3.35 mol%, 3.50 mol%, or 4.00 mol% of ZrO2; Composition 6: The tensile stress layer region contains 0.00 mol%, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol%, 0.55 mol%, 0.75 mol%, 0.95 mol%, or 1.00 mol% of B2O3; Composition 7: The tensile stress layer region contains 0.00 mol%, 0.15 mol%, 0.35 mol%, 0.55 mol%, 0.75 mol%, 0.95 mol%, or 1.00 mol% Na2O; Composition 8: The tensile stress layer region contains 0.00 mol%, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol%, or 0.50 mol% K2O; Composition 9: The tensile stress layer region contains 0.00 mol%, 0.50 mol%, 0.70 mol%, 0.85 mol%, 1.10 mol%, 1.25 mol%, 1.35 mol%, 1.45 mol%, or 1.60 mol% of CaO.

14. The chemically strengthened glass-ceramic according to claim 1, characterized in that, The composition of the tensile stress layer region, expressed as a molar percentage of each oxide, satisfies the following: The Li2O / P2O5 value is 18.200, 18.500, 19.000, 19.500, 20.000, 20.500, 21.000, 21.500, 22.000, 22.500, 23.000, 23.500, 24.000, 24.500, 25.000, or 25.500; and / or, The value of 10×(ZrO2+P2O5) / Li2O is 1.500, 1.550, 1.600, 1.700, 1.800, 1.900, 1.95 or 2.000; and / or, The value of 99×(CaO+ZrO2) / (Li2O+Na2O+1000×K2O) is 2.600, 2.800, 3.000, 3.500, 4.000, or 5.000; and / or, The value of (5.6×B2O3+10×Al2O3+6.5×CaO) / ZrO2 is 12.200, 13.000, 14.000, 15.000, 16.000, 17.000, 18.000, 19.000 or 20.

000.

15. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The composition of the tensile stress layer region, expressed as a molar percentage of each oxide, also satisfies the following: 0.180≤5×P2O5 / (Li2O+0.5Al2O3)≤0.250; and / or, 0.100≤P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3)≤2.200; and / or, 4.000≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤6.

000.

16. The chemically strengthened glass-ceramic according to claim 15, characterized in that, The composition of the tensile stress layer region, expressed as a molar percentage of each oxide, also satisfies the following: The values ​​of 5×P₂O₅ / (Li₂O+0.5Al₂O₃) are 0.180, 0.184, 0.190, 0.200, 0.210, 0.220, 0.230, 0.240, 0.245, or 0.250; and / or, The value of (SiO2-7Al2O3-Li2O) / (P2O5+ZrO2) is 4.000, 4.200, 4.500, 5.000, 5.500 or 6.000; and / or, The value of P2O5×(CaO+ZrO2+Li2O+Al2O3) / (Na2O+K2O+B2O3) is 0.100, 0.150, 0.190, 0.200, 0.205, 0.210, 0.250, 0.300, 0.350, 0.380, 0.400, 0.600, 0.800, 1.000, 1.200, 1.400, 1.600, 1.800, 2.000, or 2.

200.

17. The chemically strengthened glass-ceramic according to any one of claims 1-2, characterized in that, The composition of the tensile stress layer region, expressed as a molar percentage of each oxide, satisfies the following: 0.184≤5×P2O5 / (Li2O+0.5Al2O3)≤0.245; and / or 18.200≤Li2O / P2O5≤25.000; and / or 0.190 ≤ P2O5 × (CaO + ZrO2 + Li2O + Al2O3) / (Na2O + K2O + B2O3) ≤ 2.180; and / or 1.500≤10×(ZrO2+P2O5) / Li2O≤1.900; and / or 4.200≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤5.900; and / or 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤4.950; and / or 15.000≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.

000.

18. The chemically strengthened glass-ceramic according to any one of claims 1-2, characterized in that, The composition of the tensile stress layer region, expressed as a molar percentage of each oxide, satisfies the following: 0.186≤5×P2O5 / (Li2O+0.5Al2O3)≤0.243; and / or 18.500≤Li2O / P2O5≤24.700; and / or 0.190 ≤ P2O5 × (CaO + ZrO2 + Li2O + Al2O3) / (Na2O + K2O + B2O3) ≤ 2.170; and / or 1.550≤10×(ZrO2+P2O5) / Li2O≤1.850; and / or 4.600≤(SiO2-7Al2O3-Li2O) / (P2O5+ZrO2)≤5.850; and / or 2.680≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤4.930; and / or 16.000≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.

