CN117776534B

CN117776534B - Reinforced glass ceramic with high strength and application thereof

Info

Publication number: CN117776534B
Application number: CN202311800642.5A
Authority: CN
Inventors: 谢晓兰; 周靖鹏; 黄昊; 冉荣霞
Original assignee: Chongqing Aureavia Hi Tech Glass Co Ltd
Current assignee: Chongqing Aureavia Hi Tech Glass Co Ltd
Priority date: 2023-12-25
Filing date: 2023-12-25
Publication date: 2025-02-18
Anticipated expiration: 2043-12-25
Also published as: CN117776534A

Abstract

The present application provides a high-strength reinforced glass-ceramic and its application, wherein the reinforced glass-ceramic contains a main crystalline phase (Zn, Mg) _Al2O4 _crystalline phase and a secondary crystalline phase tetragonal _ZrO2 crystalline phase. The reinforced glass-ceramic contains a compressive stress layer region extending from the surface of the reinforced glass-ceramic to the compression depth, and has a tensile stress layer region inside the reinforced glass-ceramic. The depth of the compressive stress layer of the reinforced glass-ceramic DOL_0 ≥ 0.21t, t is the thickness of the reinforced glass-ceramic, |CT_AV| ≥ 70MPa, and by satisfying the above DOL_0 and |CT_AV|, the reinforced glass-ceramic is given a specific stress structure, thereby making the reinforced glass-ceramic have excellent drop impact resistance and high mechanical strength.

Description

Reinforced glass ceramic with high strength and application thereof

Technical Field

The application relates to the technical field of glass ceramics, in particular to reinforced glass ceramics with high strength and application thereof.

Background

A common situation in which protective glass for electronic equipment breaks is drop breakage due to dropping. The drop process is analyzed, generally, by the impact of the glass surface with sharp objects of comparable or greater hardness (e.g., fine sand, cement, small stones) resulting in localized failure, a hemispherical crack propagation source is formed at the failure point, the impact energy is partially attenuated, the remaining energy is further propagated, when the glass surface compressive stress level is insufficient to counteract the remaining energy, the crack propagates through the glass surface region, and when the longitudinal crack passes through the depth of the compressive stress layer to the tensile stress layer (or tensile stress layer) region, the crack propagates rapidly in the tensile stress region, causing the crack to penetrate the entire glass, resulting in glass breakage or fracture.

It can be seen that the depth of layer of compressive stress and the deep stress conditions exhibited by glass articles are closely related to their resistance to drop damage. When the depth of the compressive stress layer is fixed, the greater the deep stress, the more the drop crash residual energy can be counteracted by the surface compressive stress level. And when the surface compressive stress level is insufficient to offset the rest energy of the drop impact, the deeper the depth of the compressive stress layer the glass has, the more advantageous it is to offset the energy driving crack propagation.

Therefore, in order to further improve the drop impact resistance of glass ceramics, it is necessary to develop a strengthened glass ceramic having a large depth of layer of deep stress and ultra-high compressive stress, and having a high mechanical strength, in particular, a high-strength transparent strengthened glass ceramic having excellent light transmittance or transmittance at the same time.

Disclosure of Invention

The application aims to provide a reinforced glass ceramic with high strength and application thereof, wherein the reinforced glass ceramic has larger deep stress and ultrahigh compression stress layer depth, and a specific stress structure is formed, so that the reinforced glass ceramic is endowed with excellent anti-drop impact performance.

The technical scheme provided by the application is as follows:

In a first aspect, a tempered glass ceramic is provided, wherein the tempered glass ceramic comprises a primary crystalline phase (Zn, mg) Al ₂O₄ crystalline phase and a secondary crystalline phase tetragonal ZrO ₂ crystalline phase, the tempered glass ceramic comprises a compressive stress layer region extending from the surface of the tempered glass ceramic to a compressive depth and is provided with a tensile stress layer region inside, the compressive stress layer depth DOL_0 of the tempered glass ceramic is more than or equal to 0.21t, preferably more than or equal to 0.21t and less than or equal to 0.25t, t is the thickness of the tempered glass ceramic, and the energy CT_AV energy of the tempered glass ceramic is more than or equal to 70MPa, preferably more than or equal to 70MPa and less than or equal to CT_AV energy of the tempered glass ceramic is more than or equal to 110MPa. The tempered glass ceramic of the present application has a (Zn, mg) Al ₂O₄ crystal phase (solid solution of zinc spinel and magnesium spinel) having high hardness and high modulus as a main crystal phase, and imparts high intrinsic strength or intrinsic strength to the tempered glass ceramic. Meanwhile, the super high compression stress layer depth and the larger deep stress of the reinforced glass ceramic endow the reinforced glass ceramic with a specific stress structure. Through the synergistic effect of the specific crystal phase structure and the specific stress structure, the reinforced glass ceramic has ultrahigh mechanical strength, and particularly has excellent drop impact resistance.

In some embodiments of the application, the total content of (Zn, mg) Al ₂O₄ and tetragonal ZrO ₂ phases is 25.00wt% to 70.00wt%, preferably 30.00wt% to 50.00wt%, based on the mass of the tempered glass ceramic, wherein the ratio of (Zn, mg) Al ₂O₄ and tetragonal ZrO ₂ phases (i.e., the mass ratio of (Zn, mg) Al ₂O₄ and tetragonal ZrO ₂ phases) is 1.00 to 18.00, preferably 1.00 to 15.00, and/or the average crystal size of (Zn, mg) Al ₂O₄ phases is 3.0nm to 10.0nm, preferably 4.0nm to 7.5nm, more preferably 4.5nm to 7.5nm, and/or the tempered glass ceramic is transparent in the visible light range. When the ratio (mass ratio Z) of the total content W of crystal phases, (Zn, mg) Al ₂O₄ crystal phase and tetragonal ZrO ₂ crystal phase in the tempered glass ceramic and the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase are within the above-described ranges, a specific crystal phase structure of the tempered glass ceramic is imparted, which is not only advantageous for obtaining a desired stress structure at the time of chemical tempering of the glass ceramic for chemical tempering, but also enables the tempered glass ceramic obtained through tempering to achieve excellent optical transparency.

In some embodiments of the application, the composition at the center of the tempered glass-ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂2.00mol％～8.00mol％、MgO 3.00mol％～7.50mol％、ZnO 7.00mol％～13.00mol％、Na₂O1.00mol％～10.00mol％、Li₂O 2.50mol％～10.00mol％., which by employing the glass formulation described above, is advantageous in ensuring that a chemically tempered glass-ceramic is produced that meets high intrinsic strength and that has spinel as the predominant crystalline phase, thereby helping to achieve a tempered glass-ceramic that meets the desired stress structure.

In some embodiments of the application, the tempered glass ceramic comprises 15.00wt% to 45.00wt% of (Zn, mg) Al ₂O₄ crystalline phases. The (Zn, mg) Al ₂O₄ crystal is a crystal having high hardness and high modulus, and by precipitating a proper amount of (Zn, mg) Al ₂O₄ in the glass ceramic, high intrinsic strength or intrinsic strength can be imparted to the glass ceramic. Meanwhile, the content of the (Zn, mg) Al ₂O₄ crystal phase is controlled, so that the glass ceramic meets a specific crystal phase structure, and the glass ceramic is favorable for ensuring that the glass ceramic is chemically strengthened to obtain an ideal stress structure.

In some embodiments of the application, W _{[(Zn,Mg)Al2O4]} is the weight percent of (Zn, mg) Al ₂O₄ crystal phase in the tempered glass ceramic, W _[Al2O3] is the weight percent of Al ₂O₃ in the tempered glass ceramic, W _[MgO] is the weight percent of MgO in the tempered glass ceramic, W _[ZnO] is the weight percent of ZnO in the tempered 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 tempered glass ceramic, C is 1.50.ltoreq.c.ltoreq.1.85. By optimizing the composition and structure so that the crystal phase content of the (Zn, mg) Al ₂O₄ crystal phase and the content of Al ₂O₃, mgO, znO in the glass ceramic satisfy the ranges of the above-mentioned feature C, it is possible to ensure that the glass ceramic for chemical strengthening is subjected to chemical strengthening to obtain a desired stress structure, and further to obtain high mechanical strength, particularly excellent damage resistance, of the strengthened glass ceramic.

In some embodiments of the application, A has a value of 10.00% to 25.00%, preferably 14.00% to 25.00%, and/or

The value of B is 7.50% -12.50%, preferably 8.00% -12.00%. By having the values of A and B meet the above ranges, it is advantageous to ensure that C meets its range of values.

In some embodiments of the application, CS_50 of the strengthened glass ceramic is greater than or equal to 100MPa, preferably, CS_50 of greater than or equal to 100MPa is greater than or equal to 250MPa. The cs_50 range of the tempered glass ceramic is within the above range, indicating that the compressive stress at a depth of 50 μm from the surface of the tempered glass ceramic is high, indicating that the tempered glass ceramic has a high surface stress level.

In some embodiments of the application, the consolidated glass ceramic has a vickers hardness greater than or equal to 790kgf/mm ², preferably 790kgf/mm ²～1000kgf/mm². The vickers hardness of the tempered glass ceramic is within the above range, which indicates that the tempered glass ceramic has high hardness, thereby ensuring excellent mechanical properties.

In some embodiments of the application, the strengthened glass ceramic has a fracture toughness 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, e.g., may preferably be 1.55 MPa-m ^1/2～2.00MPa·m^1/2. The fracture toughness of the reinforced glass ceramic is in the range, which indicates that the reinforced glass ceramic has high fracture toughness, thereby ensuring that the reinforced glass ceramic has excellent mechanical properties.

In some embodiments of the application, the reinforced glass-ceramic has a CT_CV|of 80MPa or more, preferably 80MPa or more and CT_CV|of 150MPa or less. The fact that the reinforced glass ceramic is CT_CV is within the range shows that the reinforced glass ceramic has higher tensile stress level, further reflects higher surface stress level, and further ensures excellent damage resistance.

In some embodiments of the present application, in the X-ray diffraction spectrum of the tempered glass ceramic, a peak with a maximum peak intensity value in characteristic peaks with a 2θ angle ranging from 28 ° to 32 ° is taken as a first characteristic peak, a peak with a maximum peak intensity value in characteristic peaks with a 2θ angle ranging from 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak to the second characteristic peak is 0.80 to 1.50, preferably the peak intensity ratio X is 0.85 to 1.30. In the XRD ray diffraction pattern, the peak intensity of the characteristic peaks can reflect the integrity of crystals in the glass ceramic, and the application is favorable for obtaining proper crystal integrity by enabling the peak intensity ratio of the two characteristic peaks to be in the range, thereby being favorable for obtaining better optical effect and strengthening effect.

In some embodiments of the present application, in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

The half-peak width W _[400] of the [400] crystal face characteristic peak is 0.650-1.800 degrees, and preferably W _[400] is 0.900-1.600 degrees;

the half-peak width W _[311] of the [311] crystal face characteristic peak is 0.900-2.800 degrees, and preferably W _[311] is 1.100-2.230 degrees;

The half-width W _[440] of the [440] crystal face characteristic peak is 0.750 DEG to 2.000 DEG, and preferably W _[440] is 0.900 DEG to 1.600 deg. In the present application, the half-width of the [400] crystal plane characteristic peak, the [311] crystal plane characteristic peak, and the [440] crystal plane characteristic peak reflect the size of the (Zn, mg) Al ₂O₄ crystal in the glass ceramic, and by satisfying the above ranges, it is advantageous to ensure that the glass ceramic for chemical strengthening has a specific crystal size and crystal phase structure, and further to ensure that the strengthened glass ceramic obtains desired optical properties and stress levels.

In some embodiments of the application, the composition at the center of the strengthened glass ceramic, in terms of mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％. in the glass system of the application, K ₂O、CaO、B₂O₃ or BaO as an optional component, the proper amount of which can provide some improvement in the shaping, devitrification, chemical strengthening or optical effects of the glass ceramic.

In some embodiments of the application, the composition at the center of the strengthened glass ceramic, including ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％. by appropriate adjustments of MgO, znO, li ₂ O or Na ₂ O content, in terms of mole percent of oxides, helps ensure that the primary crystalline phase content in the chemically strengthened glass ceramic meets the desired level, while also helping ensure that the chemically strengthened glass ceramic achieves the desired chemical strengthening effect, thereby obtaining a strengthened glass ceramic with high stress levels.

In some embodiments of the application, the composition at the center of the strengthened glass ceramic, including ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％. by adjusting the amount of each necessary oxide in an amount based on mole percent of oxide, helps ensure that the desired crystalline phase structure and glass network structure, which can achieve high stress levels, are achieved with the chemically strengthened glass ceramic, and thus helps achieve a strengthened glass ceramic with high stress levels.

