Spinel glass ceramic and application thereof

Abstract

According to the spinel glass ceramic and the application thereof provided by the invention, the spinel glass ceramic has a specific composition and a crystal phase structure, so that not only is the spinel glass ceramic endowed with high intrinsic strength, but also the spinel glass ceramic can obtain an expected stress structure after chemical strengthening treatment; particularly, the depth of an ultra-high compression stress layer and the large deep layer stress are achieved. The reinforced spinel glass ceramic with high mechanical strength and damage resistance can be prepared by using the spinel glass ceramic.

Description

[0001] This application is a divisional application of Chinese invention patent application filed on June 7, 2024, with application number 202410741381.2 and title "A spinel glass-ceramic and its application". Technical Field

[0002] This application relates to the field of glass and ceramic technology, and in particular to a spinel glass-ceramic and its applications. Background Technology

[0003] Common causes of glass breakage in electronic devices include drop breakage, crushing breakage due to contact with other objects, and impact breakage due to heavy objects falling on the glass. Analyzing the drop breakage process, it generally occurs when the glass surface collides with a sharp object of similar or greater hardness (such as fine sand, cement, or small stones), causing localized damage. A hemispherical crack propagation source forms at the point of failure. Some of the impact energy is attenuated, and the remaining energy propagates further. When the compressive stress level on the glass surface is insufficient to offset the remaining energy, the crack propagates through the glass surface area. When a longitudinal crack penetrates the compressive stress layer and reaches the tensile stress layer (or tensile stress layer), the crack propagates rapidly in the tensile stress zone, penetrating the entire glass and causing it to break or fracture. Similarly, crushing or impact breakage occurs primarily when the force of the crushing or impact exceeds the compressive stress level on the glass surface, causing the glass to be unable to withstand the energy of the impact.

[0004] It is evident that the surface stress level, compressive stress layer depth, and deep stress state of glass products are closely related to their resistance to drop damage, compression damage, and impact damage. When the compressive stress layer depth is constant, the greater the deep stress, the more residual energy from drop impacts, compression, or impacts can be offset by the surface compressive stress level. Conversely, when the surface compressive stress level is insufficient to offset the residual energy from drop impacts, compression, or impacts, a deeper compressive stress layer is more beneficial in offsetting the energy driving crack propagation.

[0005] Therefore, in order to further improve the drop impact resistance and extrusion resistance of glass ceramics with spinel as the main crystalline phase, it is necessary to develop a spinel glass ceramic that can obtain a large deep stress and ultra-high compressive stress layer depth through chemical strengthening, and to use this spinel glass ceramic to prepare a strengthened glass ceramic with high mechanical strength. Summary of the Invention

[0006] The purpose of this application is to provide a spinel glass-ceramic and its application. This spinel glass-ceramic can be chemically strengthened to obtain a reinforced spinel glass-ceramic with a large deep stress and ultra-high compressive stress layer depth, thereby improving the mechanical strength and damage resistance of the reinforced spinel glass-ceramic, especially its resistance to drop impact and compression.

[0007] The technical solution provided in this application is as follows:

[0008] In a first aspect, a spinel glass-ceramic is provided, wherein the spinel glass-ceramic comprises, by molar percentage of oxides: SiO2 35.00 mol%~60.00 mol%, Al2O3 20.00 mol%~40.00 mol%, ZrO2 2.00 mol%~8.00 mol%, MgO 3.00 mol%~7.50 mol%, ZnO 7.00 mol%~13.00 mol%, Na2O 1.00 mol%~10.00 mol%, and Li2O 2.50 mol%~10.00 mol%.

[0009] The spinel glass-ceramic contains 15.00% to 45.00% by weight of (Zn,Mg)Al2O4 crystalline phase in the spinel glass-ceramic.

[0010] Take W [(Zn，Mg)Al2O4] W represents the weight percentage of the (Zn,Mg)Al2O4 crystal phase in the spinel glass-ceramic. [Al2O3] W represents the weight percentage of Al2O3 in the spinel glass-ceramic. [MgO] W represents the weight percentage of MgO in the spinel glass-ceramic. [ZnO] The weight percentage of ZnO in the spinel glass-ceramic;

[0011] A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2,

[0012] B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] + W [ZnO] ),

[0013] C=A / B, and in the spinel glass-ceramic, 1.50≤C≤1.85.

[0014] The spinel glass-ceramic of this application possesses a specific composition and crystal phase structure. Utilizing the synergistic effect of this composition and crystal phase structure, not only is the spinel glass-ceramic endowed with high intrinsic strength, but it also ensures that the spinel glass-ceramic achieves the desired stress structure after chemical strengthening treatment, particularly the ultra-high compressive stress layer depth and large deep-layer stress. Using this spinel glass-ceramic, strengthened spinel glass-ceramics with high mechanical strength and high damage resistance can be prepared.

[0015] In some embodiments of this application, in the spinel glass-ceramic, the value of A is 10.00% to 25.00%, preferably 14.00% to 25.00%; and / or, the value of B is 7.50% to 12.50%, preferably 8.00% to 12.00%. By ensuring that the values ​​of A and B meet the above ranges, it helps to ensure that the composition and structure of the spinel glass-ceramic meet the range of C.

[0016] In some embodiments of this application, the spinel glass-ceramic further comprises a tetragonal ZrO2 crystal phase, wherein the total content of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase accounts for 25.00% to 70.00% by weight of the spinel glass-ceramic, preferably 30.00% to 50.00% by weight. When the total content W of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase in the spinel glass-ceramic is within the above range, it can ensure that the spinel glass-ceramic has a large number of crystals that can hinder crack propagation, which is beneficial to improving the intrinsic strength or inherent strength of the spinel glass-ceramic.

[0017] In some embodiments of this application, the ratio of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase in the spinel glass-ceramic is 1.00~18.00, preferably 1.00~15.00. When the ratio of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase in the spinel glass-ceramic (i.e., the mass ratio Z of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase) is within the above range, it can impart a specific crystal phase structure to the spinel glass-ceramic. This crystal phase structure is not only beneficial for improving the intrinsic strength or inherent strength of the spinel glass-ceramic, but also beneficial for obtaining the desired stress structure during chemical strengthening of the spinel glass-ceramic.

[0018] In some embodiments of this application, the average crystal size of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic is 3.0 nm to 10.0 nm, preferably 4.0 nm to 8.0 nm, more preferably 4.0 nm to 7.5 nm, and even more preferably 4.5 nm to 7.5 nm. When the average crystal size of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic is within the above range, it not only helps to improve the light transmittance of the spinel glass-ceramic while ensuring its strength, but also helps to improve its ion exchange performance, enabling it to achieve the desired stress level through chemical strengthening.

[0019] In some embodiments of this application, the spinel glass-ceramic composition, based on the molar percentage of oxides, further includes: K₂O 0.00 mol%~5.00 mol%, CaO 0.00 mol%~10.00 mol%, B₂O₃ 0.00 mol%~10.00 mol%, and BaO 0.00 mol%~5.00 mol%. In the glass system of this application, K₂O, CaO, B₂O₃, or BaO are optional components, and their appropriate use can improve the forming effect, crystallization effect, chemical strengthening effect, or optical effect of the spinel glass-ceramic.

[0020] In some embodiments of this application, the spinel glass-ceramic composition, based on the molar percentage of oxides, includes: SiO2 35.00 mol%~60.00 mol%, Al2O3 20.00 mol%~40.00 mol%, ZrO2 2.00 mol%~8.00 mol%, MgO 4.00 mol%~7.00 mol%, ZnO 9.00 mol%~12.00 mol%, Na2O 2.00 mol%~10.00 mol%, and Li2O 3.00 mol%~10.00 mol%. By appropriately adjusting the content of MgO, ZnO, Li2O, or Na2O, it is helpful to ensure that the content of the main crystalline phase in the spinel glass-ceramic meets the desired level, and also to help ensure that the spinel glass-ceramic achieves the desired chemical strengthening effect, thereby obtaining a strengthened spinel glass-ceramic with a high stress level.

[0021] In some embodiments of this application, the spinel glass-ceramic composition, based on the molar percentage of oxides, includes: SiO2 35.00 mol%~50.00 mol%, Al2O3 25.00 mol%~35.00 mol%, ZrO2 3.00 mol%~5.00 mol%, MgO 4.00 mol%~7.00 mol%, ZnO 9.00 mol%~12.00 mol%, Na2O 2.00 mol%~10.00 mol%, and Li2O 3.00 mol%~10.00 mol%. By appropriately adjusting the content of each necessary oxide, it is helpful to ensure that the spinel glass-ceramic achieves the desired crystal phase structure and glass network structure capable of achieving high stress levels, thereby facilitating the acquisition of reinforced spinel glass-ceramics with high stress levels.

[0022] In some embodiments of this application, the composition of the spinel glass-ceramic, based on the molar percentage of each oxide in the composition, satisfies the following:

[0023] 1.30≤ZnO / MgO≤2.50; and / or,

[0024] 0.05≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.20; and / or,

[0025] 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60; and / or,

[0026] 0.26≤Na2O / Li2O≤3.00.

[0027] By ensuring that the spinel glass-ceramic of this application satisfies at least one of the above-mentioned relationships ZnO / MgO, Li2O / (Al2O3-(MgO+ZnO)+SiO2), (Al2O3-(MgO+ZnO)) / SiO2, and Na2O / Li2O, it is helpful to further adjust the network structure and crystal phase structure of the spinel glass-ceramic, so that the spinel glass-ceramic forms a specific microstructure that helps to obtain the desired stress level.

[0028] In some embodiments of this application, the composition of the spinel glass-ceramic, based on the molar percentage of each oxide in the composition, also satisfies the following:

[0029] 12.00 mol% ≤ ZnO + MgO ≤ 20.00 mol%, preferably 13.00 mol% ≤ ZnO + MgO ≤ 17.30 mol%; and / or,

[0030] 9.00 mol% ≤ Al₂O₃⁻(MgO + ZnO) ≤ 22.00 mol%, preferably 10.00 mol% ≤ Al₂O₃⁻(MgO + ZnO) ≤ 20.00 mol%; and / or,

[0031] 5.00 mol% ≤ Na2O + Li2O ≤ 15.00 mol%, preferably 6.00 mol% ≤ Na2O + Li2O ≤ 13.50 mol%.

[0032] The spinel glass-ceramic of this application satisfies at least one of the above-mentioned relationships ZnO+MgO, Al2O3-(MgO+ZnO), and Na2O+Li2O, which helps to obtain a high content of (Zn,Mg)Al2O4 crystal phase with high hardness and high modulus, thereby further improving the intrinsic strength or inherent strength of the spinel glass-ceramic, or helping to further improve the ion exchange effect of the spinel glass-ceramic to obtain the desired stress level.

[0033] In some embodiments of this application, the spinel glass-ceramic is transparent in the visible light range.

[0034] In some embodiments of this application, the transmittance of the 0.7 mm thick spinel glass-ceramic under 550 nm wavelength light is greater than or equal to 85%. The fact that the transmittance of the 0.7 mm thick spinel glass-ceramic under 550 nm wavelength light is within the above range indicates that the spinel glass-ceramic of this application has high light transmittance. Furthermore, the spinel glass-ceramic of this application can also obtain high mechanical strength and high damage resistance through chemical strengthening treatment, effectively broadening the application scenarios and fields of the spinel glass-ceramic of this application.

[0035] By enabling spinel glass-ceramics to achieve specific crystal phase structures, it is beneficial to achieve both high intrinsic strength and improved chemical strengthening effects. This allows for the attainment of ultra-high compressive stress layer depth and greater deep stress through chemical strengthening, thereby enhancing the mechanical strength and damage resistance of spinel glass-ceramics. Furthermore, the relevant characteristics of X-ray diffraction patterns can reflect the crystal phase structure of the glass-ceramic, including crystal phase composition and crystal size.

[0036] In some embodiments of this application, in the X-ray diffraction pattern of the spinel glass-ceramic, the peak with the maximum intensity among the characteristic peaks with a 2θ angle in the range of 28° to 32° is selected as the first characteristic peak, and the peak with the maximum intensity among the characteristic peaks with a 2θ angle in the range of 36° to 38° is selected as the second characteristic peak. The peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50, preferably 0.85 to 1.30. When the peak intensity ratio X of the spinel glass-ceramic is within the above range, it indicates that the spinel glass-ceramic has achieved suitable crystal integrity, thereby helping to ensure that the spinel glass-ceramic obtains better optical and strengthening effects.

[0037] In some embodiments of this application, in the X-ray diffraction pattern of the spinel glass-ceramic, the characteristic peak of the

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

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

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

[0038] The full width at half maximum (W) of the characteristic peak of the

[400] crystal plane is...

[400] The range is 0.650° to 1.800°, with W being the preferred value.

[400] The range is from 0.900° to 1.600°.

[0039] The full width at half maximum (W) of the characteristic peak of the

[311] crystal plane is...

[311] The range is 0.900° to 2.800°, with W being the preferred value.

[311] The range is from 1.100° to 2.230°.

[0040] The full width at half maximum (W) of the characteristic peak of the

[440] crystal plane is

[440] The range is 0.750° to 2.000°, with W being the preferred value.

[440] The W value ranges from 0.900° to 1.600°. (This refers to the W value of spinel glass-ceramics.)

