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

Abstract

The application relates to the technical field of lithium-aluminum-silicate glasses, and provides a lithium-aluminum-silicon substrate glass with high Young's modulus and a chemically strengthened glass thereof, wherein the substrate glass comprises the following components in terms of 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; wherein Y2O3+La2O3 is 4.0-8.0 mol%; and the chemically strengthened glass is obtained by chemical strengthening of the substrate glass. The substrate glass and the chemically strengthened glass according to the application have reasonable component content, good combination effect, high Young's modulus and high stress performance, good acid resistance, and good mass production performance, and can meet the development requirements of cover protection glass in high-end mobile phone products.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lithium aluminum silicate glass, in particular to a lithium aluminum silicon substrate glass with high Young's modulus and a chemically strengthened glass thereof. BACKGROUND

[0002] The cover protection glass of electronic devices needs to have high drop resistance performance. Since the microcrystalline glass has high Young's modulus (about 100 GPa) and high stress performance, it can meet the requirements of high drop resistance performance and can be widely used in the cover protection glass of electronic devices such as mobile phones. However, the production raw material of the microcrystalline glass contains a high content of lithium oxide, so the manufacturing cost is very high, resulting in the high price of the microcrystalline glass. In addition, the production process of the microcrystalline glass is complex and needs to be nucleated and crystallized, resulting in large fluctuation of the yield of the production finished product and poor repeatability. At present, the raw material cost of the lithium aluminum silicon glass product is low, and the crystallization step is not needed, and the processing technology is simpler than that of the microcrystalline glass, which has obvious production advantages. However, the Young's modulus of the lithium aluminum silicon glass is only about 80 GPa, and the drop resistance performance is much worse than that of the microcrystalline glass, which is difficult to meet the development needs of the cover protection glass of electronic devices such as mobile phones.

[0003] In the prior art, the Young's modulus of the lithium aluminum silicon glass has been significantly improved by adding dense oxides such as yttrium oxide, lanthanum oxide and niobium oxide. However, the direct addition of dense oxides such as yttrium oxide, lanthanum oxide and niobium oxide will cause the decrease of ion exchange amount, and then the surface stress level of the glass will be reduced, and the improvement of the drop resistance performance will be limited. In addition, the addition of the above dense oxides will also increase the crystallization temperature of the glass, which will easily crystallize at a lower viscosity, and then the production and forming of the glass will be difficult, resulting in the problems of poor mass production and the like. SUMMARY

[0004] Based on the above situation, the purpose of the present application is to solve the shortcomings of the prior art, and to provide a lithium aluminum silicon substrate glass with good acid resistance and high Young's modulus, and which can be mass produced. In addition, the lithium aluminum silicon substrate glass can be chemically strengthened to obtain a chemically strengthened glass with high stress.

[0005] In a first aspect, the present application provides a lithium aluminum silicon substrate glass, which comprises the following components in terms of mole percentage of oxides:

[0006] SiO2 60.0-70.0mol%;

[0007] Al2O3 8.0-15.0mol%;

[0008] MgO 1.0-8.0mol%;

[0009] Li20 7.0-12.0 mol%;

[0010] Na20 2.0-5.0 mol%;

[0011] and Y203and La203;

[0012] wherein Y203+ La203is 4.0-8.0 mol%.

[0013] In some embodiments of the present application, the Si02is 63.0-70.0 mol%, preferably 63.0-67.0 mol%, and / or the Al203is 8.0-13.0 mol%, preferably 9.0-12.0 mol%, in terms of mole percent of oxides.

[0014] In some embodiments of the present application, the Al203 / Si02in the substrate glass is ≤ 0.2, in terms of mole percent of oxides.

[0015] In some embodiments of the present application, the Y203+ La203in the substrate glass is 5.0-7.0 mol%, in terms of mole percent of oxides.

[0016] In some embodiments of the present application, the La203 / (Y203+ La203) in the substrate glass is 0.25-0.7, preferably 0.4-0.7, in terms of mole percent of oxides.

[0017] In some embodiments of the present application, the substrate glass further comprises the following components, in terms of mole percent of oxides:

[0018] K20 0-2.0 mol%;

[0019] Zr02 0-2.0 mol%;

[0020] B203 0-5.0 mol%;

[0021] P205 0-5.0 mol%;

[0022] CaO 0-8.0 mol%;

[0023] SrO 0-3.0 mol%.

[0024] In some embodiments of the present application, the substrate glass has a Young's modulus of 95-130 GPa, preferably 96-120 GPa.

[0025] In some embodiments of the present application, the substrate glass has a bifurcation threshold of 49,000 MPa / mm to 60,000 MPa / mm, preferably 50,000 MPa / mm to 58,000 MPa / mm.

[0026] In some embodiments of the present application, the substrate glass has a crystallization upper limit temperature of 1,100°C to 1,330°C.

[0027] In some embodiments of the present application, the substrate glass has a crystallization upper limit temperature corresponding to a viscosity of 10 2.2 dPa·s or more, preferably 10 2.5 dPa·s or more.

[0028] In some embodiments of the present application, the substrate glass has an etching amount of 7 mg / cm 2 or less in a 5 wt% HCl solution at 95°C for 24 hours.

[0029] In a second aspect, the present application provides a chemically strengthened glass, which is obtained by chemically strengthening the substrate glass as described above.

[0030] In some embodiments of the present application, the chemical strengthening of the substrate glass comprises single-step chemical strengthening or multi-step chemical strengthening.

[0031] In some embodiments of the present application, the single-step chemical strengthening uses a salt bath containing NaNO3, preferably the content of NaNO3 in the salt bath is 30 wt% to 100 wt%.

[0032] In some embodiments of the present application, the single-step chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, preferably the content of KNO3 in the mixed salt bath is 80 wt% to 100 wt%, and the content of NaNO3 is 0 wt% to 20 wt%.

[0033] In some embodiments of the present application, the single-step chemical strengthening has a temperature of 380°C to 500°C, and more preferably the ion exchange time of the single-step chemical strengthening is 3 hours to 10 hours.

