3D curved surface microcrystalline glass, chemically strengthened microcrystalline glass, and preparation method and application of 3D curved surface microcrystalline glass and chemically strengthened microcrystalline glass

Abstract

The invention belongs to the technical field of glass, and particularly relates to 3D curved glass ceramics, chemically strengthened glass ceramics and a preparation method and application of the 3D curved glass ceramics and chemically strengthened glass ceramics, and the 3D curved glass ceramics comprise the following components in percentage by mole of oxides: 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; 10 * (ZrO2 + P2O5) / Li2O is greater than or equal to 1.500 and less than or equal to 2.000; (SiO2-7Al2O3-Li2O) / (P2O5 + ZrO2) is greater than or equal to 4.000 and less than or equal to 6.000. According to the invention, the generation of a main crystal phase can be ensured, and meanwhile, the whole product shows a relatively uniform display effect.

Description

[0001] This divisional patent application is a divisional application of the patent application with the application number 202311801461.4, the application date of December 25, 2023, and the invention title of "3D Curved Microcrystalline Glass, Chemically Strengthened Microcrystalline Glass and Their Manufacturing Methods and Applications". Technical Field

[0002] This application belongs to the technical field of glass, and specifically relates to a 3D curved microcrystalline glass, a chemically strengthened microcrystalline glass, and their manufacturing methods and applications. Background Art

[0003] With the development of electronic display technology, glass has gradually replaced plastic materials and is applied in display devices as a protective cover material. At the same time, with the diversified applications of electronic products, 3D curved screens such as curved screen mobile phones and smart watches are gradually becoming popular. Among them, 3D curved microcrystalline glass has gradually attracted industry attention due to its superior strength performance compared to ordinary 3D curved glass.

[0004] For 3D curved microcrystalline glass used in display screens with high requirements for optical display effects, its mass production is difficult. A large reason is that when producing large-sized prefabricated microcrystalline glass for preparing 3D curved microcrystalline glass, it is difficult to ensure the uniformity of composition and temperature field, and it is easy to produce prefabricated microcrystalline glass products with local optical defects. Moreover, this problem still exists after the prefabricated microcrystalline glass is thermally bent, which leads to the local appearance of an undesired color or an uneven display effect of the overall 3D curved microcrystalline glass, and even easily causes fragmentation during the thermal bending process.

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

[0006] In order to improve output, when the production line mass-produces 3D curved microcrystalline glass with a spodumene and lithium disilicate crystal phase structure, it generally first produces large-sized substrate glass bricks, such as substrate glass bricks with specifications of (200mm - 500mm) × (100mm - 500mm) × (10mm - 40mm) in length, width, and thickness. Then, the substrate glass bricks are heat-treated to obtain prefabricated microcrystalline glass products. Considering that the microcrystalline glass in this system usually undergoes a certain degree of crystallization during the thermal bending process, the crystallization degree of the obtained prefabricated microcrystalline glass products is generally lower than that of the final 3D curved microcrystalline glass products. Then, the prefabricated microcrystalline glass products are cold-worked to prepare multiple plane microcrystalline glass sheets of the required specification sizes. After that, the obtained plane microcrystalline glass sheets are thermally bent to prepare 3D curved microcrystalline glass products.

[0007] However, in the existing glass-ceramic solutions with spodumene and lithium disilicate as the main crystal phases, when mass-producing large-sized prefabricated glass-ceramic products, optical defects in the prefabricated glass-ceramic bricks are extremely likely to occur. The main manifestations are that the b-value differences in different regions of the obtained prefabricated glass-ceramic bricks are relatively large, with local areas showing undesired colors, being prone to chipping, and this difference cannot be improved through subsequent hot bending processes. As a result, the b-value differences in different regions of the 3D curved glass-ceramic obtained through hot bending treatment are also relatively large, further affecting the overall display effect of the 3D curved glass-ceramic and making it difficult for the obtained 3D curved glass-ceramic to meet the application requirements of display screen covers. Even some prefabricated glass-ceramic products will break during the hot bending process, resulting in a decrease in production yield.

[0008] The purpose of this application is to overcome the problems of low production yield, easy chipping of 3D curved glass-ceramic sheets, and easy display defects when mass-producing 3D curved glass-ceramic products with spodumene and lithium disilicate as the main crystal phases in the prior art. A 3D curved glass-ceramic is provided, and its preparation method and application are also provided.

[0009] To achieve the above purpose, the following technical solutions are provided:

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

[0011] In terms of the molar percentage of oxides, the composition of the 3D curved glass-ceramic includes:

[0012] 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%;

[0013] Based on the content expressed as the molar percentage of each oxide in the composition of the 3D curved glass-ceramic, the composition of the 3D curved glass-ceramic satisfies:

[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 contents of each oxide are within the appropriate range and the proportion of the contents of the oxides is combined with specific conditions, it can ensure the formation of the main crystal phase during the mass production of 3D curved microcrystalline glass products. At the same time, it can ensure that the overall 3D curved microcrystalline glass products prepared show a relatively uniform display effect, effectively avoiding the problem that the b-value difference in different regions of the 3D curved microcrystalline glass products prepared in mass production is relatively large and the display effect is poor.

[0019] It should be noted that in the above formulas of this application, the content percentages in moles are substituted into each formula, that is, the mole unit does not participate in the calculation of the formula. Exemplarily, if the content of P₂O₅ in moles 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 contents expressed in mole percentages 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. By further adjusting the content relationship between each component, it is beneficial to ensure that the 3D curved microcrystalline glass obtains excellent optical performance and mechanical strength performance.

[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 the 3D curved microcrystalline glass.

[0024] 4. The 3D curved microcrystalline glass according to any one of Technical Solutions 1 - 3, wherein, based on the mole percentages of the oxides, the composition of the 3D curved microcrystalline glass includes:

[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%. By adjusting the content relationship of the necessary oxides, it is beneficial to further improve the network structure of the 3D curved surface microcrystalline glass, thereby facilitating the large-scale production effect of the prefabricated microcrystalline glass and ensuring the excellent optical performance and strength performance of the mass-produced 3D curved surface microcrystalline glass products.

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

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

[0028] 7. The 3D curved surface microcrystalline glass according to any one of Technical Solutions 1 - 6, wherein, based on the content expressed in the molar percentage of each oxide in the composition of the 3D curved surface microcrystalline glass, the composition of the 3D curved surface 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 surface microcrystalline glass according to any one of Technical Solutions 1 - 7, wherein, based on the contents expressed in mol percentages of the respective oxides in the composition of the 3D curved surface microcrystalline glass, the composition of the 3D curved surface 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 surface microcrystalline glass according to any one of Technical Solutions 1-8, wherein when the thickness is 0.6 mm, the optical b value of the 3D curved surface microcrystalline glass is ≤ 1.00, preferably the optical b value is ≤ 0.70, and more preferably the optical b value is ≤ 0.55. The smaller the b value, the better the optical performance of the 3D curved surface microcrystalline glass and the better the overall display effect.

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

[0046] Among them, the positions of the nine places are: (1) the test positions where the test circles I are located near the four corners of the main surface, a total of four places; (2) the test positions where the four test circles II are formed with the points closest to the middle of the long side or short side of the main surface on the line formed by the centers of the above four test circles I, a total of four places; (3) the position where the test circle III is formed with the center point of the main surface as the center.

[0047] 11. A base glass, which can be used to prepare the 3D curved surface microcrystalline glass according to any one of Technical Solutions 1-10. Among them, in terms of the molar percentage of oxides, the composition of the base glass includes:

[0048] 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%;

[0049] Based on the content expressed by the molar percentage of each oxide in the base glass composition, the composition of the base glass satisfies:

[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 making the base glass meet the above composition requirements, not only can a good melting condition of the base glass block be ensured, but also a prefabricated microcrystalline glass block with good overall uniformity, good display effect, excellent optical properties, excellent mechanical properties, and main crystal phases of spodumene crystal phase and lithium disilicate crystal phase can be prepared. Furthermore, it is beneficial to thermally bend a 3D curved microcrystalline glass product with excellent optical and mechanical properties.

[0057] 12. According to the base glass described in Technical Solution 11, wherein: through synchronous thermal analysis test, under the protective atmosphere of nitrogen, the base 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 temperature T1 of the first exothermic peak is 600 °C - 730 °C, the temperature T2 of the second exothermic peak is 740 °C - 800 °C, and T1 and T2 satisfy the relationship: 100 °C ≥ T2 - T1 ≥ 40 °C, preferably 80 °C ≥ T2 - T1 ≥ 50 °C. A large-sized base glass block made of a base glass solution that meets the characteristics of a specific DSC curve is heat-treated under the process conditions of a production line for mass-producing microcrystalline glass, and a prefabricated microcrystalline glass block with optical properties and display effects that meet the requirements for use in a display screen can be obtained, which can well solve the problems such as large differences in b values in different regions of the glass block, local appearance of undesired colors, flower chips, and poor display that easily occur during mass production of prefabricated microcrystalline glass blocks in the prior art.

[0058] 13. According to the base glass described in Technical Solution 12, wherein: in the T g - T2 temperature range, the upper limit temperature T max (Li2SiO3) of the lithium metasilicate crystal phase precipitated in the base glass and the upper limit temperature T max (SiO2) of the quartz crystal phase precipitated in the base glass are measured. T max(Li2SiO3)≥T max (SiO2), wherein T g is the glass transition temperature of the base glass. By making the base glass satisfy that the upper precipitation temperature Tmax(SiO2) of the quartz crystal phase is lower than the upper precipitation temperature Tmax(Li2SiO3) of the lithium metasilicate crystal phase within a specific temperature range, it can be ensured that the base glass effectively avoids the precipitation of the quartz crystal phase under specific heat treatment process conditions for preparing a pre-crystallized glass with spodumene and lithium disilicate as the main crystal phases. Combined with the subsequent hot bending process, the lithium metasilicate crystal phase can also be transformed into the desired lithium disilicate crystal phase, thereby avoiding the adverse effects of the quartz crystal phase and the lithium metasilicate crystal phase on the optical effect of the microcrystalline glass.