In some embodiments of the application, the composition at the center of the tempered glass ceramic, in mole percent of each oxide in the composition, satisfies:

ZnO/MgO of 1.30-2.50, and/or

Li ₂O/(Al₂O₃-(MgO+ZnO)+SiO₂ or less than 0.05 or less than 0.20 and/or

0.19-0 (Al ₂O₃-(MgO+ZnO))/SiO₂ -0.60; and/or)

0.26≤Na₂O/Li₂O≤3.00。

In some embodiments of the application, the composition at the center of the tempered glass ceramic, in mole percent of each oxide in the composition, further satisfies:

12.00mol% or less ZnO+MgO 20.00mol% or less, preferably 13.00mol% or less ZnO+MgO 17.30mol%, and/or

9.00Mol% or less Al ₂O₃ - (MgO+ZnO) or less 22.00mol%, preferably 10.00mol% or less Al ₂O₃ - (MgO+ZnO) or less 20.00mol%, and/or

Na ₂O+Li₂ O15.00 mol% or less, preferably 6.00mol% or less and Na ₂O+Li₂ O13.50 mol% or less.

In some embodiments of the application, the 0.7mm thick tempered glass ceramic has a transmittance of greater than or equal to 85.00% at 550nm wavelength light. The transmittance of the tempered glass ceramic with the thickness of 0.7mm under the light with the wavelength of 550nm is in the range, which shows that the tempered glass ceramic has high light transmittance, and meanwhile, the tempered glass ceramic also has high mechanical strength, particularly excellent drop impact resistance, and effectively widens the application scenes and the application fields of the tempered glass ceramic.

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

In some embodiments of the application, the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

In a second aspect, there is provided a glass device made from the strengthened glass ceramic of any one of the preceding embodiments.

In a third aspect, an electronic device is provided that includes the strengthened glass ceramic of any one of the preceding embodiments.

In some embodiments of the application, the electronic device comprises at least one of a cell phone, a tablet, a smart wearable, a display, and a television.

One or more of the technical schemes of the application have the following advantages or beneficial effects:

The application provides a strengthened glass ceramic with high strength and application thereof, wherein the strengthened glass ceramic takes a (Zn, mg) Al ₂O₄ crystal phase (a solid solution of zinc spinel and magnesium spinel) with high hardness and high modulus as a main crystal phase, and the high intrinsic strength or the intrinsic strength of the strengthened glass ceramic is provided. Meanwhile, the super high compression stress layer depth and the larger deep stress of the reinforced glass ceramic endow the reinforced glass ceramic with a specific stress structure. Through the synergistic effect of the specific crystal phase structure and the specific stress structure, the reinforced glass ceramic has ultrahigh mechanical strength and high damage resistance, and particularly has excellent drop impact resistance.

Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.

Drawings

In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the application, and other embodiments may be obtained according to these drawings to those skilled in the art.

FIG. 1 is a schematic structural diagram of a strengthened glass ceramic according to 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;

FIG. 2 is a graph showing XRD diffraction patterns of chemically strengthened glass ceramics in examples 1 to 2 and comparative examples 6 to 9;

FIG. 3 is an XRD diffraction pattern of the glass ceramic for chemical strengthening in comparative example 8;

FIG. 4 is an XRD diffraction pattern of the glass ceramic for chemical strengthening in example 2;

FIG. 5 is an XRD diffraction pattern of the glass ceramic for chemical strengthening in comparative example 10;

FIG. 6 is an XRD diffraction pattern of the glass ceramic for chemical strengthening in comparative example 11;

FIG. 7 is a graph showing transmittance of the glass ceramic for chemical strengthening in example 1 under different wavelength conditions;

FIG. 8 is an XRD diffraction pattern of the glass ceramic for chemical strengthening of example 1 before and after chemical strengthening;

FIG. 9 is a graph showing the transmittance curves of the glass ceramic for chemical strengthening of example 1 under different wavelength conditions before and after chemical strengthening.

Detailed Description

The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments obtained by the person skilled in the art based on the present application fall within the scope of protection of the present application.

Interpretation of the terms

DOL_0-depth of layer of compressive stress, also referred to as depth of layer of compressive stress, refers to the distance in the thickness direction from either surface of the tempered glass ceramic to a location near the surface where the compressive stress is zero.

CT_AV-refers to the absolute value of the average tensile stress in the tensile stress layer, specifically the absolute value of the average of all tensile stresses in the tensile stress layer.

Composition at the center of the tempered glass-ceramic refers to composition at or near the center of the depth of the tempered glass-ceramic.

CS_50 is the compressive stress value at a depth of 50 μm from the surface of the strengthened glass ceramic in the thickness direction.

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

The base glass is glass which has not been subjected to nucleation treatment, crystallization treatment or strengthening treatment.

Crystalline phase content the mass of crystalline phase in the glass ceramic is the percentage of the total mass of the glass ceramic.

Peak intensity refers to the height of diffraction peaks in the XRD pattern.

Half-width refers to the width of the half-peak height of the diffraction peak in the XRD pattern, and is generally expressed in terms of angle or 2 theta value.

In the present application, the glass ceramic for chemical strengthening means a glass ceramic material that can be used for performing chemical strengthening treatment to prepare a strengthened glass ceramic.

Glass ceramics, also known as glass ceramics, are a type of solid composite materials that contain both glass and microcrystalline phases (or also known as crystalline phases, crystalline phases).

Theoretically, when the depth of the compressive stress layer extending inward from the two major surfaces of the glass article is equal or approximately equal and the sum of the depths of the compressive stress layers is equal to the thickness of the tensile stress layer, i.e., the depth d of the compressive stress layer 11 on each side is approximately equal to 25% of the thickness t of the glass 10, as shown in FIG. 1, the thickness of the tensile stress layer 12 is approximately equal to 50% of the thickness t of the glass 10, and the glass will reach the desired depth of the compressive stress layer. However, in practice, this objective is achieved in almost no glass articles in the prior art, on the one hand, in which this depth of layer of compressive stress is relatively difficult to achieve, and on the other hand, in existing glass articles, higher depths of layer of compressive stress tend to be accompanied by a decrease in the level of surface stress, which is accompanied by a decrease in the overall strength of the glass article. Because the diffusion of ions is more difficult to be more inward in the ion exchange process of the chemical strengthening treatment, and the diffusion amount is increased by simply increasing alkali metal ions, the problems of bursting and fragmentation caused by overlarge internal stress are very easy to occur when the depth is not yet higher. In addition, in many glass products, after the exchange ions diffuse to a certain depth and the stress reaches a certain degree, stress relaxation occurs, the depth is slightly increased or not increased, but the stress is obviously reduced, and the strength of the glass product is reduced. Therefore, it is currently only possible to bring the depth of compressive stress of the glass article as close as possible to the desired effect.

In view of the above, a strengthened glass ceramic having an ultra-high compressive stress layer depth and a large deep stress and applications thereof are provided. Through the synergistic effect of the specific crystal phase structure and the specific stress structure, the reinforced glass ceramic has ultrahigh mechanical strength and high damage resistance, and particularly has excellent drop impact resistance.

In some embodiments of the present application, a tempered glass ceramic is provided that includes a primary crystalline phase (Zn, mg) Al ₂O₄ phase and a secondary crystalline phase tetragonal ZrO ₂ phase. The tempered glass ceramic includes a compressive stress layer region extending from a surface of the tempered glass ceramic to a compressive depth and has a tensile stress layer region inside the tempered glass ceramic. The depth of the compressive stress layer DOL_0 of the reinforced glass ceramic is more than or equal to 0.21t, preferably, DOL_0 is more than or equal to 0.21t and less than or equal to 0.25t, and t is the thickness of the reinforced glass ceramic. In some embodiments, DOL_0 may be 0.21t to 0.24t, 0.22t to 0.24t, 0.23t to 0.24t, or 0.21t to 0.23t in the strengthened glass ceramic. In some embodiments, dol—0 may be 0.21t, 0.22t, 0.23t, 0.24t, or 0.25t, or a value within a range of values ending in any two of the above. In some embodiments, 147 μm.ltoreq.DOL_0.ltoreq.175 μm when the thickness t of the tempered glass ceramic is 0.7mm, specifically, DOL_0 may be 147 μm, 154 μm, 161 μm, 168 μm or 175 μm, or a value within a range of values ending with any two of the above values. The reinforced glass ceramic has an |CT_AV| of 70MPa or more, preferably 70MPa or more and CT_AV| of 110MPa or less. In some embodiments, the reinforced glass ceramic may have an |CT_AV| of 73MPa to 108MPa, 75MPa to 105MPa, 78MPa to 100MPa, 80MPa to 98MPa, or 83MPa to 95MPa. In some embodiments, the |CT_AV| may be 70MPa, 73MPa, 75MPa, 78MPa, 80MPa, 83MPa, 85MPa, 88MPa, 90MPa, 93MPa, 95MPa, 98MPa, 100MPa, 103MPa, 105MPa, 108MPa, or 110MPa, or a value within a range of values ending in any two of the foregoing. The reinforced glass ceramic with the main crystal phase of spinel (Zn, mg) Al ₂O₄ crystal phase has the ultra-high compression stress layer depth and the larger tensile stress level, so that the reinforced glass ceramic can be endowed with high mechanical strength, and the damage resistance of the reinforced glass ceramic, particularly the drop impact resistance of the reinforced glass ceramic, is greatly improved.

The thickness t of the tempered glass ceramic is not particularly limited as long as the object of the present application can be achieved, and the thickness t of the tempered glass ceramic satisfies, for example, 0.2 mm.ltoreq.t.ltoreq.5 mm, preferably 0.2 mm.ltoreq.t.ltoreq.2 mm.

In some embodiments of the present application, the total content W of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase is 25.00wt% to 70.00wt%, preferably 30.00wt% to 50.00wt%, based on the mass of the tempered glass ceramic, wherein the ratio of the (Zn, mg) Al ₂O₄ crystal phase to the tetragonal ZrO ₂ crystal phase (i.e., the mass ratio Z of the (Zn, mg) Al ₂O₄ crystal phase to the tetragonal ZrO ₂ crystal phase) is 1.00 to 18.00, preferably 1.00 to 15.00. In some embodiments of the present application, in the tempered glass ceramic, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase is 3.0nm to 10.0nm, preferably 4.0nm to 7.5nm, more preferably 4.5nm to 7.5nm. In some embodiments of the application, the tempered glass ceramic is transparent in the visible range. In the application, the wavelength range of visible light is 380 nm-780 nm, and the expression "transparent in the visible light range" means that the transmittance to visible light is more than 80%.

For spinel glass ceramics comprising a primary crystalline phase (Zn, mg) Al ₂O₄ crystalline phase and a secondary crystalline phase tetragonal ZrO ₂ crystalline phase, simply by increasing and introducing the absolute number and kind of ion-exchangeable metal ions, it is not ensured that ultra-high stress depth of layer and deep stress are achieved. On the one hand, when the content of Li ⁺ and Na ⁺ in the glass ceramic exceeds a certain amount, the problem that the transparent glass ceramic cannot be obtained easily occurs, and on the other hand, the stress distribution of the glass ceramic after chemical strengthening is commonly influenced by the composition and crystal phase structure of the glass ceramic, and simply increasing the absolute number and the kind of alkali metal ions capable of carrying out ion exchange not only can lead to the change of the composition of the glass ceramic, but also can not ensure that the glass ceramic obtains the crystal phase structure capable of realizing the expected stress distribution.

Without being bound by theory, the composition and crystalline phase structure of the glass-ceramic are in very close relationship with the stress distribution or stress structure after chemical strengthening, and by making the glass-ceramic meet the specific composition and crystalline phase structure, it can be ensured that an ultra-high compressive stress layer depth and a large deep stress are obtained after chemical strengthening of the glass-ceramic.

In some embodiments of the present application, the total content W of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase may 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 a range of values inclusive of any two of the above values, calculated on a mass basis of the strengthened glass ceramic. In some embodiments, the total crystalline phase content W of the (Zn, mg) Al ₂O₄ crystalline phase and the tetragonal ZrO ₂ crystalline phase may be 25.00wt% to 68.00wt%, 28.00wt% to 65.00wt%, 32.00wt% to 60.00wt%, 35.00wt% to 55.00wt%, or 40.00wt% to 50.00wt%, based on the mass of the strengthened glass ceramic. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the present application, the ratio (mass ratio Z) of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase in the tempered glass ceramic described above may 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 a numerical range constituted by any two of the above values as an end point. In some embodiments, in the tempered glass ceramic, the ratio (mass ratio Z) of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase may be 2.00 to 17.00, 4.00 to 15.00, 6.00 to 12.00, or 8.00 to 10.00. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the present application, in the tempered glass ceramic described above, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase may be 3.0nm、4.0nm、4.2nm、4.5nm、4.8nm、5.0nm、5.2nm、5.5nm、5.8nm、6.0nm、6.2nm、6.5nm、6.8nm、7.0nm、7.2nm、7.5nm、8.0nm、9.0nm or 10.0nm, or a value within a range of values defined by terminating any two of the above values. In some embodiments, in the tempered glass ceramic, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase may be 4.0nm to 9.0nm, 4.0nm to 7.5nm, 4.5nm to 7.5nm, 5.0nm to 8.0nm, or 6.0nm to 7.0nm. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the tempered glass ceramic comprises 15.00wt% to 45.00wt% of a (Zn, mg) Al ₂O₄ crystalline phase. The (Zn, mg) Al ₂O₄ crystal is a crystal having high hardness and high modulus, and by precipitating a proper amount of (Zn, mg) Al ₂O₄ in the glass ceramic, high intrinsic strength or intrinsic strength can be imparted to the glass ceramic. Meanwhile, the content of the (Zn, mg) Al ₂O₄ crystal phase is controlled, so that the glass ceramic meets a specific crystal phase structure, and the glass ceramic is favorable for ensuring that the glass ceramic is chemically strengthened to obtain an ideal stress structure. In some embodiments of the present application, the (Zn, mg) Al ₂O₄ crystal phase in the tempered glass ceramic may have a crystal phase content W _{[(Zn,Mg)Al2O4]} of 15.00wt％、18.00wt％、20.00wt％、23.00wt％、25.00wt％、28.00wt％、30.00wt％、33.00wt％、35.00wt％、38.00wt％、40.00wt％、43.00wt％ or 45.00wt% or a value within a range of values defined by terminating any two of the above values. In some embodiments, the crystal phase content W _{[(Zn,Mg)Al2O4]} of the (Zn, mg) Al ₂O₄ crystal phase in the tempered glass ceramic may be 18.00wt% to 44.00wt%, 20.00wt% to 42.00wt%, 24.00wt% to 40.00wt%, 28.00wt% to 38.00wt%, or 30.00wt% to 35.00wt%.