[0034] In some embodiments of the present application, the multi-step chemical strengthening comprises two-step chemical strengthening, wherein the first-step chemical strengthening uses a salt bath containing NaNO3, preferably the content of NaNO3 in the salt bath is 70 wt% to 100 wt%; and the second-step chemical strengthening uses a salt bath containing KNO3, preferably the content of KNO3 in the salt bath is 60 wt% to 100 wt%.

[0035] In some embodiments of the present application, the multi-step chemical strengthening comprises two-step chemical strengthening, the first step chemical strengthening uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-100wt%, and the content of KNO3 is 0-30wt%; the second step chemical strengthening 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%.

[0036] In some embodiments of the present application, the temperature of the first step chemical strengthening is 380-500℃, and the ion exchange time is preferably 3-10h.

[0037] In some embodiments of the present application, the temperature of the second step chemical strengthening is 380-500℃, and the ion exchange time is preferably 1-10h.

[0038] In some embodiments of the present application, the CS_50 of the chemically strengthened glass is 100-150MPa; preferably, the CS_50 is 105-150MPa; more preferably, the CS_50 is 110-140MPa.

[0039] In some embodiments of the present application, the DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, and t is the thickness of the chemically strengthened glass.

[0040] In some embodiments of the present application, the CT_LD of the chemically strengthened glass is 45000-60000MPa / mm, and the CT_LD value is preferably 45000-57000MPa / mm.

[0041] In a third aspect, the present application provides a preparation method of the chemically strengthened glass as described above, comprising the following steps:

[0042] (1) mixing raw materials according to the composition of the base glass, melting and forming, and then cooling and annealing to obtain the base glass;

[0043] (2) chemically strengthening the base glass to obtain the chemically strengthened glass.

[0044] In some embodiments of the present application, the chemical strengthening comprises single-step chemical strengthening or multi-step chemical strengthening.

[0045] In some embodiments of the present application, the single-step chemical strengthening uses a salt bath containing NaNO3, and the content of NaNO3 in the salt bath is preferably 30-100wt%.

[0046] In some embodiments of the present application, the single-step chemical strengthening employs a mixed salt bath containing NaNO3 and KNO3, preferably the mixed salt bath contains 80-100wt% of KNO3 and 0-20wt% of NaNO3.

[0047] In some embodiments of the present application, the single-step chemical strengthening is performed at a temperature of 380-500℃, and preferably the ion exchange time is 3-10h.

[0048] In some embodiments of the present application, the multi-step chemical strengthening comprises two steps, wherein the first step employs a salt bath containing NaNO3, preferably the salt bath contains 70-100wt% of NaNO3; and the second step employs a salt bath containing KNO3, preferably the salt bath contains 60-100wt% of KNO3.

[0049] In some embodiments of the present application, the multi-step chemical strengthening comprises two steps, the first step employs a mixed salt bath containing NaNO3 and KNO3, wherein the mixed salt bath contains 70-100wt% of NaNO3 and 0-30wt% of KNO3; and the second step employs a mixed salt bath containing NaNO3 and KNO3, wherein the mixed salt bath contains 80-100wt% of KNO3 and 0-20wt% of NaNO3.

[0050] In some embodiments of the present application, the first step is performed at a temperature of 380-500℃, and preferably the ion exchange time is 3-10h.

[0051] In some embodiments of the present application, the second step is performed at a temperature of 380-500℃, and preferably the ion exchange time is 1-10h.

[0052] In a fourth aspect, the present application provides a glass device, comprising the lithium-aluminum-silicon-based substrate glass or the chemically strengthened glass as described above.

[0053] In a fifth aspect, the present application provides an electronic device, comprising the lithium-aluminum-silicon-based substrate glass or the chemically strengthened glass as described above.

[0054] In some embodiments of the present application, the electronic device comprises one or more of a mobile phone, a tablet, a smart wearable, a display, or a television.

[0055] Compared with the prior art, the present application has the following beneficial effects:

[0056] 1. The present application controls the lithium aluminum silicon substrate glass to have high Young's modulus and good acid resistance by controlling Y2O3+La2O3 to be between 4-8 mol%; the substrate glass has high stress characteristics after chemical strengthening.

[0057] 2. The present application controls the lithium aluminum silicon substrate glass to have good acid resistance by controlling SiO2>60 mol% and Al2O3<17 mol%, and the acid resistance of the lithium aluminum silicon substrate glass can be further improved by adding ZrO2.

[0058] 3. The present application controls La2O3 / (Y2O3+La2O3)≥0.25, preferably ≥0.4, so that the lithium aluminum silicon substrate glass has a crystallization upper limit temperature of 1100-1330°C, and the viscosity corresponding to the crystallization upper limit temperature is 10 2.2 dPa·s or more; further having mass production characteristics. BRIEF DESCRIPTION OF DRAWINGS

[0059] Figure 1 It is a schematic diagram of the immediate fracture test stress release device; in the figure: 1-height adjusting guide rail, 2-starting adjusting guide rail, 3-press head, 4-chemically strengthened glass sample.

[0060] Figure 2 It is a crack damage state diagram of the immediate fracture test.

[0061] Figure 3 It is a schematic diagram of the present application placing a long quartz tank in a gradient furnace. DETAILED DESCRIPTION

[0062] The technical solutions in the embodiments of the present application will be described clearly and completely in the embodiments of the present application in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. All other embodiments obtained by those skilled in the art based on the present application belong to the scope of protection of the present application.

[0063] The related special names involved in the present application are explained as follows.

[0064] In the present application, the substrate glass is a glass matrix material which has not been subjected to nucleation treatment, crystallization treatment and strengthening treatment.