[0059] 14. The base glass according to any one of technical solutions 11-13, wherein, in terms of molar percentage of oxides, the composition of the base glass includes:

[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%. By adjusting the content relationship of the necessary oxides, it is beneficial to further improve the network structure of the glass, thereby facilitating the preparation of a pre-crystallized glass with large size and good overall uniformity, and further ensuring the preparation of a 3D curved microcrystalline glass with excellent optical and strength properties.

[0061] 15. A method for preparing a 3D curved microcrystalline glass according to any one of technical solutions 1-10, wherein the method comprises the following steps:

[0062] (1) Heat-treat the base glass according to any one of technical solutions 11-14 to obtain a pre-crystallized glass product containing lithium metasilicate crystal phase, lithium disilicate crystal phase and spodumene crystal phase, and the crystallinity is not less than 60.00 wt%.

[0063] (2) Process the prefabricated glass-ceramic product obtained in step (1) into a planar glass-ceramic sheet with the required specification dimensions, and perform a thermoforming treatment on the obtained planar glass-ceramic sheet to obtain a 3D curved glass-ceramic. The 3D curved glass-ceramic contains a spodumene crystal phase and a lithium disilicate crystal phase, and the spodumene crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the 3D curved glass-ceramic.

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

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

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

[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 according to any one of technical solutions 1 - 10. The chemically strengthened glass-ceramic contains a compressive stress layer region extending from the surface of the chemically strengthened glass-ceramic to the compressive depth, and has a tensile stress inside the chemically strengthened glass-ceramic. Forming a compressive stress layer on the surface of the 3D curved glass-ceramic is beneficial to further improving the mechanical properties of the 3D curved glass-ceramic.

[0068] 20. A glass device, wherein the glass device comprises the 3D curved glass-ceramic according to any one of technical solutions 1 - 10 or comprises the chemically strengthened glass-ceramic according to technical solution 19.

[0069] 21. An electronic device, wherein the electronic device includes the 3D curved surface microcrystalline glass as described in any one of Technical Solutions 1-10 or the 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] Through the above technical solutions, especially when the contents of various oxides are within a suitable range and in combination with a specific proportion of the oxide contents under specific conditions, it is possible to ensure the formation of the main crystal phase during the mass production of 3D curved surface microcrystalline glass products. At the same time, it can ensure that the overall display effect of the prepared 3D curved surface microcrystalline glass products is relatively uniform, effectively avoiding the problem that the b-value difference in different regions of the 3D curved surface microcrystalline glass products prepared in mass production is relatively large and presenting a poor display effect.

[0073] When the large-size substrate glass brick prepared by the glass solution of the present application is heat-treated to prepare a prefabricated microcrystalline glass brick, it can ensure that the overall b-value of the main surface of the prefabricated microcrystalline glass brick is close, thereby ensuring that the 3D curved surface microcrystalline glass obtained therefrom also presents a good display effect. By adopting the specific composition solution of the present application, it is possible to ensure that 3D curved surface microcrystalline glass with better optical properties is obtained, which is beneficial to realizing the industrial mass production of 3D curved surface microcrystalline glass and improving the yield of 3D curved surface microcrystalline glass products. At the same time, the microcrystalline glass prepared by adopting the above substrate glass formula solution can be chemically strengthened to prepare a chemically strengthened microcrystalline glass with excellent strength properties, especially excellent anti-drop performance.

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

[0075] During the mass production of 3D curved surface microcrystalline glass with the main crystal phases of spodumene and lithium disilicate, the products with poor optical display basically have cristobalite (SiO2) heterophase. However, by adjusting the composition solution of the substrate glass in the present application, the upper limit temperature T max (SiO2) of the precipitation of quartz crystal phase in the substrate glass is lower than the upper limit temperature T max (Li2SiO3) of the precipitation of lithium monosilicate crystal phase, it can ensure that the precipitation of quartz crystal phase is effectively avoided under specific heat treatment process conditions for preparing prefabricated microcrystalline glass with the main crystal phases of spodumene and lithium disilicate. Combined with the subsequent hot bending process, the lithium monosilicate crystal phase can also be transformed into the required lithium disilicate crystal phase, thereby avoiding the adverse effects of quartz crystal phase and lithium monosilicate crystal phase on the optical effect of the glass. Description of the Drawings

[0076] To more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings required for the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and thus should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0077] Figure 1 It is the heating DSC curve graph of the base glass of Example 1;

[0078] Figure 2 It is the heating DSC curve graph of the base glass of Example 10;

[0079] Figure 3 It is the heating DSC curve graph of the base glass of Comparative Example 1;

[0080] Figure 4 It is the heating DSC curve graph of the base glass of Comparative Example 2;

[0081] Figure 5 It is the structural schematic diagram of Li3PO4 crystal attached with lithium silicate crystal;

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

[0083] Figure 7 It is the schematic diagram of nine test positions when performing b-value tests at nine places on the main surface of the glass-ceramics;

[0084] Figure 8 It is the XRD diffraction pattern of the prefabricated glass-ceramics obtained after the base glass of Example 2 undergoes the heat treatment process C;

[0085] Figure 9 It is the XRD diffraction pattern of the prefabricated glass-ceramics obtained after the base glass of Comparative Example 2 undergoes the heat treatment process C;

[0086] Figure 10 It is the XRD diffraction curves at the position with the maximum b-value and the position with the minimum b-value of the 3D curved glass-ceramics of Example 1;

[0087] Figure 11 It is the XRD diffraction curves at the position with the maximum b-value and the position with the minimum b-value of the 3D curved glass-ceramics of Comparative Example 6;

[0088] Figure 12 It is the picture of the prefabricated glass-ceramics of Comparative Example 7 cracking during the 3D hot bending forming process;

[0089] Figure 13 It is the transmittance curve graph of the 3D curved glass-ceramics of Example 1. DETAILED DESCRIPTION

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

[0091] Glossary and test methods:

[0092] Base glass: refers to glass that has not been nucleated, crystallized or strengthened.

[0093] Glass-ceramics: also known as glass ceramics, is a type of solid composite material that contains both a glass phase and a crystal phase (also called a microcrystalline phase or a crystalline phase) and is prepared by targeted and controlled crystallization of the base glass.

[0094] 3D curved glass-ceramics: also known as 3D curved glass ceramics, is made by cold grinding, hot bending, hot pressing and other methods to bend the flat glass-ceramics, thereby making the two main surfaces of the flat glass-ceramics curved.

[0095] Chemically strengthened glass-ceramics: It is a solid composite material obtained after chemical strengthening treatment of glass-ceramics. During high-temperature chemical strengthening treatment, alkali metal ions with large ionic radius (such as potassium ions and sodium ions) in the molten salt bath will replace alkali metal ions with small ionic radius (such as sodium ions and lithium ions) in the glass-ceramics, thereby generating a volume difference of exchange ions and generating compressive stress on the surface of the glass-ceramics.

[0096] Main crystalline phase: refers to a crystalline phase having a higher weight content than other crystalline phases present in the microcrystalline glass.

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

[0098] Flowery pieces: refers to the situation where the main surface of the glass piece shows partial coloration and / or the overall coloration of the glass piece is uneven when strong light enters the glass piece from the side. Figure 8 As shown in the figure, products with flower chips are defined as defective products during the production process because they cannot meet the display requirements of the display cover glass.

[0099] Glass transition temperature: T g , unit ℃, also known as the brittle 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 annealing temperature, at which the internal stress generated by the uneven cooling of glass products can be eliminated. T g Obtained from the DSC curve of the substrate glass, which is manifested as a step in the DSC curve where the baseline changes in the endothermic direction. For the two extended lines of the baseline before and after the step and the inflection points of the curve, make tangents respectively, and 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 50 μm starting from the main surface of the chemically strengthened glass-ceramics.

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

[0102] |CT_AV|: Absolute value of the average tensile stress in the tensile stress layer, specifically referring to 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: Test using SLP-2000 from Shihara of Japan, light source wavelength is 518 nm, SOC = 25.5 (nm / cm) / MPa, refractive index = 1.54, exposure time: 300 usec.

[0104] When testing the surface of CS_50, |CT_AV|, and DOL_0, it is necessary to first drop the conduction liquid on the stress meter, then wipe the sample of the chemically strengthened glass-ceramics to be tested clean, place it on the test path, and test its stress value. Among them, the stress meter is SLP-2000 and the conduction liquid used is the conduction liquid with a refractive index of 1.51.

[0105] Transmittance: During the process where the incident light flux travels from the irradiated surface or the incident surface of the medium to the other side and leaves, the ratio of the radiant energy that is projected and transmitted through the object to the total radiant energy projected onto the object.

[0106] b value: Belongs to the Lab color model, a color mode formulated by the International Commission on Illumination. The positive and negative values of the b value represent yellow and blue.

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

[0108] Precursor: A form of existence before obtaining the target object.

[0109] Residual glass phase: Refers to the amorphous part in the glass-ceramics.

[0110] Synchronous thermal analysis test: Using a Mettler Toledo TGA / DSC3+ synchronous thermal analyzer, the test is carried out according to the required process, and the obtained curve is called the DSC curve, including the heating DSC curve.

[0111] Test conditions for the heating DSC curve: After grinding the substrate glass and sieving it through a 200-mesh sieve, the sample to be tested is obtained. Weigh about 20 mg of the sample and heat it from room temperature to 900 °C at a heating rate of 10 °C / min under a nitrogen protective atmosphere to obtain the heating DSC curve of the sample. The differential thermal analysis instrument used in this application for testing the heating DSC curve is a Mettler Toledo TGA / DSC3+ synchronous thermal analyzer. The standard substance used in the test is α-Al2O3 powder. The container for placing the sample is a platinum crucible. The ambient temperature where the instrument is placed is 24 °C, and the air humidity is 40%.

[0112] Thickness of the glass: Measured by a laser thickness gauge.