[400] W

[311] W

[440] Within the aforementioned range, it is indicated that the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic has a suitable average crystal size, satisfying a specific crystal phase structure. This not only contributes to imparting high intrinsic strength or inherent strength to the spinel glass-ceramic but also helps ensure that the spinel glass-ceramic achieves an ideal stress structure through chemical strengthening. Simultaneously, it helps the spinel glass-ceramic obtain the desired optical properties.

[0041] In a second aspect, a glass device is provided, which is made of spinel glass-ceramic as described in any of the foregoing embodiments.

[0042] Thirdly, an electronic device is provided that includes the spinel glass-ceramic of any of the foregoing embodiments.

[0043] In some embodiments of this application, the electronic device includes at least one of a mobile phone, a tablet computer, a smart wearable device, a display, and a television.

[0044] One or more technical solutions of this application have the following advantages or beneficial effects:

[0045] This application provides a spinel glass-ceramic with a specific composition and crystal phase structure. Utilizing the synergistic effect of this composition and crystal phase structure, not only is the spinel glass-ceramic endowed with high intrinsic strength, but it also ensures that the spinel glass-ceramic achieves the desired stress structure after chemical strengthening treatment, particularly the ultra-high compressive stress layer depth and large deep-layer stress. Using this spinel glass-ceramic, strengthened spinel glass-ceramics with high mechanical strength and high damage resistance can be prepared. Of course, implementing any product or method of this application does not necessarily require achieving all the advantages described above simultaneously. Attached Figure Description

[0046] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other embodiments can be obtained based on these drawings.

[0047] Figure 1 This is a schematic diagram of the structure of reinforced glass ceramics in the prior art, where 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.

[0048] Figure 2 Comparison of XRD diffraction patterns of spinel glass ceramics in Examples 1-3 and Comparative Examples 6-9;

[0049] Figure 3 This is a schematic diagram of the XRD diffraction curve fitting of the spinel glass-ceramic in Example 6;

[0050] Figure 4 The XRD diffraction pattern of the spinel glass-ceramic in Comparative Example 8 is shown.

[0051] Figure 5 The XRD diffraction pattern of the spinel glass-ceramic in Example 1 is shown below.

[0052] Figure 6 The XRD diffraction pattern of the spinel glass-ceramic in Comparative Example 10 is shown.

[0053] Figure 7The XRD diffraction pattern of the spinel glass-ceramic in Comparative Example 11 is shown.

[0054] Figure 8 The transmittance curves of the spinel glass-ceramic in Example 1 under different wavelength conditions are shown.

[0055] Figure 9 The XRD diffraction comparison diagrams of the spinel glass-ceramic before and after chemical strengthening in Example 1 are shown.

[0056] Figure 10 This is a comparison of the transmittance curves of the spinel glass-ceramic before and after chemical strengthening under different wavelength conditions in Example 1.

[0057] Figure 11 The XRD diffraction pattern of the spinel glass-ceramic in Example 2 is shown below.

[0058] Figure 12 This is a schematic diagram of the single-bar static pressure strength test process in this application;

[0059] Figure 13 This is a schematic diagram of the fixture used for testing the static pressure strength of a single rod in this application;

[0060] Figure 14 This is a cross-sectional structural schematic diagram of the fixture for testing the static pressure strength of a single rod according to this application. Detailed Implementation

[0061] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0062] Terminology Explanation

[0063] DOL_0: Compressive stress layer depth, also known as compressive stress layer depth, refers to the distance along the thickness direction from any surface of the reinforced glass ceramic (such as the reinforced spinel glass ceramic obtained by chemical strengthening treatment in this application) to the position near that surface where the compressive stress is zero.

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

[0065] CS_50: refers to the compressive stress value at a depth of 50μm from the surface of the reinforced glass ceramic along the thickness direction.

[0066] |CT_CV|: refers to the absolute value of the maximum tensile stress in the tensile stress layer, specifically the absolute value of the maximum value among all tensile stresses in the tensile stress layer.

[0067] Crystal phase content: refers to the percentage of the mass of the crystalline phase in the glass ceramic relative to the total mass of the glass ceramic.

[0068] Peak intensity: refers to the height of the diffraction peak in an XRD pattern.

[0069] Half-peak width: refers to the width of the half-peak height of a diffraction peak in an XRD pattern, usually expressed as an angle or 2θ value.

[0070] Substrate glass: refers to glass that has not undergone nucleation, crystallization, or strengthening treatment, or is also called base glass.

[0071] Glass-ceramics: also known as microcrystalline glass or crystallized glass, are a type of solid composite material that simultaneously contains a glass phase and a microcrystalline phase (or crystalline phase, crystallized phase, crystalline phase).

[0072] Theoretically speaking, when the compressive stress layers extending inward from the two main surfaces of a glass product are equal or approximately equal in depth, and the sum of the depths of the two compressive stress layers equals the thickness of the tensile stress layer, that is, when... Figure 1 As shown, the depth d of the compressive stress layer 11 on both sides is approximately 25% of the thickness t of the glass 10, and the thickness of the tensile stress layer 12 is approximately 50% of the thickness t of the glass 10. This achieves the ideal compressive stress layer depth. However, in reality, almost no glass product in the current technology has achieved the goal of the compressive stress layer depth d being approximately 25% of the glass thickness t. This is partly because achieving this compressive stress layer depth is difficult, and partly because in existing glass products, a higher compressive stress layer depth is often accompanied by a decrease in surface stress level, leading to a reduction in the overall strength of the glass product. This is because during the ion exchange process of chemical strengthening treatment, ion diffusion becomes increasingly difficult as it progresses. Simply increasing the diffusion amount by adding alkali metal ions can easily lead to breakage or shattering due to excessive internal stress before a higher depth is reached. Furthermore, in many glass products, after the exchanged ion diffusion reaches a certain depth and the stress reaches a certain level, stress relaxation occurs. The depth may increase slightly or not at all, but the stress will decrease significantly, resulting in a decrease in the strength of the glass product. Therefore, currently, the compressive stress depth of glass products can only be made as close as possible to this ideal effect. For spinel glass-ceramics containing the (Zn,Mg)Al2O4 crystal phase as the main crystalline phase (in this application, (Zn,Mg)Al2O4 represents a solid solution of zinc spinel and magnesium spinel, or also called zinc-aluminum spinel-magnesium-aluminum spinel solid solution, zinc-magnesium spinel solid solution, zinc-spinel-magnesium spinel solid solution, zinc-magnesium-aluminum spinel solid solution), simply increasing and introducing the absolute number and type of ion-exchangeable metal ions cannot guarantee the achievement of ultra-high stress layer depth and deep stress. On the one hand, when the Li inside the spinel glass-ceramic...+ and Na + When the content exceeds a certain amount, it can easily affect the network structure and crystal phase structure of spinel glass ceramics, leading to the problem of not being able to obtain the desired spinel glass ceramics. On the other hand, the stress distribution and stress effect that glass ceramics can obtain after chemical strengthening are affected by both the composition and crystal phase structure of the glass ceramics. Simply increasing the absolute number and types of alkali metal ions that can undergo ion exchange cannot guarantee that spinel glass ceramics will obtain a crystal phase structure that can achieve the desired stress distribution.

[0073] Not limited by theory, the composition and crystal phase structure of spinel glass ceramics are closely related to the stress distribution or stress structure after chemical strengthening. By making spinel glass ceramics meet specific composition and crystal phase structure, it is possible to obtain strengthened spinel glass ceramics with ultra-high compressive stress layer depth and large deep stress after chemical strengthening, thereby achieving high mechanical strength and high damage resistance of spinel glass ceramics.

[0074] In view of this, a spinel glass-ceramic with a specific composition and crystal phase structure, which can be chemically strengthened to obtain a desired stress structure, and its application are provided.

[0075] In some embodiments of this application, a spinel glass-ceramic is provided, wherein the composition of the spinel glass-ceramic, based on the molar percentage of oxides, comprises: 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%, and Li2O 2.50mol%~10.00mol%.

[0076] The spinel glass-ceramic contains 15.00% to 45.00% by weight of (Zn,Mg)Al2O4 crystalline phase in the spinel glass-ceramic.

[0077] Take W [(Zn，Mg)Al2O4] W represents the weight percentage of the (Zn,Mg)Al2O4 crystal phase in the spinel glass-ceramic. [Al2O3] W represents the weight percentage of Al2O3 in the spinel glass-ceramic. [MgO] W represents the weight percentage of MgO in the spinel glass-ceramic. [ZnO] The weight percentage of ZnO in the spinel glass-ceramic;

[0078] A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2,

[0079] B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] + W [ZnO] ),

[0080] C=A / B, and in the spinel glass-ceramic, 1.50≤C≤1.85.

[0081] It should be understood that the spinel glass-ceramic of this application is obtained by heat treatment of a substrate glass. Therefore, based on the molar percentage of oxides, the composition of the spinel glass-ceramic is the same as that of the substrate glass. That is, in this application, the composition of the substrate glass used to prepare the spinel glass-ceramic, based on the molar percentage of oxides, includes: 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%, and Li2O 2.50mol%~10.00mol%.

[0082] After heat treatment of a substrate glass that meets the above range to obtain a spinel glass ceramic that meets a specific crystal phase structure and has a specific glass network structure, the spinel glass ceramic can be chemically strengthened to obtain a strengthened spinel glass ceramic with ultra-high compressive stress layer depth and large deep stress.

[0083] In the glass system of this application, SiO2 is the forming oxide of the glass network and is an indispensable component constituting the glass network structure. An appropriate amount of SiO2 can increase the stability and mechanical strength of the glass, but excessive SiO2 increases the viscosity of the substrate glass, making glass melting more difficult and thus reducing the formability of the substrate glass. Therefore, in this application, the SiO2 content in the substrate glass or spinel glass-ceramic is 35.00 mol% to 60.00 mol%, calculated as mol% of oxide.

[0084] In some embodiments of this application, the SiO2 content can be 35.00 mol%, 37.00 mol%, 40.00 mol%, 42.00 mol%, 45.00 mol%, 47.00 mol%, 50.00 mol%, 52.00 mol%, 55.00 mol%, 57.00 mol%, or 60.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the SiO2 content can be 36.00 mol% to 58.00 mol%, 38.00 mol% to 56.00 mol%, 40.00 mol% to 52.00 mol%, 42.00 mol% to 50.00 mol%, or 44.00 mol% to 48.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0085] In the glass system of this application, an appropriate amount of Al2O3 can promote the precipitation of the main crystalline phase and inhibit the precipitation of other impurity phases such as quartz. It also helps to increase the ion exchange rate during the chemical strengthening process. However, excessive Al2O3 can drastically increase the difficulty of melting the substrate glass and easily lead to crystallization devitrification during normal cooling due to excessively rapid crystallization. Therefore, in this application, the Al2O3 content in the substrate glass or spinel glass-ceramic is 20.00 mol% to 40.00 mol%, calculated as mol% of oxide.

[0086] In some embodiments of this application, the content of Al2O3 can be 20.00 mol%, 21.00 mol%, 22.00 mol%, 23.00 mol%, 24.00 mol%, 25.00 mol%, 26.00 mol%, 27.00 mol%, 28.00 mol%, 29.00 mol%, 30.00 mol%, 31.00 mol%, 32.00 mol%, 33.00 mol%, 34.00 mol%, 35.00 mol%, 36.00 mol%, 37.00 mol%, 38.00 mol%, 39.00 mol%, or 40.00 mol%, or a value within a range of values ​​with any two of the above values ​​as endpoints. In some embodiments, the Al2O3 content can be 22.00 mol%~38.00 mol%, 24.00 mol%~36.00 mol%, 26.00 mol%~34.00 mol%, or 28.00 mol%~32.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0087] In the glass system of this application, ZrO2 is an effective nucleating agent. During the heat treatment of the substrate glass, ZrO2 precipitates in the substrate glass in the form of crystals, which become nuclei for the subsequent growth of the main crystalline phase. Within a certain glass composition range, the content of ZrO2 affects the formation of the substrate glass, the crystal shape, crystal type, and crystal size of the glass ceramic obtained by heat treatment of the substrate glass. By controlling the composition of the substrate glass to meet the requirement of an appropriate amount of ZrO2, ZrO2 can be preferentially precipitated, followed by the growth of the main crystalline phase spinel crystal. Too low a content of ZrO2 will affect the precipitation of the spinel crystalline phase; while too high a content of ZrO2 will make the melting of the substrate glass more difficult and easily cause white unmelted matter to appear in the substrate glass. Therefore, in this application, the content of ZrO2 in the composition of the substrate glass or spinel glass ceramic is 2.00 mol% to 8.00 mol%, calculated as mol% of oxide.

[0088] In some embodiments of this application, the ZrO2 content can be 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, or 8.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the ZrO2 content can be 2.50 mol% to 7.50 mol%, 3.50 mol% to 7.00 mol%, 4.50 mol% to 6.50 mol%, or 5.00 mol% to 6.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0089] In the glass system of this application, MgO and ZnO are essential components as the main crystalline phase spinel, which can promote spinel precipitation and reduce the melting difficulty to some extent. However, excessive MgO and ZnO can easily lead to excessive growth of spinel grains, making it difficult to obtain spinel glass ceramics with high transparency. Therefore, in this application, based on the mol% of oxides, the content of MgO in the composition of the substrate glass or spinel glass ceramic is 3.00 mol% to 7.50 mol%, and the content of ZnO is 7.00 mol% to 13.00 mol%.