[0065] In the present application, the chemically strengthened glass is a strengthened glass treated by high-temperature ion exchange process. In a high-temperature salt bath, alkali metal ions with large ion radius (such as potassium ions, sodium ions) replace alkali metal ions with small ion radius (such as sodium ions, lithium ions) in the glass, thereby generating an exchange ion volume difference, and generating a high-to-low compressive stress from the surface to the inside of the surface layer of the substrate glass, hindering and delaying the expansion of glass micro-cracks, and achieving the purpose of improving the mechanical strength of the glass.

[0066] In the present application, surface CS refers to surface compressive stress. After chemical strengthening, the alkali metal ions (such as sodium ions, lithium ions) with small radii on the surface of the substrate glass are replaced by alkali metal ions (such as potassium ions, sodium ions) with large radii. Due to the crowding effect of the alkali metal ions with large radii, the surface of the glass thus generates compressive stress. It can be measured by stress meter FSM-6000 of Japan Morita.

[0067] In the present application, CS_50 refers to the compressive stress value at a depth of 50 μm from the surface of the glass.

[0068] In the present application, DOL_0 refers to the depth of the compressive stress layer, also known as the depth of the compressive stress layer, which refers to the distance from any surface of the glass to the position close to the surface where the compressive stress is zero. It can be measured by stress meter SLP-2000 of Japan Morita.

[0069] In the present application, 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, which is referred to as the tensile stress line density. The substrate glass is placed in a salt bath to form a strengthened layer (i.e. a compressive stress layer) by ion exchange. During ion exchange, a tensile stress layer is formed inside the glass. The tensile stress layer has an upper boundary spaced apart from the upper surface of the chemically strengthened glass and a lower boundary spaced apart from the lower surface of the chemically strengthened glass. A curve drawn with the tensile stress Y-axis and the distance from the upper boundary X-axis at a point on a line segment in the tensile stress layer, which is perpendicular to the upper boundary and the lower boundary and whose upper and lower endpoints fall on the upper boundary and the lower boundary respectively, is referred to 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 referred to as the tensile stress line density, that is, the ratio of the sum of the tensile stresses of the chemically strengthened glass measured by the SLP-2000 stress meter to the thickness of the glass.

[0070] In the present application, CT_LD max refers to the maximum tensile stress line density. The maximum tensile stress line density (CT_LD) value that can be obtained by ion exchange chemical strengthening of the substrate glass under a certain salt bath condition is the maximum tensile stress line density CT_LD max that can be obtained by the substrate glass under the salt bath condition. This data can represent the strengthenable performance / ion exchange performance of the substrate glass.

[0071] In the present application, the bifurcation threshold refers to the minimum tensile stress line density value of the chemically strengthened glass prepared from a certain formula substrate glass when the glass crack bifurcates in the immediate fracture test, that is, the bifurcation threshold of the chemically strengthened glass prepared from the formula substrate glass.

[0072] In a first aspect, the present application provides a lithium aluminum silicon-based substrate glass, comprising the following components in terms of mole percent of oxides:

[0073] SiO260.0-70.0 mol %;

[0074] Al2O38.0-15.0 mol %;

[0075] MgO 1.0-8.0 mol %;

[0076] Li2O 7.0-12.0 mol %;

[0077] Na2O 2.0-5.0 mol %;

[0078] ZrO20.3-2.0 mol %;

[0079] and Y2O3 and La2O3;

[0080] wherein Y2O3 + La2O3 is 4.0-8.0 mol %.

[0081] In the present application, SiO2 is a necessary component for forming the glass framework. High content of SiO2 can ensure that the glass has high strength, thermal expansion resistance, chemical stability and other excellent properties. However, the stability of the framework has little effect on improving the density of the glass, so it generally has little effect on the Young's modulus and mechanical strength of the glass. Since SiO2 has a tendency to increase the viscosity of the glass melt, too high a content of SiO2 will make the glass difficult to melt and form, thereby increasing the difficulty of melting and producing the glass. In some embodiments of the present application, the substrate glass described herein comprises 60.0-70.0 mol % of SiO2 in terms of mole percent of oxides. In some embodiments of the present application, the substrate glass comprises 63.0-70.0 mol % of SiO2, preferably 63.0-67.0 mol % of SiO2 in terms of mole percent of oxides. In some embodiments of the present application, the content of SiO2 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 a value within a range formed by any two of the above values as endpoints.

[0082] Al2O3 forms aluminum-oxygen tetrahedron in glass and connects non-bridging oxygen in the silicon-oxygen network framework, which can increase the strength of the network framework, further enhancing the strength, structural stability and chemical stability of the glass. In the lithium-aluminum-silicon glass system, the chemical stability of Al2O3 is not as good as that of SiO2, such as acid resistance, when the proportion of Al2O3 in the network structure increases, the acid resistance of the glass will decrease; and Al2O3 is the main component of lithium-aluminum-silicon glass system to form its crystallization phase of spodumene, and the addition of excessive Al2O3 will quickly increase the crystallization tendency of the glass, increase the difficulty of glass melting, and thus increase the production difficulty and production cost of the glass. In some embodiments of the present application, the substrate glass described herein includes 8.0-15.0 mol% of Al2O3, in terms of mole percentage of oxides. In some embodiments of the present application, the substrate glass includes 8.0-13.0 mol% of Al2O3, preferably 9.0-12.0 mol% of Al2O3, in terms of mole percentage of oxides. In some embodiments of the present application, the content of Al2O3 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 any two of the above values as endpoints.

[0083] The present application uses alkaline earth metal oxide MgO as the network modifier of the glass, which can adjust the viscosity-temperature performance of the glass, thereby improving the melting performance of the glass. In some embodiments of the present application, the substrate glass described herein includes 1.0-8.0 mol% of MgO, in terms of mole percentage of oxides. In some embodiments of the present application, the content of MgO 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 a value within a range formed by any two of the above values as endpoints.

[0084] Li2O as the network modifier alkali metal component of the glass, makes the silicon-oxygen network of the glass broken, forms a large number of non-bridging oxygen, makes the structure of the glass loose, can greatly reduce the melting temperature, forming temperature of the glass. At the same time, the alkali metal ions in Li2O make the glass have the possibility of ion exchange strengthening. In some embodiments of the present application, the substrate glass described in the present application comprises 7.0-12.0 mol% of Li2O in terms of mole percentage of oxide. In some embodiments of the present application, the content of Li2O 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 formed by any two of the above values as endpoints.