[0113] Optical property test of glass-ceramics with a thickness of less than 2 mm: In this application, the haze, L, a, and b values of the glass-ceramics are tested in the transmission mode using a Konica Minolta spectrophotometer CM-3600A from Japan. The test aperture of the spectrophotometer CM-3600A used is 25.6 mm. The transmittance and its curve are tested using a Shimadzu UV-2000 ultraviolet-visible spectrophotometer. 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: Import the test results (RAW format) of XRD into the X-ray diffraction data Rietveld refinement software JADE Standard 8.6 for fitting and analysis to determine the crystal phase in the glass-ceramics sample.

[0115] The crystal content in this application refers to the percentage of crystals or crystal phases in the mass of the glass-ceramics, which is a weight percentage.

[0116] Determination of crystal content: Import the test results (RAW format) of XRD into the X-ray diffraction data Rietveld refinement software JADE Standard 8.6 for fitting and calculation to obtain the crystal content in the glass-ceramics sample. Specifically, the ratio of the area of the fitted crystal phase peaks to the area of all the fitted peaks is the crystal content.

[0117] Average crystal size test: Based on the result data obtained by XRD test, according to the Scherrer formula D = Kλ / (βcosθ), the average crystal size of the sample can be calculated. Where λ is the X-ray wavelength, λ = 0.154056 nm, β is the full width at half maximum of the diffraction peak, K = 0.89, and θ is the Bragg diffraction angle. Specifically, the RAW file (diffraction pattern) output by the XRD instrument is curve-fitted in the JADE Standard 8.6 software. The Jade outputs a fitting report. According to the angle 2θ value and Peak FWHM value (full width at half maximum of the diffraction peak) corresponding to each diffraction peak in the fitting report, and converting the Peak FWHM value to radian system: β = (FWHM / 180×3.14), after calculating the grain size of each diffraction peak through the Scherrer formula D = Kλ / (βcosθ) and averaging, the average crystal size is obtained.

[0118] Test method for the upper limit temperature of crystal phase precipitation: Heat the substrate glass at a heating rate of 10 °C / min, so that the substrate glass is heated to Tg, Tg + 5 °C, Tg + 10 °C, Tg + 15 °C respectively, and continue the heat treatment with an increment of 5 °C until T2. The heat treatment time at each temperature is 30 - 240 min (the heat treatment time at each corresponding temperature in the examples and comparative examples of this application is 240 min). Test the crystal phase composition in the samples obtained by treating the substrate glass under the above different heat treatment temperature conditions to obtain the upper limit temperature of the precipitation of lithium metasilicate (Li2SiO3) crystal phase and quartz (SiO2) crystal phase.

[0119] Here, the "upper limit temperature of the precipitation of lithium metasilicate crystal phase" specifically refers to g In the temperature range of T

[0120] -T2, the highest temperature at which lithium metasilicate crystal phase precipitates in the substrate glass. Beyond this temperature, lithium metasilicate will not precipitate in the substrate glass. g -T2, the highest temperature at which quartz crystal phase precipitates in the substrate glass. Beyond this temperature, quartz will not precipitate in the substrate glass. The standard XRD diffraction pattern of quartz appearing in the glass-ceramics is as Figure 6 shown.

[0121] Here, T g is the glass transition temperature of the substrate glass, and T2 is the temperature of the second exothermic peak in the heating DSC curve obtained when the substrate glass is subjected to DSC test.

[0122] If a certain crystal phase always exists at the T2 temperature point, it means that its upper limit temperature of precipitation is greater than T2.

[0123] Fixed-point height drop test:

[0124] (1) Stick a 120-mesh sandpaper on the lower surface of a 187-g model machine, and place the model machine on a Wonder Inno drop tester.

[0125] (2) Place a microcrystalline glass sample piece to be tested with specifications of 50 mm × 50 mm × 0.6 mm in length, width, and thickness on a smooth marble slab directly below the model machine, with the microcrystalline glass sample piece facing the sandpaper.

[0126] (3) Let the model machine impact and fall from a fixed height of 1.0 m, impacting the microcrystalline glass sample piece directly below the model machine. If the microcrystalline glass sample piece does not break, after replacing the sandpaper on the lower surface of the model machine, repeat the above drop impact process until the microcrystalline glass breaks, and record the number of drops at the time of breakage.

[0127] Take at least 10 identical microcrystalline glass sample pieces in each batch for fixed-height drop tests, and calculate the average value of the test results of the 10 microcrystalline glass pieces to characterize the drop resistance of the microcrystalline glass.

[0128] Surface Na2O concentration test: The surface Na2O concentration is equal to the mass of surface Na2O / the total mass of surface oxides, where the total mass of surface oxides includes oxides such as SiO2, Al2O3, P2O5, ZrO2, Na2O, K2O, CaO that can be accurately tested by XRF, and does not include the content of oxides such as Li2O, B2O3 that cannot be accurately tested by XRF. The surface Na2O concentration of the chemically strengthened microcrystalline glass in this application is measured by an X-ray fluorescence spectrometer (XRF), and the equipment used for the test is Thermo Scientific ARL TM PERFORM'X. The target material is Rh (rhodium), the tube voltage of the X-ray tube is 40 KW, the current is 60 mA, the collimator is 0.15, the crystal is selected as LiF200, the detector is selected as FPC, the test range is a 29-mm circle, and the analysis software is UniQuant non-standard analysis. When using XRF for testing, non-standard testing is used, and the concentrations of elements with atomic numbers 6 and below or their oxides in the glass are not tested. That is, in this application, when the surface Na2O concentration is measured 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 spodumene (LiAlSi4O 10 ) crystal phase and lithium disilicate (Li2Si2O5) crystal phase, and the spodumene crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the 3D curved microcrystalline glass.

[0130] The 3D curved surface microcrystalline glass of the present application is obtained by heat treatment and hot bending treatment of the base glass. Therefore, it can be understood that, calculated on an oxide basis, the composition of the base glass is the same as that of the 3D curved surface microcrystalline glass.

[0131] In the present application, calculated on a molar percentage basis of oxides, the composition of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass includes:

[0132] 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%;

[0133] Based on the content expressed as the molar percentage of each oxide in the composition of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass, the composition of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass satisfies:

[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 contents of each oxide are within a suitable range and in a specific proportion under specific conditions, it can ensure the formation of the main crystal phase during the mass production of 3D curved surface microcrystalline glass products. At the same time, it can ensure that the overall 3D curved surface microcrystalline glass products prepared show a relatively uniform display effect, effectively avoiding the problem that the b-value difference in different regions of the 3D curved surface microcrystalline glass products prepared in mass production is relatively large and the display effect is poor.

[0141] In the glass system of the present application, SiO₂ is an oxide that forms the glass network framework, used to stabilize the network structures of the substrate glass and the 3D curved surface microcrystalline glass, and is an important component of crystal phases such as lithium silicate, spodumene, β-spodumene, and quartz. When the substrate glass is heat-treated to form microcrystalline glass, the content of SiO₂ should be high enough to form a sufficient amount of spodumene crystals and lithium silicate crystals. When the content of SiO₂ is too low, the glass tends to have a higher coefficient of thermal expansion and the thermal shock resistance decreases; when the content of SiO₂ is too high, it will lead to poor meltability of the glass or an increase in the viscosity of the molten glass liquid, making it difficult for the glass liquid to be clarified, increasing the forming difficulty of the glass, reducing the productivity, and also resulting in a longer crystallization heat treatment time for the substrate glass. In some embodiments, the microcrystalline glass or the substrate glass of the present application both contain 60.00 mol% - 71.00 mol% of SiO₂. In some embodiments, the 3D curved surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass can both 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 surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass can both 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 the numerical range formed 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 surface microcrystalline glass or the substrate glass with the required performance of the present application can be obtained.

[0142] In the glass system of the present application, Al2O3 can be used to construct the glass skeleton and is an essential component for forming spodumene. Al2O3 is coordinated around the crystal nucleus to form a "center - shell" structure. This structure makes it difficult for the crystal nucleus components to be supplied from the outer part of the shell, so the crystal nucleus is not easy to grow and is prone to form multiple tiny grains. An appropriate amount of Al2O3 can stabilize the glass network structure, improve mechanical properties and chemical durability, inhibit the phase separation of the glass, reduce the thermal expansion coefficient and increase the strain point. When the content of Al2O3 is too low, the glass tends to have a higher thermal expansion coefficient, its chemical durability decreases, and the crystal nucleus becomes larger, and the glass - ceramic is prone to cloudiness. When the content of Al2O3 is too high, the meltability of the glass becomes poor, production becomes difficult, and the precipitation of mullite crystals easily causes the glass to devitrify. In some embodiments, both the 3D curved glass - ceramic of the present application or the base glass for preparing the 3D curved glass - ceramic contain 1.50 mol% - 5.00 mol% of Al2O3. In some embodiments, the 3D curved glass - ceramic or the base glass for preparing the 3D curved glass - ceramic can 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 base glass for preparing the 3D curved glass - ceramic can 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 the numerical range formed 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 or base glass with the required performance of the present application can be obtained.

[0143] In the glass system of the present application, Li2O is the main component of the spodumene crystal phase and the lithium silicate crystal phase, and is also a necessary component for chemical strengthening. An appropriate amount of Li2O is beneficial to ensuring that the properties of the 3D curved surface glass-ceramics, such as transparency, melting and forming effect, crystallization ability, chemical strengthening performance, etc., all meet the requirements. When the content of Li2O is too low, the glass is prone to precipitate crystal phases, such as mullite, etc., causing the glass to devitrify, the melting property to decrease or the viscosity to increase, making it difficult to clarify and difficult to form; when the content of Li2O 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 damaged. In some embodiments, both the 3D curved surface glass-ceramics of the present application or the substrate glass for preparing the 3D curved surface glass-ceramics contain 20.00 mol%-30.00 mol% of Li2O. In some embodiments, the 3D curved surface glass-ceramics or the substrate glass for preparing the 3D curved surface glass-ceramics can each 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 surface glass-ceramics or the substrate glass for preparing the 3D curved surface glass-ceramics can each 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 the numerical range formed 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 surface glass-ceramics or substrate glass with the required properties of the present application can be obtained.