[0090] In some embodiments of this application, the MgO content can be 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, or 7.50 mol%, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the MgO content can be 3.50 mol% to 7.50 mol%, 4.50 mol% to 7.00 mol%, or 5.00 mol% to 6.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0091] In some embodiments of this application, the ZnO content can be 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, 10.00 mol%, 10.50 mol%, 11.00 mol%, 11.50 mol%, 12.00 mol%, 12.50 mol%, or 13.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the ZnO content can be 7.50 mol% to 12.50 mol%, 8.50 mol% to 12.00 mol%, 9.50 mol% to 11.50 mol%, or 10.00 mol% to 11.00 mol%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0092] In the glass system of this application, increasing the Na₂O content helps to obtain higher surface compressive stress, and also helps to reduce the melting temperature of the substrate glass and the crystal precipitation temperature when the substrate glass is used to prepare spinel glass-ceramics. However, excessive Na₂O can easily lead to ceramization of the substrate glass during annealing, or can easily lead to the precipitation of undesirable impurity phases during the heat treatment preparation of spinel glass-ceramics, thereby affecting the optical properties of the spinel glass-ceramics; while too little Na₂O can easily lead to an increase in the heat treatment temperature when the substrate glass is used to prepare spinel glass-ceramics, or can easily lead to direct phase separation or precipitation of undesirable impurity phases during the preparation of spinel glass-ceramics, thereby obtaining opaque glass-ceramics. Therefore, in this application, the Na₂O content in the composition of the substrate glass or spinel glass-ceramics is 1.00 mol% to 10.00 mol%, calculated as mol% of oxides.

[0093] In some embodiments of this application, the content of Na₂O can be 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, or 10.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the content of Na₂O can be 1.50 mol% to 9.50 mol%, 2.50 mol% to 9.00 mol%, 3.50 mol% to 8.50 mol%, 4.50 mol% to 7.50 mol%, or 5.00 mol% to 7.00 mol%. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges, as long as the spinel glass-ceramic with the desired performance of this application can be obtained.

[0094] In the glass system of this application, increasing the Li2O content helps to obtain higher deep compressive stress, improve the Young's modulus of the glass ceramic, and simultaneously help to reduce the melting temperature of the substrate glass and the crystal precipitation temperature during the preparation of spinel glass ceramics from the substrate glass. However, excessive Li2O can easily lead to ceramization of the substrate glass during annealing, or the precipitation of undesirable impurity phases during the heat treatment preparation of spinel glass ceramics from the substrate glass, or excessive crystal growth during heat treatment, thereby affecting the optical properties of the spinel glass ceramics. On the other hand, too little Li2O can easily lead to an increase in the heat treatment temperature during the preparation of spinel glass ceramics from the substrate glass, or a decrease in the deep stress that can be obtained during the chemical strengthening of spinel glass ceramics. Therefore, in this application, the Li2O content in the composition of the substrate glass or spinel glass ceramics is 2.50 mol% to 10.00 mol%, calculated as mol% of oxides.

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

[0096] In this application, the spinel glass-ceramic contains 15.00% to 45.00% by weight of (Zn,Mg)Al2O4 crystalline phase. When the content of (Zn,Mg)Al2O4 crystalline phase in the spinel glass-ceramic is within the above range, it indicates that the spinel glass-ceramic has a large number of crystals with high hardness and high modulus, which can endow the spinel glass-ceramic with high intrinsic strength. At the same time, by controlling the content of (Zn,Mg)Al2O4 crystalline phase, the spinel glass-ceramic can meet a specific crystal phase structure, which is beneficial to ensure that the spinel glass-ceramic obtains an ideal stress structure after chemical strengthening.

[0097] In some embodiments of this application, the crystal phase content W of the (Zn,Mg)Al2O4 crystal phase in the spinel glass-ceramic is... [(Zn，Mg)Al2O4] The values ​​can be 15.00 wt%, 18.00 wt%, 20.00 wt%, 23.00 wt%, 25.00 wt%, 28.00 wt%, 30.00 wt%, 33.00 wt%, 35.00 wt%, 38.00 wt%, 40.00 wt%, 43.00 wt%, or 45.00 wt%, or values ​​within a range defined by any two of the above values ​​as endpoints. In some embodiments, the phase content W of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic is... [(Zn，Mg)Al2O4] It can be 16.00 wt%~45.00 wt%, 18.00 wt%~43.00 wt%, 20.00 wt%~42.00 wt%, 22.00 wt%~40.00 wt%, or 25.00 wt%~35.00 wt%.

[0098] In some embodiments of this application, W is taken [(Zn，Mg)Al2O4] W represents the weight percentage of the (Zn,Mg)Al2O4 crystal phase in spinel glass-ceramics. [Al2O3] The weight percentage of Al2O3 in spinel glass-ceramics, W [MgO] W represents the weight percentage of MgO in spinel glass-ceramics. [ZnO] The weight percentage of ZnO in spinel glass ceramics; A=(1-W [(Zn，Mg)Al2O4] / 2)×W [Al2O3] / 2, B=(1-W [(Zn，Mg)Al2O4] )×(W [MgO] +W [ZnO] ), C = A / B, in spinel glass ceramics, 1.50≤C≤1.85.

[0099] By optimizing the composition and structure, the content of the (Zn,Mg)Al2O4 crystal phase, as well as the contents of Al2O3, MgO, and ZnO in the spinel glass-ceramic, are made to meet the range of characteristic C mentioned above. This ensures that the spinel glass-ceramic, after chemical strengthening, obtains the desired stress structure, thereby enabling the strengthened spinel glass-ceramic to achieve high mechanical strength, especially excellent damage resistance. In some embodiments, in the above-mentioned spinel glass-ceramic, the value of C, calculated according to formula C, can be 1.52~1.82, 1.56~1.75, 1.60~1.70, or 1.62~1.68. In some embodiments, in the above-mentioned spinel glass-ceramic, the value of C, calculated according to formula C, can be 1.51, 1.53, 1.55, 1.58, 1.60, 1.62, 1.65, 1.68, 1.70, 1.72, 1.75, 1.78, 1.80, 1.82 or 1.85, or a value within a range of values ​​formed by any two of the above values ​​as endpoints.

[0100] In some embodiments of this application, W [Al2O3] It ranges from 35.00 wt% to 50.00 wt%.

[0101] In some embodiments of this application, W [MgO] It ranges from 2.50 wt% to 4.00 wt%.

[0102] In some embodiments of this application, W [ZnO] The concentration ranges from 9.50 wt% to 14.50 wt%.

[0103] Overall, by ensuring that the composition and structure of spinel glass-ceramics meet the aforementioned characteristics, and by ensuring that the content of the (Zn,Mg)Al2O4 crystal phase in the spinel glass-ceramics falls within the aforementioned range, the spinel glass-ceramics can possess a specific crystal phase structure and a specific glass network structure. This improves the chemical strengthening effect of the spinel glass-ceramics, enabling them to obtain the desired stress structure through chemical strengthening treatment. For example, they can achieve an ultra-high compressive stress layer depth and a large deep stress, resulting in a high stress level. Consequently, the strengthened spinel glass-ceramics can achieve high mechanical strength and high damage resistance.

[0104] In some embodiments of this application, in the spinel glass-ceramic, the value of A is 10.00% to 25.00%, preferably 14.00% to 25.00%; and / or, the value of B is 7.50% to 12.50%, preferably 8.00% to 12.00%. By ensuring that the values ​​of A and B meet the above ranges, it helps to ensure that the composition and structure of the spinel glass-ceramic meet the range of C, and helps to ensure that the spinel glass-ceramic meets specific structural requirements that are conducive to obtaining the desired stress level.

[0105] In some embodiments of this application, the value of A can be 10.00%, 11.00%, 12.00%, 13.00%, 14.00%, 15.00%, 16.00%, 17.00%, 18.00%, 19.00%, 20.00%, 21.00%, 22.00%, 23.00%, 24.00%, or 25.00%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0106] In some embodiments of this application, the value of B can be 7.50%, 8.00%, 8.50%, 9.00%, 9.50%, 10.00%, 10.50%, 11.00%, 11.50%, 12.00%, or 12.50%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0107] In some embodiments of this application, the spinel glass-ceramic further comprises a tetragonal ZrO2 crystal phase, and the total content of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase accounts for 25.00% to 70.00% by weight of the spinel glass-ceramic, preferably 30.00% to 50.00% by weight. When the total content W of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase in the spinel glass-ceramic is within the above range, it can ensure that the spinel glass-ceramic has a large number of crystals that can hinder crack propagation, which is beneficial to improving the intrinsic strength or inherent strength of the spinel glass-ceramic.

[0108] In some embodiments of this application, the total crystal phase content W of (Zn,Mg)Al2O4 and tetragonal ZrO2 can be 25.00 wt%, 28.00 wt%, 30.00 wt%, 33.00 wt%, 35.00 wt%, 38.00 wt%, 40.00 wt%, 43.00 wt%, 45.00 wt%, 48.00 wt%, 50.00 wt%, 53.00 wt%, 55.00 wt%, 58.00 wt%, 60.00 wt%, 63.00 wt%, 65.00 wt%, 68.00 wt%, or 70.00 wt%, or a value within a range of values ​​with any two of the above values ​​as endpoints. In some embodiments, the total content W of the (Zn,Mg)Al2O4 and tetragonal ZrO2 crystal phases can be 26.00 wt%~68.00 wt%, 28.00 wt%~66.00 wt%, 30.00 wt%~65.00 wt%, 32.00 wt%~60.00 wt%, 35.00 wt%~55.00 wt%, 38.00 wt%~50.00 wt%, or 40.00 wt%~48.00 wt%. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other ranges, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0109] In some embodiments of this application, the ratio of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase in the spinel glass-ceramic is 1.00 to 18.00, preferably 1.00 to 15.00. When the ratio of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase in the spinel glass-ceramic (i.e., the mass ratio Z of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase) is within the above range, it can impart a specific crystal phase structure to the spinel glass-ceramic. This crystal phase structure is not only beneficial for improving the intrinsic strength or inherent strength of the spinel glass-ceramic, but also beneficial for obtaining the desired stress structure after chemical strengthening.

[0110] In some embodiments of this application, the ratio (mass ratio Z) of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase can be 1.00, 2.00, 3.00, 4.00, 5.00, 6.00, 7.00, 8.00, 9.00, 10.00, 11.00, 12.00, 13.00, 14.00, 15.00, 16.00, 17.00, or 18.00, or values ​​within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0111] In some embodiments of this application, the content W of the tetragonal ZrO2 crystal phase is determined based on the quality of the spinel glass-ceramic. [ZrO2] The content ranges from 2.00 wt% to 16.00 wt%. The tetragonal ZrO2 and (Zn,Mg)Al2O4 crystal phases together determine the internal crystal structure of spinel glass ceramics. By satisfying specific content ranges, it is beneficial to ensure the structural strength of spinel glass ceramics and to ensure that spinel glass ceramics obtain an ideal stress structure after chemical strengthening.

[0112] In some embodiments of this application, the tetragonal ZrO2 crystal phase content W in the spinel glass-ceramic [ZrO2] It can be 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, 6.00 wt%, 7.00 wt%, 8.00 wt%, 9.00 wt%, 10.00 wt%, 11.00 wt%, 12.00 wt%, 13.00 wt%, 14.00 wt%, 15.00 wt%, or 16.00 wt%, or a value within a range of values ​​with any two of the above values ​​as endpoints.

[0113] In some embodiments of this application, the average crystal size of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic is 3.0 nm to 10.0 nm, preferably 4.0 nm to 8.0 nm, more preferably 4.0 nm to 7.5 nm, and even more preferably 4.5 nm to 7.5 nm. When the average crystal size of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic is within the above range, it not only helps to improve the light transmittance of the spinel glass-ceramic while ensuring its strength, but also helps to improve its ion exchange performance, enabling it to achieve the desired stress level through chemical strengthening.

[0114] In some embodiments of this application, the average crystal size of the (Zn,Mg)Al2O4 phase can be 3.0 nm, 4.0 nm, 4.2 nm, 4.5 nm, 4.8 nm, 5.0 nm, 5.2 nm, 5.5 nm, 5.8 nm, 6.0 nm, 6.2 nm, 6.5 nm, 6.8 nm, 7.0 nm, 7.2 nm, 7.5 nm, 8.0 nm, or 10.0 nm, or a value within a range defined by any two of the above values ​​as endpoints. In some embodiments, the average crystal size of the (Zn,Mg)Al2O4 phase can be 4.0 nm to 9.0 nm, 4.5 nm to 8.0 nm, 4.5 nm to 7.5 nm, or 4.5 nm to 7.0 nm. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application can be obtained.

[0115] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic used to prepare the spinel glass-ceramic, based on the molar percentage of oxides, includes: 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%, K2O 0.00mol%~5.00mol%, CaO 0.00mol%~10.00mol%, B2O3 0.00mol%~10.00mol%, and BaO 0.00mol%~5.00mol%.

[0116] In addition to the necessary components for preparing the spinel glass-ceramic of this application, K2O, CaO, B2O3 or BaO are optional components in the glass system of this application. Appropriate use can improve the forming effect, crystallization effect, chemical strengthening effect or optical effect of spinel glass-ceramic.

[0117] In the formulation system of this application, K2O is an optional component that helps improve glass formability. Because K... + Radius greater than Na +Adding an appropriate amount of K2O can reduce the tendency of the substrate glass to crystallize during the preparation process and increase the transparency and gloss of spinel glass ceramics. In this application, the K2O content in the substrate glass or spinel glass ceramic is 0.00 mol% to 5.00 mol%, calculated as mol% of oxides. Adding K2O within this range not only achieves the aforementioned effects but also does not easily cause a decrease in the chemical stability and hardness of the spinel glass ceramic, thus preventing breakage.

