Toughened glass ceramic with high strength and use thereof

Abstract

The present application provides a toughened glass ceramic with a high strength and the use thereof. The toughened glass ceramic comprises a major crystal phase, i.e., a (Zn, Mg)Al2O4 crystal phase, and a secondary crystal phase, i.e., a tetragonal ZrO2 crystal phase. The toughened glass ceramic includes a compressive stress layer region extending from a surface of the toughened glass ceramic to a depth of compression, and there is a tensile stress layer region inside the toughened glass ceramic. The depth DOL_0 of a compressive stress layer of the toughened glass ceramic is greater than or equal to 0.21 t, wherein t is the thickness of the toughened glass ceramic; |CT_AV|≥70 MPa; and the toughened glass ceramic is endowed with a specific stress structure by satisfying the DOL_0 and |CT_AV|, and therefore the toughened glass ceramic has good drop impact resistance and a high mechanical strength.

Description

A reinforced glass ceramic with high strength and its application

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on December 25, 2023, with application number 202311800642.5 and application name “A reinforced glass-ceramic with high strength and its application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application relates to the technical field of glass ceramics, and in particular to a reinforced glass ceramic with high strength and applications thereof. Background Art

[0003] A common cause of glass breakage in electronic devices is when the protective glass is dropped. Analysis of the drop process reveals that the glass surface collides with a sharp object of equal or greater hardness (such as sand, cement, or pebbles), causing localized damage. This creates a hemispherical crack propagation source at the point of failure, partially attenuating the collision energy. The remaining energy propagates further. When the compressive stress level on the glass surface is insufficient to offset the remaining energy, the crack propagates through the glass surface. When a longitudinal crack penetrates the compressive stress layer and reaches the tensile stress layer (also known as the tensile stress layer), the crack rapidly propagates in this tensile stress zone, penetrating the entire glass and causing it to shatter or break.

[0004] It can be seen that the depth of the compressive stress layer and the deep stress of a glass product are closely related to its drop damage resistance. When the depth of the compressive stress layer is constant, the greater the deep stress, the more the surface compressive stress level can offset the residual energy of the drop collision. If the surface compressive stress level is insufficient to offset the residual energy of the drop collision, the deeper the compressive stress layer of the glass, the more it can offset the energy driving crack propagation.

[0005] Therefore, in order to further improve the drop impact resistance of glass ceramics, it is necessary to develop a reinforced glass ceramic with large deep stress and ultra-high compressive stress layer depth and high mechanical strength, especially high-strength transparent reinforced glass ceramic with excellent light transmittance or transmittance.

[0006] Summary of the Invention

[0007] The purpose of this application is to provide a high-strength reinforced glass-ceramic and its application, wherein the reinforced glass-ceramic has a large deep stress and an ultra-high compressive stress layer depth, forming a specific stress structure, thereby giving the reinforced glass-ceramic excellent drop impact resistance.

[0008] The technical solutions provided in this application are as follows:

[0009] In the first aspect, a reinforced glass-ceramic is provided, wherein the reinforced glass-ceramic contains a main crystal phase (Zn, Mg)Al2O4 crystal phase and a secondary crystal phase tetragonal ZrO2 crystal phase; the reinforced glass-ceramic contains a compressive stress layer region extending from the surface of the reinforced glass-ceramic to a compression depth, and has a tensile stress layer region inside; the compressive stress layer depth DOL_0 of the reinforced glass-ceramic is ≥0.21t, preferably, 0.21t≤DOL_0≤0.25t, t is the thickness of the reinforced glass-ceramic; the |CT_AV| of the reinforced glass-ceramic is ≥70MPa, preferably, 70MPa≤|CT_AV|≤110MPa. The reinforced glass ceramics of the present application have a (Zn, Mg)Al2O4 crystal phase (in the present application, (Zn, Mg)Al2O4 is used to represent the solid solution of zinc spinel and magnesium spinel, or also called zinc aluminum spinel-magnesium aluminum spinel solid solution, zinc magnesium spinel solid solution, zinc spinel-magnesium spinel solid solution, zinc magnesium aluminum spinel solid solution) with high hardness and high modulus as the main crystal phase, which gives the reinforced glass ceramics high intrinsic strength or inherent strength. At the same time, the ultra-high compressive stress layer depth and large deep stress of the reinforced glass ceramics of the present application give the reinforced glass ceramics a specific stress structure. Through the synergistic effect of the specific crystal phase structure and the specific stress structure, the reinforced glass ceramics of the present application have ultra-high mechanical strength, and especially the reinforced glass ceramics have excellent drop impact resistance.

[0010] In some embodiments of the present application, based on the mass of the strengthened glass-ceramics, the total content of (Zn, Mg)Al2O4 crystal phase and tetragonal ZrO2 crystal phase is 25.00wt% to 70.00wt%, preferably 30.00wt% to 50.00wt%, wherein the ratio of (Zn, Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase (i.e., the mass ratio of (Zn, Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase) is 1.00 to 18.00, preferably 1.00 to 15.00; and / or, in the strengthened glass-ceramics, the average crystal size of the (Zn, Mg)Al2O4 crystal phase is 3.0nm to 10.0nm, preferably 4.0nm to 7.5nm, more preferably 4.5nm to 7.5nm; and / or, the strengthened glass-ceramics is transparent in the visible light range. When the total crystal phase content W, the ratio of (Zn, Mg)Al2O4 crystal phase and tetragonal ZrO2 crystal phase (mass ratio Z), and the average crystal size of the (Zn, Mg)Al2O4 crystal phase in the strengthened glass-ceramics are within the above-mentioned ranges, the strengthened glass-ceramics are endowed with a specific crystal phase structure. This crystal phase structure is not only beneficial for the chemically strengthened glass-ceramics to obtain the desired stress structure during chemical strengthening, but also enables the strengthened glass-ceramics obtained after strengthening to achieve excellent optical transmittance.

[0011] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic, calculated by molar percentage of oxides, includes: SiO 35.00 mol% to 60.00 mol%, Al 2 O 20.00 mol% to 40.00 mol%, ZrO 2 2.00 mol% to 8.00 mol%, MgO 3.00 mol% to 7.50 mol%, ZnO 7.00 mol% to 13.00 mol%, Na 2 O 1.00 mol% to 10.00 mol%, and Li 2.50 mol% to 10.00 mol%. Adopting the above glass formulation is conducive to ensuring the preparation of chemically strengthened glass-ceramics that meet high intrinsic strength and have spinel as the main crystal phase, thereby facilitating the production of strengthened glass-ceramics that meet the desired stress structure.

[0012] In some embodiments of the present application, the reinforced glass-ceramic contains a (Zn, Mg)Al2O4 crystalline phase accounting for 15.00 wt% to 45.00 wt% of the reinforced glass-ceramic. (Zn, Mg)Al2O4 crystals have high hardness and high modulus. By precipitating an appropriate amount of (Zn, Mg)Al2O4 in the glass-ceramic, it is possible to impart high intrinsic strength or inherent strength to the glass-ceramic. At the same time, by controlling the content of the (Zn, Mg)Al2O4 crystalline phase, the glass-ceramic satisfies a specific crystalline phase structure, which helps ensure that the chemical strengthening of the glass-ceramic obtains an ideal stress structure.

[0013] In some embodiments of the present application, W [(Zn，Mg)Al2O4] is the weight percentage of (Zn, Mg)Al2O4 phase in the strengthened glass ceramic, W [Al2O3] is the weight percentage of Al2O3 in the strengthened glass ceramic, W [MgO] is the weight percentage of MgO in the strengthened glass ceramic, W [ZnO] is the weight percentage of ZnO in the strengthened glass ceramic,

[0014] A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2,

[0015] B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] +W [ZnO] ),

[0016] C = A / B, and in the strengthened glass-ceramic, 1.50 ≤ C ≤ 1.85. By optimizing the composition and structure to ensure that the (Zn, Mg)Al2O4 crystalline phase content, as well as the Al2O3, MgO, and ZnO contents in the glass-ceramic meet the aforementioned characteristic C range, the chemically strengthened glass-ceramic can achieve the desired stress structure after chemical strengthening, thereby achieving high mechanical strength and, in particular, excellent damage resistance.

[0017] In some embodiments of the present application, the value of A is 10.00% to 25.00%, preferably 14.00% to 25.00%; and / or,

[0018] The value of B is 7.50% to 12.50%, preferably 8.00% to 12.00%. By ensuring that the values ​​of A and B are within the above range, it is beneficial to ensure that C meets its value range.

[0019] In some embodiments of the present application, the CS_50 of the strengthened glass-ceramic is ≥ 100 MPa, preferably 100 MPa ≤ CS_50 ≤ 250 MPa. A CS_50 value within the above range indicates that the strengthened glass-ceramic has high compressive stress at a depth of 50 μm from the surface, indicating that the strengthened glass-ceramic has a relatively high surface stress level.

[0020] In some embodiments of the present application, the Vickers hardness of the reinforced glass-ceramic is greater than or equal to 790 kgf / mm 2 , preferably 790kgf / mm 2 ~1000kgf / mm 2 The Vickers hardness of the strengthened glass-ceramic is within the above range, indicating that the strengthened glass-ceramic has high hardness, thereby ensuring that it has excellent mechanical properties.

[0021] In some embodiments of the present application, the fracture toughness of the reinforced glass-ceramic is greater than or equal to 1.00 MPa·m 1 / 2 , preferably greater than or equal to 1.20 MPa·m 1 / 2 , more preferably greater than or equal to 1.55 MPa·m 1 / 2 , for example, it may be preferably 1.55 MPa·m 1 / 2 ~2.00MPa·m 1 / 2 The fracture toughness of the reinforced glass-ceramic is within the above range, indicating that the reinforced glass-ceramic has high fracture toughness, thereby ensuring that it has excellent mechanical properties.

[0022] In some embodiments of the present application, the reinforced glass-ceramic has a |CT_CV| value of ≥ 80 MPa, preferably 80 MPa ≤ |CT_CV| ≤ 150 MPa. A |CT_CV| value within the above range indicates that the reinforced glass-ceramic has a high tensile stress level, which in turn reflects a high surface stress level, thereby ensuring excellent damage resistance.

[0023] In some embodiments of the present application, in the X-ray diffraction pattern of the strengthened glass-ceramic, the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 28° to 32° is taken as the first characteristic peak, and the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 36° to 38° is taken as the second characteristic peak. The peak intensity ratio X of the first characteristic peak to the second characteristic peak is 0.80 to 1.50, preferably 0.85 to 1.30. In the XRD diffraction pattern, the peak intensity of the characteristic peak can reflect the integrity of the crystals in the glass-ceramic. By ensuring that the peak intensity ratio of the above two characteristic peaks is within this range, the present application helps to obtain suitable crystal integrity, thereby helping to achieve better optical and strengthening effects.

[0024] In some embodiments of the present application, in the X-ray diffraction pattern of the strengthened glass-ceramic, the characteristic peak of the

[0400] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 44° to 46°, the characteristic peak of the

[0311] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 34° to 38°, and the characteristic peak of the

[0440] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 64° to 67°;

[0025] The half-peak width W of the characteristic peak of the

[0400] crystal plane

[0400] 0.650°~1.800°, preferably W

[0400] 0.900° to 1.600°;

[0026] The half-peak width W of the characteristic peak of the

[0311] crystal plane

[0311] 0.900°~2.800°, preferably W

[0311] 1.100° to 2.230°;

[0027] The half-peak width W of the

[0440] crystal plane characteristic peak

[0440] 0.750°~2.000°, preferably W

[0440] In the present application, the half-widths of the characteristic peaks of the

[0400] crystal plane, the

[0311] crystal plane, and the

[0440] crystal plane can reflect the size of the (Zn, Mg)Al2O4 crystals in the glass-ceramics. By meeting the above ranges, it is beneficial to ensure that the chemically strengthened glass-ceramics have a specific crystal size and crystal phase structure, thereby helping to ensure that the strengthened glass-ceramics obtain the desired optical properties and stress levels.

[0028] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic further comprises, by mole percentage of oxides, 0.00 mol% to 5.00 mol% of K2O, 0.00 mol% to 10.00 mol% of CaO, 0.00 mol% to 10.00 mol% of B2O3, and 0.00 mol% to 5.00 mol% of BaO. In the glass system of the present application, K2O, CaO, B2O3, or BaO are optional components. Their appropriate use can improve the forming, crystallization, chemical strengthening, or optical properties of the glass-ceramic.

[0029] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic, calculated by molar percentage of oxides, includes: 35.00 mol% to 60.00 mol% SiO2, 20.00 mol% to 40.00 mol% Al2O3, 2.00 mol% to 8.00 mol% ZrO2, 4.00 mol% to 7.00 mol% MgO, 9.00 mol% to 12.00 mol% ZnO, 2.00 mol% to 10.00 mol% Na2O, and 3.00 mol% to 10.00 mol% Li2O. Properly adjusting the content of MgO, ZnO, Li2O, or Na2O helps ensure that the main crystalline phase content in the chemically strengthened glass-ceramic meets a desired level, and also helps ensure that the chemically strengthened glass-ceramic achieves the desired chemical strengthening effect, thereby obtaining a strengthened glass-ceramic with a high stress level.

[0030] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic, calculated by mole percentage of oxides, includes: 35.00 mol% to 50.00 mol% SiO2, 25.00 mol% to 35.00 mol% Al2O3, 3.00 mol% to 5.00 mol% ZrO2, 4.00 mol% to 7.00 mol% MgO, 9.00 mol% to 12.00 mol% ZnO, 2.00 mol% to 10.00 mol% Na2O, and 3.00 mol% to 10.00 mol% Li2O. Properly adjusting the content of each essential oxide helps ensure that the chemically strengthened glass-ceramic achieves a desired crystalline phase structure and glass network structure capable of achieving a high stress level, thereby facilitating the production of strengthened glass-ceramics with a high stress level.