[0144] In the glass system of the present application, P2O5 is a glass-forming oxide, which exists in the network structure in the form of phosphorus oxygen tetrahedron [PO4]. P2O5 appears preferentially during the heat treatment process, first causing phase separation and segregation of the glass to form an amorphous precursor phase Li3PO4. Then, Li3PO4 serves as a heterogeneous nucleation site, and crystal phases such as lithium silicate grow attached to the amorphous Li3PO4. With the increase in the content of P2O5, the number of heterogeneous nucleation sites increases, and the grains nucleated with Li3PO4 are effectively refined, which is beneficial to improving the overall transmittance, glass uniformity and reducing the b value of the glass-ceramics. Within a certain range of P2O5, the gain effect reaches the best. However, when the content of P2O5 is too high, the upper limit temperature of crystallization increases, and more Li3PO4 crystals are easily formed, resulting in insufficient Li2O content for forming lithium silicate and spodumene, and further leading to the easy precipitation of quartz crystals in the substrate glass, causing a decrease in the transmittance of the glass-ceramics and the overall optical uniformity of the glass-ceramics. Even worse, it causes the substrate glass to directly crystallize during melting and forming. When the content of P2O5 is too low, it is easy to precipitate large ZrO2 crystals, causing the glass to devitrify.

[0145] In some embodiments, the 3D curved glass-ceramics of the present application or the substrate glass for preparing the 3D curved glass-ceramics both contain 0.80 mol% - 1.50 mol% of P2O5. The P2O5 within this content range is beneficial to ensuring high transmittance, good optical uniformity and significantly reducing the b value of the 3D curved glass-ceramics, and the gain effect reaches the best. In some embodiments, the 3D curved glass-ceramics or the substrate glass for preparing the 3D curved glass-ceramics may both 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 glass-ceramics or the substrate glass for preparing the 3D curved glass-ceramics may both 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 the numerical range formed 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-ceramics or substrate glass with the required performance of the present application can be obtained.

[0146] In the glass system of the present application, since P2O5 preferentially forms amorphous Li3PO4 during the heat treatment process, and the increase in P2O5 will inevitably compete for more Li2O, resulting in a decrease in the formation amounts of lithium silicate and spodumene. Therefore, a certain amount of Li2O needs to be supplemented. In this regard, in the system of the present application, based on the contents expressed in terms of the molar percentages of the respective oxides in the composition of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics, the compositions of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics all satisfy: 18.200 ≤ Li2O / P2O5 ≤ 25.500, where the chemical formulas in the formula represent the molar percentages of the oxides, which is conducive to ensuring the formation of the main crystal phase and improving the strength performance of the glass. In some embodiments, 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0147] In some embodiments, based on the contents expressed in terms of the molar percentages of the respective oxides in the composition of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics, the compositions of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics all satisfy: 0.180 ≤ 5×P2O5 / (Li2O + 0.5Al2O3) ≤ 0.250, where the chemical formulas in the formula represent the molar percentages of the oxides, which is thus conducive to forming the main crystal phases of spodumene 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0148] In some embodiments, in terms of the content expressed by the molar percentage of each oxide in the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass, the compositions of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass both satisfy: 4.000 ≤ (SiO2 - 7Al2O3 - Li2O) / (P2O5 + ZrO2) ≤ 6.000, where the chemical formulas in the formula represent the molar percentages of the oxides, which is beneficial to ensuring the optical properties of the 3D curved surface 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0149] In the glass system of the present application, an appropriate amount of ZrO2 can increase the viscosity, hardness, elastic modulus, refractive index, chemical stability of the glass and reduce the thermal expansion coefficient of the glass. ZrO2 does not act as a nucleating agent in the glass-ceramics with spodumene and lithium silicate structures. After heat treatment, ZrO2 exists in the residual glass phase, effectively improving the mechanical properties of the residual glass phase. However, excessive ZrO2 will increase the melting difficulty of the base glass, and white zircon precipitation will occur during discharging, which is not conducive to the production of transparent glass-ceramics. In some embodiments, the 3D curved glass-ceramics of the present application or the base glass for preparing the 3D curved glass-ceramics both contain 2.00 mol%-4.00 mol% of ZrO2. ZrO2 within this content range is beneficial to the production of transparent 3D curved glass-ceramics and is beneficial to improving the mechanical properties of the 3D curved glass-ceramics. In some embodiments, the 3D curved glass-ceramics or the base glass for preparing the 3D curved glass-ceramics can both 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 glass-ceramics or the base glass for preparing the 3D curved glass-ceramics can both 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% of ZrO2, or ZrO2 within the numerical range formed 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-ceramics or base glass with the required performance of the present application can be obtained.

[0150] In some embodiments, in terms of the content expressed by the molar percentage of each oxide in the composition of the 3D curved surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass, the composition of the 3D curved surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass all satisfies: 1.500 ≤ 10×(ZrO2 + P2O5) / Li2O ≤ 2.000, where the chemical formula in the formula represents the molar percentage of the oxide, which is beneficial to ensuring the strength performance of the 3D curved surface 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0151] In the glass system of the present application, B2O3 helps to reduce the melting temperature of the base glass. B2O3 takes borate triangles [BO3] and borate tetrahedrons [BO4] as structural units. As the content of B2O3 increases, the relative contents of borate triangles and borate tetrahedrons change, resulting in a reversal of the structure and properties. An appropriate amount of B2O3 helps to reduce the melting temperature of the base glass and improve the performance of the 3D curved surface glass-ceramics, such as transmittance and overall uniformity. However, when the addition amount of B2O3 is too large, on the one hand, the borate tetrahedrons [BO4] with a three-dimensional framework structure are transformed into borate triangles [BO3] with a two-dimensional layered structure. The three-coordinated borate triangles [BO3] are not as strong as the borate tetrahedrons [BO4], which will open the network structure. At the same time, the increase in the content of B2O3 in the residual glass phase will reduce the viscosity of the residual glass phase and promote the growth of crystals such as lithium metasilicate. On the other hand, it will reduce the temperature of the second exothermic peak of the DSC curve of the base glass, increase the precipitation of SiO2 crystal phases (such as cristobalite), affect the glass transmittance, and at the same time, deteriorate the overall uniformity of the glass brick. In some embodiments, the 3D curved surface glass-ceramics of the present application or the base glass for preparing the 3D curved surface glass-ceramics both contain 0.00 mol%-1.00 mol% of B2O3. In some embodiments, the glass-ceramics or the base glass may each 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 surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics may each 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 the numerical range formed 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 surface glass-ceramics or the base glass with the required performance of the present application can be obtained.

[0152] In the glass system of the present 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 and play roles such as regulating the grain size. The presence of an appropriate amount of Na2O is beneficial to promoting the precipitation of the lithium disilicate crystal phase, reducing the crystallization tendency of the glass, increasing the transmittance of the glass, and at the same time, improving the thermal stability, chemical stability, mechanical strength and weather resistance of the glass. In some embodiments, the 3D curved surface microcrystalline glass of the present application or the substrate glass for preparing the 3D curved surface microcrystalline glass contains 0.00 mol%-1.00 mol% of Na2O. In some embodiments, the 3D curved surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass can 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 surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass can contain 0.00 mol%, 0.15 mol%, 0.35 mol%, 0.55 mol%, 0.75 mol%, 0.95 mol% or 1.00 mol% of Na2O, or Na2O within the numerical range formed 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 surface microcrystalline glass or the substrate glass with the required performance of the present application can be obtained.

[0153] In the glass system of the present application, K2O is an external oxide of the glass network. An appropriate amount of K2O can reduce the crystallization tendency of the glass and increase the transparency and luster of the glass. However, when the content of K2O is too high, the crystallization ability of the glass becomes stronger, the glass is prone to devitrification, and the crystallized glass is prone to breakage. The ionic radius of K + is larger than that of Li which is the main crystal phase + , and it is not easy to enter the crystal. Therefore, after crystallization, K +It remains in the glass phase. Therefore, in some embodiments, the 3D curved surface microcrystalline glass of the present application or the substrate glass for preparing the 3D curved surface microcrystalline glass contains 0.00 mol%-0.50 mol% of K2O. In some embodiments, the 3D curved surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass may each 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 surface microcrystalline glass or the substrate glass for preparing the 3D curved surface microcrystalline glass may each contain 0.00 mol%, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol% or 0.50 mol% of K2O, or K2O within the numerical range formed 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 surface microcrystalline glass or the substrate glass with the required performance of the present application can be obtained.

[0154] In the glass system of the present application, CaO is beneficial to increasing the chemical stability and mechanical strength of the glass. CaO reduces the viscosity of the glass, enhances the fusibility and formability of the glass, and is also beneficial to adjusting the thermal expansion coefficient and refractive index of the glass-ceramics. However, when the content of CaO is excessive, the glass is prone to devitrification after crystallization treatment. Excessive CaO remaining in the glass phase generates a refractive index difference with the main crystal phase, which will lead to a decrease in the transmittance and an increase in the haze of the glass-ceramics. In some embodiments, the 3D curved glass-ceramics of the present application or the substrate glass for preparing the 3D curved glass-ceramics both contain 0.00 mol%-1.60 mol% of CaO. In some embodiments, the 3D curved glass-ceramics or the substrate glass for preparing the 3D curved glass-ceramics can both 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 glass-ceramics or the substrate glass for preparing the 3D curved glass-ceramics can both 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% of CaO, or CaO within the numerical range formed 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-ceramics or substrate glass with the required performance of the present application can be obtained.