[0118] In some embodiments of this application, the K₂O content can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, or 5.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0119] In the formulation system of this application, B2O3 is an optional component that helps reduce the melting difficulty of the substrate glass. An appropriate amount of B2O3 also promotes the precipitation of spinel. However, excessive B2O3 can easily lead to opacity or the precipitation of impurities that affect the transparency of spinel glass-ceramics during heat treatment of the substrate glass. In this application, the content of B2O3, calculated as mol% of oxides, can be from 0.00 mol% to 10.00 mol%.

[0120] In some embodiments of this application, the content of B2O3 can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, or 10.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0121] In the formulation system of this application, BaO is an optional component that is beneficial to improving the melting effect of the substrate glass. An appropriate amount of BaO can also inhibit grain growth to a certain extent, thereby improving the optical properties of spinel glass-ceramics. However, excessive BaO can easily affect the chemical strengthening effect of spinel glass-ceramics, greatly reducing the stress level that can be obtained. In this application, the BaO content, calculated as mol% of oxides, is 0.00 mol% to 5.00 mol%.

[0122] In some embodiments of this application, the BaO content can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, or 5.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0123] In the formulation system of this application, CaO is an optional component that helps reduce the viscosity of the molten glass and enhance the formability of the substrate glass. Appropriate amounts of CaO also help increase the strain point and Young's modulus, and improve the ion exchange capacity of the spinel glass-ceramic. Simultaneously, appropriate amounts of CaO can increase the gloss and transparency of the substrate glass, reduce its crystallization tendency, and slow down its hardening rate. However, excessive CaO can easily lead to an increase in glass density, thereby affecting the ion exchange performance of the spinel glass-ceramic. In this application, the CaO content, calculated as mol% of oxides, is 0.00 mol% to 10.00 mol%.

[0124] In some embodiments of this application, the CaO content can be 0.00 mol%, 0.50 mol%, 1.00 mol%, 1.50 mol%, 2.00 mol%, 2.50 mol%, 3.00 mol%, 3.50 mol%, 4.00 mol%, 4.50 mol%, 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, or 10.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0125] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic used to prepare spinel glass-ceramics, based on the molar percentage of oxides, includes: 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%, K2O 0.00mol%~5.00mol%, CaO 0.00mol%~10.00mol%, B2O3 0.00mol%~10.00mol%, and BaO 0.00mol%~5.00mol%. By appropriately adjusting the content of MgO, ZnO, Li2O, or Na2O, it is helpful to ensure that the content of the main crystalline phase in spinel glass ceramics meets the desired level, and at the same time, it is helpful to ensure that spinel glass ceramics achieve the desired chemical strengthening effect, thereby obtaining strengthened spinel glass ceramics with high stress levels.

[0126] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic used to prepare the spinel glass-ceramic, based on the molar percentage of oxides, includes: 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%, K2O 0.00mol%~5.00mol%, CaO 0.00mol%~10.00mol%, B2O3 0.00mol%~10.00mol%, and BaO 0.00mol%~5.00mol%. By appropriately adjusting the content of each necessary oxide, it is helpful to ensure that spinel glass ceramics achieve the desired crystal phase structure and glass network structure that can achieve high stress levels, thereby facilitating the acquisition of reinforced spinel glass ceramics with high stress levels.

[0127] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, satisfies: 1.30≤ZnO / MgO≤2.50; by ensuring that ZnO and MgO satisfy a specific content relationship, it is beneficial to ensure the formation of the desired main crystal phase structure.

[0128] In some embodiments of this application, the ZnO / MgO value can be 1.30, 1.40, 1.50, 1.60, 1.70, 1.80, 1.90, 2.00, 2.10, 2.20, 2.30, 2.40, or 2.50, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0129] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, satisfies: 0.05≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.20. By ensuring that Li2O, Al2O3, MgO, ZnO, and SiO2 satisfy a specific content relationship, it helps to improve the ion exchange performance of spinel glass-ceramic, and helps to achieve a high compressive stress layer depth and a large deep stress through chemical strengthening of spinel glass-ceramic, thereby helping to improve the mechanical strength and damage resistance of spinel glass-ceramic, especially its drop impact resistance.

[0130] In some embodiments of this application, the value of Li2O / (Al2O3-(MgO+ZnO)+SiO2) can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, or 0.20, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0131] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, satisfies: 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60. By ensuring that Al2O3, MgO, ZnO, and SiO2 satisfy a specific content relationship, it is possible to guarantee that there is an appropriate amount of Al in the residual glass phase of the spinel glass-ceramic. On the one hand, this helps to leverage the synergistic effect of Si and Al, enabling the residual glass phase to form a specific network structure, thereby improving the intrinsic strength of the spinel glass-ceramic. On the other hand, it helps to promote ion exchange and improve the chemical strengthening effect of the spinel glass-ceramic.

[0132] In some embodiments of this application, the value of (Al2O3-(MgO+ZnO)) / SiO2 can be 0.19, 0.20, 0.23, 0.25, 0.28, 0.30, 0.33, 0.35, 0.38, 0.40, 0.43, 0.45, 0.48, 0.50, 0.53, 0.55, 0.58, or 0.60, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0133] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, satisfies: 0.26≤Na2O / Li2O≤3.00. By ensuring that Na and Li satisfy a specific content relationship, it helps to ensure that the spinel glass-ceramic obtains the desired surface stress level and deep stress level after chemical strengthening, thereby obtaining the desired stress structure and achieving high mechanical strength and high damage resistance.

[0134] In some embodiments of this application, the value of Na₂O / Li₂O can be 0.26, 0.30, 0.50, 0.80, 1.00, 1.20, 1.50, 1.80, 2.00, 2.20, 2.30, 2.50, 2.80, or 3.00, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0135] By ensuring that the composition of the spinel glass-ceramic of this application satisfies at least one of the above-mentioned relationships ZnO / MgO, Li2O / (Al2O3-(MgO+ZnO)+SiO2), (Al2O3-(MgO+ZnO)) / SiO2, and Na2O / Li2O, it is helpful to further adjust the network structure and crystal phase structure of the spinel glass-ceramic, so that the spinel glass-ceramic forms a specific microstructure that helps to obtain the desired stress level.

[0136] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, also satisfies: 12.00 mol% ≤ ZnO + MgO ≤ 20.00 mol%, preferably 13.00 mol% ≤ ZnO + MgO ≤ 17.30 mol%. By ensuring that the composition contains sufficient amounts of ZnO and MgO, it helps to ensure that a sufficient amount of the main crystalline phase can precipitate in the spinel glass-ceramic, thereby enabling it to form the desired crystalline phase structure.

[0137] In some embodiments of this application, the value of ZnO+MgO can be 12.00 mol%, 13.00 mol%, 13.30 mol%, 13.50 mol%, 13.80 mol%, 14.00 mol%, 14.30 mol%, 14.50 mol%, 14.80 mol%, 15.00 mol%, 15.30 mol%, 15.50 mol%, 15.80 mol%, 16.00 mol%, 16.30 mol%, 16.50 mol%, 16.80 mol%, 17.00 mol%, 17.30 mol%, 18.00 mol%, 19.00 mol%, or 20.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0138] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, also satisfies: 9.00 mol % ≤ Al2O3-(MgO+ZnO) ≤ 22.00 mol%, preferably 10.00 mol % ≤ Al2O3-(MgO+ZnO) ≤ 20.00 mol%. By making the content of Al2O3 in the composition higher than that of MgO and ZnO, while ensuring the formation of the main crystalline phase, an appropriate amount of Al can be present in the residual glass phase. On the one hand, this helps to exert the synergistic effect of Si and Al, enabling the residual glass phase to form a specific network structure, thereby improving the intrinsic strength of the spinel glass-ceramic. On the other hand, it helps to promote ion exchange and improve the chemical strengthening effect of the spinel glass-ceramic.

[0139] In some embodiments of this application, the value of Al2O3-(MgO+ZnO) can be 9.00 mol%, 10.00 mol%, 11.00 mol%, 12.00 mol%, 13.00 mol%, 14.00 mol%, 15.00 mol%, 16.00 mol%, 17.00 mol%, 18.00 mol%, 19.00 mol%, 20.00 mol%, 21.00 mol%, or 22.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0140] In some embodiments of this application, the composition of the substrate glass or spinel glass-ceramic, based on the molar percentage of each oxide in the composition, further satisfies: 5.00 mol% ≤ Na₂O + Li₂O ≤ 15.00 mol%, preferably 6.00 mol% ≤ Na₂O + Li₂O ≤ 13.50 mol%. By ensuring sufficient amounts of Na and Li in the composition, the ion exchange performance of the spinel glass-ceramic is improved, thereby ensuring that the spinel glass-ceramic, after chemical strengthening, achieves the desired surface stress level and deep stress level, thus obtaining the desired stress structure and realizing the high mechanical strength and high damage resistance of the strengthened spinel glass-ceramic.

[0141] In some embodiments of this application, the value of Na₂O + Li₂O can be 5.00 mol%, 5.50 mol%, 6.00 mol%, 6.50 mol%, 7.00 mol%, 7.50 mol%, 8.00 mol%, 8.50 mol%, 9.00 mol%, 9.50 mol%, 10.00 mol%, 10.50 mol%, 11.00 mol%, 11.50 mol%, 12.00 mol%, 12.50 mol%, 13.00 mol%, 13.50 mol%, 14.00 mol%, 14.50 mol%, or 15.00 mol%, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0142] By ensuring that the spinel glass-ceramic of this application satisfies at least one of the above-mentioned relationships ZnO+MgO, Al2O3-(MgO+ZnO), and Na2O+Li2O, it is helpful to obtain a high content of (Zn,Mg)Al2O4 crystal phase with high hardness and high modulus, so as to further improve the intrinsic strength or inherent strength of the spinel glass-ceramic, or to further improve the ion exchange effect of the spinel glass-ceramic to obtain the desired stress level.

[0143] In this application, each substance in the above-mentioned relationships ZnO / MgO, Li2O / (Al2O3-(MgO+ZnO)+SiO2), (Al2O3-(MgO+ZnO)) / SiO2, Na2O / Li2O, ZnO+MgO, Al2O3-(MgO+ZnO), and Na2O+Li2O represents the molar percentage content of the corresponding substance. For example, ZnO represents the molar percentage content of ZnO, MgO represents the molar percentage content of MgO, etc., which will not be elaborated further in this application.

[0144] In some embodiments of this application, the spinel glass-ceramic is transparent in the visible light range. In this application, the visible light range refers to light in the wavelength range of 360nm to 740nm; "transparent in the visible light range" means that the average transmittance of visible light is greater than 80%.

[0145] In some embodiments of this application, the transmittance of a 0.7 mm thick spinel glass-ceramic under 550 nm wavelength light is greater than or equal to 85%. The fact that the transmittance of the 0.7 mm thick spinel glass-ceramic under 550 nm wavelength light falls within this range indicates that the spinel glass-ceramic of this application has high light transmittance. Furthermore, the spinel glass-ceramic of this application can also achieve high mechanical strength and high damage resistance through chemical strengthening treatment, exhibiting excellent drop impact resistance, effectively broadening the application scenarios and fields of the spinel glass-ceramic of this application. In some embodiments of this application, the transmittance T can be 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, or a value within a range defined by any two of the above values ​​as endpoints.

[0146] By enabling spinel glass-ceramics to achieve specific crystal phase structures, it is beneficial to achieve both high intrinsic strength and improved chemical strengthening effects. This allows for the attainment of ultra-high compressive stress layer depth and greater deep stress through chemical strengthening, thereby enhancing the mechanical strength and damage resistance of spinel glass-ceramics. Furthermore, the relevant characteristics of X-ray diffraction patterns can reflect the crystal phase structure of the glass-ceramic, including crystal phase composition and crystal size.

[0147] In some embodiments of this application, in the X-ray diffraction pattern of the spinel glass-ceramic, the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 28° to 32° is selected as the first characteristic peak, and the peak with the maximum peak intensity among the characteristic peaks with a 2θ angle in the range of 36° to 38° is selected as the second characteristic peak. The peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50, preferably 0.85 to 1.30. A peak intensity ratio X within the above range indicates that the spinel glass-ceramic has achieved suitable crystal integrity, thereby helping to ensure that the spinel glass-ceramic obtains better optical and strengthening effects. In some embodiments of this application, the peak intensity ratio X can be 0.80, 0.90, 1.00, 1.10, 1.20, 1.30, 1.40, or 1.50, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific implementations, any of the above ranges can be combined with any other ranges, as long as the spinel glass-ceramic with the desired performance of this application can be obtained.

[0148] In some embodiments of this application, in the X-ray diffraction pattern of the spinel glass-ceramic, the characteristic peak of the

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

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

[440] crystal plane of the (Zn,Mg)Al2O4 phase is located in the range of 64° to 67° at a 2θ angle; the full width at half maximum (FWHM) of the

[400] crystal plane characteristic peak is W

[400] The angle is 0.650° to 1.800°, with W being preferred.

[400] The full width at half maximum (WW) of the characteristic peaks of the crystal plane ranges from 0.900° to 1.600°;

[311]

[311] The angle is 0.900° to 2.800°, with W being preferred.

[311] The full width at half maximum (WW) of the characteristic peaks of the crystal plane ranges from 1.100° to 2.230°;

[440]

[440] The angle is 0.750° to 2.000°, with W being preferred.

