Lithium aluminosilicate-based glass with high young's modulus and chemically strengthened glass thereof

Abstract

This application relates to the field of lithium aluminum silicate glass technology, and provides a high Young's modulus lithium aluminum silicate substrate glass and its chemically strengthened glass. The substrate glass, based on the molar percentage of oxides, comprises the following components: SiO2 60.0-70.0 mol%; Al2O3 8.0-15.0 mol%; MgO 1.0-8.0 mol%; Li2O 7.0-12.0 mol%; Na2O 2.0-5.0 mol%; and Y2O3 and La2O3; wherein Y2O3+La2O3 is 4.0-8.0 mol%. The chemically strengthened glass is obtained by chemically strengthening the substrate glass. The substrate glass and chemically strengthened glass of this application have reasonable component contents, achieving a good combined effect. The combination of components results in a glass with high Young's modulus and high stress performance, good acid resistance, and excellent mass production performance, meeting the development needs of cover glass in high-end mobile phone products.

Description

[0001] This application is a divisional application of Chinese patent application filed on October 19, 2023, with application number 202311355205.7 and invention title "Lithium aluminum silicon substrate glass with high Young's modulus and chemically strengthened glass thereof". Technical Field

[0002] This application relates to the field of lithium aluminum silicate glass technology, and in particular to a lithium aluminum silicate substrate glass with high Young's modulus and its chemically strengthened glass. Background Technology

[0003] Cover glass for electronic devices needs to have high drop resistance. Since its invention, glass-ceramics, with its high Young's modulus (around 100 GPa) and high stress resistance, has met the requirements for high drop resistance and has been widely used in cover glass for electronic devices such as mobile phones. However, the raw materials for producing glass-ceramics contain a high content of lithium oxide, resulting in high manufacturing costs and expensive prices. Furthermore, the production process of glass-ceramics is complex, requiring nucleation-crystallization steps, leading to large fluctuations in yield and poor repeatability. Currently, lithium aluminum silicon glass (LiSi) products have lower raw material costs, do not require a crystallization step, and have a simpler processing technology than glass-ceramics, offering significant production advantages. However, LiSi has a Young's modulus of only around 80 GPa, and its drop resistance is far inferior to that of glass-ceramics, making it difficult to meet the development needs of cover glass for electronic devices such as mobile phones.

[0004] Existing technologies have shown that adding dense oxides such as yttrium oxide, lanthanum oxide, and niobium oxide can significantly improve the Young's modulus of lithium aluminum silicon glass. However, directly adding dense oxides such as yttrium oxide, lanthanum oxide, and niobium oxide will lead to a decrease in ion exchange capacity, which in turn will reduce the surface stress level of the glass, thus limiting the improvement in drop resistance. In addition, adding the above-mentioned dense oxides will also increase the crystallization temperature of the glass, making it easier to crystallize at lower viscosity, which will make the glass production and forming difficult, resulting in poor mass production. Summary of the Invention

[0005] Based on the above, the purpose of this application is to overcome the shortcomings of the existing technical solutions and provide a lithium aluminum silicon substrate glass that has both good acid resistance and high Young's modulus and can be mass-produced. In addition, the lithium aluminum silicon substrate glass can be chemically strengthened to obtain chemically strengthened glass with high stress.

[0006] In a first aspect, this application provides a lithium aluminum silicon substrate glass, wherein the substrate glass comprises the following components based on the molar percentage of oxides:

[0007] SiO2 60.0-70.0 mol%;

[0008] Al2O3 8.0-15.0 mol%;

[0009] MgO 1.0-8.0 mol%;

[0010] Li₂O 7.0-12.0 mol%;

[0011] Na₂O 2.0-5.0 mol%;

[0012] and Y2O3 and La2O3;

[0013] The content of Y₂O₃ + La₂O₃ is 4.0-8.0 mol%.

[0014] In some embodiments of this application, the SiO2 is 63.0-70.0 mol%, preferably 63.0-67.0 mol%, based on the molar percentage of oxides; and / or the Al2O3 is 8.0-13.0 mol%, preferably 9.0-12.0 mol%.

[0015] In some embodiments of this application, the Al2O3 / SiO2 ratio in the substrate glass is ≤0.2, based on the molar percentage of oxides.

[0016] In some embodiments of this application, the Y₂O₃ + La₂O₃ content in the substrate glass is 5.0-7.0 mol%, based on the molar percentage of oxides.

[0017] In some embodiments of this application, the La2O3 / (Y2O3+La2O3) content in the substrate glass is 0.25-0.7 based on the molar percentage of oxides; preferably, it is 0.4-0.7.

[0018] In some embodiments of this application, the substrate glass further comprises the following components, based on the molar percentage of oxides:

[0019] K2O 0-2.0 mol%;

[0020] ZrO2 0-2.0 mol%;

[0021] B2O3 0-5.0 mol%;

[0022] P2O5 0-5.0 mol%;

[0023] CaO 0-8.0 mol%;

[0024] SrO 0-3.0 mol%.

[0025] In some embodiments of this application, the Young's modulus of the substrate glass is 95 GPa-130 GPa, preferably 96 GPa-120 GPa.

[0026] In some embodiments of this application, the bifurcation threshold of the substrate glass is 49000MPa / mm-60000MPa / mm, preferably 50000MPa / mm-58000MPa / mm.

[0027] In some embodiments of this application, the upper limit temperature for crystallization of the substrate glass is 1100℃-1330℃.

[0028] In some embodiments of this application, the viscosity corresponding to the upper limit of crystallization temperature of the substrate glass is 10. 2.2 dPa·s or higher, preferably 10 2.5 dPa·s or above.

[0029] In some embodiments of this application, the substrate glass is etched in a 5wt% HCl solution at 95°C for 24 hours, with an etch amount ≤7mg / cm². 2 .

[0030] Secondly, this application provides a chemically strengthened glass, which is obtained by chemically strengthening a substrate glass as described above.

[0031] In some embodiments of this application, the chemical strengthening of the substrate glass includes single-step chemical strengthening or multi-step chemical strengthening.

[0032] In some embodiments of this application, the single-step chemical enhancement employs a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%.

[0033] In some embodiments of this application, the single-step chemical enhancement employs a mixed salt bath containing NaNO3 and KNO3, preferably with the KNO3 content in the mixed salt bath being 80-100 wt% and the NaNO3 content being 0-20 wt%.

[0034] In some embodiments of this application, the temperature of the single-step chemical enhancement is 380℃-500℃, and more preferably, the ion exchange time of the single-step chemical enhancement is 3h-10h.

[0035] In some embodiments of this application, the multi-step chemical strengthening includes two-step chemical strengthening, wherein the first step of chemical strengthening uses a salt bath containing NaNO3, preferably with a NaNO3 content of 70-100 wt%; and the second step of chemical strengthening uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%.

[0036] In some embodiments of this application, the multi-step chemical strengthening includes two-step chemical strengthening. The first step of chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-100 wt% and the content of KNO3 is 0-30 wt%. The second step of chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-100 wt% and the content of NaNO3 is 0-20 wt%.