In some embodiments of the application, the crystalline phase content W _[ZrO2] of the tetragonal ZrO ₂ crystalline phase is 2.00wt% to 16.00wt% based on the mass of the strengthened glass ceramic. The tetragonal ZrO ₂ crystalline phase and the (Zn, mg) Al ₂O₄ crystalline phase jointly determine the crystalline phase structure inside the glass ceramic, and the structural strength of the glass ceramic is guaranteed by meeting a specific content range, so that the ideal stress structure of the glass ceramic after chemical strengthening is guaranteed. In some embodiments of the present application, the crystalline phase content W _[ZrO2] of the tetragonal ZrO ₂ crystalline phase in the tempered glass ceramic may 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 a range of values defined by the end points of any two of the above values.

In some embodiments of the application, the inclusion of ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂2.00mol％～8.00mol％、MgO 3.00mol％～7.50mol％、ZnO 7.00mol％～13.00mol％、Na₂O1.00mol％～10.00mol％、Li₂O 2.50mol％～10.00mol％. in the center of the strengthened glass-ceramic, in terms of mole percent of oxides, by employing this glass formulation approach, advantageously ensures that a chemically strengthened glass-ceramic is produced that meets high intrinsic strength and that has spinel as the predominant crystalline phase, thereby helping to achieve a strengthened glass-ceramic that meets the desired stress structure.

It is understood that after chemical strengthening has been performed and ion exchange process, the composition of the glass-ceramic article at the surface may be different from the composition of the glass-ceramic prior to its ion exchange process. This is because, in the glass ceramic just formed (e.g., the glass ceramic for chemical strengthening in the present application) at the time of ion exchange, one type of alkali metal ion (e.g., li ⁺ or Na ⁺) at the surface of the glass ceramic is replaced with a larger alkali metal ion (e.g., na ⁺ or K ⁺), respectively. In embodiments, however, the glass composition and phase set at or near the depth center of the glass-ceramic article will still be the same as the composition of the glass-ceramic just formed. That is, in the present application, the composition and phase set at the center of the tempered glass ceramic subjected to chemical tempering are the same as those of the glass ceramic just formed (e.g., the glass ceramic for chemical tempering in the present application).

Meanwhile, the glass ceramic for chemical strengthening in the present application is produced from a base glass by heat treatment, and therefore, the composition of the glass ceramic for chemical strengthening is the same as that of the base glass in terms of mole percent based on oxides. That is, in the present application, the composition of the base glass for preparing a glass ceramic for chemical strengthening or the glass ceramic for chemical strengthening, in terms of mole percent of oxides, each includes ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂2.00mol％～8.00mol％、MgO 3.00mol％～7.50mol％、ZnO 7.00mol％～13.00mol％、Na₂O1.00mol％～10.00mol％、Li₂O 2.50mol％～10.00mol％. after heat treatment with the base glass satisfying the above-described range to prepare a glass ceramic for chemical strengthening satisfying a specific crystal phase structure, the glass ceramic for chemical strengthening can be obtained by chemical strengthening to a strengthened glass ceramic having an ultra-high compressive stress layer depth and a large deep stress.

In the glass system of the present application, siO ₂ is a glass network forming oxide, and is an indispensable component for constituting the glass network structure. The SiO ₂ in proper amount can increase the stability and mechanical strength of the glass and simultaneously give consideration to the formability of the glass. In the present application, the content of SiO ₂ in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 35.00mol% to 60.00mol% in terms of mol% of the oxide. In some embodiments of the application, the SiO ₂ may be present in an amount of 35.00mol%, 37.00mol%, 40.00mol%, 42.00mol%, 45.00mol%, 47.00mol%, 50.00mol%, 52.00mol%, 55.00mol%, 57.00mol% or 60.00mol%, or in a range of values between any two of the foregoing values. In some embodiments, the content of SiO ₂ may 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 any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system, a proper amount of Al ₂O₃ can promote the precipitation of main crystalline phases, inhibit the precipitation of other impurity phases such as quartz and the like, avoid the problem that the glass is easy to devitrify and devitrify in the normal cooling process caused by high devitrify rate, and simultaneously be beneficial to increasing the ion exchange rate in the strengthening process and improving the stress structure. In the present application, the content of Al ₂O₃ in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 20.00mol% to 40.00mol% in terms of mol% of the oxide. In some embodiments of the application, the Al ₂O₃ content may 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 a range of values defined by any two of the above values as endpoints. In some embodiments, the content of Al ₂O₃ may be 21.00mol% to 38.00mol%, 22.00mol% to 36.00mol%, 23.00mol% to 34.00mol%, or 25.00mol% to 32.00mol%. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system of the application, zrO ₂ is an effective nucleating agent, and in the heat treatment process of the substrate glass, zrO ₂ is firstly separated out in the substrate glass in a crystal form, and ZrO ₂ crystals become crystal nuclei for the subsequent growth of main crystal phase crystals. The proper amount of ZrO ₂ is advantageous for forming spinel glass ceramics having a specific crystalline phase structure. In the present application, the content of ZrO ₂ in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 2.00mol% to 8.00mol% in terms of mol% of the oxide. In some embodiments of the application, the ZrO ₂ may be present in an amount of 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 in a range of values between any two of the values recited above. In some embodiments, the content of ZrO ₂ may 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 any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system, mgO and ZnO are essential components of spinel serving as main crystal phases, and proper amounts of MgO and ZnO are beneficial to ensuring that the main crystal phases with expected contents are formed, and meanwhile, the melting difficulty of the base material glass can be reduced to a certain extent. However, excessive amounts of MgO and ZnO tend to cause excessive growth of spinel grains, and it is difficult to obtain glass ceramics for chemical strengthening having high transparency. In the application, in the composition at the center of the base glass, the glass ceramic for chemical strengthening or the glass ceramic for strengthening, the content of MgO is 3.00mol% to 7.50mol% and the content of ZnO is 7.00mol% to 13.00mol% in terms of mol% of oxide.

In some embodiments of the application, the MgO content may be 3.00mol%, 3.50mol%, 4.00mol%, 4.50mol%, 5.00mol%, 5.50mol%, 6.00mol%, 6.50mol%, 7.00mol%, or 7.50mol%, or a value within a range of values ending in any two of the above values. In some embodiments, the content of MgO may be 3.50mol% to 7.00mol%, 4.00mol% to 6.50mol%, or 4.50mol% to 6.00mol%. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the ZnO content may be 7.00mol％、7.50mol％、8.00mol％、8.50mol％、9.00mol％、9.50mol％、10.00mol％、10.50mol％、11.00mol％、11.50mol％、12.00mol％、12.50mol％ or 13.00mol% or a value within a range of values defined by the endpoints of any two of the above. In some embodiments, the content of ZnO may be 7.50mol% to 12.50mol%, 8.50mol% to 12.00mol%, 9.50mol% to 11.50mol%, or 10.00mol% to 11.00mol%. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system of the present application, an appropriate amount of Na ₂ O contributes to the glass-ceramic achieving high surface compressive stress in chemical strengthening and to the glass-ceramic achieving high surface stress levels. Meanwhile, the proper amount of Na ₂ O can reduce the melting temperature of the substrate glass and the temperature of crystal precipitation when the substrate glass is used for preparing the glass ceramic for chemical strengthening, and can also avoid ceramic formation in the annealing process of the substrate glass and the precipitation of undesired impurity phases when the substrate glass is used for preparing the glass ceramic for chemical strengthening by heat treatment. In the present application, the content of Na ₂ O in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 1.00mol% to 10.00mol% in terms of mol% of the oxide. In some embodiments of the application, the Na ₂ O content may 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 a range of values defined by any two of the above values as endpoints. In some embodiments, the content of Na ₂ O may be 1.50mol% to 9.50mol%, 2.50mol% to 8.50mol%, 3.50mol% to 7.50mol%, 4.50mol% to 6.50mol%, or 5.00mol% to 6.00mol%. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system of the application, a proper amount of Li ₂ O is beneficial to the glass ceramic to obtain higher deep compression stress and high compression stress layer depth in chemical strengthening, and is beneficial to the glass ceramic to obtain high deep stress level. Meanwhile, a proper amount of Li ₂ O is beneficial to improving the Young modulus of the glass ceramic, can reduce the melting temperature of the substrate glass and the temperature of crystal precipitation when the substrate glass is used for preparing the glass ceramic for chemical strengthening, can also avoid ceramic formation in the annealing process of the substrate glass, and can avoid the problem that undesirable impurity phases are precipitated or overgrowth of crystals occurs when the substrate glass is used for preparing the glass ceramic for chemical strengthening by heat treatment. Too low Li ₂ O tends to reduce the deep-layer stress that can be obtained when chemically strengthening the glass-ceramic for chemical strengthening. In the present application, the content of Li ₂ O in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 2.50mol% to 10.00mol% in terms of mol% of the oxide.

In some embodiments of the application, the Li ₂ O content may be 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 10.00 mole percent, or a value within a range of values defined by any two of the above. In some embodiments, the content of Li ₂ O may be 3.00mol% to 9.50mol%, 4.00mol% to 8.50mol%, 5.00mol% to 7.50mol%, or 6.00mol% to 7.00mol%. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, W _{[(Zn,Mg)Al2O4]} is the weight percent of the (Zn, mg) Al ₂O₄ crystalline phase to the tempered glass ceramic, W _[Al2O3] is the weight percent of Al ₂O₃ to the tempered glass ceramic, W _[MgO] is the weight percent of MgO to the tempered glass ceramic, and W _[ZnO] is the weight percent of ZnO to the tempered 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, in the reinforced glass ceramic, C is more than or equal to 1.50 and less than or equal to 1.85.

By optimizing the composition and structure so that the crystal phase content of the (Zn, mg) Al ₂O₄ crystal phase and the content of Al ₂O₃, mgO, znO in the glass ceramic satisfy the ranges of the above-mentioned feature C, it is possible to ensure that the glass ceramic for chemical strengthening is subjected to chemical strengthening to obtain a desired stress structure, and further to obtain high mechanical strength, particularly excellent damage resistance, of the strengthened glass ceramic.

In some embodiments of the application, A is 10.00% -25.00%, preferably 14.00% -25.00%, and/or B is 7.50% -12.50%, preferably 8.00% -12.00%. By having the values of A and B meet the above ranges, it is advantageous to ensure that C meets its range of values. In some embodiments of the application, a may have a value of 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 a range of values defined by any two of the above values as endpoints. In some embodiments of the application, B may take a value of 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 range of values ending in any two of the foregoing values. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

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

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

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

In some embodiments of the application, CS_50 of the strengthened glass ceramic is greater than or equal to 100MPa, preferably, 100MPa is greater than or equal to CS_50 is less than or equal to 250MPa. The cs_50 range of the tempered glass ceramic is within the above range, which indicates that the compressive stress of the tempered glass ceramic at a depth of 50 μm from the surface is high, and further indicates that the tempered glass ceramic has a higher surface stress level, thereby effectively improving the damage resistance of the tempered glass ceramic. In some embodiments of the application, the cs_50 of the strengthened glass-ceramic may be 100MPa、110MPa、120MPa、130MPa、140MPa、150MPa、160MPa、170MPa、180MPa、190MPa、200MPa、210MPa、220MPa、230MPa、240MPa or 250MPa, or a value within a range of values defined by any two of the above values as endpoints. In some embodiments, the CS_50 of the strengthened glass ceramic may be 110 to 240MPa, 120 to 230MPa, 130 to 220MPa, 140 to 210MPa, 150 to 200MPa, 160 to 190MPa, or 170 to 180MPa.