000.

19. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The chemically strengthened glass-ceramic contains a lithium feldspar crystal phase and a lithium disilicate crystal phase, wherein the lithium feldspar crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the chemically strengthened glass-ceramic.

20. The chemically strengthened glass-ceramic according to claim 15, characterized in that, The chemically strengthened glass-ceramic contains a lithium feldspar crystal phase and a lithium disilicate crystal phase, wherein the lithium feldspar crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the chemically strengthened glass-ceramic.

21. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, In the chemically strengthened glass-ceramics, the total content of lithium feldspar and lithium disilicate phases accounts for more than 60.00 wt% of the mass of the chemically strengthened glass-ceramics; and / or, In the chemically strengthened glass-ceramic, the average crystal size does not exceed 100 nm.

22. The chemically strengthened glass-ceramic according to claim 20, characterized in that, In the chemically strengthened glass-ceramics, the total content of lithium feldspar and lithium disilicate phases accounts for more than 60.00 wt% of the mass of the chemically strengthened glass-ceramics; and / or, In the chemically strengthened glass-ceramic, the average crystal size does not exceed 100 nm.

23. The chemically strengthened microcrystalline glass according to claim 21, characterized in that, In the chemically strengthened glass-ceramics, the total content of lithium feldspar crystal phase and lithium disilicate crystal phase accounts for more than 70.00 wt% of the mass of the chemically strengthened glass-ceramics.

24. The chemically strengthened glass-ceramic according to claim 21, characterized in that, In the chemically strengthened glass-ceramics, the total content of lithium feldspar crystal phase and lithium disilicate crystal phase accounts for more than 80.00 wt% of the mass of the chemically strengthened glass-ceramics.

25. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The chemically strengthened microcrystalline glass does not contain a quartz crystal phase.

26. The chemically strengthened glass-ceramic according to claim 22, characterized in that, The chemically strengthened microcrystalline glass does not contain a quartz crystal phase.

27. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The chemically strengthened microcrystalline glass is transparent in the visible light range.

28. The chemically strengthened glass-ceramic according to claim 26, characterized in that, The chemically strengthened microcrystalline glass is transparent in the visible light range.

29. The chemically strengthened microcrystalline glass according to claim 27, characterized in that, The transmittance of 0.6mm thick chemically strengthened microcrystalline glass is not less than 90% in the visible light range.

30. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, When the thickness is 0.6 mm, the optical b-value of the chemically strengthened microcrystalline glass is ≤1.00; And / or, when the thickness of the chemically strengthened glass-ceramic is 0.6 mm, the haze is ≤0.20%.

31. The chemically strengthened microcrystalline glass according to claim 28, characterized in that, When the thickness is 0.6 mm, the optical b-value of the chemically strengthened microcrystalline glass is ≤1.00; And / or, when the thickness of the chemically strengthened glass-ceramic is 0.6 mm, the haze is ≤0.20%.

32. The chemically strengthened microcrystalline glass according to claim 30, characterized in that, When the thickness is 0.6 mm, the optical b-value of the chemically strengthened microcrystalline glass is ≤0.

70.

33. The chemically strengthened microcrystalline glass according to claim 30, characterized in that, When the thickness is 0.6 mm, the optical b-value of the chemically strengthened microcrystalline glass is ≤0.

55.

34. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The chemically strengthened glass-ceramic is made by chemically strengthening 3D curved glass-ceramic.

35. The chemically strengthened microcrystalline glass according to claim 31, characterized in that, The chemically strengthened glass-ceramic is made by chemically strengthening 3D curved glass-ceramic.

36. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0wt%-20.0wt%.

37. The chemically strengthened microcrystalline glass according to claim 15, characterized in that, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0wt%-20.0wt%.

38. The chemically strengthened microcrystalline glass according to claim 35, characterized in that, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0wt%-20.0wt%.