[0037] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 3h-10h.

[0038] In some embodiments of this application, the temperature of the second step of chemical strengthening is 380°C-500°C, and the preferred ion exchange time is 1h-10h.

[0039] In some embodiments of this application, the CS_50 of the chemically strengthened glass is 100MPa-150MPa; preferably, the CS_50 is 105MPa-150MPa; more preferably, the CS_50 is 110MPa-140MPa.

[0040] In some embodiments of this application, the DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, where t is the thickness of the chemically strengthened glass.

[0041] In some embodiments of this application, the CT_LD of the chemically strengthened glass is 45000MPa / mm-60000MPa / mm, preferably 45000MPa / mm-57000MPa / mm.

[0042] Thirdly, this application provides a method for preparing the chemically strengthened glass as described above, comprising the following steps:

[0043] (1) Select the raw materials according to the composition of the substrate glass, mix them, melt and form them, and then cool and anneal them to obtain the substrate glass;

[0044] (2) Chemically strengthen the substrate glass to obtain chemically strengthened glass.

[0045] In some embodiments of this application, the chemical strengthening includes single-step chemical strengthening or multi-step chemical strengthening.

[0046] In some embodiments of this application, the single-step chemical enhancement employs a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%.

[0047] In some embodiments of this application, the single-step chemical enhancement employs a mixed salt bath containing NaNO3 and KNO3, preferably with the KNO3 content in the mixed salt bath being 80-100 wt% and the NaNO3 content being 0-20 wt%.

[0048] In some embodiments of this application, the temperature of the single-step chemical enhancement is 380℃-500℃, and more preferably, the ion exchange time of the single-step chemical enhancement is 3h-10h.

[0049] In some embodiments of this invention, the multi-step chemical strengthening includes two-step chemical strengthening, wherein the first step of chemical strengthening uses a salt bath containing NaNO3, preferably with a NaNO3 content of 70-100 wt%; and the second step of chemical strengthening uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%.

[0050] In some embodiments of this application, the multi-step chemical strengthening includes two-step chemical strengthening. The first step of chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-100 wt% and the content of KNO3 is 0-30 wt%. The second step of chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-100 wt% and the content of NaNO3 is 0-20 wt%.

[0051] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 3h-10h.

[0052] In some embodiments of this application, the temperature of the second step of chemical strengthening is 380°C-500°C, and the preferred ion exchange time is 1h-10h.

[0053] Fourthly, this application provides a glass device, which includes the above-mentioned lithium aluminum silicon substrate glass or the above-mentioned chemically strengthened glass.

[0054] Fifthly, this application provides an electronic device, which includes the aforementioned lithium aluminum silicon substrate glass or the aforementioned chemically strengthened glass.

[0055] In some embodiments of this application, the electronic device includes one or more of a mobile phone, tablet computer, smart wearable device, display, or television.

[0056] Compared with the prior art, this application has the following beneficial effects:

[0057] 1. This application controls the lithium aluminum silicon substrate glass to have a high Young's modulus and good acid resistance by controlling the Y2O3+La2O3 content to between 4-8 mol%. The substrate glass has high stress characteristics after chemical strengthening.

[0058] 2. This application controls the lithium aluminum silicon substrate glass to have good acid resistance by controlling SiO2 > 60 mol% and Al2O3 < 17 mol%. Adding ZrO2 can further improve the acid resistance of the lithium aluminum silicon substrate glass.

[0059] 3. This application controls the ratio of La2O3 / (Y2O3+La2O3) to be ≥0.25, preferably ≥0.4, so that the upper limit temperature for crystallization of lithium aluminum silicon substrate glass is 1100℃-1330℃, and the viscosity corresponding to the upper limit temperature for crystallization is 10. 2.2 Above dPa·s; thus possessing mass production characteristics. Attached Figure Description

[0060] Figure 1 This is a schematic diagram of the stress relief device for an immediate fracture test; in the diagram: 1-height adjustment guide rail, 2-start adjustment guide rail, 3-pressure head, 4-chemically strengthened glass sample.

[0061] Figure 2 Diagram showing the crack failure state during an immediate fracture test.

[0062] Figure 3 This is a schematic diagram of placing a long quartz trough inside a gradient furnace, as per this application. Detailed Implementation

[0063] This application will clearly and completely describe the technical solutions of the embodiments of this application 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.

[0064] The relevant proprietary names involved in this application are explained as follows.

[0065] In this application, the substrate glass is a glass matrix material that has not undergone nucleation, crystallization, or strengthening treatment.

[0066] In this application, chemically strengthened glass refers to strengthened glass that has undergone a high-temperature ion exchange process. In a high-temperature salt bath, alkali metal ions with large ionic radii (such as potassium ions and sodium ions) replace alkali metal ions with small ionic radii (such as sodium ions and lithium ions) in the glass, thereby creating a volume difference in the exchanged ions. This generates compressive stress from the surface to the interior of the substrate glass, which decreases from high to low, hindering and delaying the propagation of microcracks in the glass, thus improving the mechanical strength of the glass.

[0067] In this application, surface CS refers to surface compressive stress. After the substrate glass is chemically strengthened, alkali metal ions with smaller surface radii (such as sodium ions and lithium ions) are replaced with alkali metal ions with larger surface radii (such as potassium ions and sodium ions). Due to the crowding effect of the larger alkali metal ions, compressive stress is generated on the glass surface. This stress can be measured by the Orihara FSM-6000 stress meter from Japan.

[0068] In this application, CS_50 refers to the compressive stress value at a depth of 50 μm from the glass surface.

[0069] In this application, DOL_0: compressive stress layer depth, also known as compressive stress layer depth, refers to the distance from any surface of the glass to the location near which the compressive stress is zero. It can be measured by the Orihara SLP-2000 stress meter from Japan.

[0070] In this application, CT_LD refers to the ratio of the definite integral of the tensile stress curve of chemically strengthened glass to the thickness of the chemically strengthened glass, denoted as tensile stress linear density. The substrate glass is placed in a salt bath for ion exchange to form a strengthening layer (i.e., a compressive stress layer). During the ion exchange process, a tensile stress layer is formed inside the glass. This tensile stress layer has an upper boundary at a certain distance from the upper surface of the chemically strengthened glass and a lower boundary at a certain distance from the lower surface of the chemically strengthened glass. The curve plotted with the magnitude of the tensile stress at a point on a line segment within the tensile stress layer that is perpendicular to both the upper and lower boundaries, with its upper and lower endpoints falling on the upper and lower boundaries respectively, as the Y-axis, and the distance of the corresponding point from the upper boundary as the X-axis, is denoted as the tensile stress curve. The ratio of the definite integral of the tensile stress curve to the thickness of the chemically strengthened glass is denoted as the tensile stress linear density, which is also the ratio of the sum of the tensile stresses of the chemically strengthened glass measured by the SLP-2000 stress meter to the glass thickness.

[0071] In this application, CT_LD max This refers to the maximum tensile stress linear density. The maximum tensile stress linear density (CT_LD) that can be obtained by ion-exchange chemical strengthening of the substrate glass under specific salt bath conditions is the maximum tensile stress linear density CT_LD that the substrate glass can achieve under those salt bath conditions. max This data can characterize the strengthenability / ion-exchangeability of the substrate glass.