[440] The W value ranges from 0.900° to 1.600°. (This refers to the W value of spinel glass-ceramics.)

[400] W

[311] W

[440] Within the aforementioned range, it is indicated that the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic has a suitable average crystal size, satisfying a specific crystal phase structure. This not only contributes to imparting high intrinsic strength or inherent strength to the spinel glass-ceramic but also helps ensure that the spinel glass-ceramic achieves an ideal stress structure through chemical strengthening. Simultaneously, it helps the spinel glass-ceramic obtain the desired optical properties.

[0149] In some embodiments of this application, W

[400] The value can be 0.650°, 0.700°, 0.800°, 0.900°, 1.000°, 1.100°, 1.200°, 1.300°, 1.400°, 1.500°, 1.600°, 1.700°, or 1.800°, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0150] In some embodiments of this application, W

[311] The value can be 0.900°, 1.000°, 1.100°, 1.200°, 1.300°, 1.400°, 1.500°, 1.600°, 1.700°, 1.800°, 1.900°, 2.000°, 2.100°, 2.200°, 2.2300°, 2.300°, 2.400°, 2.500°, 2.600°, 2.700°, or 2.800°, or a value within a range defined by any two of the above values ​​as endpoints. It should be understood that, in specific embodiments, any of the above ranges can be combined with any other range, as long as the spinel glass-ceramic with the desired properties of this application is obtained.

[0151] In some embodiments of this application, W

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

[0152] This application does not impose any particular limitation on the thickness t of the spinel glass ceramic, as long as the purpose of this application can be achieved. For example, the thickness t of the spinel glass ceramic satisfies: 0.2mm≤t≤5.0mm, preferably 0.2mm≤t≤2.0mm.

[0153] In this application, the spinel glass-ceramic or the strengthened spinel glass-ceramic prepared therefrom can be 2D, 2.5D, 3D, or irregularly shaped glass articles. In this application, the spinel glass-ceramic or the strengthened spinel glass-ceramic prepared therefrom can be glass articles of equal or unequal thickness.

[0154] In some embodiments of this application, the spinel glass ceramic in any of the foregoing embodiments can be chemically strengthened to obtain a strengthened spinel glass ceramic with high mechanical strength and high damage resistance. The strengthened spinel glass ceramic includes a compressive stress layer region extending from the surface of the strengthened spinel glass ceramic to the compression depth, and has a tensile stress layer region inside.

[0155] It should be understood that after chemical strengthening treatment and ion exchange, the surface composition of a glass-ceramic article may differ from that of the glass-ceramic before the ion exchange process. This is because, during ion exchange, the newly formed glass-ceramic (e.g., the spinel glass-ceramic in this application) contains a certain type of alkali metal ion (e.g., Li) at its surface. + Or Na + They will be respectively affected by larger alkali metal ions (e.g., Na+). + or K + The glass composition and phase composition at or near the center of the depth of the glass-ceramic article are replaced by the glass composition of the newly formed glass-ceramic. That is, in this application, the composition and phase composition at the center of the chemically strengthened spinel glass-ceramic are the same as those of the spinel glass-ceramic in this application.

[0156] Meanwhile, in the spinel glass-ceramic of this application, neither the main crystalline phase (Zn, Mg)Al2O4 nor the secondary crystalline phase tetragonal ZrO2 contains alkali metal ions, and therefore does not participate in the ion exchange during the chemical strengthening process. Based on this, the crystal phase structure of the strengthened spinel glass-ceramic obtained through chemical strengthening in this application is essentially the same as that of spinel glass-ceramic. That is, the homogeneous phase structure characteristics, such as the crystal phase content, crystal composition, crystal size, and X-ray diffraction pattern characteristics, of the strengthened spinel glass-ceramic obtained through the chemical strengthening process in this application are essentially the same as those of the spinel glass-ceramic in this application. Figure 9 As shown, in Example 1, the XRD patterns of the spinel glass-ceramic before chemical strengthening and the chemically strengthened spinel glass-ceramic are basically the same. Additionally, as... Figure 10 As shown in this application, the transmittance of spinel glass ceramics before and after chemical strengthening is basically the same as that of strengthened spinel glass ceramics. In other words, in this application, by using spinel glass ceramics with high transmittance, chemical strengthening treatment can be used to obtain strengthened spinel glass ceramic products with the same excellent transmittance.

[0157] In some embodiments of this application, the compressive stress layer depth DOL_0 of the aforementioned reinforced spinel glass-ceramic is ≥0.21t, preferably 0.21t ≤ DOL_0 ≤ 0.25t, where t is the thickness of the reinforced spinel glass-ceramic. For example, when the thickness t of the reinforced glass-ceramic is 0.7 mm, 147 μm ≤ DOL_0 ≤ 175 μm. Specifically, DOL_0 can be 147 μm, 154 μm, 161 μm, 168 μm, or 175 μm, or a value within a range defined by any two of the above values ​​as endpoints. The presence of the aforementioned DOL_0 in the reinforced spinel glass-ceramic indicates that it possesses an extremely high compressive stress layer depth, thereby more effectively counteracting the energy driving crack propagation during external impact processes.

[0158] In some embodiments of this application, the CS_50 of the aforementioned reinforced spinel glass-ceramic is ≥100MPa, preferably 100MPa≤CS_50≤250MPa. The fact that the CS_50 of the reinforced spinel glass-ceramic falls within this range indicates high compressive stress at a depth of 50μm from the surface, thus demonstrating a high surface stress level and effectively improving its drop impact resistance.

[0159] In some embodiments of this application, the aforementioned reinforced spinel glass-ceramic has a |CT_AV| ≥ 70 MPa, preferably 70 MPa ≤ |CT_AV| ≤ 110 MPa. The presence of the aforementioned |CT_AV| in the reinforced spinel glass-ceramic indicates that the spinel glass-ceramic possesses significant deep stress, directly reflecting a high surface stress level, which is beneficial for offsetting more external impact energy.

[0160] In some embodiments of this application, the |CT_CV| of the aforementioned reinforced spinel glass-ceramic is ≥80 MPa, preferably 80 MPa ≤ |CT_CV| ≤ 150 MPa. A |CT_CV| within this range indicates that the reinforced spinel glass-ceramic possesses significant deep-seated stress and also reflects a high level of surface stress, thus helping to offset more external impact energy.

[0161] In some embodiments of this application, the Vickers hardness of the above-mentioned reinforced spinel glass-ceramic is greater than or equal to 790 kgf / mm². 2 The preferred value is 790 kgf / mm 2 Up to 1000 kgf / mm 2 The Vickers hardness of reinforced spinel glass-ceramics falls within the above range, indicating that reinforced spinel glass-ceramics possess high hardness, thereby ensuring their excellent mechanical properties.

[0162] In some embodiments of this application, the fracture toughness of the above-mentioned reinforced spinel glass-ceramic is greater than or equal to 1.00 MPa·m. 1 / 2 Preferably, it is greater than or equal to 1.20 MPa·m 1 / 2 In some embodiments, the fracture toughness of the above-mentioned reinforced spinel glass-ceramic can be 1.00~2.00 MPa·m. 1 / 2 1.20 MPa·m 1 / 2 ~2.00MPa·m 1 / 2 Or 1.55 MPa·m 1 / 2 ~2.00MPa·m 1 / 2 The fracture toughness of reinforced spinel glass-ceramics falls within the above range, indicating that reinforced spinel glass-ceramics possess high fracture toughness, thereby ensuring their excellent mechanical properties.

[0163] In some embodiments of this application, the 0.7mm thick reinforced spinel glass-ceramic is subjected to a drop test using 80-grit sandpaper. The average drop height resisted by the reinforced spinel glass-ceramic is greater than or equal to 1.00m, preferably greater than or equal to 1.40m. In some embodiments, the 0.7mm thick reinforced spinel glass-ceramic is subjected to a drop test using 80-grit sandpaper. The average drop height resisted by the reinforced spinel glass-ceramic can be 1.00m~2.50m, 1.40m~2.50m, or 1.50mm~2.50m. The fact that the average drop height H of the 0.7mm thick reinforced spinel glass-ceramic is within the above range indicates that the reinforced spinel glass-ceramic has high damage resistance, especially excellent drop impact resistance.

[0164] In some embodiments of this application, a 0.7mm thick reinforced spinel glass-ceramic is extruded using a 10mm diameter round-headed metal pressure bar. The static compressive strength that the reinforced spinel glass-ceramic can withstand from a single bar is tested. The static compressive strength that the reinforced spinel glass-ceramic can withstand from a single bar is greater than 500N, preferably greater than 550N. This indicates that the reinforced spinel glass-ceramic has good extrusion resistance and good compressive strength.

[0165] The spinel glass-ceramic in any of the foregoing embodiments of this application may be prepared by methods including but not limited to the following steps:

[0166] (1) Preparation of substrate glass: The substrate glass or spinel glass ceramic is prepared according to the composition of the substrate glass or spinel glass ceramic in any of the above embodiments, expressed as the molar percentage of oxides. After being mixed evenly, it is prepared by conventional methods known in the art for preparing substrate glass. The substrate glass preparation methods here include, but are not limited to, float glass, overflow glass, rolling glass, casting glass, continuous melting glass and other methods. This application does not limit the parameters in the preparation process, as long as the substrate glass with the required performance of this application can be obtained.

[0167] (2) Preparation of spinel glass-ceramics: The substrate glass obtained in step (1) is subjected to heat treatment, which includes, but is not limited to, one-step heat treatment or multi-step heat treatment, to obtain the spinel glass-ceramics in any of the foregoing embodiments of this application. This application does not limit the various parameters in the preparation process, as long as the spinel glass-ceramics with the properties required by this application can be obtained.

[0168] In some embodiments of this application, the preparation method of the substrate glass in step (1) above may include, but is not limited to, the following steps: preparing the substrate glass or spinel glass ceramic according to the composition of any of the aforementioned embodiments, mixing them evenly, melting, molding, cooling, and annealing to obtain the substrate glass. This application does not impose any particular restrictions on the melting temperature and time, as long as all components are sufficiently melted. Preferably, the melting temperature is 1550℃~1800℃, and the melting time is 3h~12h. This application does not limit the molding method, as long as the purpose of this application is achieved; for example, it can be cast into a molding mold to form a glass brick. This application does not limit the cooling temperature, as long as the purpose of this application is achieved. Preferably, the cooling temperature is 800℃~1000℃. This application does not limit the annealing temperature and time, as long as the purpose of this application is achieved. Preferably, the annealing temperature is 500℃~700℃, and the time is 20h~26h.

[0169] In some embodiments of this application, the heat treatment in step (2) above includes nucleation treatment and crystallization treatment. Preferably, the temperature T1 of the nucleation treatment is 600℃~850℃, more preferably T1 is 650℃~850℃. In some embodiments, the temperature T1 of the nucleation treatment can 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 any two of the above values ​​as endpoints. Preferably, the nucleation treatment time t1 is 0h~72h, more preferably t1 is 0h~24h, and even more preferably t1 is 0h~8h. In some embodiments, the nucleation treatment time t1 can 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 defined by any two of the above values ​​as endpoints. Preferably, the crystallization treatment temperature T2 is 700℃~1000℃. In some embodiments, the crystallization treatment temperature T2 can 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 defined by any two of the above values ​​as endpoints. Preferably, the crystallization treatment time t2 is 10 min to 400 min, and more preferably 10 min to 120 min. In some embodiments, the crystallization treatment time t2 can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 150 min, 170 min, 200 min, 220 min, 250 min, 280 min, 300 min, 320 min, 350 min, 370 min, or 400 min, or a value within a range of values ​​defined by any two of the above values ​​as endpoints.

[0170] In this application, when heat-treating a substrate glass to prepare spinel glass-ceramics, the heat treatment can be performed in one step, or in two or more steps. A single-step heat treatment means that nucleation is not performed separately; the temperature is directly increased in one step, and nucleation and target crystal growth occur at the temperature reached in that single step, which can be understood as direct crystallization. A two-step heat treatment means that two heating processes are performed: first nucleation (nucleation treatment), and then target crystal growth (crystallization treatment). If multiple steps are performed, the nucleation and / or crystallization stages employ a stepped heating method; that is, the entire heat treatment process involves multiple (more than two) heating stages.

[0171] In this application, the nucleation process involves heating to a predetermined nucleation temperature (also known as the nucleation temperature) and holding the temperature for a certain period of time after reaching the nucleation temperature; the holding time is the nucleation time. The crystallization process involves heating to a predetermined crystallization temperature (also known as the crystallization temperature) and holding the temperature for a certain period of time after reaching the crystallization temperature; the holding time is the crystallization time.

[0172] In some embodiments of this application, during step (2) of the heat treatment, the heating rate is preferably controlled to be 5 K / min to 15 K / min, more preferably 5 K / min to 10 K / min. In some embodiments, the heating rate can be 5 K / min, 6 K / min, 7 K / min, 8 K / min, 9 K / min, 10 K / min, 11 K / min, 12 K / min, 13 K / min, 14 K / min, or 15 K / min, or a value within a range of any two of the above values ​​as endpoints.

[0173] In some embodiments of this application, the spinel glass ceramic obtained in step (2) above can be chemically strengthened to obtain the strengthened spinel glass ceramic in any of the above embodiments.