[0155] In some embodiments, based on the content expressed as the molar percentage of each oxide in the composition of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass, the compositions of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass both satisfy: 0.100 ≤ P2O5×(CaO + ZrO2 + Li2O + Al2O3) / (Na2O + K2O + B2O3) ≤ 2.200, where the chemical formulas in the formula represent the molar percentages of the oxides, thus facilitating the formation of 3D curved surface microcrystalline glass with a specific structure and excellent properties (especially the forming properties, optical properties and strength properties of the 3D curved surface microcrystalline glass). 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0156] In some embodiments, based on the content expressed as the molar percentage of each oxide in the composition of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass, the compositions of the 3D curved surface microcrystalline glass or the base glass for preparing the 3D curved surface microcrystalline glass both satisfy: 2.600 ≤ 99×(CaO + ZrO2) / (Li2O + Na2O + 1000×K2O) ≤ 5.000, where the chemical formulas in the formula represent the molar percentages of the oxides, thus facilitating the formation of 3D curved surface microcrystalline glass with a specific structure and excellent properties (especially the strength property of the 3D curved surface microcrystalline glass). 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0157] In some embodiments, in terms of the content expressed as the molar percentage of each oxide in the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics, the composition of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics all satisfies: 12.200 ≤ (5.6×B2O3 + 10×Al2O3 + 6.5×CaO) / ZrO2 ≤ 20.000, where the chemical formulas in the formula represent the molar percentage of the oxides, thereby facilitating the formation of 3D curved surface glass-ceramics with a specific structure and excellent properties (especially the optical properties and mechanical properties of the 3D curved surface glass-ceramics). In some embodiments, 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 can be a value within the numerical range formed by any two of the above specific numerical values as endpoints.

[0158] In some embodiments, the 3D curved surface glass-ceramics is transparent in the visible light range. Here, the visible light refers to the light within the wavelength range of 360 nm - 780 nm. "Being transparent in the visible light range" means that the transmittance is greater than 80% under the light within the wavelength range of 360 nm - 780 nm, and can meet the optical performance requirements of the front cover display effect. In some embodiments, the transmittance of the 0.6 mm thick 3D curved surface glass-ceramics in the visible light range is not less than 90%.

[0159] In some embodiments, in terms of the molar percentage of oxides, the composition of the 3D curved surface glass-ceramics or the base glass for preparing the 3D curved surface glass-ceramics all 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 surface glass-ceramics does not contain quartz crystal phase. The standard XRD diffraction pattern of quartz appearing in the glass-ceramics is as Figure 6As shown. In the glass-ceramics with the main crystalline phases of spodumene crystalline phase and lithium disilicate crystalline phase, if quartz crystalline phase precipitates, it will have an adverse effect on the optical properties of the glass-ceramics, easily leading to a decrease in the transmittance of the glass-ceramics, and also easily making the overall uniformity of the glass-ceramic bricks worse, and then there will be a problem of a large difference in the b value in different regions of the glass. The oxide ratios of the present application can enable the base glass to mass-produce 3D curved glass-ceramics without quartz crystalline phase under specific heat treatment process conditions.

[0161] In some embodiments, in the 3D curved glass-ceramics, the total content of spodumene crystalline phase and lithium disilicate crystalline phase accounts for more than 60.00 wt% of the mass of the 3D curved glass-ceramics, preferably more than 70.00 wt%, and more preferably more than 80.00 wt%. A higher content of spodumene crystalline phase and lithium disilicate crystalline phase is beneficial to improving the mechanical strength of the 3D curved glass-ceramics. The weight percentage of the total content of spodumene crystalline phase and lithium disilicate crystalline phase in the mass of the glass-ceramics 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 the crystallinity within the numerical range formed by any two of the above specific values as endpoints. It should be understood that in the specific embodiments, any of the above ranges can be combined with any other range as long as the 3D curved glass-ceramics with the required performance of the present application can be obtained.

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

[0163] In some embodiments, the glass-ceramics contain one or more of a lithium metasilicate (Li2SiO3) crystal phase, a lithium phosphate (Li3PO4) crystal phase, and a spodumene crystal phase as secondary crystal phases. In some embodiments, in the glass-ceramics, the secondary crystal phases account for 20.00 wt% or less of the mass of the transparent glass-ceramics. The glass-ceramics of the present application have a low content of secondary crystal phases, which is more conducive to ensuring a high content of the main crystal phase, and thus ensuring the excellent mechanical strength performance of the glass-ceramics. In some embodiments, the growth of secondary phases such as a lithium metasilicate (Li2SiO3) crystal phase is usually accompanied by the lithium phosphate (Li3PO4) crystal phase, as Figure 5 shown.

[0164] In some embodiments, in the transparent glass-ceramics, the lithium metasilicate crystal phase accounts for 8.00 wt% or less of the mass of the transparent glass-ceramics, and the total amount of the lithium phosphate crystal phase and the spodumene crystal phase accounts for 8.00 wt% or less of the mass of the transparent glass-ceramics.

[0165] In some embodiments, in the 3D curved glass-ceramics, the average crystal size does not exceed 100 nm, and can be, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, or an average crystal size within the numerical range formed 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 transparent 3D curved glass-ceramics with the required performance of the present application can be obtained.

[0166] In some embodiments, the crystallinity of the 3D curved glass-ceramics ≥ 70.00 wt%, preferably the crystallinity ≥ 80.00 wt%, which is beneficial to improving the mechanical strength performance of the glass-ceramics. The "crystallinity" here refers to the percentage of the content of all crystal phases / crystals in the 3D curved glass-ceramics in the mass of the 3D curved glass-ceramics, and can be, for example, 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 the numerical range formed 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-ceramics with the required performance of the present application can be obtained.

[0167] In some embodiments, when the thickness is 0.6 mm, the optical b value of the 3D curved surface microcrystalline glass is ≤ 1.00, preferably the optical b value is ≤ 0.70, and more preferably the optical b value is ≤ 0.55. In some embodiments, the optical b value of the 3D curved surface 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 the numerical range formed 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 surface microcrystalline glass with the required performance of the present application can be obtained.

[0168] Among them, the positions of the nine places are as Figure 7 shown, and are respectively: (1) the test positions of the test circles I near the four corners of the main surface, a total of four places; (2) the test positions of the four test circles II formed with the points closest to the middle of the long side or the short side of the main surface on the line formed by the centers of the above four test circles I as the centers, a total of four places; (3) the position of the test circle III formed with the center point of the main surface as the center. Among them, the diameter of the test circle depends on the size of the test window (which is a circle) of the instrument.

[0169] In some embodiments, when the thickness is 0.6 mm, the range of the b values at the nine places on the main surface of the 3D curved surface microcrystalline glass is ≤ 0.30, preferably the range of the b values at the nine places on the main surface is ≤ 0.10, and more preferably the range of the b values at the nine places on the main surface is ≤ 0.06. In some embodiments, the range of the b values at the nine places on the main surface of the 3D curved surface 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 of values formed 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 surface microcrystalline glass with the required performance of the present application can be obtained.

[0170] In some embodiments, when the thickness of the 3D curved surface microcrystalline glass is 0.6 mm, the haze is ≤ 0.20%, and under the light with a wavelength of 550 nm, the transmittance of the microcrystalline glass is ≥ 90.00%. Here, the b value refers to the b value at any position of the microcrystalline glass. In some embodiments, the transmittance of the 550-nm wavelength light of the 0.6-mm thick microcrystalline glass 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 the transmittance within the numerical range formed by any two of the above specific numerical 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 microcrystalline glass with the required performance of the present application can be obtained.

[0171] As described above, the range of the b values at nine positions on the main surface of the 3D curved surface microcrystalline glass batch-produced in the present application is small, that is, the b values in different regions of the 3D curved surface microcrystalline glass are close; moreover, the 3D curved surface microcrystalline glass of the present application has a high transmittance, a low b value, and a low haze, which indicates that the 3D curved surface microcrystalline glass batch-produced by the production line in the present application has excellent optical properties and good display uniformity, and can meet the application requirements of the display screen cover plate.

[0172] The present application also provides a substrate glass, which can be used to prepare the above-mentioned 3D curved surface microcrystalline glass. Among them, in terms of the molar percentage of oxides, the composition of the substrate glass is the same as that of the aforementioned 3D curved surface microcrystalline glass.

[0173] In some embodiments, through synchronous thermal analysis testing, in a protective atmosphere of nitrogen, 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 temperature T1 of the first exothermic peak is 600 °C - 730 °C, the temperature T2 of the second exothermic peak is 740 °C - 800 °C, and T1 and T2 satisfy the relationship: 100 °C ≥ T2 - T1 ≥ 40 °C, preferably 80 °C ≥ T2 - T1 ≥ 50 °C.

[0174] In some embodiments, in the T g -T2 temperature range, the upper limit temperature T max (Li2SiO3) of the precipitation of the lithium metasilicate crystal phase in the substrate glass and the upper limit temperature T max (SiO2) of the precipitation of the quartz crystal phase in the substrate glass are tested. T max (Li2SiO3) ≥ T max (SiO2), where T gis 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-sized substrate glass bricks made of a specific substrate glass solution that meets specific thermal properties are heat-treated under the process conditions of a production line for mass-producing 3D curved microcrystalline glass, and prefabricated microcrystalline glass bricks with a uniform b-value distribution can be obtained. And for the planar microcrystalline glass products made by slicing the prefabricated microcrystalline glass bricks, 3D curved microcrystalline glass with better display effects can be obtained through thermoforming. Moreover, by making the substrate glass meet the requirement that the upper limit temperature Tmax(SiO2) of the precipitation of quartz crystal phase is lower than the upper limit temperature Tmax(Li2SiO3) of the precipitation of lithium metasilicate crystal phase within a specific temperature range, it can be ensured that during the heat treatment process conditions for preparing prefabricated microcrystalline glass with spodumene and lithium disilicate as the main crystal phases, the precipitation of quartz crystal phase can be effectively avoided. Combined with the subsequent thermoforming process, the lithium metasilicate crystal phase can also be transformed into the required lithium disilicate crystal phase, thereby avoiding the adverse effects of quartz crystal phase and lithium metasilicate crystal phase on the optical properties of microcrystalline glass.

[0176] Before preparing large-sized prefabricated microcrystalline glass bricks, substrate glass samples can be made according to the glass formula. Through the above-mentioned obtained characteristics, it can be verified in advance whether the glass solution is suitable for mass-producing qualified 3D curved microcrystalline glass products on the production line. If not, adjustments can be made in a timely manner, which can greatly save time and costs and effectively avoid waste of resources.