[0072] In this application, the bifurcation threshold refers to the minimum tensile stress linear density value of chemically strengthened glass when the glass crack bifurcates in an immediate fracture test, which is the bifurcation threshold of chemically strengthened glass prepared from the substrate glass of that formulation.

[0073] In a first aspect, this application provides a lithium aluminum silicon substrate glass, wherein the substrate glass comprises the following components based on the molar percentage of oxides:

[0074] SiO2 60.0-70.0 mol%;

[0075] Al2O3 8.0-15.0 mol%;

[0076] MgO 1.0-8.0 mol%;

[0077] Li₂O 7.0-12.0 mol%;

[0078] Na₂O 2.0-5.0 mol%;

[0079] ZrO2 0.3-2.0 mol%;

[0080] and Y2O3 and La2O3;

[0081] The content of Y₂O₃ + La₂O₃ is 4.0-8.0 mol%.

[0082] In this application, SiO2 is an essential component constituting the glass framework. A high SiO2 content ensures the glass possesses excellent properties such as high strength, resistance to thermal expansion, and chemical stability. However, the stability of the framework has little effect on improving the glass density, so its influence on the Young's modulus and mechanical strength is generally limited. Since SiO2 tends to increase the viscosity of molten glass, an excessively high SiO2 content can make the glass difficult to melt and form, thereby increasing the difficulty of melting and production. In some embodiments of this application, the substrate glass comprises 60.0-70.0 mol% SiO2, based on the molar percentage of oxides. In some embodiments of this application, the substrate glass comprises 63.0-70.0 mol% SiO2, preferably 63.0-67.0 mol% SiO2, based on the molar percentage of oxides. In some embodiments of this application, the SiO2 content in the substrate glass can be 60.0 mol%, 61.0 mol%, 62.0 mol%, 63.0 mol%, 63.10 mol%, 64.0 mol%, 64.50 mol%, 65.0 mol%, 66.0 mol%, 67.0 mol%, 68.0 mol%, 69.0 mol%, 70.0 mol%, or any two of the above values ​​as endpoints within a range.

[0083] Al₂O₃ forms aluminum-oxygen tetrahedra in glass and connects non-bridging oxygen in the silicon-oxygen network structure, increasing the strength of the network structure and further enhancing the glass's strength, structural stability, and chemical stability. In lithium-aluminum-silicon glass systems, Al₂O₃'s chemical stability is inferior to SiO₂, for example, in acid resistance. Increasing the proportion of Al₂O₃ in the network structure leads to a decrease in the glass's acid resistance. Furthermore, Al₂O₃ is the main component forming the crystalline phase spodumene in lithium-aluminum-silicon glass systems; excessive addition of Al₂O₃ rapidly increases the glass's crystallization tendency, increasing the difficulty of glass melting, thereby increasing the difficulty and cost of glass production. In some embodiments of this application, the substrate glass comprises 8.0-15.0 mol% Al₂O₃, preferably 9.0-12.0 mol% Al₂O₃, based on the molar percentage of oxides. In some embodiments of this application, the Al2O3 content in the substrate glass can be 8.0 mol%, 8.5 mol%, 9.0 mol%, 9.5 mol%, 10.0 mol%, 10.5 mol%, 11.0 mol%, 11.5 mol%, 12.0 mol%, 12.5 mol%, 13.0 mol%, 13.5 mol%, 14.0 mol%, 14.5 mol%, 15.0 mol%, or a value within a range formed by using any two of the above values ​​as endpoints.

[0084] This application uses alkaline earth metal oxide MgO as the network outer layer of the glass, which can adjust the viscosity-temperature properties of the glass, thereby improving its melting performance. In some embodiments of this application, the substrate glass comprises 1.0-8.0 mol% MgO, based on the molar percentage of oxides. In some embodiments of this application, the MgO content in the substrate glass can be 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 5.0 mol%, 5.5 mol%, 6.0 mol%, 6.5 mol%, 7.0 mol%, 7.5 mol%, 8.0 mol%, or any two of the above values ​​as endpoints within a range.

[0085] Li₂O, as an alkali metal component in the glass network, causes the silicon-oxygen network of the glass to break down, forming a large amount of non-bridging oxygen, making the glass structure porous and significantly reducing the melting and forming temperatures. Simultaneously, the alkali metal ions in Li₂O enable the glass to undergo ion exchange strengthening. In some embodiments of this application, the substrate glass comprises 7.0-12.0 mol% Li₂O, based on the molar percentage of oxides. In some embodiments of this application, the Li₂O content in the substrate glass can be 7.0 mol%, 7.5 mol%, 8.0 mol%, 8.5 mol%, 9.0 mol%, 9.5 mol%, 10.0 mol%, 10.5 mol%, 11.0 mol%, 11.5 mol%, 12.0 mol%, or a value within a range defined by any two of the above values ​​as endpoints.

[0086] Na₂O, as an alkali metal component in the glass network, causes the silicon-oxygen network of the glass to break down, forming a large amount of non-bridging oxygen, making the glass structure porous and significantly reducing the melting and forming temperatures. Simultaneously, the alkali metal ions in Na₂O enable the glass to undergo ion exchange strengthening. In some embodiments of this application, the substrate glass comprises 2.0-5.0 mol% Na₂O, based on the molar percentage of oxides. In some embodiments of this application, the Na₂O content in the substrate glass can be 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 5.0 mol%, or any two of the above values ​​within a range defined by endpoints.

[0087] This application uses Y₂O₃ and La₂O₃ as network modifiers for glass, which can reduce the high-temperature viscosity of the glass, facilitating glass melting and the elimination of internal defects; it can also improve the Young's modulus and micro Vickers hardness of the glass, while simultaneously enhancing its chemical strengthening properties and increasing the stress effect generated per unit ion exchange in chemically strengthened glass. Furthermore, when Y₂O₃ and La₂O₃ are mixed and added to lithium aluminum silicon glass, the crystallization tendency is less than that of using Y₂O₃ or La₂O₃ alone. From the perspective of balancing high Young's modulus and crystallization tendency, the content of Y₂O₃ + La₂O₃ is controlled within a reasonable range. In some embodiments of this application, the substrate glass comprises Y₂O₃ and La₂O₃, and the content of Y₂O₃ + La₂O₃ is 4.0-8.0 mol%, preferably 5.0-7.0 mol%. In some embodiments of this application, the content of Y2O3+La2O3 in the substrate glass can be 4.0 mol%, 4.5 mol%, 5.0 mol%, 5.5 mol%, 6.0 mol%, 6.5 mol%, 7.0 mol%, 7.5 mol%, 8.0 mol%, or any two of the above values ​​as endpoints within a range.

[0088] In some embodiments of this application, the substrate glass comprises 2.0-5.0 mol% Y₂O₃, based on the molar percentage of oxides. In some embodiments of this application, the Y₂O₃ content in the substrate glass can be 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 5.0 mol%, or a value within a range defined by any two of the above values ​​as endpoints.