[0174] In some embodiments of this application, the salt bath used for chemical strengthening treatment of spinel glass ceramics is a molten salt containing potassium salt and / or sodium salt. The potassium salt includes one or more of potassium nitrate, potassium sulfate, and potassium carbonate, preferably potassium nitrate; the sodium salt includes at least one of sodium nitrate, sodium sulfate, and sodium carbonate, preferably sodium nitrate. Preferably, the temperature T3 of the salt bath for chemical strengthening treatment is 380℃~600℃, more preferably 400℃~550℃, and even more preferably 400℃~500℃. In some embodiments, the temperature T3 of the salt bath for chemical strengthening treatment can be 380℃, 400℃, 425℃, 450℃, 475℃, 500℃, 525℃, 550℃, 575℃, or 600℃, or a value within a range defined by any two of the above values. Preferably, the chemical strengthening treatment time t3 is 1h~48h, more preferably 2h~24h, and even more preferably 2h~15h. In some embodiments, the chemical strengthening treatment time t3 can be 1h, 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, or 48h, or a value within a range defined by any two of the above values. In some embodiments of this application, a certain amount (e.g., 0wt%~0.5wt%) of lithium salt can be added to the salt bath. By employing the above-described chemical strengthening treatment process, spinel glass-ceramics with specific compositions and structures can be strengthened to obtain strengthened spinel glass-ceramics with excellent surface stress characteristics and excellent deep stress characteristics, thereby ensuring that the obtained strengthened spinel glass-ceramics have high mechanical strength and excellent damage resistance.

[0175] It should be understood that chemical enhancement treatment can be performed in one step, or in two or more steps. In this application, the temperature of the chemical enhancement treatment is the temperature of the salt bath; when the chemical enhancement treatment includes two or more steps, the time of the chemical enhancement treatment is the sum of the times of each chemical enhancement treatment step. In some embodiments of this application, when the chemical enhancement treatment includes two or more steps, the temperature and time of each chemical enhancement treatment step may be the same or different.

[0176] In this application, the spinel glass-ceramic in any of the foregoing embodiments can be used to manufacture glass devices with high strength. These glass devices may include, but are not limited to, workbenches, other surfaces, appliance doors, floor tiles, wall panels, storage containers, mobile phone screens, mobile phone back panels, electronic device frames, vehicle windshields, aircraft windshields, or spacecraft windshields, etc. The spinel glass-ceramic provided in this application, after chemical strengthening treatment, can achieve a high stress level, thereby obtaining high mechanical strength and high damage resistance, especially excellent drop impact resistance. Glass devices prepared using the spinel glass-ceramic of this application after chemical strengthening can also be guaranteed to have excellent mechanical properties.

[0177] In this application, the spinel glass-ceramic in any of the foregoing embodiments can be used in electronic devices.

[0178] In some embodiments of this application, the electronic device includes at least one of a mobile phone, tablet computer, smart wearable device, display, and television. For example, the electronic device may include, but is not limited to, a mobile phone, tablet computer, smart wearable device, display, or television. Smart wearable devices may include, but are not limited to, electronic watches, smart bracelets, smart glasses, etc., and displays may include, but are not limited to, high-definition displays, automotive displays, and aerial displays. Exemplarily, the electronic device may include a housing and electronic components partially located within the housing. The housing includes a front surface, a rear surface, and a side surface. The electronic components include a display device located on or adjacent to the front surface of the housing. The spinel glass-ceramic provided in this application, after chemical strengthening, can be applied to the front surface and / or the rear surface and / or the side surface of the housing. In some embodiments, the front surface and / or the rear surface of the housing may be of equal or unequal thickness. In some embodiments, the front surface and / or the rear surface of the housing may be 2D, 2.5D, 3D, or irregularly shaped.

[0179] Test method:

[0180] 1. X-ray diffraction (XRD) test

[0181] The sample to be tested was pulverized and ground into particles with a diameter of less than 75 μm. The ground sample was then analyzed using an X-ray diffractometer to obtain XRD diffraction peak curves and XRD diffraction data. The JADE Standard 8.6 software was then used to analyze the XRD diffraction data to determine the crystal phase of the sample. The X-ray diffractometer used was a Shimadzu XRD-6100, with an incident angle range of 2θ = 10° to 80°, a scanning speed of 6° / min, an operating voltage of 40 kV, and an operating current of 30 mA. The sample to be tested was a chemically strengthened glass-ceramic or a strengthened glass-ceramic.

[0182] Average crystal size: Using the XRD test results, the average crystal size of the sample can be calculated according to the Scherrer formula D=Kλ / (βcosθ). Here, λ is the X-ray wavelength (λ=0.154056nm), β is the full width at half maximum (FWHM) of the diffraction peak (K=0.89), and θ is the Bragg diffraction angle. Specifically, the RAW file (diffraction pattern) output from the XRD instrument is curve-fitted in JADEStandard 8.6 software. Jade outputs a fitting report. Based on the angle 2θ and Peak FWHM value corresponding to each diffraction peak in the fitting report, and converting the Peak FWHM value to radians: β=(FWHM / 180×3.14), the crystal size of each diffraction peak is calculated using the Scherrer formula D=Kλ / (βcosθ), and then averaged to obtain the average crystal size.

[0183] The average crystal size of the (Zn,Mg)Al2O4 phase was determined by performing phase retrieval and curve fitting on the RAW file (diffraction pattern) output from the XRD instrument using JADE Standard 8.6 software. In the fitting report, the 2θ angle and Peak FWHM value corresponding to three diffraction peaks in the (Zn,Mg)Al2O4 phase within the ranges of 34°–38°, 44°–46°, and 64°–67° were selected. The Peak FWHM value was then converted to radians: β = (FWHM / 180 × 3.14). The crystal size of the three diffraction peaks was calculated using the Scherrer formula D = Kλ / (βcosθ) and then averaged to obtain the average crystal size of the (Zn,Mg)Al2O4 phase. Here, λ is the X-ray wavelength (λ = 0.154056 nm), β is the full width at half maximum (FWHM) of the diffraction peak (K = 0.89), and θ is the Bragg diffraction angle.

[0184] Crystal phase content: The XRD test results (RAW format) are imported into JADE Standard 8.6 software for fitting and calculation to obtain the content of each crystal phase in the glass-ceramic, and then the total content of each crystal phase in the glass-ceramic can be calculated. The ratio of the fitted crystal phase peak area to the fitted total peak area is the crystal phase content of the corresponding crystal phase. The ratio of the fitted (Zn,Mg)Al2O4 crystal phase peak area to the fitted total peak area is the crystal phase content W of the (Zn,Mg)Al2O4 crystal phase. [(Zn，Mg)Al2O4] The ratio of the area of ​​the fitted tetragonal ZrO2 crystal phase peak to the area of ​​all fitted peaks is the crystal phase content W of the tetragonal ZrO2 crystal phase. [ZrO2] According to W [(Zn，Mg)Al2O4] and W [ZrO2] The ratio (mass ratio Z) of (Zn,Mg)Al2O4 crystal phase and tetragonal ZrO2 crystal phase and the total crystal phase content W were calculated.

[0185] Peak intensity ratio: Import the XRD test results (RAW format) into JADE Standard 8.6 software, use the peak finding function to determine the 2θ position of the peak and its corresponding original intensity, and calculate the peak intensity ratio. Specifically, it is the peak intensity ratio X of the first characteristic peak and the second characteristic peak.

[0186] Half-width at half-maximum (HWHM): Import the XRD test results (RAW format) into JADE Standard 8.6 software for phase retrieval and curve fitting. The output fitting report provides the 2θ position of the peak, the corresponding crystal plane, HWHM, and the fitting intensity. Calculate the ratio based on the fitting intensity of the corresponding crystal plane.

[0187] Specifically, the fitting peak intensity I of the characteristic peak of the

[400] crystal plane.

[400]

[311] Fitted peak intensity of crystal plane characteristic peak I

[311] The fitting peak intensity I of the characteristic peaks of the

[440] crystal plane

[440] The full width at half maximum (WW) of the characteristic peaks of the

[400] crystal plane

[400] The full width at half maximum (WW) of the characteristic peaks of the

[311] crystal plane

[311] The full width at half maximum (WW) of the characteristic peaks of the

[440] crystal plane

[440] I

[400] / I

[311] and I

[440] / I

[311] .

[0188] Considering the impact of noise on peak finding during the testing process, the XRD diffraction peak curve can be smoothed no more than three times.

[0189] 2. Testing of |CT_AV|, DOL_0, CS_50, and |CT_CV|

[0190] The test was conducted using an SLP-2000 stress meter with a light source wavelength of 518 nm, SOC = 25.5 (nm / cm) / MPa, refractive index = 1.60, and exposure time of 300 µsec.

[0191] When testing surfaces CS_50, |CT_AV|, DOL_0, and |CT_CV|, a conductive liquid needs to be applied to the stress meter first. Then, the reinforced spinel glass-ceramic sample to be tested should be wiped clean and placed on the test path to measure its stress value. The stress meter used is an SLP-2000, and the conductive liquid used has a refractive index of 1.51.

[0192] 3. Thickness test

[0193] The thickness of spinel glass ceramics was measured using a micrometer.

[0194] It should be understood that during chemical strengthening treatment, the degree of ion exchange in the thickness direction of spinel glass ceramics changes in a gradient from the surface to the center. The increase (mass) of the total Na-K and / or Li-Na exchange amount generally does not exceed 1% of the total mass of the sample. Therefore, the expansion effect in the thickness direction is extremely slight. That is, the thickness change of spinel glass ceramics before and after chemical strengthening is very small and can be approximated as having no change at all.

[0195] 4. Optical performance testing

[0196] The sample to be tested was cleaned in an ultrasonic cleaner under the following conditions: cleaning time: 10 min; cleaning agent: detergent diluted 10 times; cleaning temperature: 55±10℃; cleaning frequency: 30±10 kHz. The transmittance of the sample at different wavelengths was then measured using a haze meter, referring to the standard GB / T 7962.12-2010 "Test Methods for Colorless Optical Glass Part 12: Spectral Internal Transmittance". The haze meter used in this patent is a Konica Minolta CM-3600A spectrophotometer. The sample to be tested was chemically strengthened glass-ceramic or reinforced glass-ceramic.

[0197] 5. Vickers hardness (HV) test

[0198] Strengthened spinel glass-ceramics with clean surfaces free from visible scratches, dents, and cracks were selected as samples. A digital display VTD405 Vickers hardness tester (Beijing Woway Technology Co., Ltd.) was used to test the Vickers hardness of the glass-ceramics according to the national standard GB / T37900-2019 "Test Methods for Hardness and Fracture Toughness of Ultrathin Glass - Small Load Vickers Indentation Method". The load was 300 gf, and the loading time was 10 s. The validity of the indentation conformed to the national standard GB / T 16534-2009 "Test Method for Room Temperature Hardness of Fine Ceramics". In this application, a glass-ceramic sample with dimensions of 50 mm × 50 mm × 0.7 mm was used for the Vickers hardness test. Measurements were taken at three different locations on the same sample surface, and the average value was selected as the final test result.

[0199] 6. Test of surface K2O concentration

[0200] In this application, the surface K₂O concentration of the reinforced spinel glass-ceramic was measured using X-ray fluorescence spectrometry (XRF). The instrument used was a Thermo Scientific ARL PERFORM'X, with a target material of Rh (rhodium), a tube voltage of 40 kW, a current of 60 mA, a collimator of 0.15, a LiF₂O₀ crystal, an FPC detector, a 29 mm circle for the test, UniQuant standard-free analysis software, and the X_UQ method in the OXSAS analysis software. Specifically, the K content on the surface of the reinforced glass-ceramic was measured by XRF, and then the surface K₂O concentration was calculated as follows: Surface K₂O concentration = (Surface K content × Relative molecular mass of K₂O) / (Relative atomic mass of K × 2). It should be understood that the surface K content = K mass / Total mass of elements, and the total mass of elements = Total mass of oxides.

[0201] The K₂O concentration on the surface of reinforced spinel glass-ceramics is calculated as: K₂O mass / total oxide mass. This oxide includes SiO₂, Al₂O₃, ZrO₂, Na₂O, and K₂O, which can be accurately measured by XRF, but excludes oxides such as B₂O₃, which cannot be accurately measured by XRF. XRF testing uses a standard-free method and does not measure the concentration of elements with atomic numbers 6 and below, or their oxides, in the reinforced spinel glass-ceramics. In other words, the total oxide mass measured by XRF when testing the K₂O concentration on the surface of reinforced spinel glass-ceramics does not include the mass of elements with atomic numbers 6 and below, or their oxides, in the reinforced spinel glass-ceramics.

[0202] 7. Average sandpaper drop resistance test

[0203] The average sandpaper drop resistance height refers to the sum of the sandpaper drop resistance heights measured for each sample in multiple reinforced spinel glass-ceramic samples from the same embodiment or comparative example, divided by the number of reinforced spinel glass-ceramic samples. This ratio characterizes the drop damage resistance performance of reinforced spinel glass-ceramic. Ten identical reinforced spinel glass-ceramic samples from each batch were tested, and the average sandpaper drop resistance height was: ;

[0204] Where n is the number of reinforced spinel glass-ceramic samples tested in each batch, and hi is the sandpaper drop height resistance of a single sample test.

[0205] The test method for the drop height resistance of a single sample against sandpaper is as follows:

[0206] Step 1: Attach 80-grit sandpaper to the lower surface of the 160g model machine and place the model machine on the Green Map LT-SKDL-CD drop tester;

[0207] Step 2: Place the reinforced spinel glass-ceramic sample (50mm x 50mm x 0.7mm) directly beneath the model machine, with the sample facing the sandpaper. Drop the model machine from a certain height onto the sample. If the sample does not break, increase the drop height in a predictable pattern. For example, start with a drop height of 0.4m, and if the sample does not break, increase the height by 0.1m each time until the sample breaks.