In some embodiments of the application, the consolidated glass ceramic has a vickers hardness greater than or equal to 790kgf/mm ², preferably 790kgf/mm ²～1000kgf/mm². The vickers hardness of the reinforced glass ceramic is in the range, which indicates that the reinforced glass ceramic has high hardness, further ensures that the reinforced glass ceramic has excellent mechanical properties, and is favorable for obtaining a glass ceramic product with excellent damage resistance. In some embodiments of the application, the vickers hardness of the strengthened glass ceramic may be 790kgf/mm²、800kgf/mm²、810kgf/mm²、820kgf/mm²、830kgf/mm²、840kgf/mm²、850kgf/mm²、860kgf/mm²、870kgf/mm²、880kgf/mm²、890kgf/mm²、900kgf/mm²、910kgf/mm²、920kgf/mm²、930kgf/mm²、940kgf/mm²、950kgf/mm²、960kgf/mm²、970kgf/mm²、980kgf/mm²、990kgf/mm² or 1000kgf/mm ², or a value within a range of values ending in any two of the values described above. In some embodiments, the vickers hardness of the strengthened glass ceramic described above may be 800kgf/mm²～980kgf/mm²、820kgf/mm²～960kgf/mm²、840kgf/mm²～940kgf/mm²、860kgf/mm²～920kgf/mm² or 880kgf/mm ²～900kgf/mm².

In some embodiments of the application, the strengthened glass ceramic has a fracture toughness 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, e.g., may preferably be 1.55 MPa-m ^1/2～2.00MPa·m^1/2. The fracture toughness of the reinforced glass ceramic is in the range, which indicates that the reinforced glass ceramic has high fracture toughness, further ensures that the reinforced glass ceramic has excellent mechanical properties, and is favorable for obtaining glass ceramic products with excellent damage resistance. In some embodiments of the application, the fracture toughness of the strengthened glass ceramic may be 1.00MPa·m¹ ^/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 ending in any two of the above. In some embodiments, the fracture toughness of the strengthened glass ceramic may 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.

In some embodiments of the application, the reinforced glass-ceramic has a CT_CV|of 80MPa or more, preferably 80MPa or more and CT_CV|of 150MPa or less. In the above range, the |CT_CV| of the reinforced glass ceramic shows that the reinforced glass ceramic has higher tensile stress level, and further reflects that the reinforced glass ceramic has higher surface stress level, so that the reinforced glass ceramic has excellent mechanical property, and is favorable for obtaining glass ceramic products with excellent damage resistance. In some embodiments of the 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 a range of values ending in any two of the foregoing values. In some embodiments, the reinforced glass-ceramic may have a ct_cv| of 85mpa to 150mpa, 90mpa to 145mpa, 95mpa to 140mpa, 100mpa to 135mpa, or 110mpa to 130mpa.

The relevant characteristics of the X-ray diffraction pattern can reflect the crystal phase structure of the glass ceramic, including the crystal phase composition, the crystal size and the like. The glass ceramic meets a specific crystal phase structure, so that the glass ceramic is favorable for obtaining high intrinsic strength, and the chemical strengthening effect of the glass ceramic is improved, so that the glass ceramic can obtain the depth of an ultra-high compression stress layer and larger deep stress through chemical strengthening, and further the mechanical strength and damage resistance of the glass ceramic are improved.

It is to be understood that, in the glass ceramic of the present application, the primary (Zn, mg) Al ₂O₄ crystal phase and the secondary tetragonal ZrO ₂ crystal phase are each free of alkali metal ions and thus do not participate in ion exchange during chemical strengthening, and therefore, the crystal phase structure of the chemically strengthened glass ceramic of the present application is substantially the same as that of the glass ceramic for chemical strengthening. That is, the crystalline phase content, the crystal composition, the crystal size, and the characteristic of the average crystalline phase structure of the tempered glass ceramic obtained by the chemical tempering process of the present application are substantially the same as those of the glass ceramic for chemical tempering, and as shown in fig. 8, the XRD patterns of the glass ceramic for chemical tempering before chemical tempering and the tempered glass ceramic after chemical tempering are substantially the same in example 1.

In some embodiments of the present application, in the X-ray diffraction pattern of the tempered glass ceramic, a peak with a maximum peak intensity value in a characteristic peak with a 2θ angle ranging from 28 ° to 32 ° is taken as a first characteristic peak, a peak with a maximum peak intensity value in a characteristic peak with a 2θ angle ranging from 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak to the second characteristic peak is 0.80 to 1.50, preferably the peak intensity ratio X is 0.85 to 1.30. In the XRD ray diffraction pattern, the peak intensity of the characteristic peaks can reflect the integrity of crystals in the glass ceramic, and the application is favorable for obtaining proper crystal integrity by enabling the peak intensity ratio of the two characteristic peaks to be in the range, thereby being favorable for obtaining better optical effect and strengthening effect. In some embodiments of the 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 ending in any two of the foregoing values. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the present application, in the X-ray diffraction pattern of the tempered glass ceramic, the [400] characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within the range of 44 DEG to 46 DEG, the [311] characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within the range of 34 DEG to 38 DEG, the [440] characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within the range of 64 DEG to 67 DEG, the half-peak width W _[400] of the [400] characteristic peak is 0.650 DEG to 1.800 DEG, preferably W _[400] is 0.900 DEG to 1.600 DEG, the half-peak width W _[311] of the [311] characteristic peak is 0.900 DEG to 2.800 DEG, preferably W _[311] is 1.100 DEG to 2.230 DEG, and the half-peak width W _[440] of the [440] characteristic peak is 0.750 DEG to 2.000 DEG, preferably W _[440] is 0.900 DEG to 1.600 deg. In the present application, the half-width of the [400] crystal face characteristic peak, the [311] crystal face characteristic peak, and the [440] crystal face characteristic peak can reflect the size of the crystal in the glass ceramic, and by satisfying the above ranges, it is advantageous to ensure that the glass ceramic for chemical strengthening has a specific crystal size and crystal phase structure, and further to ensure that the strengthened glass ceramic obtains desired optical properties and stress levels.

In some embodiments of the application, W _[400] may have a value of 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 range of values ending in any two of the above. In some embodiments of the application, W _[311] may have a value of 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 range of values defined by any two of the above. In some embodiments of the application, W _[440] may have a value of 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 range of values ending in any two of the foregoing values. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition of the substrate glass for preparing the glass ceramic for chemical strengthening or the chemically strengthened glass ceramic at the center thereof in terms of mole percent of oxides also comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％., wherein K ₂O、CaO、B₂O₃ or BaO is taken as an optional component in the glass system of the application, and proper amount of the composition can be used for improving the forming effect, crystallization effect, chemical strengthening effect or optical effect of the glass ceramic to a certain extent.

In the glass system of the application, a proper amount of K ₂ O is helpful for improving the formability of the base material glass and reducing the crystallization tendency of the base material glass in the preparation process. In the present application, the content of K ₂ O in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 0.00mol% to 5.00mol% in terms of mol% of the oxide. In some embodiments of the application, K ₂ O may be 0.00 mole%, 0.50 mole%, 1.00 mole%, 1.50 mole%, 2.00 mole%, 2.50 mole%, 3.00 mole%, 3.50 mole%, 4.00 mole%, 4.50 mole%, or 5.00 mole%, or a value within a range of values ending in any two of the foregoing. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system, a proper amount of B ₂O₃ is beneficial to reducing the melting difficulty of the base material glass, promoting the precipitation of spinel in a main crystal phase and effectively avoiding the occurrence of opacification or precipitation of impurity phases affecting the optical performance of the glass ceramic when the glass ceramic for chemical strengthening is prepared by heat treatment of the base material glass. In the present application, the content of B ₂O₃ in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 0.00mol% to 10.00mol% in terms of mol% of the oxide. In some embodiments of the application, B ₂O₃ may be 0.00mol％、0.50mol％、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 10.00 mole percent, or a range of values between any two of the values recited above. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system, a proper amount of BaO is beneficial to improving the melting effect of the base material glass, and can inhibit the growth of crystal grains to a certain extent, so that the glass system has a certain improvement effect on the optical performance of glass ceramics. In the present application, the content of BaO in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 0.00mol% to 5.00mol% in terms of mol% of the oxide. In some embodiments of the application, baO may be 0.00mol%, 0.50mol%, 1.00mol%, 1.50mol%, 2.00mol%, 2.50mol%, 3.00mol%, 3.50mol%, 4.00mol%, 4.50mol%, or 5.00mol%, or a value within a range of values defined by any two of the above values as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the glass system of the present application, an appropriate amount of CaO helps to reduce the viscosity of the glass liquid, improve the formability, strain point and young's modulus of the glass, and helps to improve the ion exchange capacity of the glass ceramic. At the same time, proper amount of CaO is helpful for improving the gloss and transparency of the glass, reducing the crystallization tendency of the base material glass and slowing down the hardening speed of the glass. In the present application, the CaO content in the composition at the center of the base glass, the chemically strengthened glass ceramic, or the strengthened glass ceramic is 0.00mol% to 10.00mol% in terms of mol% of the oxide. In some embodiments of the application, caO may be 0.00mol％、0.50mol％、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 number within a range of values ending in any two of the above. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition of the substrate glass or chemically strengthened glass-ceramic at the center, in terms of mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO3.00mol％～7.50mol％、ZnO 7.00mol％～13.00mol％、Na₂O 1.00mol％～10.00mol％、Li₂O2.50mol％～10.00mol％、K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％., which by employing the glass formulation described above, facilitates ensuring that a chemically strengthened glass-ceramic is produced that meets high intrinsic strength and that has spinel as the predominant crystalline phase, thereby facilitating achieving a strengthened glass-ceramic that meets the desired stress structure.

In some embodiments of the application, the composition of the substrate glass or chemically strengthened glass-ceramic at the center thereof, in terms of mole percent of oxides, each comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O3.00mol％～10.00mol％、K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％., by appropriate amounts of the necessary oxides, helps ensure that the chemically strengthened glass-ceramic achieves the desired crystalline phase structure and glass network structure that can achieve high stress levels, and thus facilitates obtaining a strengthened glass-ceramic with high stress levels.

In some embodiments of the application, the composition of the substrate glass or chemically strengthened glass-ceramic at the center thereof, in terms of mole percent of oxides, each comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O3.00mol％～10.00mol％、K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％., by appropriate amounts of adjustment of the MgO, znO, li ₂ O or Na ₂ O content, helps ensure that the primary crystalline phase content in the chemically strengthened glass-ceramic meets the desired level, while also helping ensure that the chemically strengthened glass-ceramic achieves the desired chemical strengthening effect, thereby obtaining a strengthened glass-ceramic with a high stress level.

In some embodiments of the present application, the composition at the center of the substrate glass or chemically strengthened glass-ceramic, in terms of mole percent of each oxide in the composition, satisfies 1.30.ltoreq.ZnO/MgO.ltoreq.2.50, and by satisfying a specific content relationship of ZnO and MgO, it is advantageous to ensure that the desired primary crystal phase structure is formed. In some embodiments of the application, the ZnO/MgO value may 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 value within a range of values ending in any two of the foregoing values. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition of the substrate glass of the glass ceramic for chemical strengthening or the chemically strengthened glass ceramic at the center of the glass ceramic for chemical strengthening is 0.05-Li ₂O/(Al₂O₃-(MgO+ZnO)+SiO₂ -0.20, and the ion exchange performance of the glass ceramic is improved by making Li ₂O、Al₂O₃, mgO, znO and SiO ₂ meet a specific content relationship, so that the glass ceramic is enabled to obtain high depth of layer of compressive stress and larger deep stress through chemical strengthening, and further the damage resistance performance of the strengthened glass ceramic, especially the drop impact resistance performance of the strengthened glass ceramic is improved. In some embodiments of the application, li ₂O/(Al₂O₃-(MgO+ZnO)+SiO₂) may have a value of 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 range of values ending in any two of the foregoing. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition of the base glass of the chemically strengthened glass ceramic or the chemically strengthened glass ceramic at the center thereof is 0.19.ltoreq.0.60, and by satisfying the specific content relationships of Al ₂O₃, mgO, znO and SiO ₂, it is possible to ensure that the residual glass phase of the glass ceramic has a proper amount of Al, on the one hand, to assist in developing the synergistic effect of Si and Al, and to form the residual glass phase into a specific network structure, thereby increasing the intrinsic strength of the glass ceramic, and on the other hand, to assist in promoting the ion exchange, thereby improving the chemical strengthening effect of the glass ceramic.