[0089] In some embodiments of this application, the substrate glass comprises 2.0-5.0 mol% La₂O₃ by mole percentage of oxides. In some embodiments of this application, the La₂O₃ content in the substrate glass can be 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 5.0 mol%, or a value within a range defined by any two of the above values ​​as endpoints.

[0090] In this application, the La2O3 content cannot be too high because the tendency to crystallize increases abruptly when focusing solely on a single dense oxide, and Y2O3 is more conducive to improving stress performance than La2O3. From the perspective of balancing crystallization and high stress performance, this application controls the value of La2O3 / (Y2O3+La2O3) within a suitable range. In some embodiments of this application, the La2O3 / (Y2O3+La2O3) in the substrate glass, based on the molar percentage of oxides, is 0.25-0.70, preferably 0.40-0.70. In some embodiments of this application, the value of La2O3 / (Y2O3+La2O3) in the substrate glass can be 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, or a value within a range formed by any two of the above values ​​as endpoints.

[0091] In some embodiments of this application, the Al2O3 / SiO2 ratio in the substrate glass is ≤0.2, based on the molar percentage of oxides. In some embodiments of this application, the Al2O3 / SiO2 ratio in the substrate glass can be 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, or a value within a range defined by any two of the above values ​​as endpoints.

[0092] In some embodiments of this application, the substrate glass comprises 0-2.0 mol% K₂O, based on the molar percentage of oxides. In some embodiments of this application, the K₂O content in the substrate glass can be 0.0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, or any two of the above values ​​as endpoints within a range. K₂O, as an alkali metal component in the glass's network exterior, causes the silicon-oxygen network of the glass to break down, forming a large amount of non-bridging oxygen, resulting in a porous glass structure and significantly reducing the glass's melting and forming temperatures.

[0093] In some embodiments of this application, the substrate glass comprises 0-2.0 mol% ZrO2, based on the molar percentage of oxides. In some embodiments of this application, the ZrO2 content in the substrate glass can be 0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, or a value within a range formed by any two of the above values ​​as endpoints.

[0094] In some embodiments of this application, the substrate glass comprises 0-5.0 mol% B2O3, based on the molar percentage of oxides. In some embodiments of this application, the B2O3 content in the substrate glass can be 0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.50 mol%, 5.0 mol%, or a value within a range defined by any two of the above values ​​as endpoints.

[0095] In some embodiments of this application, the substrate glass comprises 0-5.0 mol% P2O5, based on the molar percentage of oxides. In some embodiments of this application, the P2O5 content in the substrate glass can be 0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.50 mol%, 5.0 mol%, or any two of the above values ​​as endpoints within a range. P2O5 is a component constituting the network, which can reduce the difficulty of melting the glass and increase the ion diffusion rate for chemical strengthening; however, it reduces the chemical durability of the glass and easily causes phase separation, thus lowering the devitrification temperature.

[0096] In some embodiments of this application, the substrate glass comprises 0-8.0 mol% CaO, based on the molar percentage of oxides. In some embodiments of this application, the CaO content in the substrate glass can be 0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 5.0 mol%, 5.5 mol%, 6.0 mol%, 6.5 mol%, 7.0 mol%, 7.5 mol%, 8.0 mol%, or a value within a range formed by any two of the above values ​​as endpoints.

[0097] In some embodiments of this application, the substrate glass comprises 0-3.0 mol% SrO, based on the molar percentage of oxides. In some embodiments of this application, the SrO content in the substrate glass can be 0 mol%, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 2.5 mol%, 3.0 mol%, or a value within a range formed by any two of the above values ​​as endpoints.

[0098] In some embodiments of this application, the Young's modulus of the substrate glass is 95 GPa-130 GPa, preferably 96 GPa-120 GPa. In some embodiments of this application, the Young's modulus of the substrate glass can be 95 GPa, 96 GPa, 97 GPa, 98 GPa, 99 GPa, 100 GPa, 101 GPa, 102 GPa, 103 GPa, 104 GPa, 105 GPa, 106 GPa, 107 GPa, 108 GPa, 109 GPa, 110 GPa, 111 GPa, 112 GPa, 113 GPa, 114 GPa, 115 GPa, 116 GPa, 117 GPa, 118 GPa, 119 GPa, 120 GPa, or a value within a range formed by using any two of the above values ​​as endpoints. This application does not impose any particular limitations on the testing methods and instruments for Young's modulus, as long as they can achieve the purpose of this application, such as using the acoustic method for determination.

[0099] In some embodiments of this application, the bifurcation threshold of the substrate glass is 49000 MPa / mm-60000 MPa / mm, preferably 50000 MPa / mm-58000 MPa / mm. In some embodiments of this application, the bifurcation threshold value of the chemically strengthened glass can be 49000 MPa / mm, 49500 MPa / mm, 50000 MPa / mm, 50500 MPa / mm, 51000 MPa / mm, 51500 MPa / mm, 52000 MPa / mm, 52500 MPa / mm, 53000 MPa / mm, 53500 MPa / mm, 54000 MPa / mm, 54... Values ​​within a range formed by using 500MPa / mm, 55000MPa / mm, 55500MPa / mm, 56000MPa / mm, 56500MPa / mm, 57000MPa / mm, 57500MPa / mm, 58000MPa / mm, 58500MPa / mm, 59000MPa / mm, 59500MPa / mm, 60000MPa / mm, or any two of the above values ​​as endpoints.

[0100] In some embodiments of this application, the upper limit temperature for crystallization of the substrate glass is 1100-1330℃. In some embodiments of this application, the upper limit temperature for crystallization can be 1100℃, 1110℃, 1120℃, 1130℃, 1140℃, 1150℃, 1160℃, 1170℃, 1180℃, 1190℃, 1200℃, 1210℃, 1220℃, 1230℃, 1240℃, 1250℃, 1260℃, 1270℃, 1280℃, 1290℃, 1300℃, 1310℃, 1320℃, 1330℃, or any two of the above values ​​forming a range.

[0101] In some embodiments of this application, the viscosity corresponding to the upper limit of crystallization temperature of the substrate glass is 10. 2.2 dPa·s or higher, preferably 10 2.5 Above dPa·s. In some embodiments of this application, the viscosity corresponding to the upper limit of crystallization temperature can be 10. 2.2 dPa·s, 10 2.3 dPa·s, 10 2.4 dPa·s, 10 2.5 dPa·s, 10 2.6 dPa·s, 10 2.7 dPa·s, 10 2.8 dPa·s, 10 2.9 dPa·s, 10 3.0 dPa·s, 10 3.1 The value is within the range formed by using dPa·s or any two of the above values ​​as endpoints.