39. The chemically strengthened microcrystalline glass according to claim 36, characterized in that, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10.0 wt%, 11.0 wt%, 12.0 wt%, 13.0 wt%, 14.0 wt%, 15.0 wt%, 16.0 wt%, 17.0 wt%, 18.0 wt%, 19.0 wt%, or 20.0 wt%.

40. The chemically strengthened microcrystalline glass according to claim 1, characterized in that, The chemically strengthened glass-ceramic has a CS_50 of 143-200 MPa, where CS_50 refers to the compressive stress value at a depth of 50 μm measured from the main surface of the chemically strengthened glass-ceramic.

41. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 84-140 MPa, where |CT_AV| refers to the absolute value of the average tensile stress.

42. The chemically strengthened glass-ceramic according to claim 15, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 84-140 MPa, where |CT_AV| refers to the absolute value of the average tensile stress.

43. The chemically strengthened microcrystalline glass according to claim 38, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 84-140 MPa, where |CT_AV| refers to the absolute value of the average tensile stress.

44. The chemically strengthened microcrystalline glass according to claim 41, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 85-120 MPa.

45. The chemically strengthened microcrystalline glass according to claim 41, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 85-100 MPa.

46. ​​The chemically strengthened microcrystalline glass according to claim 41, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 90-140 MPa.

47. The chemically strengthened microcrystalline glass according to claim 41, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 100-140 MPa.

48. The chemically strengthened glass-ceramic according to claim 41, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 120-140 MPa.

49. The chemically strengthened glass-ceramic according to any one of claims 1-14, characterized in that, Using 120-grit sandpaper, the chemically strengthened microcrystalline glass with a thickness of 0.6 mm was subjected to multiple drop tests from a fixed height of 1.0 m. The chemically strengthened microcrystalline glass broke after being dropped ≥30 times.

50. The chemically strengthened microcrystalline glass according to claim 49, characterized in that, Using 120-grit sandpaper, the chemically strengthened microcrystalline glass with a thickness of 0.6 mm was subjected to multiple drop tests from a fixed height of 1.0 m. The chemically strengthened microcrystalline glass broke after being dropped ≥50 times.

51. A method for preparing chemically strengthened microcrystalline glass, characterized in that, It is used to prepare chemically strengthened glass-ceramics as described in any one of claims 1-50, the preparation method comprising chemically strengthening the 3D curved glass-ceramics, wherein the composition of the 3D curved glass-ceramics includes: Based on the molar percentage of oxides, SiO2: 60.00 mol% - 71.00 mol%, Al2O3: 1.50 mol% - 5.00 mol%, P2O5: 0.80 mol% - 1.50 mol%, ZrO2: 2.00 mol% - 4.00 mol%, Na2O: 0.00 mol% - 1.00 mol%, K2O: 0.00 mol% - 0.50 mol%, Li2O: 20.00 mol% - 30.00 mol%, CaO: 0.00 mol% - 1.60 mol%, B2O3: 0.00 mol% - 1.00 mol%. Furthermore, based on the molar percentage of each oxide, the composition of the 3D curved glass-ceramic satisfies: 18.200≤Li2O / P2O5≤25.500; 1.500≤10×(ZrO2+P2O5) / Li2O≤2.000; 2.600≤99×(CaO+ZrO2) / (Li2O+Na2O+1000K2O)≤5.000; 12.200≤(5.6B2O3+10Al2O3+6.5CaO) / ZrO2≤20.

000.

52. The method for preparing chemically strengthened microcrystalline glass according to claim 51, characterized in that, The salt bath for chemical enhancement treatment is a mixed molten salt, the composition of which includes: 0 < NaNO3 < 100 wt%, 0 < KNO3 < 100 wt%, and 0 < LiNO3 ≤ 0.2 wt%; and / or, The temperature of the salt bath used for chemical enhancement treatment is 430℃-530℃, and the chemical enhancement treatment time is 0.5h-15.0h.

53. A glass device, characterized in that, The glass device includes chemically strengthened microcrystalline glass as described in any one of claims 1-50, or chemically strengthened microcrystalline glass prepared by the method described in claims 51 or 52.

54. An electronic device, characterized in that, The electronic device includes the chemically strengthened microcrystalline glass as described in any one of claims 1-50, or the chemically strengthened microcrystalline glass prepared by the method described in claim 51 or 52.

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