[0085] Na2O as the network modifier alkali metal component of the glass, makes the silicon-oxygen network of the glass broken, forms a large number of non-bridging oxygen, makes the structure of the glass loose, can greatly reduce the melting temperature, forming temperature of the glass; at the same time, the alkali metal ions in Na2O make the glass have the possibility of ion exchange strengthening. In some embodiments of the present application, the substrate glass described in the present application comprises 2.0-5.0 mol% of Na2O in terms of mole percentage of oxide. In some embodiments of the present application, the content of Na2O 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 formed by any two of the above values as endpoints.

[0086] The application uses Y2O3 and La2O3 as network modifier components of the glass, which can reduce the high-temperature viscosity of the glass, facilitate glass melting and elimination of internal defects, improve the Young's modulus and micro Vickers hardness of the glass, and improve the chemical strengthening performance of the glass and the stress effect of the ion exchange per unit of the chemically strengthened glass. In addition, when Y2O3 and La2O3 are mixed and added to the lithium-aluminum-silicon glass, the crystallization tendency of the lithium-aluminum-silicon glass is less than that of 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 the application, the substrate glass described in the application includes Y2O3 and La2O3, and the content of Y2O3+La2O3 is 4.0-8.0 mol%, preferably 5.0-7.0 mol%, in terms of mole percentage of oxides. In some embodiments of the 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 a value within a range formed by any two of the above values as endpoints.

[0087] In some embodiments of the application, the substrate glass includes 2.0-5.0 mol% of Y2O3, in terms of mole percentage of oxides. In some embodiments of the application, the content of Y2O3 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 formed by any two of the above values as endpoints.

[0088] In some embodiments of the application, the substrate glass includes 2.0-5.0 mol% of La2O3, in terms of mole percentage of oxides. In some embodiments of the application, the content of La2O3 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 formed by any two of the above values as endpoints.

[0089] The La2O3 content in the present application cannot be too high because the crystallization tendency will suddenly increase as it tends to crystallize into the same dense oxide, and Y2O3 is more beneficial than La2O3 for improving the stress effect. The present application controls the value of La2O3 / (Y2O3+La2O3) in the substrate glass within a suitable range from the viewpoint of balancing crystallization and high stress performance. In some embodiments of the present application, the La2O3 / (Y2O3+La2O3) in the substrate glass is 0.25-0.70, preferably 0.40-0.70, in terms of mole percent of oxides. In some embodiments of the present 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.

[0090] In some embodiments of the present application, the substrate glass comprises 0-2.0 mol% of K2O, in terms of mole percent of oxides. In some embodiments of the present application, the content of K2O in the substrate glass can be 0.0 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. K2O as a network modifier alkali metal component of the glass breaks the silicon-oxygen network of the glass to form a large number of non-bridging oxygens, making the structure of the glass loose, and can greatly reduce the melting temperature and forming temperature of the glass.

[0091] In some embodiments of the present application, the substrate glass comprises 0-2.0 mol% of K2O, in terms of mole percent of oxides. In some embodiments of the present application, the content of K2O in the substrate glass can be 0.0 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. K2O as a network modifier alkali metal component of the glass breaks the silicon-oxygen network of the glass to form a large number of non-bridging oxygens, making the structure of the glass loose, and can greatly reduce the melting temperature and forming temperature of the glass.

[0092] In some embodiments of the present application, the substrate glass comprises 0-2.0 mol% of K2O, in terms of mole percent of oxides. In some embodiments of the present application, the content of K2O in the substrate glass can be 0.0 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. K2O as a network modifier alkali metal component of the glass breaks the silicon-oxygen network of the glass to form a large number of non-bridging oxygens, making the structure of the glass loose, and can greatly reduce the melting temperature and forming temperature of the glass.

[0093] In some embodiments of the application, the substrate glass comprises 0-5.0 mol% B203, in terms of mole percent of oxides. In some embodiments of the application, the content of B203in 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 formed by any two of the aforementioned values as endpoints.

[0094] In some embodiments of the application, the substrate glass comprises 0-5.0 mol% P205, in terms of mole percent of oxides. In some embodiments of the application, the content of P205in 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 formed by any two of the aforementioned values as endpoints. P205is a network-forming component, can reduce the melting difficulty of the glass, and increase the ion diffusion speed of chemical strengthening, but can reduce the chemical durability of the glass, and easily cause the glass to phase separate, and easily reduce the devitrification temperature.

[0095] In some embodiments of the application, the substrate glass comprises 0-8.0 mol% CaO, in terms of mole percent of oxides. In some embodiments of the application, the content of CaO 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 aforementioned values as endpoints.

[0096] In some embodiments of the application, the substrate glass comprises 0-3.0 mol% SrO, in terms of mole percent of oxides. In some embodiments of the application, the content of SrO 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 aforementioned values as endpoints.

[0097] In some embodiments of the present application, the substrate glass has a Young's modulus of 95 GPa to 130 GPa, preferably 96 GPa to 120 GPa. In some embodiments of the present application, the Young's modulus of the substrate glass can have a value of 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 any two of the above values as endpoints. The present application does not have a particular limitation on the test method and test instrument for the Young's modulus, as long as the object of the present application can be achieved, for example, the acoustic wave method can be used for measurement.