[0031] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic satisfies, based on the molar percentage of each oxide in the strengthened glass-ceramic composition:

[0032] 1.30≤ZnO / MgO≤2.50; and / or,

[0033] 0.05≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.20; and / or,

[0034] 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60; and / or,

[0035] 0.26≤Na2O / Li2O≤3.00.

[0036] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic further satisfies, based on the molar percentage of each oxide in the strengthened glass-ceramic composition:

[0037] 12.00 mol%≤ZnO+MgO≤20.00 mol%, preferably, 13.00 mol%≤ZnO+MgO≤17.30 mol%; and / or,

[0038] 9.00 mol%≤Al2O3-(MgO+ZnO)≤22.00 mol%, preferably, 10.00 mol%≤Al2O3-(MgO+ZnO)≤20.00 mol%; and / or,

[0039] 5.00 mol%≤Na2O+Li2O≤15.00 mol%, preferably, 6.00 mol%≤Na2O+Li2O≤13.50 mol%.

[0040] In some embodiments of the present application, the 0.7 mm thick reinforced glass-ceramic exhibits a transmittance of greater than or equal to 85.00% at a wavelength of 550 nm. The transmittance of the 0.7 mm thick reinforced glass-ceramic at a wavelength of 550 nm is within the aforementioned range, indicating that the reinforced glass-ceramic of the present application has high light transmittance. Furthermore, the reinforced glass-ceramic of the present application also exhibits high mechanical strength, particularly excellent drop impact resistance, effectively broadening the application scenarios and fields of the reinforced glass-ceramic of the present application.

[0041] In some embodiments of the present application, a 0.7 mm thick reinforced glass-ceramic is subjected to a drop resistance test using 80-grit sandpaper. The average sandpaper drop resistance height of the reinforced glass-ceramic is greater than or equal to 1.00 m, preferably greater than or equal to 1.40 m, and more preferably between 1.50 m and 2.50 m. The average sandpaper drop resistance height H of the 0.7 mm thick reinforced glass-ceramic is within the above range, indicating that the reinforced glass-ceramic of the present application has excellent drop impact resistance.

[0042] In some embodiments of the present application, the strengthened glass-ceramic is obtained by chemically strengthening a chemically strengthened glass-ceramic, and the composition of the chemically strengthened glass-ceramic is the same as the composition at the center of the strengthened glass-ceramic.

[0043] In a second aspect, a glass device is provided, which is made of the reinforced glass ceramic according to any one of the aforementioned embodiments.

[0044] In a third aspect, an electronic device is provided, comprising the reinforced glass ceramic according to any of the aforementioned embodiments.

[0045] In some embodiments of the present application, the electronic device includes at least one of a mobile phone, a tablet computer, a smart wearable, a display, and a television.

[0046] One or more technical solutions of this application have the following advantages or beneficial effects:

[0047] The present application provides a high-strength reinforced glass-ceramic and its application. The reinforced glass-ceramic of the present application is mainly composed of a (Zn, Mg)Al2O4 crystal phase (a solid solution of zinc spinel and magnesium spinel) with high hardness and high modulus, which gives the reinforced glass-ceramic high intrinsic strength or inherent strength. At the same time, the ultra-high compressive stress layer depth and large deep stress of the reinforced glass-ceramic of the present application give the reinforced glass-ceramic a specific stress structure. Through the synergistic effect of the specific crystal phase structure and the specific stress structure, the reinforced glass-ceramic of the present application has ultra-high mechanical strength and high damage resistance, especially the reinforced glass-ceramic has excellent drop impact resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] The drawings described herein are used to provide further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute improper limitations on the present application.

[0049] FIG1 is a schematic diagram of the structure of a strengthened glass-ceramic in some embodiments of the present application, wherein t is the thickness of the glass, d is the depth of the compressive stress layer, 11 is the compressive stress layer, and 12 is the tensile stress layer;

[0050] FIG2 is a comparison of XRD diffraction patterns of the chemically strengthened glass-ceramics in Examples 1 to 2 and Comparative Examples 6 to 9;

[0051] FIG3 is an XRD diffraction pattern of the chemically strengthened glass-ceramic in Comparative Example 8;

[0052] FIG4 is an XRD diffraction pattern of the chemically strengthened glass-ceramic in Example 2;

[0053] FIG5 is an XRD diffraction pattern of the chemically strengthened glass-ceramic in Comparative Example 10;

[0054] FIG6 is an XRD diffraction pattern of the chemically strengthened glass-ceramic in Comparative Example 11;

[0055] FIG7 is a transmittance curve of the chemically strengthened glass-ceramic in Example 1 under different wavelength conditions;

[0056] FIG8 is a comparison diagram of XRD diffraction of the chemically strengthened glass-ceramic in Example 1 before and after chemical strengthening;

[0057] FIG9 is a comparison diagram of transmittance curves of the chemically strengthened glass-ceramics in Example 1 under different wavelength conditions before and after chemical strengthening. DETAILED DESCRIPTION

[0058] To make the objectives, technical solutions, and advantages of this application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and examples. It is apparent that the described examples are only a portion of the embodiments of this application, rather than all of them. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0059] Explanation of terms

[0060] DOL_0: Depth of compressive stress layer, also known as depth of compressive stress layer, refers to the distance along the thickness direction from any surface of the strengthened glass-ceramic to the position close to the surface where the compressive stress is zero.

[0061] |CT_AV|: refers to the absolute value of the average tensile stress in the tensile stress layer, specifically refers to the absolute value of the average value of all tensile stresses in the tensile stress layer.

[0062] The composition at the center of the strengthened glass-ceramic refers to the composition at or near the center of the depth of the strengthened glass-ceramic, that is, the composition of the region of the strengthened glass-ceramic that has not undergone ion exchange. It should be understood that the composition at the center of the strengthened glass-ceramic is the same as or substantially the same as the composition of the glass-ceramic used to prepare the strengthened glass-ceramic, but which has not undergone chemical strengthening (that is, ion exchange).

[0063] CS_50: refers to the compressive stress value at a depth of 50μm from the surface of the strengthened glass-ceramic along the thickness direction.

[0064] |CT_CV|: refers to the absolute value of the maximum tensile stress in the tensile stress layer, specifically refers to the absolute value of the maximum value of all tensile stresses in the tensile stress layer.

[0065] Substrate glass: also known as basic glass, refers to glass that has not been treated with nucleation, crystallization and strengthening.

[0066] Crystalline phase content: the percentage of the mass of the crystal phase in the glass-ceramic to the total mass of the glass-ceramic.

[0067] Peak intensity: refers to the height of the diffraction peak in the XRD pattern.

[0068] Half-peak width: refers to the width of the half-peak height of the diffraction peak in the XRD pattern, usually expressed as an angle or 2θ value.

[0069] In the present application, chemically strengthened glass-ceramics refers to glass-ceramic materials that can be used for chemical strengthening treatment to prepare strengthened glass-ceramics.

[0070] Glass ceramics: also known as microcrystalline glass or crystallized glass, is a type of solid composite material that contains both glass phase and microcrystalline phase (or also called crystal phase, crystalline phase, crystalline phase).

[0071] Theoretically, when the depths of the compressive stress layers extending inward from both major surfaces of a glass product are equal or approximately equal, and the sum of the depths of the two compressive stress layers equals the thickness of the tensile stress layer—that is, as shown in Figure 1 , the depth d of the compressive stress layer 11 on each side is approximately 25% of the thickness t of the glass 10 , and the thickness of the tensile stress layer 12 is approximately 50% of the thickness t of the glass 10 —the glass will reach the ideal compressive stress layer depth. However, in practice, few glass products in the prior art have achieved this desired effect. This is due to the difficulty of achieving this compressive stress layer depth. Furthermore, in existing glass products, a higher compressive stress layer depth is often accompanied by a decrease in surface stress levels and a reduction in the overall strength of the glass product. This is because, during the ion exchange process of chemical strengthening, ion diffusion becomes increasingly difficult the further inward a glass product is exposed, and simply increasing the diffusion rate by adding alkali metal ions can easily lead to fragmentation and breakage due to excessive internal stress before a higher depth is reached. Furthermore, many glass products experience stress relaxation after exchange ion diffusion reaches a certain depth and stress reaches a certain level. The depth may increase slightly or not at all, but the stress may decrease significantly, leading to a decrease in the strength of the glass product. Therefore, the only approach currently available is to keep the compressive stress depth of glass products as close to this ideal as possible.

[0072] In view of this, a reinforced glass-ceramic having an ultra-high compressive stress layer depth and a large deep-seated stress, and its application, is provided. Through the synergistic effect of a specific crystal phase structure and a specific stress structure, the reinforced glass-ceramic of the present application possesses ultra-high mechanical strength and high damage resistance, and in particular, excellent drop impact resistance.

[0073] In some embodiments of the present application, a strengthened glass-ceramic is provided, comprising a primary crystalline phase (Zn, Mg)Al2O4 crystalline phase and a secondary crystalline phase tetragonal ZrO2 crystalline phase. The strengthened glass-ceramic comprises a compressive stress layer region extending from the surface of the strengthened glass-ceramic to a compression depth, and has a tensile stress layer region inside the strengthened glass-ceramic. The compressive stress layer depth DOL_0 of the strengthened glass-ceramic is ≥0.21t, preferably, 0.21t≤DOL_0≤0.25t, where t is the thickness of the strengthened glass-ceramic. In some embodiments of the present application, in the strengthened glass-ceramic, DOL_0 can be 0.21t to 0.24t, 0.22t to 0.24t, 0.23t to 0.24t, or 0.21t to 0.23t. In some embodiments of the present application, DOL_0 can be 0.21t, 0.22t, 0.23t, 0.24t, or 0.25t, or a value within a range of values ​​formed by any two of the aforementioned values, as long as the desired properties of the reinforced glass-ceramic are obtained. In some embodiments of the present application, when the thickness t of the reinforced glass-ceramic is 0.7 mm, 147 μm ≤ DOL_0 ≤ 175 μm. Specifically, DOL_0 can be 147 μm, 154 μm, 161 μm, 168 μm, or 175 μm, or a value within a range of values ​​formed by any two of the aforementioned values, as long as the desired properties of the reinforced glass-ceramic are obtained. The reinforced glass-ceramic has a |CT_AV| of ≥ 70 MPa, preferably 70 MPa ≤ |CT_AV| ≤ 110 MPa. In some embodiments of the present application, in the strengthened glass-ceramic, |CT_AV| may be 73 MPa to 108 MPa, 75 MPa to 105 MPa, 78 MPa to 100 MPa, 80 MPa to 98 MPa, or 83 MPa to 95 MPa. In some embodiments of the present application, |CT_AV| may be 70 MPa, 73 MPa, 75 MPa, 78 MPa, 80 MPa, 83 MPa, 85 MPa, 88 MPa, 90 MPa, 93 MPa, 95 MPa, 98 MPa, 100 MPa, 103 MPa, 105 MPa, 108 MPa, or 110 MPa, or a value within a range of values ​​consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic having the desired properties of the present application can be obtained. By making the reinforced glass-ceramics whose main crystal phase is the spinel (Zn, Mg)Al2O4 crystal phase have an ultra-high compressive stress layer depth and a large tensile stress level, the reinforced glass-ceramics can be given high mechanical strength, which is beneficial to greatly improve the damage resistance of the reinforced glass-ceramics, especially the drop impact resistance of the reinforced glass-ceramics.

[0074] The present application has no particular limitation on the thickness t of the strengthened glass-ceramic, as long as the purpose of the present application can be achieved. For example, the thickness t of the strengthened glass-ceramic satisfies: 0.2 mm ≤ t ≤ 5 mm, preferably 0.2 mm ≤ t ≤ 2 mm.

[0075] In some embodiments of the present application, the chemically strengthened glass-ceramic or reinforced glass-ceramic is 2D, 2.5D, 3D, or a special shape, that is, the chemically strengthened glass-ceramic can be a 2D, 2.5D, 3D, or a special shape, and the reinforced glass-ceramic can also be a 2D, 2.5D, 3D, or a special shape; and / or, the chemically strengthened glass-ceramic or reinforced glass-ceramic is of uniform thickness or unequal thickness. Those skilled in the art can make a choice based on their needs. The "unequal thickness" here means that the chemically strengthened glass-ceramic or reinforced glass-ceramic contains at least two portions of different thicknesses.

[0076] In some embodiments of the present application, the total crystalline phase content W of the (Zn, Mg)Al2O4 crystalline phase and the tetragonal ZrO2 crystalline phase is 25.00 wt% to 70.00 wt%, preferably 30.00 wt% to 50.00 wt%, calculated based on the mass of the strengthened glass-ceramic, wherein the ratio of the (Zn, Mg)Al2O4 crystalline phase to the tetragonal ZrO2 crystalline phase (referring to the mass ratio Z of the (Zn, Mg)Al2O4 crystalline phase to the tetragonal ZrO2 crystalline phase) is 1.00 to 18.00, preferably 1.00 to 15.00. In some embodiments of the present application, in the above-mentioned strengthened glass-ceramic, the average crystal size of the (Zn, Mg)Al2O4 crystalline phase is 3.0 nm to 10.0 nm, preferably 4.0 nm to 7.5 nm, and more preferably 4.5 nm to 7.5 nm. In some embodiments of the present application, the strengthened glass-ceramic is transparent in the visible light range. In the present application, the wavelength range of visible light is 360 nm to 740 nm, and “transparent in the visible light range” means that the average transmittance of visible light is greater than 80%.

[0077] For spinel glass ceramics containing the main crystal phase (Zn, Mg)Al2O4 and the secondary crystal phase tetragonal ZrO2, simply increasing and introducing the number and type of metal ions that can be ion-exchanged cannot ensure the realization of ultra-high stress layer depth and deep stress. On the one hand, when Li + and Na + When the content exceeds a certain amount, the problem of not being able to obtain transparent glass ceramics may easily arise; on the other hand, the stress distribution of glass ceramics after chemical strengthening is jointly affected by the composition and crystal structure of the glass ceramics. Simply increasing the number and type of alkali metal ions that can be ion-exchanged will not only cause changes in the composition of the glass ceramics, but also cannot guarantee that the glass ceramics will obtain a crystal structure that can achieve the desired stress distribution.