[0102] In some embodiments of this application, the substrate glass is etched in a 5wt% HCl solution at 95°C for 24 hours, with an etch amount ≤7mg / cm². 2 In some embodiments of this application, the etching amount of the substrate glass after immersion in a 5wt% HCl solution at 95°C for 24 hours can be 0.2 mg / cm³. 2 0.3 mg / cm 2 0.5 mg / cm 2 1.0 mg / cm 2 1.5 mg / cm 2 2.0 mg / cm 2 2.5 mg / cm 2 3.0 mg / cm 2 3.5 mg / cm 2 4.0 mg / cm 2 4.5 mg / cm 2 5.0 mg / cm 25.5 mg / cm 2 6.0 mg / cm 2 6.5 mg / cm 2 7.0 mg / cm 2 Alternatively, the values ​​can be any two of the above values ​​within a range formed by using them as endpoints. This application does not impose any particular limitations on the testing method and instruments for measuring the erosion amount of the substrate glass after immersion in a 5wt% HCl solution at 95°C for 24 hours, as long as the purpose of this application can be achieved.

[0103] Secondly, this application provides a chemically strengthened glass, which is obtained by chemically strengthening a substrate glass as described above.

[0104] In some embodiments of this application, the chemical strengthening of the substrate glass includes single-step chemical strengthening or multi-step chemical strengthening.

[0105] In some embodiments of this application, the single-step chemical enhancement employs a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%. In some embodiments of this application, the NaNO3 content in the salt bath can be 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, or a value within a range formed by any two of the above values ​​as endpoints.

[0106] In some embodiments of this application, the single-step chemical enhancement employs a mixed salt bath containing NaNO3 and KNO3, preferably with a KNO3 content of 80-100 wt% and a NaNO3 content of 0-20 wt%. In some embodiments of this application, the KNO3 content in the mixed salt bath can be 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the NaNO3 content in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or any two of the above values ​​as endpoints within a range.

[0107] In some embodiments of this application, the temperature for single-step chemical enhancement is 380℃-500℃, and more preferably, the ion exchange time for single-step chemical enhancement is 3h-10h. In some embodiments of this application, the temperature for single-step chemical enhancement can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time for single-step chemical enhancement can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0108] In some embodiments of this application, the multi-step chemical strengthening includes two steps. The first step uses a salt bath containing NaNO3, preferably with a NaNO3 content of 70-100 wt%. The second step uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%. In some embodiments, the NaNO3 content in the salt bath can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments, the KNO3 content in the salt bath can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range.

[0109] In some embodiments of this application, the first step of chemical fortification uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-100 wt% and the content of KNO3 is 0-30 wt%; the second step of chemical fortification uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-100 wt% and the content of NaNO3 is 0-20 wt%. In some embodiments of this application, in the first step of chemical fortification, the content of NaNO3 in the mixed salt bath can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range; the content of KNO3 in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, in the second step of chemical fortification, the content of KNO3 in the mixed salt bath can be 80wt%, 85wt%, 90wt%, 95wt%, 100wt%, or any two of the above values ​​as endpoints within a range; the content of NaNO3 in the mixed salt bath can be 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, or any two of the above values ​​as endpoints within a range.

[0110] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 3h-10h. In some embodiments of this application, the temperature of the first step of chemical strengthening can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time of the first step of chemical strengthening can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0111] In some embodiments of this application, the temperature for the second step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 1h-10h. In some embodiments of this application, the temperature for the second step of chemical strengthening can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time for the second step of chemical strengthening can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0112] In some embodiments of this application, the CS_50 of the chemically strengthened glass is 100MPa-150MPa, preferably 105MPa-150MPa, and more preferably 110MPa-140MPa. In some embodiments of this application, the CS_50 value of the chemically strengthened glass can be 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, or any two of the above values ​​as endpoints within a range. This application does not particularly limit the testing method and instrument for the surface CS_50, as long as it achieves the purpose of this application; for example, it can be measured using a stress meter FSM-6000.

[0113] In this application, the change in glass thickness before and after chemical strengthening is very small, almost negligible. That is, the difference between the thickness of the substrate glass and the thickness of the chemically strengthened glass obtained by chemically strengthening the substrate glass is very small. In some embodiments of this application, the surface stress layer depth DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, where t is the thickness of the chemically strengthened glass. In some embodiments of this application, the surface stress layer depth DOL_0 of the chemically strengthened glass can be 0.14t, 0.145t, 0.15t, 0.155t, 0.16t, 0.165t, 0.17t, 0.175t, 0.18t, 0.185t, 0.19t, 0.195t, 0.20t, 0.205t, 0.21t, 0.215t, 0.22t, 0.225t, 0.230t, 0.235t, 0.24t, 0.245t, 0.25t, or any two of the above values ​​as endpoints within a range.

[0114] The thickness of the chemically strengthened glass described in this application is not particularly limited, and can be, for example, 0.4-2.0 mm. The thickness of the chemically strengthened glass described in this application can be 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 2.0 mm, or any two of the above values ​​as endpoints within a range.

[0115] In some embodiments of this application, the CT_LD of the chemically strengthened glass is 45000MPa / mm-60000MPa / mm, preferably 45000MPa / mm-57000MPa / mm. In some embodiments of this application, the CT_LD value of the chemically strengthened glass can be 45000MPa / mm, 46000MPa / mm, 47000MPa / mm, 48000MPa / mm, 49000MPa / mm, 50000MPa / mm, 51000MPa / mm, 52000MPa / mm, 53000MPa / mm, 54000MPa / mm, 55000MPa / mm, 56000MPa / mm, 57000MPa / mm, 58000MPa / mm, 59000MPa / mm, 60000MPa / mm, or a value within a range formed by using any two of the above values ​​as endpoints. This application does not impose any particular limitations on the testing equipment and methods for CT_LD of chemically strengthened glass, as long as they can achieve the purpose of this application.

[0116] Thirdly, this application provides a method for preparing chemically strengthened glass as described above, comprising the following steps:

[0117] (1) Select the raw materials according to the composition of the substrate glass, mix them, melt and form them, and then cool and anneal them to obtain the substrate glass;

[0118] (2) Chemically strengthen the substrate glass to obtain chemically strengthened glass.

[0119] In some embodiments of this application, the chemical strengthening of the substrate glass includes single-step chemical strengthening or multi-step chemical strengthening.

[0120] In some embodiments of this application, the single-step chemical enhancement employs a salt bath containing NaNO3, preferably with a NaNO3 content of 30-100 wt%. In some embodiments of this application, the NaNO3 content in the salt bath can be 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 100 wt%, or a value within a range formed by any two of the above values ​​as endpoints.

[0121] In some embodiments of this application, the single-step chemical enhancement employs a mixed salt bath containing NaNO3 and KNO3, preferably with a KNO3 content of 80-100 wt% and a NaNO3 content of 0-20 wt%. In some embodiments of this application, the KNO3 content in the mixed salt bath can be 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the NaNO3 content in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or any two of the above values ​​as endpoints within a range.

[0122] In some embodiments of this application, the temperature for single-step chemical enhancement is 380℃-500℃, and more preferably, the ion exchange time for single-step chemical enhancement is 3h-10h. In some embodiments of this application, the temperature for single-step chemical enhancement can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time for single-step chemical enhancement can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0123] In some embodiments of this application, the multi-step chemical strengthening includes two steps. The first step uses a salt bath containing NaNO3, preferably with a NaNO3 content of 70-100 wt%. The second step uses a salt bath containing KNO3, preferably with a KNO3 content of 60-100 wt%. In some embodiments, the NaNO3 content in the salt bath during the first step can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments, the KNO3 content in the salt bath during the second step can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range.