[0098] In some embodiments of the present application, the substrate glass has a bifurcation threshold of 49,000 MPa / mm to 60,000 MPa / mm, preferably 50,000 MPa / mm to 58,000 MPa / mm. In some embodiments of the present application, the bifurcation threshold of the chemically strengthened glass can have a value of 49,000 MPa / mm, 49,500 MPa / mm, 50,000 MPa / mm, 50,500 MPa / mm, 51,000 MPa / mm, 51,500 MPa / mm, 52,000 MPa / mm, 52,500 MPa / mm, 53,000 MPa / mm, 53,500 MPa / mm, 54,000 MPa / mm, 54,500 MPa / mm, 55,000 MPa / mm, 55,500 MPa / mm, 56,000 MPa / mm, 56,500 MPa / mm, 57,000 MPa / mm, 57,500 MPa / mm, 58,000 MPa / mm, 58,500 MPa / mm, 59,000 MPa / mm, 59,500 MPa / mm, 60,000 MPa / mm, or a value within a range formed by any two of the above values as endpoints.

[0099] In some embodiments of the present application, the crystallization upper limit temperature of the substrate glass is in the range of 1100 to 1330 °C. In some embodiments of the present application, the crystallization upper limit temperature can be in the range of 1100 °C, 1110 °C, 1120 °C, 1130 °C, 1140 °C, 1150 °C, 1160 °C, 1170 °C, 1180 °C, 1190 °C, 1200 °C, 1210 °C, 1220 °C, 1230 °C, 1240 °C, 1250 °C, 1260 °C, 1270 °C, 1280 °C, 1290 °C, 1300 °C, 1310 °C, 1320 °C, 1330 °C, or a range formed between any two of the above values as the terminal points.

[0100] In some embodiments of the present application, the viscosity corresponding to the crystallization upper limit temperature of the substrate glass is 10 2.2 dPa-s or more, preferably 10 2.5 dPa-s or more. In some embodiments of the present application, the viscosity corresponding to the crystallization upper limit 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 dPa-s, or a range formed between any two of the above values as the terminal points.

[0101] In some embodiments of the present application, the etching amount of the substrate glass in 5 wt% HC1 solution at 95 °C for 24 h is less than or equal to 7 mg / cm 2 In some embodiments of the present application, the etching amount of the substrate glass in 5 wt% HC1 solution at 95 °C for 24 h can be in the range of 0.2 mg / cm 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 / cm2 2 6.0 mg / cm2 2 6.5 mg / cm2 2 7.0 mg / cm2 2 or a range formed by any two of the above values as endpoints. The test method and test apparatus for the etching amount of the substrate glass in a 5wt% HC1 solution at 95°C for 24h are not particularly limited in the present application as long as the purpose of the present application can be achieved.

[0102] In a second aspect, the present application provides a chemically strengthened glass, which is obtained by chemically strengthening the substrate glass as described above.

[0103] In some embodiments of the present application, the chemical strengthening of the substrate glass comprises single-step chemical strengthening or multi-step chemical strengthening.

[0104] In some embodiments of the present application, the single-step chemical strengthening employs a salt bath containing NaNCb, preferably the content of NaNCb in the salt bath is 30-100wt%. In some embodiments of the present application, the content of NaNCb in the salt bath can be 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, 100wt% or a range formed by any two of the above values as endpoints.

[0105] In some embodiments of the present application, the single-step chemical strengthening employs a mixed salt bath containing NaNCb and KNCb, preferably the content of KNCb in the mixed salt bath is 80-100wt% and the content of NaNCb is 0-20wt%. In some embodiments of the present application, the content of KNCb in the mixed salt bath can be 80wt%, 85wt%, 90wt%, 95wt%, 100wt% or a range formed by any two of the above values as endpoints. In some embodiments of the present application, the content of NaNCb in the mixed salt bath can be 0wt%, 5wt%, 10wt%, 15wt%, 20wt% or a range formed by any two of the above values as endpoints.

[0106] In some embodiments of the present application, the temperature of the single-step chemical strengthening is 380-500°C, and more preferably the ion exchange time of the single-step chemical strengthening is 3-10h. In some embodiments of the present application, the temperature of the single-step chemical strengthening can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 500°C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the single-step chemical strengthening can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a value within a range formed by any two of the above values as endpoints.

[0107] In some embodiments of the present application, the multi-step chemical strengthening comprises two-step chemical strengthening, wherein the first-step chemical strengthening uses a salt bath containing NaNO3, and preferably the content of NaNO3 in the salt bath is 70-100wt%; the second-step chemical strengthening uses a salt bath containing KNO3, and preferably the content of KNO3 in the salt bath is 60-100wt%. In some embodiments of the present application, the content of NaNO3 in the salt bath can be 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 100wt%, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the content of KNO3 in the salt bath can be 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 100wt%, or a value within a range formed by any two of the above values as endpoints.

[0108] In some embodiments of the present application, 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%. In some embodiments of the present application, in the first step of chemical strengthening, 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 a value within a range formed by any two of the above values as endpoints; 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 a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, in the second step of chemical strengthening, the content of KNO3 in the mixed salt bath can be 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or a value within a range formed by any two of the above values as endpoints; the content of NaNO3 in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or a value within a range formed by any two of the above values as endpoints.

[0109] In some embodiments of the present application, the temperature of the first step of chemical strengthening is 380-500°C, and the ion exchange time is preferably 3-10 h. In some embodiments of the present application, the temperature of the first step of chemical strengthening can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 500°C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the first step of chemical strengthening can be 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or a value within a range formed by any two of the above values as endpoints.

[0110] In some embodiments of the present application, the temperature of the second chemical strengthening is 380-500°C, preferably the ion exchange time is 1-10h. In some embodiments of the present application, the temperature of the second chemical strengthening can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 500°C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the second chemical strengthening can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a value within a range formed by any two of the above values as endpoints.

[0111] In some embodiments of the present application, the CS_50 of the chemically strengthened glass is 100-150MPa, preferably 105-150MPa, more preferably 110-140MPa. In some embodiments of the present application, the CS_50 of the chemically strengthened glass can be 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, or a value within a range formed by any two of the above values as endpoints. The test method and test instrument for surface CS_50 in the present application are not particularly limited as long as the purpose of the present application can be achieved, for example, measured by stress meter FSM-6000.