[0078] Without being limited by theory, the composition and crystal structure of glass ceramics are closely related to their stress distribution or stress structure after chemical strengthening. By ensuring that the glass ceramics meet the above-mentioned specific composition and crystal structure, it can be ensured that the glass ceramics obtain an ultra-high compressive stress layer depth and a large deep stress after chemical strengthening.

[0079] In some embodiments of the present application, calculated based on the mass of the strengthened glass-ceramic, the total crystalline phase content W of the (Zn, Mg)Al2O4 phase and the tetragonal ZrO2 phase can be 25.00wt%, 28.00wt%, 30.00wt%, 33.00wt%, 35.00wt%, 38.00wt%, 40.00wt%, 43.00wt%, 45.00wt%, 48.00wt%, 50.00wt%, 53.00wt%, 55.00wt%, 58.00wt%, 60.00wt%, 63.00wt%, 65.00wt%, 68.00wt% or 70.00wt%, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the required performance of the present application can be obtained. In some embodiments of the present application, the total crystalline phase content W of the (Zn, Mg)Al2O4 phase and the tetragonal ZrO2 phase, calculated based on the mass of the strengthened glass-ceramic, can be 25.00 wt% to 68.00 wt%, 28.00 wt% to 65.00 wt%, 32.00 wt% to 60.00 wt%, 35.00 wt% to 55.00 wt%, or 40.00 wt% to 50.00 wt%. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges as long as the strengthened glass-ceramic having the desired properties of the present application is obtained.

[0080] In some embodiments of the present application, in the above-mentioned strengthened glass-ceramics, the ratio of (Zn, Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase (mass ratio Z) can be 1.00, 2.00, 3.00, 4.00, 5.00, 6.00, 7.00, 8.00, 9.00, 10.00, 11.00, 12.00, 13.00, 14.00, 15.00, 16.00, 17.00 or 18.00, or a value within the numerical range formed by any two of the above-mentioned values ​​as endpoints, as long as the strengthened glass-ceramics with the required performance of the present application can be obtained. In some embodiments of the present application, the ratio (mass ratio Z) of the (Zn, Mg)Al2O4 crystalline phase to the tetragonal ZrO2 crystalline phase in the strengthened glass-ceramics may be 2.00-17.00, 4.00-15.00, 6.00-12.00, or 8.00-10.00. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the strengthened glass-ceramics having the desired properties of the present application are obtained.

[0081] In some embodiments of the present application, the average crystal size of the (Zn, Mg)Al2O4 phase in the strengthened glass-ceramics may be 3.0 nm, 4.0 nm, 4.2 nm, 4.5 nm, 4.8 nm, 5.0 nm, 5.2 nm, 5.5 nm, 5.8 nm, 6.0 nm, 6.2 nm, 6.5 nm, 6.8 nm, 7.0 nm, 7.2 nm, 7.5 nm, 8.0 nm, 9.0 nm, or 10.0 nm, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramics having the desired properties of the present application can be obtained. In some embodiments of the present application, the average crystal size of the (Zn, Mg)Al2O4 phase in the strengthened glass-ceramics may be 4.0 nm to 9.0 nm, 4.0 nm to 7.5 nm, 4.5 nm to 7.5 nm, 5.0 nm to 8.0 nm, or 6.0 nm to 7.0 nm. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic having the desired properties of the present application can be obtained.

[0082] In some embodiments of the present application, the reinforced glass-ceramics contain 15.00wt% to 45.00wt% of the (Zn, Mg)Al2O4 crystalline phase in the reinforced glass-ceramics. (Zn, Mg)Al2O4 crystals are crystals with high hardness and high modulus. By precipitating an appropriate amount of (Zn, Mg)Al2O4 in the glass-ceramics, it is possible to give the glass-ceramics high intrinsic strength or inherent strength. At the same time, by controlling the content of the (Zn, Mg)Al2O4 crystalline phase, the glass-ceramics meet a specific crystalline phase structure, which is beneficial to ensure that the glass-ceramics chemically strengthened obtain an ideal stress structure. In some embodiments of the present application, the crystalline phase content of the (Zn, Mg)Al2O4 crystalline phase in the above-mentioned reinforced glass-ceramics is W [(Zn，Mg)Al2O4] The content of the (Zn, Mg)Al2O4 crystal phase in the strengthened glass-ceramic is 15.00 wt%, 18.00 wt%, 20.00 wt%, 23.00 wt%, 25.00 wt%, 28.00 wt%, 30.00 wt%, 33.00 wt%, 35.00 wt%, 38.00 wt%, 40.00 wt%, 43.00 wt% or 45.00 wt%, or a value within a range of values ​​consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the required performance of the present application can be obtained. In some embodiments of the present application, the content of the (Zn, Mg)Al2O4 crystal phase in the strengthened glass-ceramic is W [(Zn，Mg)Al2O4] It may be 18.00 wt% to 44.00 wt%, 20.00 wt% to 42.00 wt%, 24.00 wt% to 40.00 wt%, 28.00 wt% to 38.00 wt% or 30.00 wt% to 35.00 wt%.

[0083] In some embodiments of the present application, based on the quality of the strengthened glass-ceramics, the crystal phase content of the tetragonal ZrO2 crystal phase is W [ZrO2] The content of the tetragonal ZrO2 crystal phase in the strengthened glass ceramics is 2.00 wt% to 16.00 wt%. The tetragonal ZrO2 crystal phase and the (Zn, Mg)Al2O4 crystal phase together determine the crystal phase structure inside the glass ceramics. By meeting a specific content range, it is beneficial to ensure the structural strength of the glass ceramics and to ensure that the glass ceramics obtain an ideal stress structure after chemical strengthening. In some embodiments of the present application, the crystal phase content of the tetragonal ZrO2 crystal phase in the strengthened glass ceramics is W [ZrO2] It can be 2.00wt%, 3.00wt%, 4.00wt%, 5.00wt%, 6.00wt%, 7.00wt%, 8.00wt%, 9.00wt%, 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt%, 15.00wt% or 16.00wt%, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the reinforced glass-ceramics with the required properties of this application can be obtained.

[0084] In some embodiments of the present application, the composition at the center of the strengthened glass-ceramic, calculated by molar percentage of oxides, includes: SiO 35.00 mol% to 60.00 mol%, Al 2 O 20.00 mol% to 40.00 mol%, ZrO 2 2.00 mol% to 8.00 mol%, MgO 3.00 mol% to 7.50 mol%, ZnO 7.00 mol% to 13.00 mol%, Na 2 O 1.00 mol% to 10.00 mol%, and Li 2.50 mol% to 10.00 mol%. This glass formulation ensures the preparation of chemically strengthened glass-ceramics with high intrinsic strength and spinel as the main crystalline phase, thereby facilitating the production of strengthened glass-ceramics that meet the desired stress structure.

[0085] It should be understood that after chemical strengthening and ion exchange, the composition of the glass ceramic product at the surface may be different from the composition of the glass ceramic before the ion exchange process. This is because, during ion exchange, in the newly formed glass ceramic (such as the chemically strengthened glass ceramic in this application), one type of alkali metal ion (e.g., Li + Or Na + ) are replaced by larger alkali metal ions (e.g., Na + or K + ). However, in embodiments, the glass composition and phase assembly at or near the depth center of the glass-ceramic article will still be the same as the composition of the newly formed glass-ceramic. In other words, in this application, the composition and phase assembly at the center of the strengthened glass-ceramic are the same or substantially the same as those of the newly formed glass-ceramic (e.g., the chemically strengthened glass-ceramic in this application).

[0086] The chemically strengthened glass-ceramic in this application is produced by heat-treating a base glass. Therefore, the composition of the chemically strengthened glass-ceramic, measured by mole percentage of oxides, is the same as that of the base glass. Specifically, in this application, the base glass or chemically strengthened glass-ceramic used to prepare the chemically strengthened glass-ceramic comprises, by mole percentage of oxides, 35.00 mol% to 60.00 mol% of SiO2, 20.00 mol% to 40.00 mol% of Al2O3, 2.00 mol% to 8.00 mol% of ZrO2, 3.00 mol% to 7.50 mol% of MgO, 7.00 mol% to 13.00 mol% of ZnO, 1.00 mol% to 10.00 mol% of Na2O, and 2.50 mol% to 10.00 mol% of Li2O. After heat-treating the substrate glass meeting the above range to obtain a chemically strengthened glass-ceramic meeting a specific crystal phase structure, the chemically strengthened glass-ceramic can be chemically strengthened to obtain a strengthened glass-ceramic having an ultra-high compressive stress layer depth and a large deep stress.

[0087] In the present application, SiO2 is a glass network forming oxide and is an indispensable component of the glass network structure. An appropriate amount of SiO2 can increase the stability and mechanical strength of the glass while taking into account the formability of the glass. In the present application, the content of SiO2 in the composition at the center of the substrate glass or chemically strengthened glass-ceramic or strengthened glass-ceramic, calculated as mol%, is 35.00 mol% to 60.00 mol%. In some embodiments of the present application, the content of SiO2 can be 35.00 mol%, 37.00 mol%, 40.00 mol%, 42.00 mol%, 45.00 mol%, 47.00 mol%, 50.00 mol%, 52.00 mol%, 55.00 mol%, 57.00 mol% or 60.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the desired performance of the present application is obtained. In some embodiments of the present application, the content of SiO2 can be 36.00mol% to 58.00mol%, 38.00mol% to 55.00mol%, 40.00mol% to 52.00mol%, 42.00mol% to 50.00mol%, or 44.00mol% to 48.00mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges as long as the reinforced glass-ceramic having the desired properties of the present application can be obtained.

[0088] In this application, an appropriate amount of Al2O3 can promote the precipitation of the primary crystalline phase and inhibit the precipitation of other impurities such as quartz. This can avoid the problem of glass devitrification during normal cooling caused by a rapid crystallization rate. It also helps increase the rate of ion exchange during strengthening and improve the stress structure. In this application, the Al2O3 content, calculated as mol% of oxide, in the composition at the center of the base glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic is 20.00 mol% to 40.00 mol%. In some embodiments of the present application, the content of Al2O3 can be 20.00mol%, 21.00mol%, 22.00mol%, 23.00mol%, 24.00mol%, 25.00mol%, 26.00mol%, 27.00mol%, 28.00mol%, 29.00mol%, 30.00mol%, 31.00mol%, 32.00mol%, 33.00mol%, 34.00mol%, 35.00mol%, 36.00mol%, 37.00mol%, 38.00mol%, 39.00mol% or 40.00mol%, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the reinforced glass-ceramics with the required properties of the present application can be obtained. In some embodiments of the present application, the content of Al2O3 may be 21.00 mol% to 38.00 mol%, 22.00 mol% to 36.00 mol%, 23.00 mol% to 34.00 mol%, or 25.00 mol% to 32.00 mol%. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges as long as the reinforced glass-ceramic having the desired properties of the present application is obtained.

[0089] In this application, ZrO2 acts as an effective nucleating agent. During the heat treatment of the substrate glass, ZrO2 initially precipitates in the substrate glass as crystals. These ZrO2 crystals serve as nuclei for the subsequent growth of the primary crystalline phase. An appropriate amount of ZrO2 facilitates the formation of spinel glass-ceramics with a specific crystalline structure. In this application, the ZrO2 content, calculated as mol% of oxide, in the composition at the center of the substrate glass, chemically strengthened glass-ceramics, or strengthened glass-ceramics is 2.00 mol% to 8.00 mol%. In some embodiments of the present application, the content of ZrO2 can be 2.00mol%, 2.50mol%, 3.00mol%, 3.50mol%, 4.00mol%, 4.50mol%, 5.00mol%, 5.50mol%, 6.00mol%, 6.50mol%, 7.00mol%, 7.50mol%, or 8.00mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. In some embodiments of the present application, the content of ZrO2 can be 2.50mol% to 7.80mol%, 3.00mol% to 7.50mol%, 3.50mol% to 7.00mol%, 4.00mol% to 6.50mol%, or 4.50mol% to 6.00mol%. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0090] In the present application, MgO and ZnO are necessary components of the main crystal phase spinel. An appropriate amount of MgO and ZnO is conducive to ensuring the formation of the desired content of the main crystal phase, and can also reduce the difficulty of melting the substrate glass to a certain extent. However, excessive MgO and ZnO can easily lead to excessive growth of spinel grains, making it difficult to obtain chemically strengthened glass-ceramics with high transparency. In the present application, in the composition at the center of the substrate glass or chemically strengthened glass-ceramics or strengthened glass-ceramics, the MgO content is 3.00 mol% to 7.50 mol%, and the ZnO content is 7.00 mol% to 13.00 mol%, calculated as mol% of oxides.