[0124] In some embodiments of this application, the first step of chemical fortification uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-100 wt% and the content of KNO3 is 0-30 wt%; the second step of chemical fortification uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-100 wt% and the content of NaNO3 is 0-20 wt%. In some embodiments of this application, in the first step of chemical fortification, the content of NaNO3 in the mixed salt bath can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or any two of the above values ​​as endpoints within a range; the content of KNO3 in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, in the second step of chemical fortification, the content of KNO3 in the mixed salt bath can be 80wt%, 85wt%, 90wt%, 95wt%, 100wt%, or any two of the above values ​​as endpoints within a range; the content of NaNO3 in the mixed salt bath can be 0wt%, 5wt%, 10wt%, 15wt%, 20wt%, or any two of the above values ​​as endpoints within a range.

[0125] In some embodiments of this application, the temperature of the first step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 3h-10h. In some embodiments of this application, the temperature of the first step of chemical strengthening can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time of the first step of chemical strengthening can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0126] In some embodiments of this application, the temperature for the second step of chemical strengthening is 380℃-500℃, and the preferred ion exchange time is 1h-10h. In some embodiments of this application, the temperature for the second step of chemical strengthening can be 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 500℃, or any two of the above values ​​as endpoints within a range. In some embodiments of this application, the ion exchange time for the second step of chemical strengthening can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or any two of the above values ​​as endpoints within a range.

[0127] Fourthly, this application provides a glass device, which includes the above-mentioned lithium aluminum silicon substrate glass or the above-mentioned chemically strengthened glass.

[0128] Fifthly, this application provides an electronic device, which includes the aforementioned lithium aluminum silicon substrate glass or the aforementioned chemically strengthened glass.

[0129] In some embodiments of this application, the electronic device includes: a housing including a front surface, a rear surface, and a side surface; and an electronic component partially located within the housing, the electronic component including a display located at or adjacent to the front surface of the housing; the front surface and / or the rear surface and / or the side surface comprising chemically strengthened glass as described above in this application.

[0130] In some embodiments of this application, the electronic device further includes a cover article covering the front surface of the housing or located on the display, the cover article comprising chemically strengthened glass as described above in this application.

[0131] In some embodiments of this application, the electronic device includes mobile phones, tablets, smart wearables, displays, or televisions; wherein, smart wearables include smart bracelets, smartwatches, and smart glasses, and displays include high-definition displays, automotive displays, and in-flight displays.

[0132] The various types of glass in this application were tested using the following methods:

[0133] Young's modulus test

[0134] The Young's modulus of glass was tested using the UMS-100 ultrasonic material characterization system and ultrasonic echo analysis.

[0135] Stress parameter testing

[0136] Surface stress test: Surface CS_50 and DOL_0 were tested using a stress meter SLP-2000 from Luceo (Orihara, Japan).

[0137] The test conditions were: light source wavelength 518nm, SOC = 28.6 (nm / cm) / MPa, refractive index = 1.51, and exposure time: 5000 µsec. When testing CS_50 and DOL_0, a conductive liquid needs to be applied to the stress meter first. Then, the glass sample to be tested should be wiped clean and placed on the test path to measure its stress value. The SLP-2000 uses a conductive liquid with a refractive index of 1.51.

[0138] CT_LD is calculated using the following formula:

[0139]

[0140] Where: t represents the thickness of the glass sheet in mm; DOL_0 represents the depth of the compressive stress layer in μm; CT_AV represents the internal average tensile stress, which is taken as its absolute value in MPa during calculation. It should be understood that in the formula for calculating the linear density of tensile stress, (1000t / 2-DOL_0) is obtained by substituting the data into the formula and obtaining the result; the unit is not involved in the calculation.

[0141] CT_LD max Testing: In this application, a 100wt% sodium nitrate salt bath at 450℃ was used as the test CT_LD. max Under specific salt bath conditions, an SLP-2000 stress analyzer was used to test the tensile stress linear density (CT_LD). The method was as follows: the substrate glass sample to be tested was placed in a 100wt% sodium nitrate salt bath at 450℃ for chemical strengthening. During strengthening, the glass sample was removed every 0.5 hours to test its internal CT_LD value. After each test, the glass sample was immediately placed back into the salt bath for further strengthening. The process was repeated until the next test time, and the CT_LD values ​​were recorded. When the measured CT_LD value increased to a certain value m and then began to decrease, this value m was determined to be the maximum tensile stress linear density (CT_LD) that the substrate glass sample could obtain under these salt bath conditions (450℃, 100wt% sodium nitrate salt bath). max .

[0142] Bifurcation Threshold Test: First, a substrate glass with a thickness of 0.7 mm corresponding to a certain glass formulation is tested. Ion exchange is performed in a certain salt bath, and the maximum tensile stress linear density CT_LD is obtained. max Then, chemically strengthened glass samples with different CT_LDs were obtained under these salt bath conditions, for example, CT_LD ranging from 30000 MPa / mm to CT_LD maxThe CT_LD was obtained using an SLP-2000 stress meter, increasing in increments of approximately 1000 MPa / mm, 1500 MPa / mm, or 2000 MPa / mm. For example, in this application, a 0.7 mm thick substrate glass corresponding to the glass formulation to be tested was strengthened in a 100 wt% sodium nitrate bath at 450°C to produce chemically strengthened glass samples with CT_LD values ​​of approximately 30000 MPa / mm, 31000 MPa / mm, 32000 MPa / mm, 33000 MPa / mm, 34000 MPa / mm, and 36000 MPa / mm. These chemically strengthened glass samples were then subjected to immediate fracture tests sequentially according to their CT_LD values, from lowest to highest. The center point of the chemically strengthened glass sample was used as the failure point, and a stress relief device was used to induce cracks at the failure point. Select chemically strengthened glass samples with crack bifurcation, and use the smallest CT_LD value of the chemically strengthened glass sample with crack bifurcation as the bifurcation threshold of the chemically strengthened glass prepared from the base glass of this formulation.

[0143] Immediate fracture test: The center point of the chemically strengthened glass sample is used as the fracture point. A stress release device is used to induce a crack at the fracture point, allowing the crack to extend under the internal tensile stress rather than causing a starburst due to excessive impact force. The minimum tensile stress linear density value of the chemically strengthened glass sample when the crack branches is the branching threshold. A certain number of substrate glass products are strengthened under the same salt bath conditions with different ion exchange times to obtain glass samples with different tensile stress linear densities. Fracture tests are performed on multiple glass samples obtained by strengthening them according to the tensile stress linear density values ​​from low to high. After the immediate fracture test, it is observed whether the glass sample cracks branch. The glass samples with branched cracks are identified, and the minimum tensile stress linear density (CT_LD) value corresponding to these glass samples is determined, which is the branching threshold of the chemically strengthened glass corresponding to that substrate glass.