In some embodiments of the application, the composition at the center of the substrate glass or chemically strengthened glass ceramic, in terms of mole percent of each oxide in the composition, is 0.26.ltoreq.Na ₂O/Li₂ O.ltoreq.3.00, and by having Na and Li meet specific content relationships, helps ensure that the desired surface stress level and deep stress level are achieved after chemical strengthening of the glass ceramic, thereby achieving the desired stress structure, achieving high mechanical strength and high damage resistance. In some embodiments of the application, na ₂O/Li₂ O may have a value of 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 values ending in any two of the foregoing values. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition at the center of the substrate glass or chemically strengthened glass-ceramic, in terms of mole percent of each oxide in the composition, also satisfies 12.00 mole% or less ZnO+MgO 20.00 mole% or less, preferably 13.00 mole% or less ZnO+MgO 17.30 mole% or less, by having a sufficient amount of ZnO, mgO in the composition, helps to ensure that a sufficient amount of the primary crystalline phase is precipitated in the glass-ceramic to form the desired crystalline phase structure. In some embodiments of the application, the value of ZnO+MgO may 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 20.00 mole percent, or a value within a range of values defined by any two of the above values as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition at the center of the substrate glass of the chemically strengthened glass ceramic or the chemically strengthened glass ceramic is prepared by the mole percent of each oxide in the composition, and the composition at the center of the chemically strengthened glass ceramic is 9.00 mole percent or less of Al ₂O₃ - (MgO+ZnO) or less of 22.00 mole percent, preferably 10.00 mole percent or less of Al ₂O₃ - (MgO+ZnO) or less of 20.00 mole percent, and by making the content of Al ₂O₃ higher than the sum of MgO and ZnO in the composition, an appropriate amount of Al can be made to exist in the residual glass phase under the condition that the formation of a main crystal phase is ensured, on the one hand, the synergistic effect of Si and Al is facilitated, and the residual glass phase forms a specific network structure, thereby improving the intrinsic strength of the glass ceramic, and on the other hand, the effect of promoting ion exchange and improving the chemical strengthening effect of the glass ceramic is facilitated. In some embodiments of the application, the value of Al ₂O₃ - (MgO+ZnO) may be 9.00mol％、10.00mol％、11.00mol％、12.00mol％、13.00mol％、14.00mol％、15.00mol％、16.00mol％、17.00mol％、18.00mol％、19.00mol％、20.00mol％、21.00mol％ or 22.00 mole%, or a value within a range of values defined by any two of the values recited above as endpoints. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In some embodiments of the application, the composition at the center of the substrate glass from which the chemically strengthened glass ceramic is prepared or the chemically strengthened glass ceramic is also satisfied at 5.00mol% or less of Na ₂O+Li₂ O15.00 mol% or less, preferably at 6.00mol% or less of Na ₂O+Li₂ O13.50 mol% or less, based on the mole percentages of each oxide in the composition. By having a sufficient amount of Na and Li in the composition, it is helpful to improve the ion exchange properties of the glass ceramic, thereby ensuring that the desired surface stress level and deep stress level are obtained after chemically strengthening the glass ceramic, thereby obtaining the desired stress structure, achieving high mechanical strength and high damage resistance. In some embodiments of the application, na ₂O+Li₂ O may have a value of 5.00mol％、5.50mol％、6.00mol％、6.50mol％、7.00mol％、7.50mol％、8.00mol％、8.50mol％、9.00mol％、9.50mol％、10.00mol％、10.50mol％、11.00mol％、11.50mol％、12.00mol％、12.50mol％、13.00mol％、13.50mol％、14.00mol％、14.50mol％ or 15.00mol% or a value within a range of values defined by any two of the above. It should be understood that any of the above ranges may be combined with any other ranges in particular embodiments, so long as the desired properties of the strengthened glass ceramic of the present application are obtained.

In the present application, each substance in the above relation ZnO/MgO、Li₂O/(Al₂O₃-(MgO+ZnO)+SiO₂)、(Al₂O₃-(MgO+ZnO))/SiO₂、Na₂O/Li₂O、ZnO+MgO、Al₂O₃-(MgO+ZnO)、Na₂O+Li₂O represents a mole percentage of the corresponding substance, for example, znO represents a mole percentage of ZnO, mgO represents a mole percentage of MgO, etc., and the present application will not be described in detail.

In some embodiments of the application, the 0.7mm thick tempered glass ceramic has a transmittance T at 550nm wavelength of greater than or equal to 85.00%. The transmittance of the 0.7 mm-thick reinforced glass ceramic under 550nm wavelength light is in the range, which shows that the glass ceramic has high light transmittance, and meanwhile, the reinforced glass ceramic also has excellent damage resistance, particularly excellent drop impact resistance, and effectively widens the application scenes and application fields of the reinforced glass ceramic. In some embodiments of the application, the transmittance T may be 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, or a value within a range of values ending in any two of the above. As shown in fig. 9, in the present application, the transmittance of the glass ceramic for chemical strengthening is substantially the same as that of the glass ceramic for strengthening before and after chemical strengthening, that is, in the present application, by using the glass ceramic for chemical strengthening having a high transmittance, a strengthened glass ceramic product having the same excellent transmittance can be obtained by chemical strengthening treatment.

In some embodiments of the application, a 0.7mm thick tempered glass ceramic is subjected to a drop test using 80 mesh sandpaper, and the tempered glass ceramic has an average sandpaper drop height H of greater than or equal to 1.00m, preferably greater than or equal to 1.40m, more preferably 1.50m to 2.50m. The average sandpaper drop height H of 0.7mm thick tempered glass ceramic is within the above range, indicating that the tempered glass ceramic of the present application has high mechanical strength and high damage resistance. In some embodiments of the application, the average sandpaper drop height H may be 1.50m, 1.60m, 1.70m, 1.80m, 1.90m, 2.00m, 2.10m, 2.20m, 2.30m, 2.40m, or 2.50m, or a value within a range of values ending in any two of the foregoing values.

The tempered glass ceramic of any of the foregoing embodiments of the present application may be prepared by a process including, but not limited to, the steps of:

(1) Preparing the substrate glass, namely preparing the substrate glass according to the composition at the center of the substrate glass or the reinforced glass ceramic in any of the embodiments according to the mol percent of oxides, uniformly mixing, and preparing the substrate glass by adopting a conventional method known in the art, wherein the preparation method of the substrate glass comprises the methods of, but is not limited to, float, overflow, calendaring, casting, continuous melting and the like, and the application does not limit various parameters in the preparation process so long as the transparent substrate glass with the required performance can be obtained.

(2) Preparing a glass ceramic for chemical strengthening, namely performing heat treatment on the base glass obtained in the step (1), wherein the heat treatment comprises, but is not limited to, one-step heat treatment or multi-step heat treatment, so as to obtain the glass ceramic for chemical strengthening.

(3) Chemical strengthening treatment, namely, carrying out chemical strengthening treatment on the glass ceramic for chemical strengthening obtained in the step (2) to obtain the strengthened glass ceramic in any one of the previous embodiments.

In some embodiments of the present application, the method for preparing the substrate glass in the step (1) may include, but is not limited to, the steps of batching according to the composition at the center of the substrate glass or the reinforced glass ceramic in any of the previous embodiments, melting, forming, cooling, and annealing after uniformly mixing, to obtain the substrate glass. The application is not particularly limited in melting temperature and time, so long as each component can be sufficiently melted, preferably, the melting temperature is 1550-1800 ℃, and the melting time is 3-12 h. The molding method is not limited in the present application, so long as the object of the present application can be achieved, for example, the glass block can be molded by casting into a molding die. The cooling temperature is not limited as long as the object of the present application can be achieved, and preferably the cooling temperature is 800 ℃ to 1000 ℃. The annealing temperature and time are not limited as long as the aim of the application can be fulfilled, and preferably, the annealing temperature is 500-700 ℃ and the annealing time is 20-26 h.

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 T ₁ of the nucleation treatment is 600 ℃ to 850 ℃, more preferably T ₁ is 650 ℃ to 850 ℃. In some embodiments, the temperature T ₁ of the nucleation process may be 600 ℃, 625 ℃, 650 ℃, 675 ℃, 680 ℃, 690 ℃, 700 ℃, 710 ℃, 720 ℃, 725 ℃, 730 ℃, 740 ℃, 750 ℃, 775 ℃, 800 ℃, 825 ℃, or 850 ℃ or a value within a range of values ending in any two of the above. Preferably, the nucleation time t ₁ is 0 to 72 hours, more preferably t ₁ is 0 to 24 hours, and still more preferably t ₁ is 0 to 8 hours. In some embodiments, the nucleation time t ₁ may be 0h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 16h, 24h, 32h, 40h, 48h, 56h, 64h, or 72h, or a value within a range of values ending in any two of the above. Preferably, the temperature T ₂ of crystallization treatment is 700-1000 ℃. In some embodiments, the crystallization temperature T ₂ may be 700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃、810℃、820℃、830℃、840℃、850℃、875℃、900℃、925℃、950℃、975℃ or 1000 ℃, or a value within a range of values defined by any two of the above values as endpoints. Preferably, the crystallization treatment time t ₂ is 10 min-400 min, and preferably t ₂ is 10 min-120 min. In some embodiments, the crystallization treatment time t ₂ may be 10min、20min、30min、40min、50min、60min、70min、80min、90min、100min、110min、120min、150min、170min、200min、220min、250min、280min、300min、320min、350min、370min or 400 minutes, or a value within a range of values defined by any two of the above values as endpoints.

In the present application, when the base glass is heat-treated to prepare a glass ceramic for chemical strengthening, the heat treatment may be performed in one step or may be performed in two or more steps. If the one-step heat treatment is performed, the nucleation treatment is not performed alone, and the target crystal growth is performed directly in the one-step temperature raising process, which can be understood as the crystallization treatment. If the two-step heat treatment is performed, the two-step heating process is performed, the nucleation treatment is performed first, that is, the nucleation treatment is performed, and then the target crystal growth treatment is performed, that is, the crystallization treatment is performed. If multi-step heat treatment is performed, the nucleation stage and/or the crystallization stage may be performed in a stepwise manner, i.e., the entire heat treatment process may be performed with multiple (more than two) increases in temperature.

In the present application, the nucleation is performed by heating to a predetermined temperature (also referred to as a nucleation temperature) and then maintaining the temperature for a predetermined time after the temperature reaches the nucleation temperature, wherein the time for maintaining the temperature is referred to as a nucleation time (also referred to as a nucleation time), and the crystallization is performed by heating to a predetermined temperature (also referred to as a crystallization temperature) and then maintaining the temperature for a predetermined time after the temperature reaches the crystallization temperature, wherein the time for maintaining the temperature is referred to as a crystallization time (also referred to as a crystallization time).

In some embodiments of the present application, in the step (2), the heating rate is preferably controlled to be 5K/min to 15K/min, preferably 5K/min to 10K/min, when the heat treatment is performed. In some embodiments, the rate of temperature increase may 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 range of values ending in any two of the foregoing.

In some embodiments of the application, in step (3), the salt bath for the chemical strengthening treatment is a molten salt comprising a potassium salt and/or a sodium salt, the potassium salt comprising one or more of potassium nitrate, potassium sulfate, potassium carbonate, preferably potassium nitrate, and the sodium salt comprising at least one of sodium nitrate, sodium sulfate, sodium carbonate, preferably sodium nitrate. Preferably, the temperature T ₃ of the salt bath for the chemical strengthening treatment is 380 ℃ to 600 ℃, preferably T ₃ is 400 ℃ to 550 ℃, more preferably T ₃ is 400 ℃ to 500 ℃. In some embodiments, the temperature T ₃ of the salt bath for the chemical strengthening treatment may be 380 ℃, 400 ℃, 425 ℃, 450 ℃, 475 ℃, 500 ℃, 525 ℃, 550 ℃, 575 ℃, or 600 ℃, or a value within a range of values ending in any two of the foregoing. Preferably, the time t ₃ of the chemical strengthening treatment is 1 to 48 hours, preferably t ₃ is 2 to 24 hours, more preferably t ₃ is 2 to 15 hours. In some embodiments, the time t ₃ of the chemical strengthening treatment may be 1h, 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, or 48h, or a value within a range of values ending in any two of the above. By adopting the chemical strengthening treatment process scheme, the glass ceramic for chemical strengthening with specific composition and structure can be strengthened, and the strengthened glass ceramic with excellent surface stress characteristics and excellent deep stress characteristics can be obtained, so that the obtained strengthened glass ceramic has high mechanical strength and excellent damage resistance.

It should be understood that the chemical strengthening treatment may be performed in one step or two or more steps. In the present application, the temperature of the chemical strengthening treatment is the temperature of the salt bath, and when the chemical strengthening treatment includes two or more steps, the time of the chemical strengthening treatment is the sum of the time of each step of the chemical strengthening treatment. In some embodiments of the application, when the chemical strengthening treatment comprises two or more steps, the temperature and time of each step of chemical strengthening treatment may be the same or different.

In the present application, the strengthened glass ceramic of any of the foregoing embodiments can be formed into a glass device having high strength, for example, the glass device can include, but is not limited to, countertops, other surfaces, electrical doors, tiles, siding, storage containers, cell phone screens, cell phone backplanes, electronic equipment rims, vehicle windshields, aircraft windshields, or aircraft windshields, and the like. The reinforced glass ceramic provided by the application has high mechanical strength and high damage resistance, especially excellent drop impact resistance, so that the glass device provided by the application also has excellent mechanical properties.