[0177] In some embodiments, in terms of the molar percentage of oxides, the composition of the 3D curved microcrystalline glass or the substrate glass for preparing the 3D curved microcrystalline glass both 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] Based on the content expressed by the molar percentage of each oxide in the composition of the 3D curved microcrystalline glass or the substrate glass for preparing the 3D curved microcrystalline glass, the composition of the 3D curved microcrystalline glass or the substrate glass for preparing the 3D curved microcrystalline glass both meets:

[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 microcrystalline glass, which includes the following steps:

[0188] (1) Heat-treat the aforementioned base glass to obtain a prefabricated microcrystalline glass product containing a lithium metasilicate crystal phase, a lithium disilicate crystal phase, and a spodumene crystal phase, and having a crystallinity of not less than 60.00 wt%;

[0189] (2) Process the prefabricated microcrystalline glass product obtained in step (1) into a planar microcrystalline glass sheet with the required specification dimensions, and perform a hot bending treatment on the obtained planar microcrystalline glass sheet to obtain 3D curved microcrystalline glass. The 3D curved microcrystalline glass contains a spodumene crystal phase and a lithium disilicate crystal phase, and the spodumene crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the microcrystalline glass.

[0190] In some embodiments, during the process of preparing 3D curved microcrystalline glass in this application, it may further include a process of performing conventional cold processing on the prefabricated microcrystalline glass product (such as bricks) obtained by heat-treating the base glass to obtain a planar microcrystalline glass with the required specification dimensions (such as a thickness of 0.2 mm - 2.0 mm), and then performing the hot bending treatment in step (2). Here, the cold processing includes shaping treatment, slicing treatment, CNC treatment, grinding treatment, polishing treatment, etc. commonly used in the art. Those skilled in the art can select one or more of the above methods to perform cold processing on the microcrystalline glass according to actual needs.

[0191] In this application, during the hot bending process, the further crystallization of the prefabricated glass-ceramic product may occur simultaneously, resulting in the crystallinity of the finally prepared 3D curved glass-ceramic being not less than that of the prefabricated glass-ceramic product.

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

[0193] In this application, in the above step (1), the conditions of the heat treatment have a relatively wide optional range, and those skilled in the art can select according to actual needs in the prior art. In some embodiments, in step (1), the heat treatment includes nucleation treatment and crystallization treatment. Among them, the temperature of the nucleation treatment is (Tg - 20 °C) to (Tg + 40 °C), the time of the nucleation treatment is 0 min - 6000 min, the temperature of the crystallization treatment is (T1 - 50 °C) to T1, and the time of the crystallization treatment is 30 min - 6000 min; Tg is the glass transition temperature of the substrate glass, and T1 is the temperature of the first exothermic peak in the DSC curve of the substrate glass during heating; in step (1), the heating rate of the heat treatment process is 5 °C / min - 15 °C / min. It should be understood that in this application, the nucleation treatment is to heat up to the specified nucleation treatment temperature (also called nucleation temperature), and after reaching the nucleation treatment temperature, keep warm for a certain time, and here the holding time is the time of the nucleation treatment (also called nucleation time). The crystallization treatment is to heat up to the specified crystallization treatment temperature (also called crystallization temperature), and after reaching the crystallization treatment temperature, keep warm for a certain time, and here the holding time is the time of the crystallization treatment (also called crystallization time). Adopting the above heat treatment process conditions is beneficial to obtaining a prefabricated glass-ceramic product with a specific microstructure and uniform structure, and can be used for hot bending to prepare a 3D curved glass-ceramic with spodumene crystal phase and lithium disilicate crystal phase as the main crystal phases, and excellent optical and mechanical properties.

[0194] In some embodiments, in step (1), the heat treatment includes nucleation treatment and crystallization treatment. Among them, the temperature of the nucleation treatment is (Tg - 20 °C) to (Tg + 40 °C), for example, it can be (Tg - 20 °C), (Tg - 15 °C), (Tg - 10 °C), (Tg - 5 °C), (Tg - 2 °C), Tg, (Tg + 2 °C), (Tg + 5 °C), (Tg + 10 °C), (Tg + 15 °C) or (Tg + 40 °C), or any value between these adjacent point values. Among them, Tg is the glass transition temperature of the substrate glass.

[0195] In some embodiments, in step (1), the time for nucleation treatment is 30 min - 360 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, 600 min, 1000 min, 2000 min, 3000 min, 4000 min, 5000 min or 6000 min, or any value between these adjacent point values.

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

[0197] In some embodiments, in step (1), the time for crystallization treatment is 30 min - 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 - 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 point values. The "heating rate" here includes the heating rate of the entire heat treatment process, that is, including the heating rate of the nucleation treatment process and the heating rate of the crystallization treatment process.

[0199] In some embodiments, in the above step (2), the hot bending treatment process includes at least 3 preheating stations, at least 3 hot pressing stations, and at least 3 cooling stations; the temperature of the preheating stations is 500°C - 850°C, the temperature of the hot pressing stations is 700°C - 900°C, the pressure of the hot pressing stations is 0 MPa - 1 MPa, and the temperature of the cooling stations is 500°C - 800°C. The conditions (such as temperature, pressure) of each preheating station, each hot pressing station, or each cooling station in the present application are the same or different. For example, the temperatures of each preheating station are the same or different.

[0200] In some embodiments, the temperature of the preheating stations 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 point values.

[0201] In some embodiments, the temperature of the hot pressing stations 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 point values.

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

[0203] In some embodiments, the temperature of the cooling stations 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 point values.

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

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

[0206] It should be understood that after chemical strengthening treatment, the composition at the surface of the glass-ceramic may be different from that of the freshly formed glass-ceramic (i.e., the glass-ceramic before chemical strengthening treatment and without an ion exchange process). This is because during chemical strengthening treatment, ion exchange occurs on the surface of the glass-ceramic, and one type of alkali metal ion in the freshly formed glass-ceramic (e.g., Li + or Na + ) is respectively replaced by a larger alkali metal ion (e.g., Na + or K + ). For example, Na + in the glass-ceramic exchanges with K + in the molten salt bath and is replaced by K + , and / or Li + in the glass-ceramic exchanges with Na + in the molten salt bath and is replaced by Na + . However, in an embodiment, the composition of the glass-ceramic at the center of the depth of the glass article or near the center of the depth still has the composition of the freshly formed glass-ceramic. That is, in the chemically strengthened glass-ceramic of the present application, the composition of the compressive stress layer formed by ion exchange on the surface may be different from that of the unstrengthened 3D curved glass-ceramic, while the composition at the center of the chemically strengthened glass-ceramic with a tensile stress (also called a tensile stress) inside still has the composition of the unstrengthened glass-ceramic.

[0207] In the present application, the optional range of the conditions of the chemical strengthening treatment for preparing the chemically strengthened glass-ceramic from the 3D curved glass-ceramic is relatively wide, and those skilled in the art can select according to actual needs. For example, in some embodiments, the salt bath for chemical strengthening treatment is a mixed molten salt, and the composition of the mixed molten salt 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°C - 530°C, and the time of chemical strengthening treatment 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 starting from the main surface of the chemically strengthened glass-ceramic. The range of CS_50 of this chemically strengthened glass-ceramic is within the above range, indicating that the compressive stress at a depth of 50 μm starting from the surface of the chemically strengthened glass-ceramic is high, which shows that this chemically strengthened glass-ceramic has a high surface stress level. And the more the remaining energy of the drop collision that can be offset by the higher surface compressive stress level, thus ensuring its excellent anti-damage performance.

[0209] In some embodiments, the depth of the compressive stress layer DOL_0 of the chemically strengthened glass-ceramics is 0.18t - 0.25t, where t is the thickness of the chemically strengthened glass-ceramics. When the DOL_0 of the chemically strengthened glass-ceramics is within the above range, it indicates that the chemically strengthened glass-ceramics have a high depth of the compressive stress layer, which is more conducive to offsetting the energy driving crack propagation, thereby ensuring its excellent anti-damage performance.

[0210] In some embodiments, the chemically strengthened glass-ceramics have 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-ceramics have 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. When the ∣CT_AV∣ of the chemically strengthened glass-ceramics is within the above range, it indicates that the chemically strengthened glass-ceramics have a relatively high tensile stress level, reflecting its relatively high surface stress level. The more residual energy of drop impact that can be offset by a relatively high surface compressive stress level, thereby ensuring its excellent anti-damage performance.

[0211] Meeting specific stress characteristics can ensure that the chemically strengthened glass-ceramics have excellent mechanical strength properties, especially excellent anti-drop performance.

[0212] In some embodiments, a 120-mesh sandpaper is used to conduct multiple fixed-point height drop tests on the chemically strengthened glass-ceramics with a thickness of 0.6 mm. The fixed-point height of the test is 1.0 m, and the number of times the chemically strengthened glass-ceramics drop until broken is ≥30, preferably ≥50. This shows that the chemically strengthened glass-ceramics of the present application have excellent anti-drop performance.

[0213] In some embodiments, the surface Na2O concentration of the chemically strengthened glass-ceramics is 5.0 wt% - 20.0 wt%. For example, the surface Na2O concentration of the chemically strengthened glass-ceramics 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 can be a value within the numerical range formed by any two of the above specific values as endpoints. By satisfying the surface Na2O concentration within the above range, it can not only ensure that the chemically strengthened glass-ceramics have a relatively optimal surface stress level, but also ensure that the chemically strengthened glass-ceramics have good weather resistance and chemical durability.

[0214] The 3D curved surface microcrystalline glass or chemically strengthened microcrystalline glass provided by the present application, which has excellent optical and mechanical properties, can be used for glass devices of any desired microcrystalline glass and can be used in many applications.

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

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

[0217] The embodiments of the present application are described in detail below. They are exemplary and are only used to explain the present application and should not be construed as a limitation to the present application. In the instance numbers in the following table, S refers to an embodiment, such as S1 refers to Embodiment 1; D refers to a comparative example, such as D1 refers to Comparative Example 1.