[0112] In the present application, the thickness of the glass changes very little before and after chemical strengthening, which can be almost negligible, i.e. the thickness of the base glass and the thickness of the chemically strengthened glass prepared by chemical strengthening of the base glass are very similar. In some embodiments of the present application, the surface stress layer depth DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, t is the thickness of the chemically strengthened glass. In some embodiments of the present 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 a value within a range formed by any two of the above values as endpoints.

[0113] The thickness of the chemically strengthened glass described in the present application is not particularly limited, and can be, for example, 0.4-2.0 mm. The thickness of the chemically strengthened glass described in the present 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 a value within a range formed by any two of the above values as endpoints.

[0114] In some embodiments of the present application, the CT_LD of the chemically strengthened glass is 45000 MPa / mm-60000 MPa / mm, preferably 45000 MPa / mm-57000 MPa / mm. In some embodiments of the present application, the CT_LD of the chemically strengthened glass can be 45000 MPa / mm, 46000 MPa / mm, 47000 MPa / mm, 48000 MPa / mm, 49000 MPa / mm, 50000 MPa / mm, 51000 MPa / mm, 52000 MPa / mm, 53000 MPa / mm, 54000 MPa / mm, 55000 MPa / mm, 56000 MPa / mm, 57000 MPa / mm, 58000 MPa / mm, 59000 MPa / mm, 60000 MPa / mm, or a value within a range formed by any two of the above values as endpoints. The testing equipment and testing method for the CT_LD of the chemically strengthened glass are not particularly limited in the present application, as long as the purpose of the present application can be achieved.

[0115] In a third aspect, the present application provides a method for preparing the chemically strengthened glass as described above, comprising the following steps:

[0116] (1) mixing each component of raw materials according to the composition of the base glass, melting and forming, and then cooling and annealing to obtain the base glass;

[0117] (2) chemically strengthening the base glass to obtain the chemically strengthened glass.

[0118] In some embodiments of the present application, the chemical strengthening of the base glass comprises single-step chemical strengthening or multi-step chemical strengthening.

[0119] In some embodiments of the present application, the single-step chemical strengthening uses a salt bath containing NaNO3, and preferably the content of NaNO3 in the salt bath is 30-100 wt%. In some embodiments of the present application, the content of NaNO3 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.

[0120] In some embodiments of the present application, the single-step chemical strengthening employs a mixed salt bath containing NaNCb and KNCb, preferably the content of KNCb in the mixed salt bath is 80-100 wt%, and the content of NaNCb is 0-20 wt%. In some embodiments of the present application, the content of KNCb in the mixed salt bath can be 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the content of NaNCb in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or a value within a range formed by any two of the above values as endpoints.

[0121] In some embodiments of the present application, the temperature of the single-step chemical strengthening is 380-500 °C, and more preferably the ion exchange time of the single-step chemical strengthening is 3-10 h. In some embodiments of the present application, the temperature of the single-step chemical strengthening can be 380 °C, 390 °C, 400 °C, 410 °C, 420 °C, 430 °C, 440 °C, 450 °C, 460 °C, 470 °C, 480 °C, 500 °C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the single-step chemical strengthening can be 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or a value within a range formed by any two of the above values as endpoints.

[0122] In some embodiments of the present application, the multi-step chemical strengthening comprises two-step chemical strengthening, wherein the first step chemical strengthening employs a salt bath containing NaNCb, preferably the content of NaNCb in the salt bath is 70-100 wt%; the second step chemical strengthening employs a salt bath containing KNCb, preferably the content of KNCb in the salt bath is 60-100 wt%. In some embodiments of the present application, the content of NaNCb in the salt bath in the first step chemical strengthening can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the content of KNCb in the salt bath in the second step chemical strengthening can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or a value within a range formed by any two of the above values as endpoints.

[0123] In some embodiments of the present application, 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%. In some embodiments of the present application, in the first step of chemical strengthening, 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 a value within a range formed by any two of the above values as endpoints; 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 a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, in the second step of chemical strengthening, the content of KNO3 in the mixed salt bath can be 80 wt%, 85 wt%, 90 wt%, 95 wt%, 100 wt%, or a value within a range formed by any two of the above values as endpoints; the content of NaNO3 in the mixed salt bath can be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or a value within a range formed by any two of the above values as endpoints.

[0124] In some embodiments of the present application, the temperature of the first step of chemical strengthening is 380-500°C, and the ion exchange time is preferably 3-10 h. In some embodiments of the present application, the temperature of the first step of chemical strengthening can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 500°C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the first step of chemical strengthening can be 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or a value within a range formed by any two of the above values as endpoints.

[0125] In some embodiments of the present application, the temperature of the second step of chemical strengthening is 380-500°C, preferably the ion exchange time is 1-10h. In some embodiments of the present application, the temperature of the second step of chemical strengthening can be 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 500°C, or a value within a range formed by any two of the above values as endpoints. In some embodiments of the present application, the ion exchange time of the second step of chemical strengthening can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a value within a range formed by any two of the above values as endpoints.

[0126] In a fourth aspect, the present application provides a glass device, wherein the glass device comprises the lithium-aluminum-silicon-based substrate glass described above or the chemically strengthened glass described above.

[0127] In a fifth aspect, the present application provides an electronic device, wherein the electronic device comprises the lithium-aluminum-silicon-based substrate glass described above or the chemically strengthened glass described above.

[0128] In some embodiments of the present application, the electronic device comprises: a housing comprising a front surface, a back surface, and side surfaces; and electronic components at least partially within the housing, the electronic components comprising a display at or adjacent to the front surface of the housing; the front surface or / and the back surface or / and the side surfaces comprise the chemically strengthened glass described above.

[0129] In some embodiments of the present application, the electronic device further comprises a cover article overlying the front surface of the housing or overlying the display, the cover article comprising the chemically strengthened glass described above.

[0130] In some embodiments of the present application, the electronic device comprises a mobile phone, a tablet computer, a smart wearable, a display, or a television, etc.; wherein the smart wearable comprises a smart bracelet, a smart watch, and smart glasses, etc.; the display comprises a high-definition display, a vehicle-mounted display, an aircraft-mounted display, etc.