[0091] In some embodiments of the present application, the MgO content may be 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, or 7.50 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. In some embodiments of the present application, the MgO content may be 3.50 mol% to 7.00 mol%, 4.00 mol% to 6.50 mol%, or 4.50 mol% to 6.00 mol%. It should be understood that in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0092] In some embodiments of the present application, the ZnO content can be 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, 10.00 mol%, 10.50 mol%, 11.00 mol%, 11.50 mol%, 12.00 mol%, 12.50 mol%, or 13.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. In some embodiments of the present application, the ZnO content can be 7.50 mol% to 12.50 mol%, 8.50 mol% to 12.00 mol%, 9.50 mol% to 11.50 mol%, or 10.00 mol% to 11.00 mol%. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0093] In the present application, an appropriate amount of Na2O helps the glass ceramic achieve high surface compressive stress during chemical strengthening, which is beneficial for the glass ceramic to achieve a high surface stress level. At the same time, an appropriate amount of Na2O can reduce the melting temperature of the substrate glass and the temperature at which crystals precipitate when the substrate glass is prepared into chemically strengthened glass ceramics. It can also prevent ceramicization of the substrate glass during annealing and prevent the precipitation of undesirable impurity phases when the substrate glass is heat-treated to prepare chemically strengthened glass ceramics. In the present application, the content of Na2O in the composition at the center of the substrate glass, chemically strengthened glass ceramics, or strengthened glass ceramics is 1.00 mol% to 10.00 mol%, calculated as mol% of the oxide. In some embodiments of the present application, the content of Na2O can be 1.00mol%, 1.50mol%, 2.00mol%, 2.50mol%, 3.00mol%, 3.50mol%, 4.00mol%, 4.50mol%, 5.00mol%, 5.50mol%, 6.00mol%, 6.50mol%, 7.00mol%, 7.50mol%, 8.00mol%, 8.50mol%, 9.00mol%, 9.50mol% or 10.00mol%, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the reinforced glass-ceramics with the required properties of the present application can be obtained. In some embodiments of the present application, the content of Na2O may be 1.50 mol% to 9.50 mol%, 2.50 mol% to 8.50 mol%, 3.50 mol% to 7.50 mol%, 4.50 mol% to 6.50 mol%, or 5.00 mol% to 6.00 mol%. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges as long as the reinforced glass-ceramic having the desired properties of the present application is obtained.

[0094] In the present application, an appropriate amount of Li2O helps the glass ceramics obtain higher deep compressive stress and high compressive stress layer depth during chemical strengthening, which is beneficial for making the glass ceramics obtain a high deep stress level. At the same time, an appropriate amount of Li2O is beneficial to improving the Young's modulus of the glass ceramics, and can reduce the melting temperature of the substrate glass and the temperature at which crystals precipitate when the substrate glass is prepared into chemically strengthened glass ceramics. It can also avoid ceramicization during the annealing process of the substrate glass, and avoid the problem of precipitation of undesirable impurities or excessive crystal growth when the substrate glass is heat-treated to prepare chemically strengthened glass ceramics. Too low a content of Li2O can easily lead to a decrease in the deep stress that can be obtained when chemically strengthened glass ceramics are chemically strengthened. In the present application, in terms of mol% of oxide, in the composition at the center of the substrate glass or chemically strengthened glass ceramics or strengthened glass ceramics, the content of Li2O is 2.50mol% to 10.00mol%.

[0095] In some embodiments of the present application, the content of Li2O may be 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol% or 10.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic having the desired properties of the present application is obtained. In some embodiments of the present application, the content of Li2O may be 3.00 mol% to 9.50 mol%, 4.00 mol% to 8.50 mol%, 5.00 mol% to 7.50 mol% or 6.00 mol% to 7.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic having the desired properties of the present application can be obtained.

[0096] In some embodiments of the present application, W [(Zn，Mg)Al2O4] is the weight percentage of (Zn, Mg)Al2O4 phase in the strengthened glass ceramics, W [Al2O3] is the weight percentage of Al2O3 in the strengthened glass ceramics, W [MgO] is the weight percentage of MgO in the strengthened glass ceramics, W [ZnO] is the weight percentage of ZnO in the strengthened glass-ceramic;

[0097] A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2,

[0098] B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] +W [ZnO] ),

[0099] C=A / B, in strengthened glass ceramics, 1.50≤C≤1.85.

[0100] By optimizing the composition and structure, the crystalline phase content of the (Zn, Mg)Al2O4 phase, as well as the contents of Al2O3, MgO, and ZnO in the glass ceramics meet the range of the above-mentioned characteristic C. This ensures that the chemically strengthened glass ceramics obtain the desired stress structure after chemical strengthening, thereby enabling the strengthened glass ceramics to obtain high mechanical strength, especially excellent damage resistance.

[0101] In some embodiments of the present application, the value of A is 10.00% to 25.00%, preferably 14.00% to 25.00%; and / or the value of B is 7.50% to 12.50%, preferably 8.00% to 12.00%. By ensuring that the values ​​of A and B are within the above ranges, it is helpful to ensure that C is within its value range. In some embodiments of the present application, the value of A can be 10.00%, 11.00%, 12.00%, 13.00%, 14.00%, 15.00%, 16.00%, 17.00%, 18.00%, 19.00%, 20.00%, 21.00%, 22.00%, 23.00%, 24.00% or 25.00%, or a value within the range of values ​​formed by any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the properties required by the present application can be obtained. In some embodiments of the present application, the value of B can be 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 10.50%, 11.00%, 11.50%, 12.00%, or 12.50%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0102] In some embodiments of the present application, W [Al2O3] It is 35.00wt% to 50.00wt%.

[0103] In some embodiments of the present application, W [MgO] It is 2.50wt% to 4.00wt%.

[0104] In some embodiments of the present application, W [ZnO] It is 9.50wt% to 14.50wt%.

[0105] In some embodiments of the present application, the CS_50 of the strengthened glass-ceramic is ≥100 MPa, preferably, 100 MPa≤CS_50≤250 MPa. The range of CS_50 of the strengthened glass-ceramic is within the above range, indicating that the compressive stress of the strengthened glass-ceramic at a depth of 50 μm from the surface is high, which further indicates that the strengthened glass-ceramic has a high surface stress level, thereby effectively improving the damage resistance of the strengthened glass-ceramic. In some embodiments of the present application, the CS_50 of the strengthened glass-ceramic can be 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa, 170 MPa, 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa or 250 MPa, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the performance required by the present application can be obtained. In some embodiments of the present application, the CS_50 of the strengthened glass-ceramic may be 110 MPa to 240 MPa, 120 MPa to 230 MPa, 130 MPa to 220 MPa, 140 MPa to 210 MPa, 150 MPa to 200 MPa, 160 MPa to 190 MPa, or 170 MPa to 180 MPa. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the strengthened glass-ceramic having the desired properties is obtained.

[0106] In some embodiments of the present application, the Vickers hardness of the strengthened glass-ceramic is greater than or equal to 790 kgf / mm 2 , preferably 790kgf / mm 2 ~1000kgf / mm 2 The Vickers hardness of the reinforced glass ceramic is within the above range, indicating that the reinforced glass ceramic has high hardness, thereby ensuring that it has excellent mechanical properties, which is conducive to obtaining glass ceramic products with excellent damage resistance. In some embodiments of the present application, the Vickers hardness of the reinforced glass ceramic can be 790 kgf / mm 2 、800kgf / mm 2 、810kgf / mm 2 、820kgf / mm 2 、830kgf / mm 2 、840kgf / mm 2 、850kgf / mm 2 、860kgf / mm 2 、870kgf / mm 2 、880kgf / mm 2 、890kgf / mm 2, 900kgf / mm 2 、910kgf / mm 2 、920kgf / mm 2 、930kgf / mm 2 , 940kgf / mm 2 、950kgf / mm 2 、960kgf / mm 2 、970kgf / mm 2 、980kgf / mm 2 、990kgf / mm 2 or 1000kgf / mm 2 , or a value within a range of values ​​formed by taking any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the required performance of the present application can be obtained. In some embodiments of the present application, the Vickers hardness of the strengthened glass-ceramic can be 800 kgf / mm 2 ~980kgf / mm 2 、820kgf / mm 2 ~960kgf / mm 2 、840kgf / mm 2 ~940kgf / mm 2 、860kgf / mm 2 ~920kgf / mm 2 or 880kgf / mm 2 ~900kgf / mm 2 It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramics with the desired properties of the present application can be obtained.

[0107] In some embodiments of the present application, the fracture toughness of the reinforced glass-ceramic is greater than or equal to 1.00 MPa·m 1 / 2 , preferably greater than or equal to 1.20 MPa·m 1 / 2 , more preferably greater than or equal to 1.55 MPa·m 1 / 2 , for example, it may be preferably 1.55 MPa·m 1 / 2 ~2.00MPa·m 1 / 2 The fracture toughness of the reinforced glass ceramic is within the above range, indicating that the reinforced glass ceramic has high fracture toughness, thereby ensuring that it has excellent mechanical properties, which is conducive to obtaining glass ceramic products with excellent damage resistance. In some embodiments of the present application, the fracture toughness of the reinforced glass ceramic can be 1.00 MPa·m 1 / 2 , 1.20MPa·m 1 / 2 , 1.55MPa·m 1 / 2 , 1.60MPa·m 1 / 2, 1.65MPa·m 1 / 2 , 1.70MPa·m 1 / 2 , 1.75MPa·m 1 / 2 , 1.80MPa·m 1 / 2 , 1.85MPa·m 1 / 2 , 1.90MPa·m 1 / 2 , 1.95MPa·m 1 / 2 or 2.00 MPa·m 1 / 2 , or a value within a range of values ​​consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the performance required by the present application can be obtained. In some embodiments of the present application, the fracture toughness of the reinforced glass-ceramic can be 1.20 MPa·m 1 / 2 ~2.00MPa·m 1 / 2 , 1.40MPa·m 1 / 2 ~1.80MPa·m 1 / 2 or 1.50 MPa·m 1 / 2 ~1.90MPa·m 1 / 2 It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramics with the desired properties of the present application can be obtained.

[0108] In some embodiments of the present application, the |CT_CV| of the strengthened glass-ceramic is ≥80MPa, preferably, 80MPa≤|CT_CV|≤150MPa. The |CT_CV| of the strengthened glass-ceramic is within the above range, indicating that the strengthened glass-ceramic has a higher tensile stress level, which in turn reflects that it has a higher surface stress level, thereby ensuring that it has excellent mechanical properties, which is conducive to obtaining glass-ceramic products with excellent damage resistance. In some embodiments of the present application, the |CT_CV| of the strengthened glass-ceramic can be 80MPa, 85MPa, 90MPa, 95MPa, 100MPa, 105MPa, 110MPa, 115MPa, 120MPa, 125MPa, 130MPa, 135MPa, 140MPa, 145MPa or 150MPa, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the performance required by the present application can be obtained. In some embodiments of the present application, the |CT_CV| of the aforementioned strengthened glass-ceramics may be 85 MPa to 150 MPa, 90 MPa to 145 MPa, 95 MPa to 140 MPa, 100 MPa to 135 MPa, or 110 MPa to 130 MPa. It should be understood that, in specific embodiments, any of the aforementioned ranges may be combined with any other ranges, as long as the strengthened glass-ceramics having the desired properties are achieved.

[0109] The relevant characteristics of the X-ray diffraction pattern can reflect the crystalline structure of the glass-ceramic, including crystalline composition and crystal size. By ensuring that the glass-ceramic meets a specific crystalline structure, it is beneficial for the glass-ceramic to obtain high intrinsic strength. It is also beneficial for improving the chemical strengthening effect of the glass-ceramic, enabling it to achieve ultra-high compressive stress layer depth and large deep stress through chemical strengthening, thereby improving the mechanical strength and damage resistance of the glass-ceramic.

[0110] It should be understood that in the glass-ceramics of the present application, neither the primary (Zn, Mg)Al2O4 phase nor the secondary tetragonal ZrO2 phase contains alkali metal ions and therefore does not participate in ion exchange during the chemical strengthening process. Therefore, the crystal structure of the chemically strengthened glass-ceramics of the present application is substantially the same as that of the chemically strengthened glass-ceramics. In other words, the crystal structure characteristics of the chemically strengthened glass-ceramics obtained through the chemical strengthening process of the present application, such as the crystal phase content, crystal composition, crystal size, and X-ray diffraction pattern characteristics, are substantially the same as those of the chemically strengthened glass-ceramics. As shown in FIG8 , in Example 1, the XRD patterns of the chemically strengthened glass-ceramics before chemical strengthening and the strengthened glass-ceramics after chemical strengthening are substantially the same.

[0111] In some embodiments of the present application, in the X-ray diffraction pattern of the strengthened glass-ceramic, the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 28° to 32° is taken as the first characteristic peak, and the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 36° to 38° is taken as the second characteristic peak. The peak intensity ratio X between the first characteristic peak and the second characteristic peak is 0.80 to 1.50, preferably 0.85 to 1.30. In the XRD diffraction pattern, the peak intensity of the characteristic peak can reflect the integrity of the crystals in the glass-ceramic. By ensuring that the peak intensity ratio of the above two characteristic peaks is within this range, the present application helps to obtain suitable crystal integrity, thereby helping to achieve better optical and strengthening effects. In some embodiments of the present application, the peak intensity ratio X may be 0.80, 0.90, 1.00, 1.10, 1.20, 1.30, 1.40, or 1.50, or a value within a range of values ​​defined by any two of the aforementioned values ​​as endpoints, as long as the reinforced glass-ceramic having the desired properties of the present application is obtained. It should be understood that, in specific embodiments, any of the aforementioned ranges may be combined with any other ranges, as long as the reinforced glass-ceramic having the desired properties of the present application is obtained.

[0112] In some embodiments of the present application, in the X-ray diffraction pattern of the strengthened glass-ceramic, the characteristic peak of the

[0400] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle of 44° to 46°, the characteristic peak of the

[0311] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle of 34° to 38°, the characteristic peak of the

[0440] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle of 64° to 67°, and the half-peak width W of the characteristic peak of the

[0400] crystal plane is 0.

[0400] 0.650°~1.800°, preferably W

[0400] 0.900°~1.600°;

[0311] half-peak width W of the characteristic peak of the crystal plane

[0311] 0.900°~2.800°, preferably W

[0311] 1.100°~2.230°;

[0440] half-peak width W of the characteristic peak of the crystal face

[0440] 0.750°~2.000°, preferably W

[0440] In the present application, the half-widths of the characteristic peaks of the

[0400] crystal plane, the characteristic peaks of the

[0311] crystal plane, and the characteristic peaks of the

[0440] crystal plane can reflect the size of the crystals in the glass-ceramic. By meeting the above ranges, it is helpful to ensure that the chemically strengthened glass-ceramic or strengthened glass-ceramic has a specific crystal size and crystal phase structure, thereby helping to ensure that the strengthened glass-ceramic obtains the desired optical properties and stress level.