[0144] The stress relief device is described below. Figure 1 In this setup, 1 represents the height adjustment rail, 2 represents the start adjustment rail, 3 represents the indenter, and 4 represents the chemically strengthened glass sample. The device employs pneumatic impact, using a Vickers diamond indenter fixed to the glass surface by a rail. A pressure sensor is also included, and the impact force is controlled by pneumatic pressure regulation. This ensures that the failure point only induces delayed fracture or extends only two cracks, rather than producing a starburst, minimizing the influence of external forces on the failure state. In the immediate fracture experiment, the crack extension must be as follows... Figure 2 As shown in a or b, but not as shown in Figure 2 As shown in c in the figure.

[0145] Acid resistance test

[0146] The acid resistance in this application refers to the glass's resistance to hydrochloric acid corrosion, and the acid resistance of the glass is characterized by the amount of corrosion per unit area.

[0147] Glass was prepared to a size of 50mm × 50mm × 0.7mm. It was first weighed using a balance with an accuracy of 0.0001g, then placed in a 5wt% hydrochloric acid solution and kept at 95℃ for 24 hours. After completion, the glass was removed and weighed again, and the weight of the unetched portion was subtracted to obtain the weight difference M (in grams). The area S (in cm²) of the front and back surfaces of the glass was then calculated. 2 The erosion per unit area is M / S.

[0148] Crystallization Upper Limit Temperature Test

[0149] The upper limit temperature for crystallization refers to the highest temperature at which crystals can form in the substrate glass. Above this temperature, crystals will not form in the substrate glass.

[0150] Break the substrate glass into small pieces of 2mm-5mm in size, then place them into a long quartz trough and fill it completely.

[0151] Set the temperature range for the gradient furnace with model number JKZC-XJY01, such as a temperature range of 1050-1225℃, and take at least 6 temperature points from high to low for each temperature range.

[0152] After the gradient furnace reaches the preset temperature range, the elongated quartz tank containing the sample is placed into the gradient furnace, so that the six temperature points correspond to the six locations of the glass sample in the elongated quartz tank, for reference. Figure 3 After placing the long quartz tank in a gradient furnace and maintaining a constant temperature for 60-70 minutes, remove the long quartz tank.

[0153] Observe the glass sample at different locations in the elongated quartz trough. If the glass sample becomes devitrified or foggy, it is determined that crystallization has occurred at that location. If the glass sample is completely transparent, it is determined that crystallization has not occurred at that location. (Reference) Figure 3 , Figure 3 In the long quartz trough, the upper area is a completely transparent sample, and the lower area is a devitrified sample. Some samples appear foggy between the completely transparent and devitrified samples. Observation can be performed using tools such as a magnifying glass or microscope.

[0154] Determination of the upper limit temperature for crystallization: The upper limit temperature for crystallization is between the temperature point corresponding to the completely transparent sample and the temperature point corresponding to the adjacent devitrified or foggy sample. The average value of the two temperature points is taken as the upper limit temperature for crystallization.

[0155] If all the glass samples in the elongated quartz tank crystallize within the temperature range set by the gradient furnace, then the upper limit temperature of the gradient furnace temperature range is reset, and the upper limit temperature for glass sample crystallization is determined. If none of the glass samples in the elongated quartz tank crystallize within the temperature range set by the gradient furnace, then the lower limit temperature of the gradient furnace temperature range is reset, and the upper limit temperature for glass sample crystallization is determined.

[0156] Upper limit of crystallization corresponds to viscosity

[0157] Prepare at least 250g of substrate glass and place it in an alumina crucible or platinum crucible.

[0158] Turn on the RSV-1600RT high-temperature viscometer to heat up, then place the crucible containing the substrate glass into the heating test area. Generally, heat up to the melting temperature (the temperature at which the glass viscosity is 100 poise), and the temperature can be raised to a maximum of 1680℃.

[0159] The glass was heated to 1580℃ to melt it, and held at that temperature for 20 minutes. A platinum rotor probe was then inserted into the substrate glass to test its viscosity. The glass was then cooled at a rate of 2℃ / min, and the viscosity was continuously tested until it reached approximately 100,000 poise. The test was then completed, and the platinum rotor probe was removed. The instrument recorded the test temperature and viscosity of the substrate glass at the same time and output the data. The following specific embodiments further illustrate this application.

[0160] Example 1

[0161] Weigh each raw material accurately according to the following proportions: SiO2 63.00 mol%. 、 The mixture consists of 11.00 mol% Al2O3, 2.00 mol% Y2O3, 2.00 mol% La2O3, 5.00 mol% MgO, 5.00 mol% Na2O, 10.00 mol% Li2O, and 2.00 mol% ZrO2. The total mass of the above raw materials is 1600 g. 0.4 wt% of clarifying agent sodium chloride (6.4 g sodium chloride) is added and the mixture is thoroughly mixed to obtain a mixture.

[0162] The mixture was placed in a platinum crucible and heated to 1650℃ in a high-temperature melting furnace for 10 hours. It was then poured into a molding die and cooled to 800℃ before being placed in an annealing furnace and annealed at 560℃ for 2000 minutes. The temperature was then gradually reduced to 500℃ over 300 minutes and held for 300 minutes, followed by a further reduction to 400℃ over 300 minutes and a holding time of 300 minutes. This gradual cooling process was repeated until the mixture was cooled to room temperature in the furnace, yielding a glass brick. The glass brick was then shaped and cut using a multi-wire cutter to obtain glass sheets with a thickness of 0.7 mm, such as 50 mm × 50 mm × 0.7 mm (standard dimensions) or 158.8 mm × 72.8 mm × 0.7 mm. Precision machining (CNC), thinning, and polishing were then performed to obtain the substrate glass for chemically strengthened glass.

[0163] The obtained substrate glass was subjected to two-step chemical strengthening to obtain chemically strengthened glass. The first step of chemical strengthening was chemical strengthening treatment in a 100wt% NaNO3 salt bath at 450℃ for 5 hours; the second step of chemical strengthening was chemical strengthening treatment in a 100wt% KNO3 salt bath at 450℃ for 1 hour.

[0164] Examples 2-6

[0165] Except for adjusting the raw material ratio and chemical fortification conditions as shown in Table 1, everything else is the same as in Example 1.

[0166] Comparative Examples 1-5

[0167] Except for adjusting the raw material ratio and chemical fortification conditions as shown in Table 1, everything else is the same as in Example 1.

[0168] The performance of the substrate glass and chemically strengthened glass prepared in Examples 1-6 and Comparative Examples 1-5 were tested.

[0169] The relevant parameters of the substrate glass and chemically strengthened glass in Examples 1-5 and Comparative Examples 1-6 are shown in Tables 1 and 2 below.