[0218] Embodiment 1

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

[0220] The situation of testing the substrate glass obtained in S1:

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

[0222] Ⅱ. Measure the Tg and the heating DSC curve of the substrate glass in S1, and record the first exothermic peak temperature T1, the second exothermic peak temperature T2 and their difference data in the heating DSC curve, as shown in Table 3 respectively. Figure 1 As shown, there are no exothermic peaks and endothermic peaks under the temperature conditions not involved.

[0223] Ⅲ. In the temperature range of T g -T2, test the upper limit temperature T max (Li2SiO3) of the lithium metasilicate crystal phase precipitated in the obtained substrate glass and the upper limit temperature T max (SiO2) of the quartz crystal phase precipitated in the substrate glass. T max (Li2SiO3) and T max (SiO2) are shown in Table 3 respectively, where T g is the glass transition temperature of the substrate glass.

[0224] (2) Preparation of the prefabricated glass-ceramics: Using a heat treatment roller kiln line, the substrate glass is processed through a heat treatment process to produce prefabricated glass-ceramic bricks. The heat treatment process is shown in Table 4 and includes nucleation treatment and crystallization treatment (denoted as heat treatment process C) carried out in sequence. The heating rate during the heat treatment process is 10 °C / min. After being taken out of the furnace, prefabricated glass-ceramic bricks are obtained.

[0225] The situation of testing the prefabricated glass-ceramic bricks obtained in S1:

[0226] Ⅰ. Through observation, the glass-ceramic bricks obtained in S1 are overall clear and transparent.

[0227] Ⅱ. Test the crystal phase composition, crystal phase content and crystallinity in the prefabricated glass-ceramics. The results are shown in Table 4.

[0228] Ⅲ. Test the range of the b values at nine locations on the main surface of the prefabricated glass-ceramics with the size specification of 360 mm (length) × 180 mm (width) × 30 mm (thickness). The results are shown in Table 4.

[0229] (3) Cold processing treatment of the prefabricated glass-ceramic bricks: Carry out cold processing treatment on the above-mentioned prefabricated glass-ceramic bricks. The cold processing treatment includes shaping treatment, slicing treatment, CNC treatment, grinding treatment and polishing treatment carried out in sequence to obtain a planar glass-ceramic sheet with the size of 170 mm (length) × 80 mm (width) × 0.6 mm (thickness). Test the range and average value of the b values at nine locations on the main surface of the obtained planar glass-ceramic sheet. The results are shown in Table 4.

[0230] (4) Preparation of the 3D curved glass-ceramics: Place the obtained planar glass-ceramic sheet on a 3D hot bending machine to be formed by hot bending treatment to obtain 3D curved glass-ceramics. 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 treatment process (denoted as hot bending process C1) includes 3 preheating workstations, 3 hot pressing workstations and 3 cooling workstations respectively; the temperatures of the 3 preheating workstations set in sequence are 590 °C, 680 °C and 790 °C, the temperatures and pressures of the 3 hot pressing workstations set in sequence are 790 °C / 0.4 MPa, 790 °C / 0.4 MPa and 790 °C / 0.2 MPa, and the temperatures of the 3 cooling workstations set in sequence are 790 °C, 650 °C and 600 °C; the residence time of each workstation is 90 s.

[0231] The situation of testing the 3D curved glass-ceramics obtained in S1:

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

[0233] II. The crystal phase composition in the 3D curved surface microcrystalline glass was tested, and the results are shown in Table 4. After calculation, the average crystal size in this 3D curved surface microcrystalline glass is 19 nm.

[0234] III. The XRD diffraction curves at the positions with the maximum b value and the minimum b value in nine b value tests of the 3D curved surface microcrystalline glass sheet were tested, and the comparison is as Figure 10 shown. It can be seen from Figure 10 that in this microcrystalline glass, the crystal phase structures at the position with the maximum b value and the position with the minimum b value on the main surface are basically the same or have very little difference, which indicates that the 3D curved surface microcrystalline glass sheet is relatively uniform as a whole, and the optical display effects tend to be consistent.

[0235] IV. The transmittance of the 3D curved surface microcrystalline glass was tested. As Figure 13 shown, it can be seen that the 3D curved surface microcrystalline glass of this application has a high transmittance in the visible light band range and excellent light transmittance.

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

[0237] The situation of testing the chemically strengthened microcrystalline glass obtained in S1: The CS_50, |CT_AV|, and DOL_0 of the chemically strengthened microcrystalline glass were tested using a stress tester. The obtained chemically strengthened microcrystalline glass was subjected to a 1.0 m fixed-point height anti-drop performance test through a 120-mesh sandpaper; the test data are shown in Table 5 respectively.

[0238] Examples 2 to 13

[0239] They were respectively carried out with reference to Example 1, and the hot bending treatment process was the same as that in Example 1. The differences are that the raw material compositions and their corresponding test results of each example are shown in Tables 1 - 5 respectively.

[0240] The 3D curved surface microcrystalline glasses of Examples 2 to 13 all meet the following: Overall, they are clear and transparent in appearance; the crystalline phases of the 3D curved surface microcrystalline glass are mainly Li2Si2O5, LiAlSi4O 10 , and there is no quartz crystal phase. After calculation, the average crystal size in the 3D curved surface microcrystalline glasses of Examples 2 to 13 is 10 - 50 nm.

[0241] The XRD diffraction pattern obtained after the heat treatment process C before hot bending of the base glass of Example 2 is as follows Figure 8 shown. Among them, the heating DSC curve measured for the base glass of Example 10 is as follows Figure 2 shown.

[0242] Comparative Example 1 - Comparative Example 13

[0243] They were respectively carried out with reference to Example 1, and the hot bending treatment process was the same as that of Example 1. The difference was that the raw material compositions and their corresponding test results of each comparative example are shown in Tables 6 to 11 respectively.

[0244] Among them, the heating DSC curve of Comparative Example 1 is as follows Figure 3 shown. The heating DSC curve of Comparative Example 2 is as follows Figure 4 shown, and the XRD diffraction pattern obtained after the base glass of Comparative Example 2 was subjected to the heat treatment process C is as follows Figure 9 shown. In the nine b-value tests of the glass-ceramic sheet of Comparative Example 6, the comparison of the XRD diffraction curves at the positions with the maximum b value and the minimum b value is as follows Figure 11 shown. It can be seen from the figure that there are obvious differences in the crystal phase structures at the positions with the maximum b value and the minimum b value on the main surface of this 3D curved glass-ceramic sheet, which indicates that the microstructures in different regions of this 3D curved glass-ceramic sheet are inconsistent, and this will lead to differences in its overall display effect, resulting in local color development and / or uneven overall color development on the main surface. Cracking occurred during the 3D hot bending forming process of the prefabricated glass-ceramic of Comparative Example 7, as follows Figure 12 shown.

[0245] After calculation, the average crystal size in the 3D curved glass-ceramics of Comparative Example 1 - Comparative Example 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 crystal phase does not appear, so there is no quartz disappearance temperature; the same applies to the interpretation in the corresponding tables of the comparative examples.

[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] From the examples in Tables 1 - 5 and the comparative results in Tables 6 - 11 above, it can be seen that, compared with the comparative examples, by adopting the example solutions of the present application, while satisfying the content ranges of various oxides, the following are also satisfied: 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 ≤ 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, 12.200 ≤ (5.6B2O3 + 10Al2O3 + 6.5CaO) / ZrO2 ≤ 20.000. The large-sized base material glass bricks prepared have a clear and transparent appearance, and T max (Li2SiO3) ≥ Tmax (SiO2) The 3D curved surface microcrystalline glass that facilitates 3D hot bending has good and uniform optical properties. In the heating DSC curve of the substrate glass tested by synchronous thermal analysis, there are at least two exothermic peaks at appropriate temperatures.

[0273] The large-sized substrate glass bricks prepared by the embodiments of the present application and heat-treated to obtain prefabricated microcrystalline glass bricks also have transparent and clear appearances. The difference in b values in different regions of the main surface of the prefabricated microcrystalline glass bricks is small, and the uniformity is good. Moreover, no quartz crystal phase is contained in the prefabricated microcrystalline glass. In the 3D curved surface microcrystalline glass prepared by hot bending the prefabricated microcrystalline glass, the range of b values at nine positions on the main surface is low and the average value of b values is also low, indicating that the 3D curved surface microcrystalline glass has excellent optical properties and good display effects. At the same time, by chemically strengthening the obtained 3D curved surface microcrystalline glass, a chemically strengthened microcrystalline glass with high CS_50, |CT_AV|, and DOL_0 can be obtained.

[0274] In the solutions of Comparative Examples 1-8 and Comparative Example 12, the formula of the substrate glass does not simultaneously satisfy the following: the content ranges of various oxides in the present 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, 1.500 ≤ 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, 12.200 ≤ (5.6B2O3 + 10Al2O3 + 6.5CaO) / ZrO2 ≤ 20.000. When preparing large-sized prefabricated microcrystalline glass bricks by heat-treating the large-sized substrate glass bricks prepared by these solutions, the difference in b values in different regions of the main surface of the prepared prefabricated microcrystalline glass bricks is large, and this large difference continues into the 3D curved surface microcrystalline glass obtained by hot bending, resulting in poor optical properties and causing the display effect of the 3D curved surface microcrystalline glass not to meet the usage requirements, and even cracking occurs.

[0275] In the solutions of Comparative Examples 9-10, after preparing the large-sized substrate glass bricks, milky white precipitates directly appear in the substrate glass bricks, the optical properties deteriorate, and the transmittance decreases. In the solutions of Comparative Examples 11-12, the microcrystalline glass produced in large quantities cannot achieve the required excellent mechanical properties after chemical strengthening treatment, and the anti-drop effect is significantly worse than that of the products of the present application. In the solution of Comparative Example 13, milky white precipitates and undissolved substances appear in the prepared large-sized substrate glass bricks.