In the present application, the tempered glass ceramic of any of the foregoing embodiments can be applied to an electronic device.

In some embodiments of the application, the electronic device comprises at least one of a cell phone, a tablet, a smart wearable, a display, and a television. For example, the electronic device may include, but is not limited to, a cell phone, tablet, smart wearable, display, television, or the like. Smart wear may include, but is not limited to, electronic watches, smart bracelets, smart watches, smart glasses, etc., and displays may include, but are not limited to, high definition displays, on-board displays, avionics displays, etc. Illustratively, an electronic device may include a housing including a front surface, a rear surface, and a side surface, and an electronic component partially within the housing, the electronic component including a display device at or adjacent the front surface of the housing, the strengthened glass-ceramic provided by the present application may be applied to the front and/or rear and/or side surfaces of the housing.

The testing method comprises the following steps:

1. x-ray diffraction (XRD) testing

And crushing a sample to be detected, grinding the crushed sample into a sample with the particle size smaller than 75 mu m, and testing the ground sample by using an X-ray diffractometer to obtain an XRD diffraction peak curve and XRD diffraction data. XRD diffraction data were then analyzed using JADE Standard 8.6 software to obtain the crystalline phase of the sample. The X-ray diffractometer is Shimadzu XRD-6100, the incidence angle range used in the test is 2θ=10-80 °, the scanning speed is 6 °/min, the working voltage is 40kV, and the working current is 30mA. Wherein the sample to be measured is glass ceramic for chemical strengthening or strengthened glass ceramic.

Average crystal size the average crystal size of the sample can be calculated from the result data obtained by XRD test according to Scherrer formula d=kλ/(βcos θ). Where λ is the X-ray wavelength, λ= 0.154056nm, β is the diffraction peak half-width, k=0.89, and θ is the bragg diffraction angle. Specifically, a file (diffraction pattern) of RAW output from an XRD instrument is subjected to curve fitting in JADE Standard 8.6 software, JADE outputs a fitting report, and Peak FWHM values are converted into radians according to angle 2θ values and Peak FWHM values corresponding to each diffraction Peak in the fitting report, and the crystal size of each diffraction Peak is calculated by Scherrer formula d=kλ/(βcos θ) and then averaged to obtain an average crystal size.

Average crystal size of (Zn, mg) Al ₂O₄ crystal phase the file (diffraction pattern) of RAW output by XRD instrument is subjected to phase search and curve fitting in JADE Standard 8.6 software, the output fitting report shows that the angle 2 theta value and Peak FWHM value corresponding to three diffraction peaks of (Zn, mg) Al ₂O₄ crystal phase in the range of 34 DEG to 38 DEG, 44 DEG to 46 DEG and 64 DEG to 67 DEG are selected, the Peak FWHM value is converted into radian system of beta= (FWHM/180 x 3.14), the crystal sizes of the three diffraction peaks are calculated by Scherrer formula D=Klambda/(beta cos theta) and then are averaged, and the average crystal size of (Zn, mg) Al ₂O₄ crystal phase is obtained. Where λ is the X-ray wavelength, λ= 0.154056nm, β is the diffraction peak half-width, k=0.89, and θ is the bragg diffraction angle.

Crystal phase content by introducing XRD test results (RAW format) into JADE Standard 8.6 software for fitting and calculation, the total content of each crystal phase in the glass ceramic can be calculated. The ratio of the peak area of the fitted crystal phase to the total peak area of the fitted crystal phase is the crystal phase content of the corresponding crystal phase. The ratio of the peak area of the (Zn, mg) Al ₂O₄ crystal phase to the total peak area of the fit is the crystal phase content W _{[(Zn,Mg)Al2O4]} of the (Zn, mg) Al ₂O₄ crystal phase, and the ratio of the peak area of the square ZrO ₂ crystal phase to the total peak area of the fit is the crystal phase content W _[ZrO2] of the square ZrO ₂ crystal phase. The ratio of the (Zn, mg) Al ₂O₄ crystal phase to the tetragonal ZrO ₂ crystal phase (mass ratio Z) and the total content of the crystal phases W were calculated from W _{[(Zn,Mg)Al2O4]} and W _[ZrO2].

Peak intensity ratio (RAW format) of XRD test results are imported into the JADE Standard 8.6 software to find peak values, determine the 2θ position of the peak and the corresponding original intensity, and calculate the peak intensity ratio. Specifically, the peak intensity ratio X of the first characteristic peak and the second characteristic peak is set.

Half-width, namely importing the XRD test result (RAW format) into JADE Standard 8.6 software to perform phase search and curve fitting, and obtaining the 2 theta position of the peak, the corresponding crystal face, half-width and fitting strength in the output fitting report. And calculating the ratio according to the fitting intensity of the corresponding crystal faces.

Specifically, the peak intensities of the [400] crystal face characteristic peaks I _[400], the [311] crystal face characteristic peaks I _[311], the [440] crystal face characteristic peaks I _[440], the half-peak widths of the [400] crystal face characteristic peaks W _[400], the half-peak widths of the [311] crystal face characteristic peaks W _[311], the half-peak widths of the [440] crystal face characteristic peaks W _[440]、I_[400]/I_[311] and I _[440]/I_[311] are obtained.

The XRD diffraction peak curve can be smoothed no more than three times in consideration of noise influence peak lookup during the test.

2. Testing of CT AV, DOL 0, CS 50, CT CV

The test was carried out using a stress meter SLP-2000 of Japanese Luceo (Japanese foldback), the light source wavelength was 518nm, SOC=25.5 (nm/cm)/MPa, refractive index=1.60, and exposure time: 300usec.

When testing the surfaces CS_50, |CT_AV|, DOL_0, |CT_CV|, the conducting liquid is firstly dripped on the stress meter, then the reinforced glass ceramic sample to be tested is wiped clean and placed on a test path, and the stress value is tested. Wherein the stress meter is SLP-2000 and the conducting liquid used by the stress meter is a conducting liquid with a refractive index of 1.51.

3. Thickness test

The thickness of the glass ceramic for chemical strengthening was measured using a micrometer.

It should be understood that, when the chemical strengthening treatment is performed, the degree of ion exchange varies in a gradient from the surface to the center in the thickness direction of the glass ceramic for chemical strengthening, and the total Na-K and/or Li-Na exchange amount generally does not exceed 1% of the total mass of the sample, and the difference in ionic radius is in the order of pm (picometers), so that the expansion effect in the thickness direction is extremely slight, that is, the thickness variation of the glass ceramic for chemical strengthening before and after the chemical strengthening is very small, and it can be approximately considered that the thickness is substantially unchanged.

4. Optical performance test

The sample to be tested is cleaned in an ultrasonic cleaner under the cleaning conditions including cleaning time of 10min, cleaning agent used for diluting the cleaning agent by 10 times, cleaning temperature of 55+/-10 ℃ and cleaning frequency of 30+/-10 KHZ. And then, testing the transmittance of a sample to be tested under different wavelengths by utilizing a haze meter, and referring to the standard of the ' transmission in spectrum ' of the 12 th part of a GB/T7962.12-2010 colorless optical glass testing method ', wherein the haze meter used in the patent is a Konikoku Meidad spectrocolorimeter CM-3600A. Wherein the sample to be measured is glass ceramic for chemical strengthening or strengthened glass ceramic.

5. Vickers hardness HV test

The reinforced glass ceramic with clean surface and no macroscopic damage such as scratches, pits and cracks is selected as a sample, a digital display small-load Vickers hardness tester VTD405 (Beijing Warewet technology Co., ltd.) is adopted, and the Vickers hardness of the reinforced glass ceramic is tested according to the national standard GB/T37900-2019, the small-load Vickers hardness indentation method of the ultra-thin glass hardness and fracture toughness test method, the load is 300gf, the load time is 10s, and the indentation effectiveness accords with the national standard GB/T16534-2009, the fine ceramic room temperature hardness test method. When the application is used for carrying out the Vickers hardness test, the reinforced glass ceramic sample wafer with the length, width and thickness of 50mm multiplied by 0.7mm is tested. 3 different positions are selected on the surface of the same sample for measurement, and the average value is selected as a final test result.

6. Testing of the concentration of K ₂ O on the surface

In the application, the concentration of K ₂ O on the surface of the reinforced glass ceramic is measured by an X-ray fluorescence spectrometer (XRF), the adopted equipment model is (Thermo SCIENTIFIC ARL PERFORM' X), the target material is Rh (rhodium), the light pipe voltage is 40kW, the current is 60mA, the collimator is 0.15, the crystal is LiF200, the detector is FPC, the testing range is a 29mm circle, and the analysis software is UniQuant nonstandard analysis.

The concentration of K ₂ O on the surface of the tempered glass ceramic, c=k ₂ O mass/total oxide mass, wherein the oxide contains an oxide which can be accurately tested by XRF such as SiO ₂、Al₂O₃、ZrO₂、Na₂O、K₂ O, and the oxide which cannot be accurately tested by XRF such as B ₂O₃. The XRF test was performed using an unlabeled test, and the concentrations of elements having atomic numbers 6 and 6 or less or oxides thereof in the tempered glass ceramic were not tested. That is, XRF does not include the mass of elements having atomic numbers 6 and 6 or less or oxides of the tempered glass ceramic when tested for the concentration of K ₂ O on the surface of the tempered glass ceramic.

7. Testing of average sandpaper drop height

The average anti-sand paper falling height refers to the sum of the anti-sand paper falling heights measured by each sample in the reinforced glass ceramic samples in the same embodiment or the same comparative example, and the ratio of the sum to the number of the reinforced glass ceramic samples can be used for representing the anti-falling damage performance of the reinforced glass ceramic. 10 identical reinforced glass ceramic samples are taken for testing in each batch, and the average anti-sand paper falling height is as follows:

where n is the number of tempered glass ceramic samples tested per batch and hi is the height of sandpaper drop resistance for a single sample test.

The test method of the single sample anti-sand paper falling height comprises the following steps:

Step 1, sticking 80-mesh sand paper on the lower surface of 160g of a model machine, and placing the model machine on a green map LT-SKDL-CD type drop machine;

And 2, placing a tempered glass ceramic sample to be tested with the length and width of 50mm multiplied by 0.7mm under the model machine, so that the tempered glass ceramic sample faces the sand paper. The molding machine is impacted to fall at a certain falling height, and the reinforced glass ceramic sample right below the molding machine is impacted. If the reinforced glass ceramic sample is not broken, the falling height of the molding machine is increased in a certain rule. For example, the falling height starts from 0.4m, the sample is subjected to one falling impact, if the sample is not broken, the sample is again fallen by increasing the height by 0.1m each time, until the reinforced glass ceramic sample is broken;

And 3, recording the last falling height of the reinforced glass ceramic sample when the reinforced glass ceramic sample is broken as the anti-sand paper falling height, for example, the falling height of the reinforced glass ceramic sample when the reinforced glass ceramic sample is broken is 0.5m, and the anti-sand paper falling height of the reinforced glass ceramic sample is 0.4m.

8. Density of

The application adopts an electronic density balance SD-200L of Japanese ALFA MIRAGE to test the density of the reinforced glass ceramic. The test principle is "archimedes drainage method".

9. Fracture toughness test

The test is carried out according to the national standard GB/T37900-2019 'ultra-thin glass hardness and fracture toughness test method small load Vickers hardness indentation method'. Specifically, the indentation was prepared in the same manner as the vickers hardness was measured, and the crack length in the diagonal direction of the indentation was measured to be 2C ₁、2C₂, and the maximum value thereof was not allowed to exceed the thickness of the tempered glass ceramic. At least 5 measurements of the effective indentation morphology are made on the surface of one specimen and the average is calculated as the final result value for that specimen.

Indentation fracture toughness calculation formula:

the IFR is indentation fracture toughness, the unit is one half of a square meter of megapascals (MPa.m ^1/2); E is elastic modulus of a sample, the unit is gigapascals (GPa), 2C ₁、2C₂ is crack expansion length in the diagonal direction of the indentation, the unit is millimeter (mm), d ₁、d₂ is indentation diagonal length, the unit is millimeter (mm), and F is test load value, and the unit is cattle (N).

In the above test method, the tempered glass ceramic tiles of examples and comparative examples were subjected to shaping, cutting, and polishing to obtain a tempered glass ceramic sample (e.g., polished sheet) of a desired size, and then subjected to a test, such as a glass ceramic polished sheet having a length-width thickness of 50mm×50mm×0.7 mm.

Example 1

< Preparation of substrate glass >

The glass is prepared by converting the design of the formula 1 in Table 1 into a glass production raw material formula, wherein the total mass of the prepared raw materials is 1000g, mixing for 30min by a V-shaped mixer, adding 5g of clarifying agent NaCl after uniformly mixing, transferring into a platinum crucible, melting for 5h in a 1650 ℃ lifting furnace (model of lifting furnace: SJF1750, manufacturer: nanjing Bo general Instrument technology Co., ltd.), pouring into a stainless steel mold preheated at 300 ℃, molding and cooling to 900 ℃, then placing into a 600 ℃ annealing furnace for annealing for 24h, and cooling to room temperature along with the furnace to obtain the base material glass.