[0208] Step 3: Record the height of the last drop when the reinforced spinel glass-ceramic sample breaks as the sandpaper drop height. For example, if the drop height when it breaks is 0.5m, then the sandpaper drop height of the sample is 0.4m.

[0209] 8. Density

[0210] This application uses an ALFA MIRAGE SD-200L electronic density balance from Japan to test the density of reinforced spinel. The testing principle is "Archimedes' displacement method".

[0211] 9. Fracture toughness test

[0212] The test was conducted according to the national standard GB / T 37900-2019, "Test Methods for Hardness and Fracture Toughness of Ultrathin Glass - Small Load Vickers Hardness Indentation Method". Specifically, an indentation was prepared using the same method as for measuring Vickers hardness. The crack lengths 2C1 and 2C2 in the diagonal direction of the indentation were measured, and their maximum values ​​could not exceed the thickness of the reinforced spinel glass-ceramic. At least five effective indentation morphologies were measured on the surface of one specimen, and their average value was calculated as the final result value for that specimen.

[0213] Formula for calculating indentation fracture toughness: IFR =

[0214] Wherein, IFR: indentation fracture toughness, the unit is 1 / 2 quadrillion MPa·m 1 / 2) E: Elastic modulus of the specimen, in gigapascals (GPa); 2C1, 2C2: Crack propagation length in the diagonal direction of the indentation, in millimeters (mm); d1, d2: Diagonal length of the indentation, in millimeters (mm); F: Test load value, in newtons (N).

[0215] In the above testing method, after the reinforced spinel glass-ceramic bricks in the examples and comparative examples are shaped, cut and polished, reinforced spinel glass-ceramic samples of the desired size (e.g., polished sheets) can be obtained, and then tested, for example, glass-ceramic polished sheets with a length, width and thickness of 50mm×50mm×0.7mm.

[0216] 10. Single rod static pressure strength test

[0217] like Figure 12 As shown, a circular glass-ceramic sample 10 with a diameter of 46 mm and a thickness of 0.7 mm is placed in a custom fixture 20 (e.g., Figure 13 and Figure 14 Place the sample in the sample slot 21 (as shown), then place it on the bottom ring (not shown) of the tensile testing machine (LT-850A), start the test software, and set the moving speed of the extrusion rod 30 (rod diameter 10mm, ball head diameter 10mm) to 10mm / min. Click Start Test, and the extrusion rod 30 will apply force to the center of the glass-ceramic sample 10 to be tested at the set moving speed until the glass-ceramic sample 10 to be tested breaks.

[0218] The testing software will automatically read the force (N) when the glass-ceramic sample breaks and record it as the test result. Ten glass-ceramic samples in the same state are tested, and the average value of the test results is recorded as the single-bar static compressive strength that the glass-ceramic sample under test can withstand.

[0219] The custom-made fixture used in this test method is a cylindrical fixture with a diameter of 65mm and a height of 20mm. The specific structure of this custom-made fixture is as follows: Figure 13 and Figure 14 Wherein, Φ1=65mm, Φ2=46.02mm, Φ3=44mm, h1=20mm, h2=thickness of the reinforced glass-ceramic sample to be tested, and h3=15mm. The height of the sample placement groove 21 inside the fixture is equal to the thickness of the reinforced glass-ceramic sample to be tested, allowing the sample to fit perfectly into the fixture. The stepped blind hole for placing the sample for testing within the custom fixture is coaxial with the fixture. The fixture is made of acrylic material.

[0220] Example 1

[0221] <Preparation of Substrate Glass>

[0222] According to Formula 1 in Table 1, the raw material formula for glass production was designed and prepared. The total mass of the raw materials was 1000g. Then, the mixture was mixed in a V-type mixer for 30 minutes. After mixing, 5g of clarifying agent NaCl was added. The mixture was then transferred to a platinum crucible and melted in a 1650℃ lifting furnace (lifting furnace model: SJF1750, manufacturer: Nanjing Boyuntong Instrument Technology Co., Ltd.) for 5 hours. The mixture was then poured into a stainless steel mold preheated to 300℃ and cooled. After cooling to 900℃, it was placed in a 600℃ annealing furnace for 24 hours and then cooled to room temperature with the furnace to obtain spinel glass ceramic, which is the substrate glass.

[0223] <Preparation of Spinel Glass Ceramics>

[0224] The substrate glass prepared above was heat-treated in a resistance furnace (equipment model: SLX1400-40, manufacturer: Shanghai Shengli Test Instrument Co., Ltd.) to obtain spinel glass ceramic.

[0225] Specifically, a two-step heat treatment process is employed: first, the temperature is raised to the nucleation temperature for nucleation, and then the temperature is raised to the crystallization temperature for crystallization. The heating rate during both nucleation and crystallization processes is 10 K / min. The nucleation temperature T1 is 740℃, and the nucleation time t1 is 480 min; the crystallization temperature T2 is 800℃, and the crystallization time t2 is 10 min.

[0226] As needed, the spinel glass-ceramic is sequentially cut, CNC machined (using a computer numerical control machine tool, specifically an RCG500S), and polished to obtain smooth spinel glass-ceramic sheets of the required specifications. In this application, the processed spinel glass-ceramic sheets are available in two sizes: 50mm x 50mm x 0.7mm (length x width x thickness) and a circular sample with a diameter of 46mm and a thickness of 0.7mm.

[0227] <Preparation of Strengthened Spinel Glass Ceramics>

[0228] The spinel glass-ceramic was subjected to a first-step strengthening treatment in a 100wt% NaNO3 salt bath at 450℃ for 3 hours, followed by a second-step strengthening treatment in a 100wt% KNO3 salt bath at 430℃ for 2 hours, to obtain the strengthened spinel glass-ceramic.

[0229] Examples 2 to 11

[0230] Except for adjusting the relevant preparation parameters according to Table 2, everything else is the same as in Example 1. The corresponding formulations in Table 2 are detailed in Table 1.

[0231] Examples 12-14

[0232] Except for placing the corresponding spinel glass ceramic in a 100wt% NaNO3 salt bath at 450°C for 4 hours as per Table 5 to obtain the corresponding reinforced spinel glass ceramic, the rest is the same as in Example 1.

[0233] Examples 15-17

[0234] Except for placing the corresponding spinel glass ceramic in a 100wt% KNO3 salt bath at 430°C for 4 hours as per Table 6 to obtain the corresponding reinforced spinel glass ceramic, the rest is the same as in Example 1.

[0235] Comparative Examples 1 to 11

[0236] Except for adjusting the relevant preparation parameters according to Table 2, everything else is the same as in Example 1. The corresponding formulations in Table 2 are detailed in Table 1.

[0237] Comparative Examples 12 to 15

[0238] Except for placing the corresponding spinel glass ceramic in a 100wt% NaNO3 salt bath at 450°C for 4 hours as per Table 5 to obtain the corresponding reinforced spinel glass ceramic, the rest is the same as in Example 1.

[0239] Comparative Examples 16 to 19

[0240] Except for placing the corresponding spinel glass ceramic in a 100wt% KNO3 salt bath at 430°C for 4 hours as per Table 6 to obtain the corresponding reinforced spinel glass ceramic, the rest is the same as in Example 1.

[0241] The formulations of each embodiment and comparative example are shown in Table 1, and the preparation parameters and performance tests of each embodiment and comparative example are shown in Tables 2 to 6.

[0242] Table 1

[0243] Note: " / " in Table 1 indicates that the corresponding parameter does not exist; "0.00" for oxide content in the table indicates that the component was not actively or intentionally added to the glass composition during the initial batching process, but the component may exist as an impurity.

[0244] Table 2

[0245] Note: In Table 2, " / " indicates that the corresponding parameter does not exist or the operation was not performed.

[0246] Table 3

[0247] Note: " / " in Table 3 indicates that there is no corresponding parameter; "Total content of crystal phase W" in Table 3 refers to the total content of (Zn,Mg)Al2O4 crystal phase and tetragonal ZrO2 crystal phase.

[0248] Table 4

[0249] Table 5

[0250] Table 6

[0251] Testing revealed that the spinel glass-ceramics of Examples 1-11 and Comparative Examples 1-11 all contained the primary crystalline phase (Zn, Mg)Al₂O₄ and the secondary crystalline phase tetragonal ZrO₂. XRD patterns of some examples and comparative examples are shown below. Figures 2 to 7 , Figure 9 , Figure 11 As shown.

[0252] Referring to Tables 1-4, the composition and structure of the spinel glass-ceramics in Examples 1-11 are all within the scope of the technical solution of this application. However, the composition and structure of the spinel glass-ceramics in Comparative Examples 1-11 do not fully meet the requirements of this application. Chemical strengthening using the spinel glass-ceramics in the examples of this application can achieve stress levels significantly better than the comparative examples. For example, the spinel glass-ceramics of this application can be chemically strengthened to obtain chemically strengthened spinel glass-ceramics with higher compressive stress layer depth and larger CT (compressive stress layer depth). Testing shows that the chemically strengthened spinel glass-ceramics obtained by chemical strengthening of the spinel glass-ceramics of this application have better drop damage resistance, can withstand higher single-bar static compressive strength, better extrusion resistance, higher mechanical strength, and excellent light transmittance. Specifically, as... Figure 8 As shown, the spinel glass-ceramic in Example 1 has a transmittance of over 80.00% for visible light, thus the resulting reinforced spinel glass-ceramic is transparent in the visible light range.

[0253] Examples 1-3 and Comparative Examples 6-9 all obtained spinel glass ceramics by applying different heat treatment regimes to the substrate glass of Formula 1. Their XRD diffraction patterns are as follows: Figure 2 As shown.

[0254] Reference Figure 2 , Figure 5 As shown in Table 3, the XRD pattern of the spinel glass-ceramic of Example 1 contains a first characteristic peak with a 2θ angle in the range of 28° to 32° and a second characteristic peak with a 2θ angle in the range of 36° to 38°, with a peak intensity ratio X of 1.05.

[0255] Reference Figure 2 As shown in Table 3, the XRD pattern of the spinel glass-ceramic in Comparative Example 6 does not contain a second characteristic peak with a 2θ angle in the range of 36°~38°, therefore it lacks a peak intensity ratio X. The (Zn,Mg)Al2O4 crystal phase content in the spinel glass-ceramic of Comparative Example 6 is low, and the calculation result of formula C does not meet the scope of the scheme in this application. Therefore, the stress level of the strengthened spinel glass-ceramic prepared in Comparative Example 6 is low. (Refer to...) Figure 2 As shown in Table 3, the peak intensity ratio X of the XRD pattern of the spinel glass-ceramic in Comparative Example 7 is 1.61. The content of the (Zn,Mg)Al2O4 phase in the spinel glass-ceramic of Comparative Example 7 is also relatively low. The full width at half maximum (FWHM) of some characteristic peaks on the crystal planes does not meet the requirements of this application, and the calculation results of Formula C do not meet the scope of the scheme in this application. The stress level of the strengthened spinel glass-ceramic prepared in Comparative Example 7 is also relatively low. (Refer to...) Figure 2 and Figure 4 In the XRD pattern of the spinel glass-ceramic of Comparative Example 8, peaks appear at the 2θ angle in the range of 28°~32°. The spinel glass-ceramic of Comparative Example 8 has a higher content of the (Zn,Mg)Al2O4 phase, a higher average crystal size of the (Zn,Mg)Al2O4 phase, and the full width at half maximum (FWHM) of the characteristic peaks do not meet the requirements of this application. The calculation results of Formula C also do not meet the scope of the scheme in this application. Therefore, the stress level of the strengthened spinel glass-ceramic prepared in Comparative Example 8 is lower. (Refer to...) Figure 2 In the XRD pattern of the spinel glass-ceramic of Comparative Example 9, the 2θ angle shows a peak in the range of 28° to 32°. In the spinel glass-ceramic of Comparative Example 9, the content of (Zn,Mg)Al2O4 crystal phase is also relatively high, and the average crystal size of (Zn,Mg)Al2O4 crystal phase is also relatively high. The calculation result of Formula C does not meet the scope of the scheme of this application. The stress level of the reinforced spinel glass-ceramic prepared in Comparative Example 9 is also relatively low.

[0256] Figure 3 This is a refined XRD pattern of the spinel glass-ceramic of Example 6 in Jade software. In the figure: "Original XRD Curve" is plotted using the original data obtained from the Shimadzu XRD-6100; "Fitted Curve" is plotted using the fitted data output from the RAW file obtained from the Shimadzu XRD-6100 after curve fitting in Jade software; "Uncertainty Curve" is plotted using the difference between the original XRD data and the fitted data output by Jade software; "Bragg Position of Zirconia" is the peak position of the original XRD data on the zirconia standard card matched in Jade; "Bragg Position of Zinc Magnesium Spinel" is the peak position of the original XRD data on the zinc magnesium spinel standard card matched in Jade.

[0257] Reference Figure 3As shown in Table 3, the XRD pattern of the spinel glass-ceramic in Example 6 contains a first characteristic peak with a 2θ angle in the range of 28° to 32° and a second characteristic peak with a 2θ angle in the range of 36° to 38°, with a peak intensity ratio X of 0.97.

[0258] Comparative Examples 10 and 11 both obtained spinel glass ceramics by applying different heat treatment regimes to the substrate glass of Formula 3. Their XRD diffraction patterns are as follows: Figure 6 and Figure 7 As shown.