[0131] Various glasses of the present application are tested by the following methods:

[0132] Young's modulus test

[0133] Young's modulus of the glass is tested by using the ultrasonic echo analysis method by using a UMS-100 ultrasonic material characterization system.

[0134] Stress parameter test

[0135] Surface stress test: surface CS_50, DOL_0 is tested by using a stress meter SLP-2000 of Japan Luceo (Japan Orikata).

[0136] Test conditions: light source wavelength is 518 nm, SOC = 28.6 (nm / cm) / MPa, refractive index = 1.51, exposure time: 5000 usec. When testing CS_50, DOL_0, the conductive liquid is first dripped on the stress meter, then the glass sample to be tested is wiped clean and placed on the test channel to test the stress value. The SLP-2000 uses a conductive liquid with a refractive index of 1.51.

[0137] CT_LD is calculated as follows:

[0138]

[0139] Wherein: t represents the thickness of the glass sheet, unit mm; DOL_0 represents the depth of the compressive stress layer, unit μm; CT_AV represents the average internal tensile stress, the absolute value is taken when calculating, unit MPa. It should be understood that in the formula for calculating the tensile stress line density, (1000t / 2-DOL_0) is the data substituted for calculation and the calculation result is obtained, and the unit does not participate in the calculation.

[0140] CT_LD max Test: In this application, a 450℃ 100wt% sodium nitrate salt bath is used as the test CT_LD max salt bath condition, and SLP-2000 stress meter is used as the test instrument for testing the tensile stress line density CT_LD. The specific method is as follows: the glass sample to be tested is placed in a 450℃ 100wt% sodium nitrate salt bath for chemical strengthening, and during the strengthening process, the glass sample is taken out every 0.5h to test its internal CT_LD value, and after each time the glass sample is taken out and tested, the glass sample is immediately put into the salt bath for continuous strengthening, and when the next test time point is reached, the glass sample is taken out for testing, and the above test process is repeated, and the tested CT_LD value is recorded. When it is found that the measured CT_LD value increases to a certain value m, and then the data starts to decrease, it is determined that the value m is the maximum tensile stress line density CT_LD max that the base glass sample can be strengthened to obtain in the salt bath condition, i.e. 450℃ 100wt% sodium nitrate salt bath.

[0141] Bifurcation threshold test: first test a base glass with a thickness of 0.7mm corresponding to a certain glass formula, ion exchange in a certain salt bath to obtain the maximum tensile stress line density CT_LD max . Then strengthen the chemical strengthened glass sample with different CT_LD in the salt bath condition, for example, CT_LD ranges from 30000 MPa / mm to CT_LD max, 1500 MPa / mm or 2000 MPa / mm, and the CT_LD is obtained by SLP-2000 stress meter test. For example, in this application, the base glass corresponding to the glass formula to be tested with a thickness of 0.7 mm is strengthened in a 100wt% sodium nitrate salt bath at 450°C to obtain chemical strengthened glass samples with CT_LD of about 30000 MPa / mm, about 31000 MPa / mm, about 32000 MPa / mm, about 33000 MPa / mm, about 34000 MPa / mm, and about 36000 MPa / mm, respectively. Then, the chemical strengthened glass samples are subjected to immediate fracture test in order from low to high CT_LD value. The center point of the chemical strengthened glass sample is taken as the breaking point, and a "stress release device" is used to induce cracks at the breaking point. The chemical strengthened glass sample with crack bifurcation is selected, and the smallest CT_LD value of the chemical strengthened glass sample with crack bifurcation is taken as the bifurcation threshold of the chemical strengthened glass prepared from the base glass.

[0142] Immediate fracture test: The center point of the chemical strengthened glass sample is taken as the breaking point, and a "stress release device" is used to induce cracks at the breaking point, so that the cracks extend under the action of internal tensile stress instead of starburst due to excessive impact force. When the chemical strengthened glass cracks bifurcate, the smallest tensile stress linear density value of the chemical strengthened glass sample is the bifurcation threshold. A certain number of base glass products are strengthened to obtain glass samples with different tensile stress linear densities under the same salt bath conditions by different ion exchange times. The multiple glass samples obtained by strengthening are subjected to fracture test in order from low to high tensile stress linear density value. After the immediate fracture test, it is observed whether the glass sample cracks bifurcate, and the glass sample with crack bifurcation is found out. The smallest tensile stress linear density (CT_LD) value corresponding to these glass samples is determined, which is the bifurcation threshold of the chemical strengthened glass corresponding to the base glass.

[0143] The stress release device is shown in Figure 1 , wherein 1 represents a height adjustment guide rail, 2 represents a starting adjustment guide rail, 3 represents a pressure head, and 4 represents a chemical strengthened glass sample. The device uses pneumatic impact, the probe uses a Vickers diamond pressure head and is fixed by guide rails to ensure that the pressure head impacts the glass surface vertically, and is equipped with a pressure sensor. The impact force is controlled by adjusting the air pressure to make the breaking point only induce delayed fracture or only extend two cracks instead of starburst, thereby avoiding the influence of external force on the breaking state to the greatest extent. In the immediate fracture test, the crack needs to extend as shown in a or b of Figure 2 , but not as shown in c of Figure 2 .

[0144] Acid resistance test

[0145] The acid resistance of the present application refers to the resistance of the glass to the corrosive nature of hydrochloric acid, which is characterized by the amount of corrosion per unit area.

[0146] The glass is prepared into a 50mm x 50mm x 0.7mm size, and the weight is first weighed on a precision 0.0001g balance, and then placed in a 5wt% hydrochloric acid solution at 95°C for 24h. After completion, the glass is taken out, weighed again, and the weight of the unetched glass is subtracted to obtain the weight difference M (unit: g), and the area S (unit: cm 2 ) of the front and back surfaces of the glass is calculated, and the amount of corrosion per unit area = M / S.