< Preparation of glass ceramic for chemical strengthening >

The base glass obtained above was subjected to heat treatment in a resistance furnace (equipment model: SLX1400-40, manufacturer: shanghai Lai test instruments Co., ltd.) to obtain a glass ceramic for chemical strengthening.

Specifically, a two-step heat treatment process is adopted, the temperature is firstly increased to the temperature of the nucleation treatment for the nucleation treatment, then the temperature is increased to the temperature of the crystallization treatment for the crystallization treatment, and the temperature increase rate in the nucleation treatment and the crystallization process is 10K/min. Wherein the temperature T ₁ of the nucleation treatment is 740 ℃, the time T ₁ of the nucleation treatment is 480min, the temperature T ₂ of the crystallization treatment is 800 ℃, and the time T ₂ of the crystallization treatment is 10min.

According to the requirement, cutting, CNC processing (computer numerical control, namely a numerical control machine tool, the CNC instrument and equipment model adopted by the application is RCG 500S) and polishing are sequentially carried out on the glass ceramic for chemical strengthening, and then the smooth glass ceramic sheet for chemical strengthening with the required specification is obtained. In the present application, the glass ceramic sheet for chemical strengthening was processed to have a specification of 50mm length, 50mm thickness and 0.7mm thickness.

< Preparation of tempered glass ceramic >

The glass ceramic for chemical strengthening is placed in a 100wt% NaNO ₃ salt bath at 450 ℃ for first strengthening treatment for 3 hours, then placed in a 100wt% KNO ₃ salt bath at 430 ℃ for second strengthening treatment for 2 hours, and the strengthened glass ceramic is obtained.

Example 2 to example 8

The procedure of example 1 was repeated except that the relevant preparation parameters were adjusted in accordance with Table 2. Wherein, the corresponding formula in Table 2 is shown in Table 1 in detail.

Example 9 to example 10

The same procedure as in example 1 was repeated, except that the corresponding chemically strengthened glass ceramic was placed in a salt bath of 100wt% nano ₃ at 450 ℃ for 4 hours according to table 5, to obtain the corresponding strengthened glass ceramic.

Comparative examples 1 to 11

Comparative examples 12 to 15

The formulations of each example and comparative example are shown in table 1, and the preparation parameters and performance tests of each example and comparative example are shown in tables 2 to 5.

The glass ceramics for chemical strengthening of examples 1 to 8 and comparative examples 1 to 11 each contain a primary crystalline phase (Zn, mg) Al ₂O₄ crystalline phase and a secondary crystalline phase tetragonal ZrO ₂ crystalline phase, and XRD patterns of some examples and comparative examples are shown in FIGS. 2 to 6 and 8.

Referring to tables 1 to 4, DOL_0 and |CT-AV| of the tempered glass ceramics of examples 1 to 8 are within the scope of the present application, while at least one of DOL_0 and |CT-AV| of comparative examples 1 to 11 is not within the scope of the present application, the tempered glass ceramics of the examples of the present application have both higher Vickers hardness, fracture toughness, and higher average sandpaper drop resistance, indicating that the tempered glass ceramics obtained by the examples of the present application have higher mechanical strength. Meanwhile, the transmittance of the glass ceramic for chemical strengthening in the examples for 550nm wavelength light is above 89.00%, so that the obtained strengthened glass ceramic also has excellent transmittance. Specifically, as shown in fig. 7, the chemically strengthened glass ceramic of example 1 has a transmittance of 80.00% or more for visible light, and the obtained strengthened glass ceramic is transparent in the visible light range.

Examples 1 to 2 and comparative examples 6 to 9 each obtained a chemically strengthened glass ceramic by different heat treatment systems on a base glass having a composition of formula 1, and an XRD diffraction pattern thereof was shown in FIG. 2.

Referring to fig. 2 and table 3, the XRD pattern of comparative example 6 does not have the second characteristic peak having the 2θ angle ranging from 36 ° to 38 °, and thus does not have the peak intensity ratio X, the (Zn, mg) Al ₂O₄ crystal phase content in the glass ceramic for chemical strengthening of comparative example 6 is low, the calculation result of the formula C does not satisfy the range of the present application, and the stress level of the strengthened glass ceramic manufactured in comparative example 6 is low. Referring to fig. 2 and table 3, the XRD pattern of comparative example 7 has a peak intensity ratio X of 1.61, the (Zn, mg) Al ₂O₄ crystal phase content in the chemically strengthened glass ceramic of comparative example 7 is low, the half-width of part of the characteristic peaks of crystal planes does not satisfy the requirement of the present application, the calculation result of formula C does not satisfy the range of the scheme of the present application, and the stress level of the strengthened glass ceramic produced in comparative example 7 is also low. Referring to fig. 2 and 3, in the XRD pattern of comparative example 8, the 2θ angle was divided into peaks in the range of 28 ° to 32 °, the content of the (Zn, mg) Al ₂O₄ crystal phase was high in the glass ceramic for chemical strengthening of comparative example 8, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase was high, the half-peak width of the characteristic peak of the crystal face did not satisfy the requirement of the present application, the calculation result of the formula C did not satisfy the range of the scheme of the present application, and the stress level of the strengthened glass ceramic produced in comparative example 8 was low. Referring to fig. 2, the XRD pattern of comparative example 9 shows peaks at 2θ angles ranging from 28 ° to 32 °, and the glass ceramic for chemical strengthening of comparative example 9 has a higher (Zn, mg) Al ₂O₄ crystal phase content, a higher average crystal size of the (Zn, mg) Al ₂O₄ crystal phase, and the calculation result of the formula C does not satisfy the range of the present application, and the stress level of the strengthened glass ceramic produced in comparative example 9 is also lower.

Comparative example 10 and comparative example 11 each obtained a glass ceramic for chemical strengthening by different heat treatment systems on a substrate glass having the composition of formula 5, and the XRD diffractograms thereof are shown in fig. 5 and 6.

As shown in FIG. 5, the XRD pattern of comparative example 10 shows peaks at angles of 2 theta ranging from 28 DEG to 32 DEG and from 36 DEG to 38 deg. In the glass ceramic for chemical strengthening of comparative example 10, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase was too high, and the calculation result of the formula C did not satisfy the scope of the present application, and the stress level of the strengthened glass ceramic produced in comparative example 10 was too low. The XRD pattern of comparative example 11 shows that the 2 theta angle shows a peak in the range of 28 DEG to 32 DEG as shown in FIG. 6. In the glass ceramic for chemical strengthening of comparative example 11, the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase was higher, the half-width of a part of the characteristic peaks of the crystal planes did not satisfy the requirement of the present application, the peak intensity ratio X did not satisfy the range of the scheme of the present application, the calculation result of the formula C did not satisfy the range of the scheme of the present application, and the stress level of the strengthened glass ceramic produced in comparative example 11 was lower.

Comparative examples 12 to 15 and examples 9 to 10 were obtained by different heat treatment systems on base glass having the composition of formula 1, and the reinforced glass ceramics obtained by the same chemical strengthening treatment conditions were not within the range of the present application, but the compressive stress depth of layer DOL-0 of comparative examples 12 to 15 was inferior to that of examples of the present application.

It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.

The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.

Claims

1. A tempered glass ceramic is characterized by comprising a primary crystalline phase (Zn, mg) Al ₂O₄ crystalline phase and a secondary crystalline phase tetragonal ZrO ₂ crystalline phase, wherein the tempered glass ceramic comprises a compressive stress layer region extending from the surface of the tempered glass ceramic to a compression depth and is internally provided with a tensile stress layer region, the compressive stress layer depth DOL_0 of the tempered glass ceramic is more than or equal to 0.21t, t is the thickness of the tempered glass ceramic, and the |CT_AV| of the tempered glass ceramic is more than or equal to 70MPa;

The composition at the center of the tempered glass-ceramic comprises, in mole percent of oxide ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 3.00mol％～7.50mol％、ZnO 7.00mol％～13.00mol％、Na₂O 1.00mol％～10.00mol％、Li₂O 2.50mol％～10.00mol％;

Taking W _{[(Zn,Mg)Al2O4]} as the weight percentage of (Zn, mg) Al ₂O₄ crystal phase to the reinforced glass ceramic, W _[Al2O3] as the weight percentage of Al ₂O₃ to the reinforced glass ceramic, W _[MgO] as the weight percentage of MgO to the reinforced glass ceramic, W _[ZnO] as the weight percentage of ZnO to 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, in the tempered glass ceramic, C is 1.50.ltoreq.C.ltoreq.1.85, and

The composition at the center of the tempered glass ceramic, in mole percent of each oxide in the composition, satisfies:

6.82mol%≤Na₂O+Li₂O≤15.00mol%;

Na ₂O/Li₂ O is more than or equal to 0.26 and less than or equal to 0.89; and

0.066≤Li₂O/(Al₂O₃-(MgO+ZnO)+SiO₂)≤0.20。

2. The strengthened glass ceramic of claim 1, wherein the depth of layer of compressive stress of the strengthened glass ceramic satisfies 0.21t ∈dol_0 ∈0.25t.

3. The strengthened glass ceramic of claim 1, wherein the strengthened glass ceramic meets 70MPa +.r +.ct_av +.110 MPa.

4. The tempered glass ceramic according to claim 1, wherein the total content of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase is 25.00wt% to 70.00wt% based on the mass of the tempered glass ceramic, wherein the ratio of the (Zn, mg) Al ₂O₄ crystal phase to the tetragonal ZrO ₂ crystal phase is 1.00 to 18.00, and/or wherein the average crystal size of the (Zn, mg) Al ₂O₄ crystal phase is 3.0nm to 10.0nm, and/or wherein the tempered glass ceramic is transparent in the visible light range.

5. The tempered glass ceramic according to claim 4, wherein the total content of the (Zn, mg) Al ₂O₄ crystal phase and the tetragonal ZrO ₂ crystal phase is 30.00wt% to 50.00wt%, based on the mass of the tempered glass ceramic.

6. The tempered glass ceramic according to claim 4, wherein a ratio of a (Zn, mg) Al ₂O₄ crystal phase to a tetragonal ZrO ₂ crystal phase is 1.00 to 15.00.

7. The tempered glass ceramic of claim 4, wherein an average crystal size of a (Zn, mg) Al ₂O₄ crystal phase in the tempered glass ceramic is 4.0nm to 7.5nm.

8. The tempered glass ceramic of claim 7, wherein an average crystal size of a (Zn, mg) Al ₂O₄ crystal phase in the tempered glass ceramic is 4.5nm to 7.5nm.

9. The tempered glass ceramic according to any one of claims 1 to 8, wherein the tempered glass ceramic contains a (Zn, mg) Al ₂O₄ crystal phase in an amount of 15.00 to 45.00wt% of the tempered glass ceramic.

10. A tempered glass ceramic as claimed in any of claims 1 to 8, wherein A has a value of 10.00% to 25.00%, and/or

The value of B is 7.50-12.50%.

11. The strengthened glass ceramic of claim 10 wherein a has a value of 14.00% to 25.00%.

12. The strengthened glass ceramic of claim 10 wherein B has a value of 8.00% -12.00%.

13. The strengthened glass ceramic according to claim 9, wherein a has a value of 10.00% -25.00% and/or B has a value of 7.50% -12.50%.

14. The strengthened glass ceramic according to any one of claims 1 to 8, wherein cs_50 of the strengthened glass ceramic is not less than 100MPa.

15. The strengthened glass ceramic of claim 14, wherein the strengthened glass ceramic meets cs_50 less than or equal to 100MPa and less than or equal to 250MPa.

16. The strengthened glass ceramic of claim 9, wherein cs_50 of the strengthened glass ceramic is greater than or equal to 100MPa.

17. The strengthened glass ceramic of claim 10, wherein cs_50 of the strengthened glass ceramic is greater than or equal to 100MPa.

18. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the strengthened glass ceramic has a vickers hardness of 790kgf/mm ² or more.

19. The strengthened glass ceramic of claim 18, wherein the strengthened glass ceramic has a vickers hardness of 790kgf/mm ²～1000kgf/mm².

20. The strengthened glass ceramic of claim 9, wherein the strengthened glass ceramic has a vickers hardness of greater than or equal to 790kgf/mm ².

21. The strengthened glass ceramic of claim 10, wherein the strengthened glass ceramic has a vickers hardness of greater than or equal to 790kgf/mm ².

22. The strengthened glass ceramic of claim 14, wherein the strengthened glass ceramic has a vickers hardness of greater than or equal to 790kgf/mm ².

23. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the strengthened glass ceramic has a fracture toughness of 1.00 MPa-m ^1/2 or more.

24. The strengthened glass ceramic of claim 23, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.20 MPa-m ^1/2.

25. The strengthened glass ceramic of claim 24, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.55 MPa-m ^1/2.

26. The strengthened glass ceramic of claim 9, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.00 MPa-m ^1/2.

27. The strengthened glass ceramic of claim 10, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.00 MPa-m ^1/2.

28. The strengthened glass ceramic of claim 14, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.00 MPa-m ^1/2.

29. The strengthened glass ceramic of claim 18, wherein the strengthened glass ceramic has a fracture toughness greater than or equal to 1.00 MPa-m ^1/2.

30. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the strengthened glass ceramic has a ct_cv|of 80MPa or more.

31. The strengthened glass ceramic of claim 30, wherein the strengthened glass ceramic meets a ct_cv|of 80MPa +.ltoreq.150 MPa.

32. The strengthened glass ceramic according to claim 9, wherein |ct_cv| of the strengthened glass ceramic is equal to or greater than 80MPa.

33. The strengthened glass ceramic according to claim 10, wherein |ct_cv| of the strengthened glass ceramic is equal to or greater than 80MPa.

34. The strengthened glass ceramic of claim 14, wherein |ct_cv| of the strengthened glass ceramic is equal to or greater than 80MPa.

35. The strengthened glass ceramic of claim 18, wherein |ct_cv| of the strengthened glass ceramic is equal to or greater than 80MPa.

36. The strengthened glass ceramic of claim 23, wherein |ct_cv| of the strengthened glass ceramic is equal to or greater than 80MPa.

37. The strengthened glass ceramic according to any one of claims 1 to 8, wherein in an X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak to the second characteristic peak is 0.80 to 1.50.

38. The strengthened glass ceramic of claim 37, wherein the first characteristic peak and the second characteristic peak have a peak intensity ratio X of 0.85 to 1.30.

39. The tempered glass ceramic according to claim 9, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

40. The strengthened glass ceramic according to claim 10, wherein in the X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

41. The strengthened glass ceramic according to claim 14, wherein in the X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

42. The strengthened glass ceramic according to claim 18, wherein in the X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

43. The strengthened glass ceramic according to claim 23, wherein in the X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

44. The strengthened glass ceramic according to claim 30, wherein in the X-ray diffraction pattern of the strengthened glass ceramic, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 28 ° to 32 ° is taken as a first characteristic peak, a peak having a maximum value of peak intensity among characteristic peaks having a2Θ angle in a range of 36 ° to 38 ° is taken as a second characteristic peak, and a peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50.

45. The strengthened glass ceramic according to any one of claims 1 to 8, wherein in an X-ray diffraction pattern of the strengthened glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

The half-peak width W _[400] of the [400] crystal face characteristic peak is 0.650-1.800 degrees;

the half-peak width W _[311] of the [311] crystal face characteristic peak is 0.900-2.800 degrees;

The half-peak width W _[440] of the [440] crystal face characteristic peak is 0.750-2.000 degrees.

46. The strengthened glass ceramic of claim 45 wherein the peak width at half W _[400] of the [400] crystal plane characteristic peak is 0.900 ° to 1.600 °.

47. The strengthened glass ceramic of claim 45 wherein the peak width at half W _[311] of the [311] crystal plane characteristic peak is 1.100 ° to 2.230 °.

48. The strengthened glass ceramic of claim 45 wherein the peak width at half W _[440] of the [440] crystal plane characteristic peak is 0.900 ° to 1.600 °.

49. The tempered glass ceramic of claim 9, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

50. The tempered glass ceramic of claim 10, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

51. The tempered glass ceramic of claim 14, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

52. The tempered glass ceramic of claim 18, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

53. The tempered glass ceramic of claim 23, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

54. The tempered glass ceramic of claim 30, wherein in an X-ray diffraction pattern of the tempered glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

55. The strengthened glass ceramic according to claim 37, wherein in an X-ray diffraction pattern of the strengthened glass ceramic, a [400] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 44 ° to 46 °, a [311] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 34 ° to 38 °, and a [440] crystal plane characteristic peak of the (Zn, mg) Al ₂O₄ crystal phase is located within a range of 64 ° to 67 °.

56. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the composition at the center of the strengthened glass ceramic further comprises, in mole percent of oxides ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

57. The strengthened glass ceramic of claim 9 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

58. The strengthened glass ceramic of claim 10, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

59. The strengthened glass ceramic of claim 14 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

60. The strengthened glass ceramic of claim 18 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

61. The strengthened glass ceramic of claim 23 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

62. The strengthened glass ceramic of claim 30 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

63. The strengthened glass ceramic of claim 37 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

64. The strengthened glass ceramic of claim 45 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, further comprises ：K₂O 0.00mol％～5.00mol％、CaO 0.00mol％～10.00mol％、B₂O₃ 0.00mol％～10.00mol％、BaO 0.00mol％～5.00mol％.

65. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the composition at the center of the strengthened glass ceramic in mole percent of oxides comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

66. The strengthened glass ceramic of claim 9, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

67. The strengthened glass ceramic of claim 10, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

68. The strengthened glass ceramic of claim 14, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

69. The strengthened glass ceramic of claim 18, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

70. The strengthened glass ceramic of claim 23, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

71. The strengthened glass ceramic of claim 30, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

72. The strengthened glass ceramic of claim 37 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

73. The strengthened glass ceramic of claim 45 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

74. The strengthened glass ceramic of claim 56 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～60.00mol％、Al₂O₃ 20.00mol％～40.00mol％、ZrO₂ 2.00mol％～8.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

75. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the composition at the center of the strengthened glass ceramic in mole percent of oxides comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

76. The strengthened glass ceramic of claim 9, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

77. The strengthened glass ceramic of claim 10, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

78. The strengthened glass ceramic of claim 14, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

79. The strengthened glass ceramic of claim 18, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

80. The strengthened glass ceramic of claim 23, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

81. The strengthened glass ceramic of claim 30, wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

82. The strengthened glass ceramic of claim 37 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

83. The strengthened glass ceramic of claim 45 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

84. The strengthened glass ceramic of claim 56 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

85. The strengthened glass ceramic of claim 65 wherein the composition at the center of the strengthened glass ceramic, in mole percent of oxides, comprises ：SiO₂ 35.00mol％～50.00mol％、Al₂O₃ 25.00mol％～35.00mol％、ZrO₂ 3.00mol％～5.00mol％、MgO 4.00mol％～7.00mol％、ZnO 9.00mol％～12.00mol％、Na₂O 2.00mol％～10.00mol％、Li₂O 3.00mol％～10.00mol％.

86. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the composition at the center of the strengthened glass ceramic in mole percent of each oxide in the composition of the strengthened glass ceramic satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

87. The strengthened glass ceramic of claim 9, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

88. The strengthened glass ceramic of claim 10, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

89. The strengthened glass ceramic of claim 14, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

90. The strengthened glass ceramic of claim 18, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

91. The strengthened glass ceramic of claim 23, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

92. The strengthened glass ceramic of claim 30, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

93. The strengthened glass ceramic of claim 37, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

94. The strengthened glass ceramic of claim 45 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

95. The strengthened glass ceramic of claim 56 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

96. The strengthened glass ceramic of claim 65 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

97. The strengthened glass ceramic of claim 75, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, satisfies:

ZnO/MgO of 1.30-2.50, and/or

0.19≤(Al₂O₃-(MgO+ZnO))/SiO₂≤0.60。

98. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

99. The strengthened glass ceramic of claim 98, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

13.00mol% or less ZnO+MgO% or less 17.30mol%, and/or

10.00mol%≤Al₂O₃-(MgO+ZnO)≤20.00mol%。

100. The strengthened glass ceramic of claim 9, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

101. The strengthened glass ceramic of claim 10, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

102. The strengthened glass ceramic of claim 14, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

103. The strengthened glass ceramic of claim 18, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

104. The strengthened glass ceramic of claim 23, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

105. The strengthened glass ceramic of claim 30, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

106. The strengthened glass ceramic of claim 37, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

107. The strengthened glass ceramic of claim 45 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

108. The strengthened glass ceramic of claim 56 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

109. The strengthened glass ceramic of claim 65 wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

110. The strengthened glass ceramic of claim 75, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

111. The strengthened glass ceramic of claim 86, wherein the composition at the center of the strengthened glass ceramic, in mole percent of each oxide in the composition of the strengthened glass ceramic, further satisfies:

12.00mol% or less ZnO+MgO or less than 20.00mol%, and/or

Al ₂O₃ - (MgO+ZnO) 22.00mol% or less, 9.00mol% or less, and/or

6.82mol%≤Na₂O+Li₂O≤13.50mol%。

112. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is 85.00% or more.

113. The strengthened glass ceramic of claim 9, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is greater than or equal to 85.00%.

114. The strengthened glass ceramic of claim 10, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is greater than or equal to 85.00%.

115. The strengthened glass ceramic of claim 14, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is greater than or equal to 85.00%.

116. The strengthened glass ceramic of claim 18, wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength light is greater than or equal to 85.00%.

117. The strengthened glass ceramic of claim 23, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is greater than or equal to 85.00%.

118. The strengthened glass ceramic of claim 30, wherein the transmittance of the strengthened glass ceramic at 550nm wavelength light of 0.7mm thickness is greater than or equal to 85.00%.

119. The strengthened glass ceramic of claim 37, wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength light is greater than or equal to 85.00%.

120. The strengthened glass ceramic of claim 45 wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength is greater than or equal to 85.00%.

121. The strengthened glass ceramic of claim 56 wherein the 0.7mm thick strengthened glass ceramic has a transmittance of greater than or equal to 85.00% at 550nm wavelength light.

122. The strengthened glass ceramic of claim 65 wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength light is greater than or equal to 85.00%.

123. The strengthened glass ceramic of claim 75 wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength is greater than or equal to 85.00%.

124. The strengthened glass ceramic of claim 86, wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength is greater than or equal to 85.00%.

125. The strengthened glass ceramic of claim 98, wherein the transmittance of the 0.7mm thick strengthened glass ceramic at 550nm wavelength is greater than or equal to 85.00%.

126. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of 1.00m or greater.

127. The reinforced glass-ceramic of claim 126, wherein the reinforced glass-ceramic has an average sandpaper drop resistant height of greater than or equal to 1.40m.

128. A reinforced glass ceramic as recited in claim 127, wherein the reinforced glass ceramic has an average sandpaper drop height of from 1.50m to 2.50m.

129. The strengthened glass ceramic of claim 9, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

130. The strengthened glass ceramic of claim 10, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

131. The strengthened glass ceramic of claim 14, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

132. The strengthened glass ceramic of claim 18, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

133. The strengthened glass ceramic of claim 23, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

134. The strengthened glass ceramic of claim 30, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

135. The strengthened glass ceramic of claim 37, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

136. The strengthened glass ceramic of claim 45 wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, the strengthened glass ceramic having an average sandpaper drop height of greater than or equal to 1.00m.

137. The strengthened glass ceramic of claim 56 wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, the strengthened glass ceramic having an average sandpaper drop height of greater than or equal to 1.00m.

138. The strengthened glass ceramic of claim 65, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

139. The strengthened glass ceramic of claim 75, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

140. The strengthened glass ceramic of claim 86, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

141. The strengthened glass ceramic of claim 98, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, the strengthened glass ceramic having an average sandpaper drop height of greater than or equal to 1.00m.

142. The strengthened glass ceramic of claim 112, wherein the strengthened glass ceramic is 0.7mm thick and is subjected to a drop test with 80 mesh sandpaper, and wherein the strengthened glass ceramic has an average sandpaper drop height of greater than or equal to 1.00m.

143. The strengthened glass ceramic according to any one of claims 1 to 8, wherein the strengthened glass ceramic is obtained by subjecting a chemically strengthened glass ceramic to a chemical strengthening treatment, and wherein the composition of the chemically strengthened glass ceramic is the same as the composition at the center of the strengthened glass ceramic.

144. The tempered glass ceramic according to claim 9, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic to a chemical tempering treatment.

145. The tempered glass ceramic according to claim 10, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic to a chemical tempering treatment.

146. The tempered glass ceramic according to claim 14, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic to a chemical tempering treatment.

147. The tempered glass ceramic according to claim 18, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic to a chemical tempering treatment.

148. The tempered glass ceramic according to claim 23, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic to a chemical tempering treatment.

149. The tempered glass ceramic of claim 30, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic.

150. The tempered glass ceramic of claim 37, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic.

151. The strengthened glass ceramic of claim 45 wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

152. The strengthened glass ceramic of claim 56 wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

153. The tempered glass ceramic of claim 65, wherein the tempered glass ceramic is obtained by subjecting a chemically tempered glass ceramic having the same composition as that at the center of the tempered glass ceramic.

154. The strengthened glass ceramic of claim 75, wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

155. The strengthened glass ceramic of claim 86, wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

156. The strengthened glass ceramic of claim 98, wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

157. The strengthened glass ceramic of claim 112, wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

158. The strengthened glass ceramic of claim 126, wherein the strengthened glass ceramic is obtained by chemically strengthening a chemically strengthened glass ceramic having a composition that is the same as a composition at a center of the strengthened glass ceramic.

159. A glass device made from the strengthened glass ceramic of any one of claims 1-158.

160. An electronic device comprising the strengthened glass ceramic of any one of claims 1-158.