[0113] In some embodiments of the present application, W

[0400] The value of can be 0.650°, 0.700°, 0.800°, 0.900°, 1.000°, 1.100°, 1.200°, 1.300°, 1.400°, 1.500°, 1.600°, 1.700° or 1.800°, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramics with the desired properties of the present application can be obtained. In some embodiments of the present application, W

[0311] The value of can be 0.900°, 1.000°, 1.100°, 1.200°, 1.300°, 1.400°, 1.500°, 1.600°, 1.700°, 1.800°, 1.900°, 2.000°, 2.100°, 2.200°, 2.230°, 2.300°, 2.400°, 2.500°, 2.600°, 2.700°, or 2.800°, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramics with the desired properties of the present application can be obtained. In some embodiments of the present application, W

[0440] The value of can be 0.750°, 0.800°, 0.900°, 1.000°, 1.100°, 1.200°, 1.300°, 1.400°, 1.500°, 1.600°, 1.700°, 1.800°, 1.900°, or 2.000°, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the desired properties of the present application is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the strengthened glass-ceramic with the desired properties of the present application is obtained.

[0114] In some embodiments of the present application, the composition at the center of the substrate glass, chemically strengthened glass-ceramic, or chemically strengthened strengthened glass-ceramic for preparing chemically strengthened glass-ceramic, calculated by mole percentage of oxides, further includes: 0.00 mol% to 5.00 mol% of K2O, 0.00 mol% to 10.00 mol% of CaO, 0.00 mol% to 10.00 mol% of B2O3, and 0.00 mol% to 5.00 mol% of BaO. In the present application, K2O, CaO, B2O3, or BaO are optional components, and their appropriate use can improve the forming, crystallization, chemical strengthening, or optical properties of the glass-ceramic.

[0115] In the present application, an appropriate amount of K2O helps improve the formability of the substrate glass and helps reduce the tendency of the substrate glass to crystallize during the preparation process. In the present application, the K2O content, calculated as mol% of the oxide, in the composition of the substrate glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic at the center is 0.00 mol% to 5.00 mol%. In some embodiments of the present application, the K2O content can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, or 5.00 mol%, or a value within a range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the desired properties is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the strengthened glass-ceramic with the desired properties is obtained.

[0116] In this application, an appropriate amount of B2O3 helps reduce the difficulty of melting the base glass, promotes the precipitation of the main crystalline phase, spinel, and effectively prevents opacification or precipitation of impurity phases that affect the optical properties of the glass-ceramic during heat treatment of the base glass to prepare chemically strengthened glass-ceramics. In this application, the B2O3 content in the composition at the center of the base glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic, calculated as mol% of the oxide, is 0.00 mol% to 10.00 mol%. In some embodiments of the present application, B2O3 may be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, or 10.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. It should be understood that, in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0117] In the present application, an appropriate amount of BaO helps improve the melting effect of the substrate glass and can also inhibit grain growth to a certain extent, thereby improving the optical properties of the glass-ceramic. In the present application, the BaO content, calculated as mol% of the oxide, in the composition of the substrate glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic at the center is 0.00 mol% to 5.00 mol%. In some embodiments of the present application, the BaO content can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, or 5.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramic with the desired properties is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the strengthened glass-ceramic with the desired properties is obtained.

[0118] In this application, an appropriate amount of CaO helps reduce the viscosity of the glass melt, improves the glass's formability, strain point, and Young's modulus, and helps improve the ion exchange capacity of the glass-ceramic. Furthermore, an appropriate amount of CaO helps improve the glass's gloss and transparency, reduces the tendency of the base glass to crystallize, and slows the hardening rate of the glass. In this application, the CaO content, calculated as mol% of oxide, in the composition at the center of the base glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic is 0.00 mol% to 10.00 mol%. In some embodiments of the present application, the CaO content may be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, or 10.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. It should be understood that in specific embodiments, any of the above ranges may be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0119] In some embodiments of the present application, the composition at the center of the substrate glass or chemically strengthened glass ceramic or strengthened glass ceramic for preparing chemically strengthened glass ceramic includes, by mole percentage of oxides, 35.00 mol% to 60.00 mol%, 20.00 mol% to 40.00 mol%, 2.00 mol% to 8.00 mol% of SiO2, 3.00 mol% to 7.50 mol% of Al2O3, 7.00 mol% to 13.00 mol% of ZnO, 1.00 mol% to 10.00 mol% of Na2O, 2.50 mol% to 10.00 mol% of Li2O, 0.00 mol% to 5.00 mol% of K2O, 0.00 mol% to 10.00 mol% of CaO, 0.00 mol% to 10.00 mol% of B2O3, and 0.00 mol% to 5.00 mol% of BaO. By adopting the above-mentioned glass formula scheme, it is helpful to ensure the preparation of chemically strengthened glass-ceramics that meet high intrinsic strength and have spinel as the main crystal phase, which in turn helps to obtain strengthened glass-ceramics that meet the desired stress structure.

[0120] In some embodiments of the present application, the composition at the center of the substrate glass or chemically strengthened glass ceramic or strengthened glass ceramic for preparing chemically strengthened glass ceramic includes, by mole percentage of oxides, 35.00 mol% to 50.00 mol%, 25.00 mol% to 35.00 mol%, 3.00 mol% to 5.00 mol% of SiO2, 4.00 mol% to 7.00 mol% of MgO, 9.00 mol% to 12.00 mol% of ZnO, 2.00 mol% to 10.00 mol% of Na2O, 3.00 mol% to 10.00 mol% of Li2O, 0.00 mol% to 5.00 mol% of K2O, 0.00 mol% to 10.00 mol% of CaO, 0.00 mol% to 10.00 mol% of B2O3, and 0.00 mol% to 5.00 mol% of BaO. By properly adjusting the content of each necessary oxide, it helps to ensure that the chemically strengthened glass-ceramics obtain the desired crystalline phase structure and glass network structure that can achieve a high stress level, which is conducive to obtaining strengthened glass-ceramics with a high stress level.

[0121] In some embodiments of the present application, the composition at the center of the substrate glass or chemically strengthened glass ceramic or strengthened glass ceramic for preparing chemically strengthened glass ceramic includes, by mole percentage of oxides, 35.00 mol% to 60.00 mol%, 20.00 mol% to 40.00 mol%, 2.00 mol% to 8.00 mol% of SiO2, 4.00 mol% to 7.00 mol% of MgO, 9.00 mol% to 12.00 mol% of ZnO, 2.00 mol% to 10.00 mol% of Na2O, 3.00 mol% to 10.00 mol% of Li2O, 0.00 mol% to 5.00 mol% of K2O, 0.00 mol% to 10.00 mol% of CaO, 0.00 mol% to 10.00 mol% of B2O3, and 0.00 mol% to 5.00 mol% of BaO. By appropriately adjusting the content of MgO, ZnO, Li2O or Na2O, it helps to ensure that the main crystalline phase content in the chemically strengthened glass-ceramics meets the desired level. It also helps to ensure that the chemically strengthened glass-ceramics achieve the desired chemical strengthening effect, thereby obtaining strengthened glass-ceramics with a high stress level.

[0122] In some embodiments of the present application, the composition of the substrate glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic at its center, calculated by the molar percentage of each oxide in the composition, satisfies the following: 1.30 ≤ ZnO / MgO ≤ 2.50. This specific relationship between ZnO and MgO helps ensure the formation of the desired primary crystalline phase structure. In some embodiments of the present application, the ZnO / MgO ratio can be 1.30, 1.40, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00, 2.10, 2.20, 2.30, 2.40, or 2.50, or a range of values ​​defined by any two of these values, as long as the desired properties of the strengthened glass-ceramic are achieved. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the desired properties of the strengthened glass-ceramic are achieved.

[0123] In some embodiments of the present application, the composition of the base glass for preparing chemically strengthened glass-ceramics or the center of chemically strengthened glass-ceramics or strengthened glass-ceramics, measured by the molar percentage of each oxide in the composition, satisfies: 0.05≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.20; by making Li2O, Al2O3, MgO, ZnO and SiO2 satisfy a specific content relationship, it helps to improve the ion exchange performance of the glass-ceramics, helps to make the glass-ceramics obtain a high compressive stress layer depth and a larger deep stress through chemical strengthening, and thus helps to improve the damage resistance of the strengthened glass-ceramics, especially improve its drop impact resistance. In some embodiments of the present application, the value of Li2O / (Al2O3-(MgO+ZnO)+SiO2) can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.20, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0124] In some embodiments of the present application, the composition of the base glass for preparing chemically strengthened glass-ceramics or the center of chemically strengthened glass-ceramics or strengthened glass-ceramics, measured in terms of the molar percentage of each oxide in the composition, satisfies the following: 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60; by ensuring that Al2O3, MgO, ZnO and SiO2 satisfy a specific content relationship, it is possible to ensure that there is an appropriate amount of Al in the residual glass phase of the glass-ceramics, which, on the one hand, helps to exert the synergistic effect of Si and Al, so that the residual glass phase forms a specific network structure, thereby improving the intrinsic strength of the glass-ceramics; on the other hand, it helps to promote ion exchange and improve the chemical strengthening effect of the glass-ceramics. In some embodiments of the present application, the value of (Al2O3-(MgO+ZnO)) / SiO2 can be 0.19, 0.20, 0.23, 0.25, 0.28, 0.30, 0.33, 0.35, 0.38, 0.40, 0.43, 0.45, 0.48, 0.50, 0.53, 0.55, 0.58 or 0.60, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application can be obtained.

[0125] In some embodiments of the present application, the composition of the substrate glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic at its center, calculated by the molar percentage of each oxide in the composition, satisfies the following: 0.26 ≤ Na2O / Li2O ≤ 3.00. By ensuring that the Na and Li content meet a specific relationship, it helps ensure that the glass-ceramic achieves the desired surface stress level and deep stress level after chemical strengthening, thereby achieving the desired stress structure and achieving high mechanical strength and high damage resistance. In some embodiments of the present application, the Na2O / Li2O value can be 0.26, 0.30, 0.50, 0.80, 1.00, 1.20, 1.50, 1.80, 2.00, 2.20, 2.30, 2.50, 2.80, or 3.00, or a value within a range of any two of the above values, as long as the strengthened glass-ceramic with the desired properties of the present application is obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic having the desired properties of the present application can be obtained.

[0126] In some embodiments of the present application, the composition of the base glass for preparing chemically strengthened glass-ceramics or the center of chemically strengthened glass-ceramics or strengthened glass-ceramics, calculated on the basis of the molar percentage of each oxide in the composition, further satisfies the following conditions: 12.00 mol% ≤ ZnO + MgO ≤ 20.00 mol%, preferably, 13.00 mol% ≤ ZnO + MgO ≤ 17.30 mol%. By having a sufficient amount of ZnO and MgO in the composition, it helps to ensure that a sufficient amount of main crystalline phase can be precipitated in the glass-ceramics, thereby forming a desired crystalline phase structure. In some embodiments of the present application, the value of ZnO+MgO can be 12.00mol%, 13.00mol%, 13.30mol%, 13.50mol%, 13.80mol%, 14.00mol%, 14.30mol%, 14.50mol%, 14.80mol%, 15.00mol%, 15.30mol%, 15.50mol%, 15.80mol%, 16.00mol%, 16.30mol%, 16.50mol%, 16.80mol%, 17.00mol%, 17.30mol%, 18.00mol%, 19.00mol% or 20.00mol%, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the reinforced glass-ceramics with the required properties of the present application can be obtained. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic having the desired properties of the present application can be obtained.

[0127] In some embodiments of the present application, the composition of the base glass for preparing chemically strengthened glass-ceramics or the center of chemically strengthened glass-ceramics or strengthened glass-ceramics, calculated in terms of the molar percentage of each oxide in the composition, also satisfies the following: 9.00 mol% ≤ Al2O3-(MgO+ZnO) ≤ 22.00 mol%, preferably, 10.00 mol% ≤ Al2O3-(MgO+ZnO) ≤ 20.00 mol%; by making the Al2O3 content in the composition higher than the sum of MgO and ZnO, while ensuring the formation of the main crystalline phase, an appropriate amount of Al can be present in the residual glass phase, which, on the one hand, helps to exert the synergistic effect of Si and Al, so that the residual glass phase forms a specific network structure, thereby improving the intrinsic strength of the glass-ceramics; on the other hand, it helps to promote ion exchange and improve the chemical strengthening effect of the glass-ceramics. In some embodiments of the present application, the value of Al2O3-(MgO+ZnO) can be 9.00 mol%, 10.00 mol%, 11.00 mol%, 12.00 mol%, 13.00 mol%, 14.00 mol%, 15.00 mol%, 16.00 mol%, 17.00 mol%, 18.00 mol%, 19.00 mol%, 20.00 mol%, 21.00 mol% or 22.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application can be obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application can be obtained.

[0128] In some embodiments of the present application, the composition at the center of the substrate glass, chemically strengthened glass-ceramic, or strengthened glass-ceramic for preparing a chemically strengthened glass-ceramic, calculated by mole percentage of each oxide in the composition, further satisfies the following: 5.00 mol% ≤ Na2O + Li2O ≤ 15.00 mol%, preferably, 6.00 mol% ≤ Na2O + Li2O ≤ 13.50 mol%. The presence of sufficient amounts of Na and Li in the composition helps improve the ion exchange properties of the glass-ceramic, thereby ensuring that the glass-ceramic achieves the desired surface stress level and deep stress level after chemical strengthening, thereby achieving a desired stress structure and achieving high mechanical strength and high damage resistance. In some embodiments of the present application, the value of Na2O+Li2O can be 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, 10.00 mol%, 10.50 mol%, 11.00 mol%, 11.50 mol%, 12.00 mol%, 12.50 mol%, 13.00 mol%, 13.50 mol%, 14.00 mol%, 14.50 mol%, or 15.00 mol%, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained. It should be understood that in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the reinforced glass-ceramic with the desired properties of the present application is obtained.