[0276] The preferred embodiments of the present application have been described in detail above. However, the present application is not limited thereto. Within the technical concept scope of the present application, various simple modifications can be made to the technical solutions of the present application, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A chemically strengthened microcrystalline glass, characterized in that, It includes a first region, and the first region contains a tensile stress layer region. The composition of the tensile stress layer region includes: In terms of 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%; And in terms of the content expressed by 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.

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

3. The chemically strengthened glass-ceramics according to claim 1 or 2, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: In terms of molar percentage of oxides, Composition 1, the tensile stress layer region contains SiO2 of 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%; Component II. The tensile stress layer region contains 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; Component III. The tensile stress layer region contains 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; Component IV. The tensile stress layer region contains 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; Component V. The tensile stress layer region contains 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; Component VI. The tensile stress layer region contains 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; Component VII. The tensile stress layer region contains 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; Composition VIII. The tensile stress layer region contains 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; Composition IX. The tensile stress layer region contains 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.

4. The chemically strengthened glass-ceramics according to any one of claims 1-3, characterized in that, The tensile stress layer region satisfies at least one of the following compositions: in terms of mole percentage of oxides, Composition I. 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, or SiO2 within the numerical range formed by any two of the above specific values as endpoints; Composition II. 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, or Al2O3 within the numerical range formed by any two of the above specific values as endpoints; Composition III. 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, or Li2O within the numerical range formed by any two of the above specific values as endpoints; Component IV. 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, or P2O5 within the numerical range formed by any two of the above specific numerical values as endpoints; Component V. 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, or ZrO2 within the numerical range formed by any two of the above specific numerical values as endpoints; Component VI. 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, or B2O3 within the numerical range formed by any two of the above specific numerical values as endpoints; Component VII. 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% of Na2O, or Na2O within the numerical range formed by any two of the above specific numerical values as endpoints; Component VIII. 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% of K2O, or K2O within the numerical range formed by any two of the above specific numerical values as endpoints; Component IX. 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, or CaO within the numerical range formed by any two of the above specific numerical values as endpoints.

5. The chemically strengthened glass-ceramics according to any one of claims 1-4, characterized in that, Based on the content expressed in the molar percentages of each oxide, the composition of the tensile stress layer region satisfies: The value of Li2O / P2O5 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, or a value within the numerical range formed by any two of the above specific numerical values as endpoints; 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, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints; 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, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints; and / or, (5.6×B2O3+10×Al2O3+6.5×CaO) / ZrO2 has a value of 12.200, 13.000, 14.000, 15.000, 16.000, 17.000, 18.000, 19.000 or 20.000, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints.

6. The chemically strengthened glass-ceramics according to any one of claims 1-5, characterized in that, Based on the content expressed in mole percentages of each oxide, the composition of the tensile stress layer region further satisfies: 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.

7. The chemically strengthened microcrystalline glass according to claim 6, wherein Based on the content expressed in mole percentages of each oxide, the composition of the tensile stress layer region further satisfies: The value of 5×P2O5 / (Li2O+0.5Al2O3) is 0.180, 0.184, 0.190, 0.200, 0.210, 0.220, 0.230, 0.240, 0.245 or 0.250, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints; and / or, (SiO2-7Al2O3-Li2O) / (P2O5+ZrO2) has a value of 4.000, 4.200, 4.500, 5.000, 5.500 or 6.000, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints; 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, or is a value within the numerical range formed by any two of the above specific numerical values as endpoints.

8. The chemically strengthened glass-ceramics according to any one of claims 1-7, characterized in that, Based on the content expressed in mole percentages of each oxide, the composition of the tensile stress layer region satisfies: 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.

9. The chemically strengthened glass-ceramics according to any one of claims 1-8, characterized in that, Based on the contents expressed in mole percentages of each oxide, the composition of the compressive stress layer region satisfies: 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.

10. The chemically strengthened glass-ceramics according to any one of claims 1-9, characterized in that, The chemically strengthened glass-ceramics contain spodumene crystal phase and lithium disilicate crystal phase, wherein the spodumene crystal phase and the lithium disilicate crystal phase have a higher weight percentage than other crystal phases present in the chemically strengthened glass-ceramics.

11. The chemically strengthened microcrystalline glass according to any one of claims 1-10, characterized in that, In the chemically strengthened glass-ceramics, the total content of the spodumene crystal phase and the lithium disilicate crystal phase accounts for more than 60.00 wt% of the mass of the chemically strengthened glass-ceramics, preferably more than 70.00 wt%, more preferably more than 80.00 wt%; and / or, In the chemically strengthened glass-ceramics, the average crystal size does not exceed 100 nm.

12. The chemically strengthened glass-ceramics according to any one of claims 1-11, characterized in that, The chemically strengthened glass-ceramics do not contain quartz crystal phase.

13. The chemically strengthened glass-ceramics according to any one of claims 1-12, characterized in that, The chemically strengthened glass-ceramics are transparent in the visible light range. Preferably, the transmittance of the chemically strengthened glass-ceramics with a thickness of 0.6 mm in the visible light range is not less than 90%.

14. The chemically strengthened glass-ceramics according to any one of claims 1-13, characterized in that, When the thickness is 0.6 mm, the optical b value of the chemically strengthened glass-ceramics ≤ 1.00, preferably the optical b value ≤ 0.70, more preferably the optical b value ≤ 0.55; and / or, when the thickness of the chemically strengthened glass-ceramics is 0.6 mm, the haze ≤ 0.20%.

15. The chemically strengthened glass-ceramics according to any one of claims 1-14, characterized in that, The chemically strengthened microcrystalline glass is obtained by chemically strengthening 3D curved surface microcrystalline glass.

16. The chemically strengthened glass-ceramics according to any one of claims 1-15, characterized in that, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0wt%-20.0wt%.

17. The chemically strengthened glass-ceramics according to claim 16, wherein, The surface Na2O concentration of the chemically strengthened microcrystalline glass is 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt%, 10.0wt%, 11.0wt%, 12.0wt%, 13.0wt%, 14.0wt%, 15.0wt%, 16.0wt%, 17.0wt%, 18.0wt%, 19.0wt% or 20.0wt%, or is a value within the numerical range formed by any two of the above specific values as endpoints.

18. The chemically strengthened microcrystalline glass according to any one of claims 1-17, characterized in that, The chemically strengthened microcrystalline glass further includes a compressive stress layer region extending from the surface of the chemically strengthened microcrystalline glass to the compressive depth.

19. The chemically strengthened glass-ceramics according to claim 18, wherein, The depth of the compressive stress layer DOL_0 of the chemically strengthened microcrystalline glass is 0.18t - 0.25t, where t is the thickness of the chemically strengthened microcrystalline glass; and / or, The chemically strengthened microcrystalline glass has a CS_50 of 110 - 200 MPa, and CS_50 refers to the compressive stress value at a depth of 50 μm starting from the main surface of the chemically strengthened microcrystalline glass.

20. The chemically strengthened glass-ceramics according to any one of claims 1-19, characterized in that, The chemically strengthened microcrystalline glass has a |CT_AV| of 84 - 140 MPa, and |CT_AV| refers to the absolute value of the average tensile stress.

21. The chemically strengthened glass-ceramics according to claim 20, wherein, The chemically strengthened microcrystalline glass 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.

22. The chemically strengthened glass-ceramics according to any one of claims 1-21, characterized in that, Using 120-mesh sandpaper, multiple fixed-point height drop tests are performed on the chemically strengthened microcrystalline glass with a thickness of 0.6 mm. The fixed-point height of the test is 1.0 m, and the number of times the chemically strengthened microcrystalline glass drops until it breaks is ≥30, preferably ≥50.

23. A method for preparing chemically strengthened microcrystalline glass, characterized in that, It is used to prepare the chemically strengthened microcrystalline glass as described in any one of claims 1 - 22. The preparation method includes chemically strengthening 3D curved surface microcrystalline glass. The composition of the 3D curved surface microcrystalline glass includes: In terms of molar percentage of oxides, SiO2: 60.00mol% - 71.00mol%, Al2O3: 1.50mol% - 5.00mol%, P2O5: 0.80mol% - 1.50mol%, ZrO2: 2.00mol% - 4.00mol%, Na2O: 0.00mol% - 1.00mol%, K2O: 0.00mol% - 0.50mol%, Li2O: 20.00mol% - 30.00mol%, CaO: 0.00mol% - 1.60mol%, B2O3: 0.00mol% - 1.00mol%; And in terms of the content expressed by the molar percentage of each oxide, the composition of the 3D curved surface microcrystalline glass satisfies: 18.200 ≤ Li2O / P2O5 ≤ 25.500; 1. 500 ≤ 10×(ZrO2 + P2O5) / Li2O ≤ 2,000; 2. 600 ≤ 99×(CaO + ZrO2) / (Li2O + Na2O + 1,000K2O) ≤ 5,000; 12. 200 ≤ (5.6B2O3 + 10Al2O3 + 6.5CaO) / ZrO2 ≤ 20,000.

24. The method for preparing chemically strengthened microcrystalline glass according to claim 23, characterized in that, The salt bath for chemical strengthening treatment is a mixed molten salt, and the composition of the mixed molten salt includes: 0 < NaNO3 < 100 wt%, 0 < KNO3 < 100 wt%, and 0 < LiNO3 ≤ 0.2 wt%; and / or, The temperature of the salt bath for chemical strengthening treatment is 430°C - 530°C, and the time for chemical strengthening treatment is 0.5 h - 15.0 h.

25. A glass device, characterized in that, The glass device includes the chemically strengthened glass-ceramics as described in any one of claims 1 - 22, or includes the chemically strengthened glass-ceramics prepared by the preparation method of the chemically strengthened glass-ceramics as described in claim 23 or 24.

26. An electronic device, characterized in that, The electronic device includes the chemically strengthened glass-ceramics as described in any one of claims 1 - 22, or includes the chemically strengthened glass-ceramics prepared by the preparation method of the chemically strengthened glass-ceramics as described in claim 23 or 34.

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