[0170]

[0171]

[0172] As can be seen from Tables 1 and 2 above, the content of each component and the relationship between the content of the components in Examples 1-6 are within the scope of this application, and the Young's modulus of the substrate glass is higher than 95 GPa; in terms of acid resistance, the erosion of the substrate glass after immersion in a 5wt% HCl solution at 95°C for 24 hours is ≤7 mg / cm³. 2Regarding stress performance, the maximum tensile stress linear density CT_LD that can be obtained by ion exchange on a 0.7mm thick substrate glass is... max All have a strength higher than 56,000 MPa / mm², and the bifurcation threshold of the substrate glass is higher than 50,000 MPa / mm². Furthermore, the upper limit of crystallization temperature for the substrate glass is ≤1310℃, and the viscosity corresponding to the upper limit of crystallization temperature is greater than or equal to 10. 2.2 dPa·s, which can meet the requirements of continuous melting and casting production processes.

[0173] In Comparative Example 1, the content of Y₂O₃+La₂O₃ was high, which is outside the scope of this application, resulting in poor acid resistance of the substrate glass and failing to meet the requirements; in addition, the upper limit temperature for crystallization was high, >1360℃, and the upper limit of crystallization corresponds to a viscosity <10. 2.0 The high dPa·s results in poor glass mass production performance.

[0174] In Comparative Example 2, the La2O3 / (Y2O3+La2O3) ratio is too high, which is outside the scope of this application. This results in a higher upper limit temperature for crystallization of the substrate glass, which is 1355℃. The upper limit of crystallization corresponds to a viscosity of <10. 2.0 The high dPa·s results in poor glass mass production performance.

[0175] The Y₂O₃+La₂O₃ content in Comparative Example 3 was low, which is outside the scope of this application, resulting in a high upper limit temperature for crystallization of the substrate glass, >1360℃, and the corresponding viscosity of the upper limit of crystallization is <10. 2.0 The high dPa·s results in poor glass mass production performance.

[0176] In Comparative Example 4, the contents of SiO2 and Al2O3 are outside the scope of this application, and the Al2O3 / SiO2 ratio is also outside the scope of this application, resulting in a higher upper limit temperature for crystallization of the substrate glass, >1360℃. The upper limit of crystallization corresponds to a viscosity of 10. 2.1 The low dPa·s results in poor glass mass production performance; and its acid resistance is also very poor, failing to meet requirements.

[0177] The content of Y2O3+La2O3 in Comparative Example 5 is low, which is not within the scope of this application, resulting in a low Young's modulus of the substrate glass, which does not reach 95GPa, and a bifurcation threshold ≤49000MPa / mm.

[0178] 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 chemically strengthened glass, characterized in that, The tensile stress layer of the chemically strengthened glass comprises the following components, by molar percentage of oxides: SiO2 60.0-70.0 mol% Al2O3 8.0-15.0 mol% MgO 1.0-8.0 mol% Li₂O 7.0-12.0 mol% Na₂O 2.0-5.0 mol% and Y2O3 and La2O3; The content of Y2O3+La2O3 is 4.0-8.0 mol%, and the ratio of La2O3 / (Y2O3+La2O3) is 0.45-0.65; the CS_50 of the chemically strengthened glass is 100MPa-150MPa; and the thickness t of the chemically strengthened glass is 0.4-2.0mm.

2. The chemically strengthened glass according to claim 1, characterized in that, The CS_50 of the chemically strengthened glass is 105MPa-150MPa.

3. The chemically strengthened glass according to claim 2, characterized in that, The CS_50 of the chemically strengthened glass is 110MPa-140MPa.

4. The chemically strengthened glass according to any one of claims 1 to 3, characterized in that, The DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, where t is the thickness of the chemically strengthened glass.

5. The chemically strengthened glass according to any one of claims 1 to 3, characterized in that, The CT_LD of the chemically strengthened glass is 45000MPa / mm-60000MPa / mm; CT_LD refers to the ratio of the definite integral of the tensile stress curve of the chemically strengthened glass to the thickness of the chemically strengthened glass, and is denoted as tensile stress linear density.

6. The chemically strengthened glass according to claim 5, characterized in that, The CT_LD of the chemically strengthened glass is 45000MPa / mm-57000MPa / mm.

7. A method for preparing chemically strengthened glass as described in any one of claims 1-6, comprising the following steps: (1) Select the raw materials according to the composition of the substrate glass, mix them, melt and form them, and then cool and anneal them to obtain the substrate glass; (2) Chemically strengthen the substrate glass to obtain chemically strengthened glass; The substrate glass comprises the following components, based on the molar percentage of oxides: SiO2 60.0-70.0 mol% Al2O3 8.0-15.0 mol% MgO 1.0-8.0 mol% Li₂O 7.0-12.0 mol% Na₂O 2.0-5.0 mol% and Y2O3 and La2O3; in, The concentration of Y₂O₃ + La₂O₃ is 4.0-8.0 mol.

8. The method for preparing chemically strengthened glass according to claim 7, characterized in that, The substrate glass, by molar percentage of oxides, further comprises the following components: K2O 0-2.0 mol% ZrO2 0-2.0 mol% B2O30-5.0mol% P2O50-5.0mol% CaO 0-8.0 mol% SrO 0-3.0 mol%.

9. The method for preparing chemically strengthened glass according to claim 7 or 8, characterized in that, The chemical strengthening in step (2) includes single-step chemical strengthening or multi-step chemical strengthening.

10. The method for preparing chemically strengthened glass according to claim 9, characterized in that, The single-step chemical enhancement uses a mixed salt bath containing NaNO3 and KNO3.

11. The method for preparing chemically strengthened glass according to claim 10, characterized in that, The single-step chemical enhancement uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-100wt% and the content of NaNO3 is 0-20wt%.

12. The method for preparing chemically strengthened glass according to claim 10, characterized in that, The temperature for the single-step chemical strengthening is 380℃-500℃.

13. The method for preparing chemically strengthened glass according to claim 12, characterized in that, The ion exchange time for the single-step chemical enhancement is 3h-10h.

14. The method for preparing chemically strengthened glass according to claim 9, characterized in that, The multi-step chemical enhancement includes two steps: the first step uses a salt bath containing NaNO3, and the second step uses a salt bath containing KNO3.

15. The method for preparing chemically strengthened glass according to claim 14, characterized in that, The multi-step chemical enhancement includes two chemical enhancement steps. The first step uses a salt bath containing NaNO3, with the NaNO3 content in the salt bath being 70-100 wt%. The second step uses a salt bath containing KNO3, with the KNO3 content in the salt bath being 60-100 wt%.

16. The method for preparing chemically strengthened glass according to claim 14, characterized in that, The temperature for the first step of chemical strengthening is 380℃-500℃.

17. The method for preparing chemically strengthened glass according to claim 16, characterized in that, The ion exchange time for the first step of chemical enhancement is 3-10 hours.

18. The method for preparing chemically strengthened glass according to claim 14, characterized in that, The temperature for the second step of chemical strengthening is 380℃-500℃.

19. The method for preparing chemically strengthened glass according to claim 18, characterized in that, The ion exchange time for the second step of chemical enhancement is 1-10 hours.

20. A glass device, characterized in that, Chemically strengthened glass includes the chemically strengthened glass prepared by any one of claims 1-6 or any one of claims 7-19.

21. An electronic device, characterized in that, Chemically strengthened glass includes the chemically strengthened glass prepared by any one of claims 1-6 or any one of claims 7-19.

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