[0129] In the present application, each substance in the above-mentioned relationship formulas ZnO / MgO, Li2O / (Al2O3-(MgO+ZnO)+SiO2), (Al2O3-(MgO+ZnO)) / SiO2, Na2O / Li2O, ZnO+MgO, Al2O3-(MgO+ZnO), and Na2O+Li2O represents the molar percentage content of the corresponding substance. For example, ZnO represents the molar percentage content of ZnO, MgO represents the molar percentage content of MgO, etc., and this application will not repeat them one by one.

[0130] In some embodiments of the present application, the transmittance T of the 0.7 mm thick reinforced glass ceramic under 550 nm wavelength light is greater than or equal to 85.00%. The transmittance of the 0.7 mm thick reinforced glass ceramic under 550 nm wavelength light is within the above range, indicating that the reinforced glass ceramic of the present application has high light transmittance. At the same time, the reinforced glass ceramic of the present application also has excellent damage resistance, especially excellent drop impact resistance, which effectively broadens the application scenarios and application fields of the reinforced glass ceramic of the present application. In some embodiments of the present application, the transmittance T can be 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass ceramic with the performance required by the present application can be obtained. As shown in FIG9 , in the present application, the transmittance of the chemically strengthened glass ceramics is substantially the same as the transmittance of the strengthened glass ceramics before and after chemical strengthening. That is, in the present application, by adopting chemically strengthened glass ceramics having high transmittance, strengthened glass ceramic products having the same excellent transmittance can be obtained by chemical strengthening treatment.

[0131] In some embodiments of the present application, a 0.7 mm thick reinforced glass-ceramic is subjected to a drop resistance test using 80-grit sandpaper. The average sandpaper drop resistance height H of the reinforced glass-ceramic is greater than or equal to 1.00 m, preferably the average sandpaper drop resistance height is greater than or equal to 1.40 m, and more preferably is 1.50 m to 2.50 m. The average sandpaper drop resistance height H of the 0.7 mm thick reinforced glass-ceramic is within the above range, indicating that the reinforced glass-ceramic of the present application has high mechanical strength and high damage resistance. In some embodiments of the present application, the average sandpaper drop resistance height H can be 1.50 m, 1.60 m, 1.70 m, 1.80 m, 1.90 m, 2.00 m, 2.10 m, 2.20 m, 2.30 m, 2.40 m or 2.50 m, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the reinforced glass-ceramic with the performance required by the present application can be obtained.

[0132] In some embodiments of the present application, the strengthened glass-ceramic is obtained by chemically strengthening a chemically strengthened glass-ceramic, and the composition of the chemically strengthened glass-ceramic is the same as or substantially the same as the composition at the center of the strengthened glass-ceramic.

[0133] The preparation method of the reinforced glass-ceramic in any of the aforementioned embodiments of the present application may include but is not limited to the following steps:

[0134] (1) Preparation of substrate glass: Expressed as a molar percentage of oxides, the ingredients are prepared according to the composition at the center of the substrate glass or reinforced glass-ceramic in any of the aforementioned embodiments. After uniform mixing, the substrate glass is prepared by conventional methods known in the art. The substrate glass preparation methods herein include but are not limited to float, overflow, rolling, casting or continuous melting methods. The present application does not limit the various parameters in the substrate glass preparation process, as long as a transparent substrate glass with the performance required by the present application can be obtained.

[0135] (2) Preparation of chemically strengthened glass ceramics: The base glass obtained in step (1) is subjected to heat treatment, wherein the heat treatment includes but is not limited to a one-step heat treatment or a multi-step heat treatment, to obtain chemically strengthened glass ceramics.

[0136] (3) Chemical strengthening treatment: The chemically strengthened glass ceramic obtained in step (2) is subjected to chemical strengthening treatment to obtain the strengthened glass ceramic according to any of the aforementioned embodiments.

[0137] In some embodiments of the present application, the preparation method of the substrate glass in the above step (1) may include but is not limited to the following steps: the ingredients are prepared according to the composition of the center of the substrate glass or reinforced glass ceramic in any of the aforementioned embodiments, mixed evenly, melted, formed, cooled, and annealed to obtain the substrate glass. The present application has no special restrictions on the melting temperature and time, as long as the various components can be fully melted. Preferably, the melting temperature is 1550℃~1800℃, and the melting time is preferably 3h~12h. The present application does not limit the molding method, as long as the purpose of the present application can be achieved, for example, it can be cast into a molding mold to form a glass brick. The present application does not limit the cooling temperature, as long as the purpose of the present application can be achieved. Preferably, the cooling temperature is 800℃~1000℃. The present application does not limit the annealing temperature and time, as long as the purpose of the present application can be achieved. Preferably, the annealing temperature is 500℃~700℃ and the time is 20h~26h.

[0138] In some embodiments of the present application, the heat treatment in the above step (2) includes a nucleation treatment and a crystallization treatment. Preferably, the temperature T1 of the nucleation treatment is 600°C to 850°C, more preferably T1 is 650°C to 850°C. In some embodiments of the present application, the temperature T1 of the nucleation treatment can be 600°C, 625°C, 650°C, 675°C, 680°C, 690°C, 700°C, 710°C, 720°C, 725°C, 730°C, 740°C, 750°C, 775°C, 800°C, 825°C or 850°C, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the chemically strengthened glass-ceramics with the required properties of the present application can be obtained. Preferably, the nucleation treatment time t1 is 0h to 72h, more preferably t1 is 0h to 24h, and more preferably t1 is 0h to 8h. In some embodiments of the present application, the nucleation treatment time t1 can be 0 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 16 h, 24 h, 32 h, 40 h, 48 h, 56 h, 64 h, or 72 h, or a value within a range of any two of these values, as long as the chemically strengthened glass-ceramic having the desired properties is obtained. Preferably, the crystallization treatment temperature T2 is 700°C to 1000°C. In some embodiments of the present application, the crystallization temperature T2 can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 875°C, 900°C, 925°C, 950°C, 975°C, or 1000°C, or any value within a range of values ​​consisting of any two of the above values ​​as endpoints, as long as the chemically strengthened glass-ceramic having the desired properties of the present application is obtained. Preferably, the crystallization time t2 is 10 min to 400 min, and more preferably t2 is 10 min to 120 min. In some embodiments of the present application, the crystallization treatment time t2 can be 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 150min, 170min, 200min, 220min, 250min, 280min, 300min, 320min, 350min, 370min or 400min, or a value within the numerical range formed by any two of the above values ​​as endpoints, as long as the chemically strengthened glass-ceramics with the required performance of the present application can be obtained.

[0139] In the present application, when the substrate glass is heat-treated to prepare chemically strengthened glass-ceramics, a one-step heat treatment can be performed, or a two-step or multi-step heat treatment can be performed. If a one-step heat treatment is performed, it means that the nucleation treatment is not performed separately, and the temperature is directly increased in one step, and the nucleation and target crystal growth are carried out at the temperature reached by the one-step heating process, which can be understood as directly performing a crystallization treatment. If a two-step heat treatment is performed, it means that a two-step heating process is performed, in which a nucleation treatment, i.e., a nucleation treatment, is performed first, and then a target crystal growth treatment, i.e., a crystallization treatment, is performed. If a multi-step heat treatment is performed, then the nucleation treatment stage and / or the crystallization treatment stage adopts a stepped heating method, that is, the entire heat treatment process will be heated multiple times (more than twice).

[0140] In the present application, the nucleation treatment is to raise the temperature to the specified nucleation treatment temperature (also called nucleation temperature), and after reaching the nucleation treatment temperature, keep it warm for a certain time, and the holding time here is the nucleation treatment time (also called nucleation time); the crystallization treatment is to raise the temperature to the specified crystallization treatment temperature (also called crystallization temperature), and after reaching the crystallization treatment temperature, keep it warm for a certain time, and the holding time here is the crystallization treatment time (also called crystallization time).

[0141] In some embodiments of the present application, in step (2), when performing heat treatment, the heating rate is preferably controlled to be 5K / min to 15K / min, preferably 5K / min to 10K / min. In some embodiments of the present application, the heating rate can be 5K / min, 6K / min, 7K / min, 8K / min, 9K / min, 10K / min, 11K / min, 12K / min, 13K / min, 14K / min or 15K / min, or a value within a numerical range consisting of any two of the above values ​​as endpoints, as long as the chemically strengthened glass-ceramics having the properties required by the present application can be obtained.

[0142] In some embodiments of the present application, in step (3), the salt bath for chemical strengthening treatment is a molten salt containing potassium salt and / or sodium salt, the potassium salt including one or more of potassium nitrate, potassium sulfate, and potassium carbonate, preferably potassium nitrate; the sodium salt including at least one of sodium nitrate, sodium sulfate, and sodium carbonate, preferably sodium nitrate. Preferably, the temperature T3 of the salt bath for chemical strengthening treatment is 380°C to 600°C, preferably T3 is 400°C to 550°C, and more preferably T3 is 400°C to 500°C. In some embodiments of the present application, the temperature T3 of the salt bath for chemical strengthening treatment can be 380°C, 400°C, 425°C, 450°C, 475°C, 500°C, 525°C, 550°C, 575°C or 600°C, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramics with the required properties of the present application can be obtained. Preferably, the time t3 of the chemical strengthening treatment is 1h to 48h, preferably t3 is 2h to 24h, and more preferably t3 is 2h to 15h. In some embodiments of the present application, the time t3 of the chemical strengthening treatment can be 1h, 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h or 48h, or a value within the numerical range consisting of any two of the above values ​​as endpoints, as long as the strengthened glass-ceramics with the required performance of the present application can be obtained. In some embodiments of the present application, a certain amount (e.g., 0wt% to 0.5wt%) of lithium salt can be added to the salt bath. By adopting the above-mentioned chemical strengthening treatment process scheme to strengthen chemically strengthened glass-ceramics with specific composition and structure, strengthened glass-ceramics with excellent surface stress characteristics and excellent deep stress characteristics can be obtained, thereby ensuring that the obtained strengthened glass-ceramics have high mechanical strength and excellent damage resistance.

[0143] It should be understood that when performing a chemical strengthening treatment, a single step or two or more steps may be performed. In this application, the temperature of the chemical strengthening treatment refers to the temperature of the salt bath; when the chemical strengthening treatment includes two or more steps, the duration of the chemical strengthening treatment refers to the sum of the durations of each step. In some embodiments of this application, when the chemical strengthening treatment includes two or more steps, the temperature and duration of each step may be the same or different.

[0144] In this application, the stress distribution structure of the strengthened glass-ceramic is closely related to the composition of the chemically strengthened glass-ceramic (including oxide composition and crystal phase composition), the salt bath composition, the salt bath temperature, and the chemical strengthening treatment time. Only when the chemically strengthened glass-ceramic of a specific composition is used in a suitable salt bath (with a suitable composition and a suitable temperature) and the chemical strengthening treatment is performed for a suitable time can the prepared strengthened glass-ceramic obtain a specific stress distribution structure, thereby achieving the excellent effect expected to be achieved in this application.

[0145] In the present application, the strengthened glass-ceramics of any of the aforementioned embodiments can be used to produce high-strength glass devices. For example, the glass devices may include, but are not limited to, countertops, other surfaces, appliance doors, floor tiles, wall panels, storage containers, mobile phone screens, mobile phone back panels, electronic device frames, vehicle windshields, aircraft windshields, or aircraft windshields. The strengthened glass-ceramics provided herein have high mechanical strength and high damage resistance, particularly excellent drop impact resistance, and thus the glass devices provided herein also have excellent mechanical properties.

[0146] In the present application, the reinforced glass-ceramic in any of the aforementioned embodiments can be used in electronic devices.

[0147] In some embodiments of the present application, the electronic device includes at least one of a mobile phone, a tablet computer, a smart wearable, a display, and a television. For example, the electronic device may include but is not limited to a mobile phone, a tablet computer, a smart wearable, a display, or a television. Smart wearable may include but is not limited to an electronic watch, a smart bracelet, a smart watch, smart glasses, etc., and the display may include but is not limited to a high-definition display, a car display, an aircraft display, etc. Exemplarily, the electronic device may include a housing and an electronic component partially located within the housing, the housing including a front surface, a rear surface, and a side surface, the electronic component including a display device, the display device being located at the front surface of the housing or adjacent to the front surface, and the strengthened glass ceramic provided in the present application may be applied to the front surface and / or rear surface and / or side surface of the housing. In some embodiments of the present application, the front surface and / or rear surface of the housing may be of equal thickness or unequal thickness. In some embodiments of the present application, the front surface and / or rear surface of the housing may be 2D, 2.5D, 3D, or special-shaped.

[0148] Test method:

[0149] 1. X-ray diffraction (XRD) test

[0150] The sample to be tested was crushed and ground into a particle size of less than 75 μm. The ground sample was then tested using an X-ray diffractometer to obtain XRD diffraction peak curves and XRD diffraction data. The XRD diffraction data were then analyzed using JADE Standard 8.6 software to determine the sample's crystalline phase. The X-ray diffractometer was a Shimadzu XRD-6100, with a 2θ value of 10° to 80°, a scan rate of 6° / min, an operating voltage of 40 kV, and an operating current of 30 mA. The sample to be tested was either chemically strengthened glass-ceramics or reinforced glass-ceramics.

[0151] Average crystal size: The average crystal size of the sample can be calculated using the result data obtained from the XRD test according to the Scherrer formula D = Kλ / (βcosθ). Wherein, λ is the X-ray wavelength, λ = 0.154056nm, β is the half-maximum width 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 JADE Standard 8.6 software. Jade outputs a fitting report. According to the angle 2θ value and Peak FWHM value corresponding to each diffraction peak in the fitting report, the Peak FWHM value is converted to radians: β = (FWHM / 180×3.14). The crystal size of each diffraction peak is calculated using the Scherrer formula D = Kλ / (βcosθ) and then averaged to obtain the average crystal size.