[0259] XRD patterns of spinel glass-ceramics in Comparative Example 10, such as Figure 6 As shown, the 2θ angle exhibits a peak within the range of 28° to 32°. In the spinel glass-ceramic of Comparative Example 10, the average crystal size of the (Zn,Mg)Al2O4 phase is higher than expected, and the calculation result of Formula C does not meet the range of the scheme in this application. The stress level of the strengthened spinel glass-ceramic prepared in Comparative Example 10 is lower than expected. The XRD pattern of the spinel glass-ceramic of Comparative Example 11 is shown below. Figure 7 As shown, the 2θ angle shows a tendency to split peaks in the range of 28° to 32°. In the spinel glass-ceramic of Comparative Example 11, the average crystal size of the (Zn,Mg)Al2O4 phase is also relatively high. The half-width of some characteristic peaks of the crystal plane does not meet the requirements of this application. The calculation results of Formula C also do not meet the scope of the scheme of this application. The stress level of the reinforced spinel glass-ceramic prepared in Comparative Example 11 is also relatively low.

[0260] Comparative Examples 12-15 and Examples 12-14 obtained spinel glass ceramics by applying different heat treatment regimes to the substrate glass of Formula 1. The chemically strengthened spinel glass ceramics obtained using the same chemical strengthening treatment conditions showed that the compressive stress layer depth DOL-0 of Comparative Examples 12-15 was significantly lower than that of the embodiments of this application, and their drop damage resistance height measured under 80-grit sandpaper conditions was also significantly lower than that of the technical solution of this application.

[0261] Comparative Examples 16-19 and Examples 15-17 obtained spinel glass ceramics by applying different heat treatment regimes to the substrate glass of Formula 1. The chemically strengthened spinel glass ceramics obtained using the same chemical strengthening treatment conditions showed that the single bar static compressive strength that the chemically strengthened spinel glass ceramics of Comparative Examples 16-19 could withstand was significantly lower than that of the embodiments of this application, and the surface K2O content was also significantly lower than that of the embodiments of this application.

[0262] It should be noted that, in this document, the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0263] The various embodiments in this specification are described in a related manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0264] The above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of protection of this application.

Claims

1. A reinforced spinel glass-ceramic, characterized in that, Based on the molar percentage of oxides, the core composition of the reinforced spinel glass-ceramic includes: SiO2 35.00 mol%~60.00 mol%, Al2O3 20.00 mol%~40.00 mol%, ZrO2 2.00 mol%~8.00 mol%, MgO 3.00 mol%~7.50 mol%, ZnO 7.00 mol%~13.00 mol%, Na2O 1.00 mol%~10.00 mol%, and Li2O 2.50 mol%~10.00 mol%. The reinforced spinel glass-ceramic contains 15.00% to 45.00% by weight of (Zn,Mg)Al2O4 crystalline phase; Take W [(Zn，Mg)Al2O4] W represents the weight percentage of the (Zn,Mg)Al2O4 crystal phase in the strengthened spinel glass-ceramic. [Al2O3] W represents the weight percentage of Al2O3 in the reinforced spinel glass-ceramic. [MgO] W represents the weight percentage of MgO in the strengthened spinel glass-ceramic. [ZnO] The weight percentage of ZnO in the reinforced spinel 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 reinforced spinel glass-ceramic, 1.50≤C≤1.85; and Based on the molar percentage of each oxide in the composition at the center of the reinforced spinel glass-ceramic, the composition at the center of the reinforced spinel glass-ceramic satisfies: 6.82mol%≤Na2O+Li2O≤15.00mol%; 0.26≤Na₂O / Li₂O≤1.20; and 0.069≤Li2O / (Al2O3-(MgO+ZnO)+SiO2)≤0.

20.

2. The reinforced spinel glass-ceramic according to claim 1, characterized in that, In the reinforced spinel glass-ceramic, the value of A is 10.00%~25.00%, preferably 14.00%~25.00%; and / or, the value of B is 7.50%~12.50%, preferably 8.00%~12.00%.

3. The reinforced spinel glass-ceramic according to claim 1 or 2, characterized in that, The reinforced spinel glass-ceramic further comprises a tetragonal ZrO2 crystal phase, wherein the total content of the (Zn,Mg)Al2O4 crystal phase and the tetragonal ZrO2 crystal phase accounts for 25.00% to 70.00% by weight of the reinforced spinel glass-ceramic, preferably 30.00% to 50.00% by weight; and / or, in the reinforced spinel glass-ceramic, the average crystal size of the (Zn,Mg)Al2O4 crystal phase is 3.0 nm to 10.0 nm, preferably 4.0 nm to 8.0 nm, and more preferably 4.0 nm to 7.5 nm.

4. The reinforced spinel glass-ceramic according to any one of claims 1 to 3, characterized in that, In the reinforced spinel glass-ceramic, the ratio of (Zn,Mg)Al2O4 crystal phase to tetragonal ZrO2 crystal phase is 1.00~18.00, preferably 1.00~15.

00.

5. The reinforced spinel glass-ceramic according to any one of claims 1 to 4, characterized in that, Take W [(Zn，Mg)Al2O4] W represents the weight percentage of the (Zn,Mg)Al2O4 crystal phase in the strengthened spinel glass-ceramic. [Al2O3] The weight percentage of Al2O3 at the center of the reinforced spinel glass-ceramic, W [MgO] W represents the weight percentage of MgO at the center of the reinforced spinel glass-ceramic. [ZnO] The weight percentage of ZnO at the center of the reinforced spinel 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 reinforced spinel glass-ceramic, 1.50≤C≤1.

85.

6. The reinforced spinel glass-ceramic according to any one of claims 1-5, characterized in that, The composition of the core of the reinforced spinel glass-ceramic, based on the molar percentage of oxides, further includes: K2O 0.00mol%~5.00mol%, CaO 0.00mol%~10.00mol%, B2O3 0.00mol%~10.00mol%, and BaO 0.00mol%~5.00mol%.

7. The reinforced spinel glass-ceramic according to any one of claims 1 to 6, characterized in that, Based on the molar percentage of oxides, the core composition of the reinforced spinel glass-ceramic includes: 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%, and Li2O 3.00mol%~10.00mol%.

8. The reinforced spinel glass-ceramic according to any one of claims 1 to 7, characterized in that, Based on the molar percentage of oxides, the core composition of the reinforced spinel glass-ceramic includes: 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%, and Li2O 3.00mol%~10.00mol%.

9. The reinforced spinel glass-ceramic according to any one of claims 1 to 8, characterized in that, Based on the molar percentage of each oxide in the composition at the center of the reinforced spinel glass-ceramic, the composition at the center of the reinforced spinel glass-ceramic satisfies: 1.30≤ZnO / MgO≤2.50; and / or, 0.19≤(Al2O3-(MgO+ZnO)) / SiO2≤0.60; and / or, 0.26≤Na2O / Li2O≤0.

89.

10. The reinforced spinel glass-ceramic according to any one of claims 1 to 9, characterized in that, Based on the molar percentage of each oxide in the composition at the center of the reinforced spinel glass-ceramic, the composition at the center of the reinforced spinel glass-ceramic also satisfies: 12.00 mol% ≤ ZnO + MgO ≤ 20.00 mol%, preferably 13.00 mol% ≤ ZnO + MgO ≤ 17.30 mol%; and / or, 9.00 mol% ≤ Al₂O₃⁻(MgO + ZnO) ≤ 22.00 mol%, preferably 10.00 mol% ≤ Al₂O₃⁻(MgO + ZnO) ≤ 20.00 mol%; and / or, 6.82mol%≤Na2O+Li2O≤13.50mol%.

11. The reinforced spinel glass-ceramic according to any one of claims 1 to 10, characterized in that, The reinforced spinel glass-ceramic is transparent in the visible light range.

12. The reinforced spinel glass-ceramic according to any one of claims 1 to 11, characterized in that, The 0.7 mm thick reinforced spinel glass-ceramic has a transmittance of 85% or more under 550 nm wavelength light.

13. The reinforced spinel glass-ceramic according to any one of claims 1 to 12, characterized in that, In the X-ray diffraction pattern of the reinforced spinel glass-ceramic, the peak with the maximum peak intensity among the characteristic peaks in the range of 2θ angle from 28° to 32° is taken as the first characteristic peak, and the peak with the maximum peak intensity among the characteristic peaks in the range of 2θ angle from 36° to 38° is taken as the second characteristic peak. The peak intensity ratio X of the first characteristic peak and the second characteristic peak is 0.80 to 1.50, preferably 0.85 to 1.

30.

14. The reinforced spinel glass-ceramic according to any one of claims 1 to 13, characterized in that, In the X-ray diffraction pattern of the reinforced spinel glass-ceramic, the characteristic peak of the [400] crystal plane of the (Zn,Mg)Al2O4 phase is located in the range of 44° to 46° at the 2θ angle, the characteristic peak of the [311] crystal plane of the (Zn,Mg)Al2O4 phase is located in the range of 34° to 38° at the 2θ angle, and the characteristic peak of the [440] crystal plane of the (Zn,Mg)Al2O4 phase is located in the range of 64° to 67° at the 2θ angle; The full width at half maximum (W) of the characteristic peak of the [400] crystal plane is [400] The range is 0.650° to 1.800°, with W being the preferred value. [400] The range is from 0.900° to 1.600°. The full width at half maximum (W) of the characteristic peak of the [311] crystal plane is... [311] The range is 0.900° to 2.800°, with W being the preferred value. [311] The range is from 1.100° to 2.230°; The full width at half maximum (W) of the characteristic peak of the [440] crystal plane is [440] The range is 0.750° to 2.000°, with W being the preferred value. [440] The range is from 0.900° to 1.600°.

15. The reinforced spinel glass-ceramic according to any one of claims 1 to 14, characterized in that, The reinforced spinel glass-ceramic includes a compressive stress layer region and a tensile stress layer region; the compressive stress layer depth DOL_0 of the reinforced spinel glass-ceramic is ≥0.21t, preferably 0.21t≤DOL_0≤0.25t, where t is the thickness of the reinforced spinel glass-ceramic.

16. The reinforced spinel glass-ceramic according to any one of claims 1 to 15, characterized in that, The CS_50 of the reinforced spinel glass-ceramic is ≥100MPa, preferably 100MPa≤CS_50≤250MPa, where CS_50 refers to the compressive stress value at a depth of 50μm from the surface of the reinforced spinel glass-ceramic along the thickness direction.

17. The reinforced spinel glass-ceramic according to any one of claims 1 to 16, characterized in that, The reinforced spinel glass-ceramic has a strength of |CT_AV| ≥ 70 MPa, preferably 70 MPa ≤ |CT_AV| ≤ 110 MPa, where |CT_AV| refers to the absolute value of the average tensile stress in the tensile stress layer of the reinforced spinel glass-ceramic.

18. The reinforced spinel glass-ceramic according to any one of claims 1 to 17, characterized in that, The reinforced spinel glass-ceramic has a strength of |CT_CV| ≥ 80 MPa, preferably 80 MPa ≤ |CT_CV| ≤ 150 MPa, where |CT_CV| refers to the absolute value of the maximum tensile stress in the tensile stress layer of the reinforced spinel glass-ceramic.

19. The reinforced spinel glass-ceramic according to any one of claims 1 to 18, characterized in that, The Vickers hardness of the reinforced spinel glass-ceramic is greater than or equal to 790 kgf / mm². 2 The preferred Vickers hardness is 790 kgf / mm². 2 Up to 1000 kgf / mm 2 .

20. The reinforced spinel glass-ceramic according to any one of claims 1 to 19, characterized in that, The fracture toughness of the reinforced spinel glass-ceramic is greater than or equal to 1.00 MPa·m. 1 / 2 Preferably, the fracture toughness is greater than or equal to 1.20 MPa·m. 1 / 2 .

21. The reinforced spinel glass-ceramic according to claim 20, characterized in that, The fracture toughness of the reinforced spinel glass-ceramic is 1.00~2.00 MPa·m. 1 / 2 The preferred fracture toughness is 1.20 MPa·m. 1 / 2 ~2.00MPa·m 1 / 2 More preferably, the fracture toughness is 1.55 MPa·m. 1 / 2 ~2.00MPa·m 1 / 2 .

22. The reinforced spinel glass-ceramic according to any one of claims 1 to 21, characterized in that, The 0.7mm thick reinforced spinel glass-ceramic was subjected to a drop test using 80-grit sandpaper. The average drop height resisted by the reinforced spinel glass-ceramic was greater than or equal to 1.00m, preferably greater than or equal to 1.40m.

23. The reinforced spinel glass-ceramic according to claim 22, characterized in that, The 0.7mm thick reinforced spinel glass-ceramic was subjected to a drop test using 80-grit sandpaper. The average drop height resisted by the reinforced spinel glass-ceramic was 1.00m to 2.50m, preferably 1.40m to 2.50m, and more preferably 1.50mm to 2.50m.

24. The reinforced spinel glass-ceramic according to any one of claims 1 to 23, characterized in that, The reinforced spinel glass-ceramic with a diameter of 10mm and a round head is pressed with a metal bar. The static compressive strength of the reinforced spinel glass-ceramic under single bar pressure is tested. The static compressive strength of the reinforced spinel glass-ceramic under single bar pressure is greater than 500N, preferably greater than 550N.

25. A glass device comprising any one of claims 1 to 24 reinforced spinel glass-ceramics.

26. An electronic device comprising any one of claims 1 to 24 reinforced spinel glass-ceramics.

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