[0152] Average crystal size of the (Zn, Mg)Al2O4 phase: The RAW file (diffraction pattern) output by the XRD instrument was used for phase search and curve fitting in JADE Standard 8.6 software. In the output fitting report, the 2θ values ​​and Peak Full Width (FWHM) values ​​corresponding to three diffraction peaks of the (Zn, Mg)Al2O4 phase within the 2θ range of 34° to 38°, 44° to 46°, and 64° to 67° were selected. The Peak Full Width (FWHM) values ​​were converted to radians: β = (FWHM / 180 × 3.14). The crystal sizes of the three diffraction peaks were calculated using the Scherrer formula D = Kλ / (βcosθ) and then averaged to obtain the average crystal size of the (Zn, Mg)Al2O4 phase. Where λ is the X-ray wavelength (λ = 0.154056 nm), β is the half-width (FWHM) of the diffraction peak, K = 0.89, and θ is the Bragg diffraction angle.

[0153] Crystalline phase content: Import the XRD test results (RAW format) into JADE Standard 8.6 software for fitting and calculation to obtain the content of each crystal phase in the glass ceramics, and then calculate the total content of each crystal phase in the glass ceramics. The ratio of the fitted crystal phase peak area to the fitted total peak area is the crystal phase content of the corresponding crystal phase. The ratio of the fitted crystal phase peak area of ​​the (Zn, Mg)Al2O4 crystal phase to the fitted total peak area is the crystal phase content W of the (Zn, Mg)Al2O4 crystal phase. [(Zn，Mg)Al2O4] The ratio of the peak area of ​​the tetragonal ZrO2 crystal phase to the total peak area of ​​the fitting is the crystal phase content W of the tetragonal ZrO2 crystal phase. [ZrO2] According to W [(Zn，Mg)Al2O4] and W [ZrO2] The ratio of (Zn, Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase (mass ratio Z) and the total crystal phase content W were calculated.

[0154] Peak intensity ratio: Import the XRD test results (RAW format) into JADE Standard 8.6 software and use the peak search function to determine the 2θ position of the peak and the corresponding raw intensity, and calculate the peak intensity ratio (X), which is the peak intensity ratio of the first characteristic peak to the second characteristic peak.

[0155] Half-peak width: Import XRD test results (RAW format) into JADE Standard 8.6 software for phase search and curve fitting. The output fitting report contains the peak 2θ position and corresponding crystal plane, half-peak width, and fitting intensity. Calculate the ratio based on the fitting intensity of the corresponding crystal plane.

[0156] Specifically, the fitting peak intensity I of the characteristic peak of the

[0400] crystal plane

[0400] 、

[0311] Fitting peak intensity of crystal plane characteristic peak I

[0311] 、

[0440] Fitting peak intensity of crystal plane characteristic peak I

[0440] 、

[0400] half-peak width W of the characteristic peak of the crystal plane

[0400] 、

[0311] half-peak width W of the characteristic peak of the crystal plane

[0311] 、

[0440] half-peak width W of the characteristic peak of the crystal face

[0440] , I

[0400] / I

[0311] and I

[0440] / I

[0311] .

[0157] Taking into account the influence of noise in the test process on peak search, the XRD diffraction peak curve can be smoothed no more than three times.

[0158] 2. Tests of |CT_AV|, DOL_0, CS_50, and |CT_CV|

[0159] The test was conducted using a stress meter SLP-2000 (also known as a scattered light photoelastic stress meter) with a light source wavelength of 518 nm, SOC = 25.5 (nm / cm) / MPa, a refractive index = 1.60, and an exposure time of 300 usec.

[0160] When testing surfaces CS_50, |CT_AV|, DOL_0, and |CT_CV|, first apply conductive fluid to the strain gauge. Then, clean the tempered glass-ceramic sample and place it in the test path to measure its stress. The strain gauge is an SLP-2000, and the conductive fluid used has a refractive index of 1.51.

[0161] 3. Thickness test

[0162] The thickness of chemically strengthened glass-ceramics was measured using a micrometer.

[0163] It should be understood that during chemical strengthening treatment, the degree of ion exchange varies gradually from the surface to the center of the chemically strengthened glass-ceramic in the thickness direction, and the increase (mass) in the total Na-K and / or Li-Na exchange amount generally does not exceed 1% of the total mass of the sample. Therefore, the expansion effect in the thickness direction is extremely slight. That is, the thickness change of the chemically strengthened glass-ceramic before and after chemical strengthening is very small, and it can be approximately considered that the thickness has basically not changed.

[0164] 4. Optical performance test

[0165] The test samples were cleaned in an ultrasonic cleaner under the following cleaning conditions: cleaning time: 10 minutes; cleaning agent: detergent diluted 10-fold; cleaning temperature: 55±10°C; cleaning frequency: 30±10 kHz. The transmittance of the test samples at different wavelengths was then measured using a haze meter, according to the standard "GB / T 7962.12-2010 Test Methods for Colorless Optical Glass - Part 12: Spectral Transmittance." The haze meter used in this application was a Konica Minolta CM-3600A spectrophotometer. The test samples were chemically strengthened glass-ceramics or reinforced glass-ceramics.

[0166] 5. Vickers hardness HV test

[0167] Clean, surface-free reinforced glass-ceramics free of visible scratches, pits, cracks, and other damage were selected as specimens. A digital, low-load Vickers hardness tester (VTD405, Beijing Wowei Technology Co., Ltd.) was used to test the Vickers hardness of the reinforced glass-ceramics. The test was conducted using a 300gf load and a 10s indentation method, in accordance with the national standard GB / T 37900-2019, "Test method for hardness and fracture toughness of ultra-thin glass." The indentation was validated in accordance with the national standard GB / T 16534-2009, "Test method for room-temperature hardness of fine ceramics." For this application, the Vickers hardness test was conducted on reinforced glass-ceramics specimens measuring 50mm x 50mm x 0.7mm. Measurements were taken at three different locations on the same specimen surface, and the average value was used as the final test result.

[0168] 6. Test of surface K2O concentration

[0169] In the present application, the surface K2O concentration of the strengthened glass-ceramics is measured by X-ray fluorescence spectrometer (XRF). The equipment model used is (Thermo Scientific ARL PERFORM'X), the target material is Rh (rhodium), the light tube voltage is 40kW, the current is 60mA, the collimator is 0.15, the crystal is LiF200, the detector is FPC, the test range is 29mm circle, and the analysis software is UniQuant standardless analysis. Specifically, the surface K element content of the strengthened glass-ceramics is measured by X-ray fluorescence spectrometer (XRF), and then the surface K2O concentration is calculated. The calculation method is: surface K2O concentration = (surface K element content × relative molecular mass of K2O) / (relative atomic mass of K element × 2). It should be understood that the surface K element content = K element mass / total element mass, and the total element mass = total oxide mass.

[0170] In other words, the K2O concentration on the surface of a strengthened glass-ceramic is the ratio of the mass of K2O to the total mass of oxides. Oxides include SiO2, Al2O3, ZrO2, Na2O, and K2O, which can be accurately measured by XRF, but do not include B2O3, which cannot be accurately measured by XRF. XRF testing uses a standardless method and does not measure the concentration of elements with atomic numbers 6 or lower, or their oxides, in the strengthened glass-ceramic. That is, when XRF tests the K2O concentration on the surface of strengthened glass-ceramic, the total mass of oxides measured does not include the mass of elements with atomic numbers 6 or lower, or their oxides, in the strengthened glass-ceramic.

[0171] 7. Average sandpaper drop resistance test

[0172] The average sandpaper drop height refers to the sum of the sandpaper drop heights measured for multiple reinforced glass-ceramic samples from the same embodiment or comparative example, divided by the total number of reinforced glass-ceramic samples. This can be used to characterize the drop damage resistance of reinforced glass-ceramic. Ten identical reinforced glass-ceramic samples were tested in each batch, and the average sandpaper drop height was:

[0173] Where n is the number of strengthened glass-ceramic samples tested in each batch, and hi is the sandpaper drop resistance height of a single sample tested.

[0174] Among them, the test method for a single sample's resistance to sandpaper drop height is:

[0175] Step 1: Apply 80-grit sandpaper to the bottom surface of a 160g model machine and place the model machine on a green figure LT-SKDL-CD drop machine;

[0176] Step 2: Place a strengthened glass-ceramic sample to be tested with a length, width and thickness of 50mm×50mm×0.7mm directly under the model machine, with the strengthened glass-ceramic sample facing the sandpaper, specifically, with the main surface of the strengthened glass-ceramic facing the sandpaper. Make the model machine drop from a certain drop height to impact the strengthened glass-ceramic sample directly under the model machine. If the strengthened glass-ceramic sample does not break, the drop height of the model machine is increased according to a certain pattern. For example, the drop height starts from 0.4m, and the sample is dropped once. If it does not break, increase the height by 0.1m each time and drop again until the strengthened glass-ceramic sample breaks;

[0177] Step 3: The last drop height of the tempered glass-ceramic sample when it breaks is recorded as the sandpaper drop height. For example, if the drop height is increased by 0.1m each time and the drop height when it breaks is 0.5m, the sandpaper drop height of the sample is 0.4m.

[0178] 8. Density

[0179] This application uses the Japanese ALFA MIRAGE electronic density balance SD-200L to test the density of reinforced glass ceramics. The test principle is the "Archimedes drainage method".

[0180] 9. Fracture toughness test

[0181] Testing is conducted in accordance with the national standard GB / T 37900-2019, "Ultra-thin glass hardness and fracture toughness test method—Small-load Vickers hardness indentation method." Specifically, an indentation is prepared using the same method as for Vickers hardness measurement. The diagonal crack lengths 2C1 and 2C2 are measured, with the maximum value not exceeding the thickness of the reinforced glass-ceramic. At least five effective indentation morphologies are measured on a single specimen surface, and the average value is calculated as the final result for that specimen.

[0182] Calculation formula for indentation fracture toughness:

[0183] IFR: Indentation fracture toughness, unit is MPa·m 1 / 2) ; E: elastic modulus of the specimen, in GPa; 2C1, 2C2: crack extension length in the diagonal direction of the indentation, in millimeters (mm); d1, d2: diagonal length of the indentation, in millimeters (mm); F: test load value, in Newtons (N).

[0184] In the above test method, the reinforced glass ceramic tiles in the examples and comparative examples are shaped, cut and polished to obtain reinforced glass ceramic samples of desired size (e.g., polished sheets), which are then tested, such as glass ceramic polished sheets with a length, width and thickness of 50 mm × 50 mm × 0.7 mm.

[0185] Example 1

[0186] <Preparation of Base Glass>

[0187] According to the formula 1 in Table 1, the raw materials for glass production were converted into a formula for mixing. The total mass of the raw materials was 1000 g, and then mixed in a V-type mixer for 30 minutes. After mixing, 5 g of clarifier NaCl was added, and then transferred to a platinum crucible and melted in a 1650°C lifting furnace (lifting furnace model: SJF1750, manufacturer: Nanjing Boyuntong Instrument Technology Co., Ltd.) for 5 hours. Then, it was poured into a stainless steel mold preheated at 300°C for forming and cooling. After cooling to 900°C, it was placed in a 600°C annealing furnace for annealing for 24 hours, and then cooled to room temperature with the furnace to obtain the substrate glass.

[0188] <Preparation of Chemically Strengthened Glass-Ceramics>

[0189] The prepared substrate glass was heat-treated in a resistance furnace (model SLX1400-40, manufactured by Shanghai Shengli Testing Instrument Co., Ltd.) to produce a chemically strengthened glass-ceramic. The composition of the resulting chemically strengthened glass-ceramic, calculated as the molar percentage of oxides, was identical to that of the substrate glass, as detailed in Table 1.

[0190] Specifically, a two-step heat treatment process was used: first, the temperature was raised to the nucleation temperature for nucleation, and then to the crystallization temperature for crystallization. The heating rate during the nucleation and crystallization processes was 10K / min. The nucleation temperature T1 was 740°C, and the nucleation time t1 was 480 minutes; the crystallization temperature T2 was 800°C, and the crystallization time t2 was 10 minutes.

[0191] As needed, the chemically strengthened glass-ceramic is cut, CNC machined (using a computer numerical control machine; the CNC machine used in this application is an RCG500S), and polished to produce smooth chemically strengthened glass-ceramic sheets of the desired specifications. In this application, the processed chemically strengthened glass-ceramic sheets measure 50 mm x 50 mm x 0.7 mm.

[0192] <Preparation of Strengthened Glass-Ceramics>

[0193] The chemically strengthened glass ceramics were placed in a 100wt% NaNO3 salt bath at 450°C for a first strengthening treatment for 3 hours, and then placed in a 100wt% KNO3 salt bath at 430°C for a second strengthening treatment for 2 hours to obtain strengthened glass ceramics.

[0194] Example 2 to Example 8

[0195] Except for adjusting the relevant preparation parameters according to Table 2, the rest is the same as Example 1. The corresponding formula in Table 2 is shown in Table 1.

[0196] Example 9-Example 10

[0197] The process is the same as in Example 1 except that the corresponding chemically strengthened glass-ceramics are placed in a 100 wt % NaNO 3 salt bath at 450° C. for 4 h to obtain the corresponding strengthened glass-ceramics according to Table 5.

[0198] Comparative Example 1 to Comparative Example 11

[0199] Except for adjusting the relevant preparation parameters according to Table 2, the rest is the same as Example 1. The corresponding formula in Table 2 is shown in Table 1.

[0200] Comparative Examples 12 to 15

[0201] The process is the same as in Example 1 except that the corresponding chemically strengthened glass-ceramics are placed in a 100 wt % NaNO 3 salt bath at 450° C. for 4 h to obtain the corresponding strengthened glass-ceramics according to Table 5.

[0202] The formulations of the embodiments and comparative examples are shown in Table 1, and the preparation parameters and performance tests of the embodiments and comparative examples are shown in Tables 2 to 5.

[0203] After testing, the chemically strengthened glass-ceramics of Examples 1 to 8 and Comparative Examples 1 to 11 all contain a main crystalline phase (Zn, Mg)Al2O4 phase and a secondary crystalline phase tetragonal ZrO2 phase. The XRD patterns of some of the examples and comparative examples are shown in Figures 2 to 6 and 8.

[0204] Referring to Tables 1-4, the DOL_0 and |CT-AV| values ​​of the strengthened glass-ceramics of Examples 1-8 are all within the ranges of this application, while at least one of the DOL_0 and |CT-AV| values ​​in Comparative Examples 1-11 is outside the ranges of this application. The strengthened glass-ceramics in the examples of this application simultaneously exhibit high Vickers hardness, fracture toughness, and a higher average sandpaper drop resistance, demonstrating that the strengthened glass-ceramics obtained in the examples of this application possess higher mechanical strength. Furthermore, the chemically strengthened glass-ceramics in the examples exhibit a transmittance of 89.00% or greater for 550nm wavelength light, resulting in excellent light transmittance. Specifically, as shown in Figure 7, the chemically strengthened glass-ceramics in Example 1 exhibit a visible light transmittance of 80.00% or greater, making the strengthened glass-ceramics transparent in the visible light range.

[0205] Examples 1 to 2 and Comparative Examples 6 to 9 all obtained chemically strengthened glass ceramics by subjecting the substrate glass of the composition of Formula 1 to different heat treatment regimes, and their XRD diffraction patterns are shown in FIG2 .

[0206] Referring to Figure 2 and Table 3, the XRD pattern of Comparative Example 6 does not contain a second characteristic peak with a 2θ angle in the range of 36° to 38°, and therefore does not have a peak intensity ratio X. The (Zn, Mg)Al2O4 crystal phase content in the chemically strengthened glass-ceramic of Comparative Example 6 is relatively low, and the calculation result of Formula C does not meet the scope of the present application. The stress level of the strengthened glass-ceramic produced in Comparative Example 6 is relatively low. Referring to Figure 2 and Table 3, the peak intensity ratio X of the XRD pattern of Comparative Example 7 is 1.61. The (Zn, Mg)Al2O4 crystal phase content in the chemically strengthened glass-ceramic of Comparative Example 7 is relatively low, and the half-value widths of some characteristic peaks of the crystal planes do not meet the requirements of the present application. The calculation result of Formula C also does not meet the scope of the present application, and the stress level of the strengthened glass-ceramic produced in Comparative Example 7 is also relatively low. 2 and 3 , the XRD pattern of Comparative Example 8 shows a peak at 2θ angles in the range of 28° to 32°. The (Zn, Mg)Al2O4 crystalline phase content in the chemically strengthened glass-ceramic of Comparative Example 8 is relatively high, the average crystal size of the (Zn, Mg)Al2O4 crystalline phase is relatively high, the half-width of the characteristic peak of the crystal plane does not meet the requirements of this application, and the calculation results of Formula C do not meet the scope of the scheme of this application. The stress level of the strengthened glass-ceramic prepared in Comparative Example 8 is relatively low. Referring to FIG2 , the XRD pattern of Comparative Example 9 shows a peak at 2θ angles in the range of 28° to 32°. The (Zn, Mg)Al2O4 crystalline phase content in the chemically strengthened glass-ceramic of Comparative Example 9 is also relatively high, the average crystal size of the (Zn, Mg)Al2O4 crystalline phase is also relatively high, and the calculation results of Formula C do not meet the scope of the scheme of this application. The stress level of the strengthened glass-ceramic prepared in Comparative Example 9 is also relatively low.

[0207] Comparative Examples 10 and 11 are both chemically strengthened glass ceramics obtained by using different heat treatment systems on the substrate glass of the composition of Formula 5, and their XRD diffraction patterns are shown in Figures 5 and 6.

[0208] The XRD pattern of Comparative Example 10, as shown in FIG5 , shows that the 2θ angle has peaks in the range of 28° to 32° and in the range of 36° to 38°. In the chemically strengthened glass-ceramic of Comparative Example 10, the average crystal size of the (Zn, Mg)Al2O4 crystal phase is relatively high, and the calculation result of Formula C does not meet the scope of the scheme of this application. The stress level of the strengthened glass-ceramic obtained in Comparative Example 10 is relatively low. The XRD pattern of Comparative Example 11, as shown in FIG6 , shows that the 2θ angle has peaks in the range of 28° to 32°. In the chemically strengthened glass-ceramic of Comparative Example 11, the average crystal size of the (Zn, Mg)Al2O4 crystal phase is relatively high, the half-width of the characteristic peaks of some crystal planes does not meet the requirements of this application, the peak intensity ratio X does not meet the scope of the scheme of this application, and the calculation result of Formula C does not meet the scope of the scheme of this application. The stress level of the strengthened glass-ceramic obtained in Comparative Example 11 is relatively low.

[0209] Comparative Examples 12 to 15 and Examples 9 to 10 obtained chemically strengthened glass ceramics by using different heat treatment systems on the substrate glass of the composition of Formula 1. The strengthened glass ceramics obtained using the same chemical strengthening treatment conditions, the compressive stress layer depth DOL-0 of Comparative Examples 12 to 15 are not within the scope of the present application, and their drop impact resistance is worse than that of the examples of the present application.

[0210] It should be noted that, in this article, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0211] Each embodiment in this specification is described in a related manner. The same or similar parts between the embodiments can be referred to each other. Each embodiment focuses on the differences from other embodiments.

[0212] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A reinforced glass ceramic, characterized in that: The strengthened glass-ceramic contains a main crystal phase (Zn, Mg)Al2O4 crystal phase and a secondary crystal phase tetragonal ZrO2 crystal phase; the strengthened glass-ceramic contains a compressive stress layer region extending from the surface of the strengthened glass-ceramic to the compression depth, and has a tensile stress layer region inside; the compressive stress layer depth DOL_0 of the strengthened glass-ceramic is ≥0.21t, preferably, 0.21t≤DOL_0≤0.25t, t is the thickness of the strengthened glass-ceramic; the |CT_AV| of the strengthened glass-ceramic is ≥70MPa, preferably, 70MPa≤|CT_AV|≤110MPa.

2. The reinforced glass ceramic according to claim 1, wherein Calculated based on the mass of the strengthened glass-ceramics, the total content of (Zn, Mg)Al2O4 crystal phase and tetragonal ZrO2 crystal phase is 25.00wt%~70.00wt%, preferably 30.00wt%~50.00wt%, wherein the ratio of (Zn, Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase is 1.00~18.00, preferably 1.00~15.00; and / or, in the strengthened glass-ceramics, the average crystal size of the (Zn, Mg)Al2O4 crystal phase is 3.0nm~10.0nm, preferably 4.0nm~7.5nm, more preferably 4.5nm~7.5nm; and / or, the strengthened glass-ceramics is transparent in the visible light range.

3. The reinforced glass ceramic according to claim 1 or 2, characterized in that Calculated in molar percentage of oxides, the composition at the center of the strengthened glass-ceramic includes: SiO2 35.00mol% to 60.00mol%, Al2O3 20.00mol% to 40.00mol%, ZrO2 2.00mol% to 8.00mol%, MgO 3.00mol% to 7.50mol%, ZnO 7.00mol% to 13.00mol%, Na2O 1.00mol% to 10.00mol%, and Li2O 2.50mol% to 10.00mol%.

4. The tempered glass ceramic according to any one of claims 1 to 3, characterized in that The strengthened glass-ceramic contains 15.00 wt% to 45.00 wt% of the (Zn, Mg)Al2O4 crystal phase.

5. The tempered glass ceramic according to any one of claims 1 to 4, characterized in that Take W [(Zn，Mg)Al2O4] is the weight percentage of (Zn, Mg)Al2O4 phase in the strengthened glass ceramic, W [Al2O3] is the weight percentage of Al2O3 in the strengthened glass ceramic, W [MgO] is the weight percentage of MgO in the strengthened glass ceramic, W [ZnO] is the weight percentage of ZnO in the reinforced glass ceramic, A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2, B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] +W [ZnO] ), C=A / B, and in the strengthened glass-ceramics, 1.50≤C≤1.

85.

6. The tempered glass ceramic according to any one of claims 1 to 5, characterized in that The value of A is 10.00% to 25.00%, preferably 14.00% to 25.00%; and / or, The value of B is 7.50% to 12.50%, preferably 8.00% to 12.00%.

7. The tempered glass ceramic according to any one of claims 1 to 6, characterized in that The CS_50 of the strengthened glass-ceramic is ≥100 MPa, preferably, 100 MPa≤CS_50≤250 MPa.

8. The tempered glass ceramic according to any one of claims 1 to 7, characterized in that The Vickers hardness of the reinforced glass ceramic is greater than or equal to 790 kgf / mm 2 , preferably 790kgf / mm 2 ~1000kgf / mm 2 .

9. The tempered glass ceramic according to any one of claims 1 to 8, characterized in that The fracture toughness of the reinforced glass ceramic is greater than or equal to 1.00 MPa·m 1 / 2 , preferably greater than or equal to 1.20 MPa·m 1 / 2 , more preferably greater than or equal to 1.55 MPa·m 1 / 2 .

10. The tempered glass ceramic according to any one of claims 1 to 9, characterized in that The reinforced glass-ceramic has a |CT_CV| of ≥80 MPa, preferably, 80 MPa≤|CT_CV|≤150 MPa.

11. The tempered glass ceramic according to any one of claims 1 to 10, characterized in that In the X-ray diffraction pattern of the strengthened glass-ceramic, the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 28° to 32° is taken as the first characteristic peak, and the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 36° to 38° is taken as the second characteristic peak. The peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50, and the preferred peak intensity ratio X is 0.85 to 1.

30.

12. The tempered glass ceramic according to any one of claims 1 to 11, characterized in that In the X-ray diffraction pattern of the strengthened glass-ceramic, the characteristic peak of the [400] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 44° to 46°, the characteristic peak of the [311] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 34° to 38°, and the characteristic peak of the [440] crystal plane of the (Zn, Mg)Al2O4 crystal phase is located at a 2θ angle within the range of 64° to 67°; The half-maximum width W of the characteristic peak of the [400] crystal plane is [400] 0.650°~1.800°, preferably W [400] 0.900° to 1.600°; The half-maximum width W of the characteristic peak of the [311] crystal plane is [311] 0.900°~2.800°, preferably W [311] 1.100° to 2.230°; The half-peak width W of the characteristic peak of the [440] crystal plane [440] 0.750°~2.000°, preferably W [440] 0.900° to 1.600°.

13. The tempered glass ceramic according to any one of claims 1 to 12, characterized in that Calculated by molar percentage of oxides, the composition at the center of the strengthened glass-ceramic further includes: K2O 0.00mol%-5.00mol%, CaO 0.00mol%-10.00mol%, B2O3 0.00mol%-10.00mol%, and BaO 0.00mol%-5.00mol%.

14. The tempered glass ceramic according to any one of claims 1 to 13, characterized in that Calculated in molar percentage of oxides, the composition at the center of the strengthened glass-ceramic includes: SiO2 35.00mol% to 60.00mol%, Al2O3 20.00mol% to 40.00mol%, ZrO2 2.00mol% to 8.00mol%, MgO 4.00mol% to 7.00mol%, ZnO 9.00mol% to 12.00mol%, Na2O 2.00mol% to 10.00mol%, and Li2O 3.00mol% to 10.00mol%.

15. The tempered glass ceramic according to any one of claims 1 to 14, characterized in that Calculated in molar percentage of oxides, the composition at the center of the strengthened glass-ceramic includes: SiO2 35.00mol% to 50.00mol%, Al2O3 25.00mol% to 35.00mol%, ZrO2 3.00mol% to 5.00mol%, MgO 4.00mol% to 7.00mol%, ZnO 9.00mol% to 12.00mol%, Na2O 2.00mol% to 10.00mol%, and Li2O 3.00mol% to 10.00mol%.

16. The tempered glass ceramic according to any one of claims 1 to 15, characterized in that The composition at the center of the reinforced glass-ceramic satisfies, based on the molar percentage of each oxide in the composition of the reinforced glass-ceramic, 1.30≤ZnO / MgO≤2.50; and / or, 0.05≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.20; and / or, 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60; and / or, 0.26≤Na2O / Li2O≤3.

00.

17. The tempered glass ceramic according to any one of claims 1 to 16, characterized in that Calculated by the molar percentage of each oxide in the strengthened glass-ceramic composition, the composition at the center of the strengthened glass-ceramic also satisfies: 12.00mol%≤ZnO+MgO≤20.00mol%, preferably, 13.00mol%≤ZnO+MgO≤17.30mol%; and / or, 9.00mol%≤Al2O3-(MgO+ZnO)≤22.00mol%, preferably, 10.00mol%≤Al2O3-(MgO+ZnO)≤20.00mol%; and / or, 5.00mol%≤Na2O+Li2O≤15.00mol%, preferably, 6.00mol%≤Na2O+Li2O≤13.50mol%.

18. The tempered glass ceramic according to any one of claims 1 to 17, wherein The transmittance of the 0.7 mm thick reinforced glass-ceramic at a wavelength of 550 nm is greater than or equal to 85.00%.

19. The tempered glass ceramic according to any one of claims 1 to 18, characterized in that The 0.7 mm thick reinforced glass-ceramic is subjected to a drop resistance test using 80-grit sandpaper. The average sandpaper drop resistance height of the reinforced glass-ceramic is greater than or equal to 1.00 m, preferably greater than or equal to 1.40 m, and more preferably 1.50 m to 2.50 m.

20. The tempered glass ceramic according to any one of claims 1 to 19, characterized in that The reinforced glass ceramic is obtained by subjecting a chemically strengthened glass ceramic to a chemical strengthening treatment, and the composition of the chemically strengthened glass ceramic is the same as the composition at the center of the reinforced glass ceramic.

21. A glass device made of the tempered glass ceramic according to any one of claims 1 to 20.

22. An electronic device comprising the tempered glass ceramic according to any one of claims 1 to 20.

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