[0147] Crystallization upper limit temperature test

[0148] The crystallization upper limit temperature refers to the highest temperature at which the base glass produces crystals, and above this temperature, the base glass does not crystallize.

[0149] The base glass is broken into small pieces of 2mm-5mm in size, and then placed in a long quartz tank and covered.

[0150] The gradient furnace of model JKZC-XJY01 is set to a temperature interval, such as 1050-1225°C, and at least 6 temperature points are taken from high to low in each temperature interval.

[0151] After the gradient furnace reaches the preset temperature interval, the long quartz tank with the sample is placed in the gradient furnace, so that the 6 temperature points correspond to the glass samples at 6 positions in the long quartz tank. Referring to Figure 3 After the long quartz tank is placed in the gradient furnace for constant temperature for 60-70min, the long quartz tank is taken out.

[0152] The glass samples at different positions in the long quartz tank are observed, and if the glass sample appears to be devitrified, fogged, or crystallized, the glass sample is determined to be crystallized, and if the glass sample is completely transparent, the glass sample is determined to be not crystallized. Referring to Figure 3 , Figure 3 In the long quartz tank, the upper region is a completely transparent sample, the lower region is a devitrified sample, and there are partially fogged samples between the completely transparent sample and the devitrified sample. When observing, tools such as magnifying glasses, microscopes, etc. can be used.

[0153] Determination of the crystallization upper limit temperature: the crystallization upper limit temperature range is between the temperature point corresponding to the completely transparent sample and the temperature point corresponding to the adjacent devitrified or fogged sample, and the average of the two temperature points is taken as the crystallization upper limit temperature.

[0154] If all the glass samples in the long quartz tank are crystallized within the temperature range set by the gradient furnace, the upper limit temperature of the temperature range of the gradient furnace is reset, and the crystallization upper limit temperature of the glass sample is determined; if all the glass samples in the long quartz tank are not crystallized within the temperature range set by the gradient furnace, the lower limit temperature of the temperature range of the gradient furnace is reset, and the crystallization upper limit temperature of the glass sample is determined.

[0155] Crystallization upper limit corresponds to viscosity

[0156] Prepare 250g or more of the base material glass, and then place it in a corundum crucible or a platinum crucible.

[0157] Turn on the high-temperature viscometer of model RSV-1600RT and heat it up, then place the crucible containing the base material glass into the heating test area, and generally heat it up to the melting temperature (the melting temperature is the temperature when the viscosity of the glass is 100 poise), and the temperature can be heated up to 1680°C at the highest.

[0158] Heat the glass to 1580°C to melt it, and after keeping it at this temperature for 20 minutes, place the platinum rotor probe into the base material glass to test the viscosity of the base material glass; then reduce the temperature at a rate of 2°C / min, and continuously test the viscosity of the base material glass until the viscosity is about 100000 poise, after which the platinum rotor probe is removed. The instrument records the test temperature and test viscosity of the base material glass at the same time, and outputs the data. The present application is further illustrated by specific examples as follows.

[0159] Example 1

[0160] Accurately weigh each raw material according to the following proportions: SiO2 63.00mol%, Al2O3 11.00mol%, Y2O32.00mol%, La2O3 2.00mol%, MgO 5.00mol%, Na2O 5.00mol%, Li2O 10.00mol%, ZrO22.00mol%; the total mass of the above-mentioned raw materials is 1600g, 0.4wt% of clarifying agent sodium chloride (6.4g of sodium chloride) is added, and they are mixed thoroughly to obtain a mixture.

[0161] The mixture is placed in a platinum crucible, heated to 1650°C in a high-temperature smelting furnace for 10 h, then poured into a forming mold to cool and form, after cooling to 800°C, placed in an annealing furnace, annealed at 560°C for 2000 min; then cooled to 500°C in 300 min, kept for 300 min, then cooled to 400°C in 300 min, kept for 300 min, then cooled to 300°C in 300 min, kept for 300 min, to realize gradient slow cooling; then cooled to room temperature in the furnace, to obtain a glass brick; the obtained glass brick is shaped and cut using a multi-wire cutting machine, to obtain a glass sheet with a thickness of 0.7 mm, such as 50 mm x 50 mm x 0.7 mm (specification size), 158.8 mm x 72.8 mm x 0.7 mm, etc.; precise mechanical processing (CNC), thinning, and polishing are performed, to obtain a base glass of the chemically strengthened glass.

[0162] The obtained base glass is subjected to two-step chemical strengthening, to obtain a chemically strengthened glass; wherein the first step of chemical strengthening is chemical strengthening treatment in a 100 wt% NaNO3 salt bath at 450°C for 5 hours; the second step of chemical strengthening is chemical strengthening treatment in a 100 wt% KNO3 salt bath at 450°C for 1 hour.

[0163] Examples 2-6

[0164] Except for adjusting the raw material ratio and chemical strengthening treatment conditions as shown in Table 1, the rest is the same as Example 1.

[0165] Comparative Examples 1-5

[0166] Except for adjusting the raw material ratio and chemical strengthening treatment conditions as shown in Table 1, the rest is the same as Example 1.

[0167] The base glass and the chemically strengthened glass of the chemically strengthened glass prepared in Examples 1-6 and Comparative Examples 1-5 are respectively subjected to performance testing.

[0168] The relevant parameters of the base glass and the chemically strengthened glass in Examples 1-5 and Comparative Examples 1-6 are shown in Table 1 and Table 2 as follows.

[0169]

[0170]

[0171] As can be seen from Table 1 and Table 2 above, the content of each component and the content relationship between components in Examples 1-6 are within the scope of the present application, and the Young's modulus of the base glass is all higher than 95 GPa; in terms of acid resistance, the erosion amount of the base glass immersed in a 5 wt% HCl solution at 95°C for 24 h is all ≤7 mg / cm 2; in terms of stress performance, the maximum tensile stress linear density CT_LD of the ion exchanged 0.7 mm thick base substrate glass is 60 MPa / mm max are all higher than 56000 MPa / mm, and the bifurcation threshold of the base substrate glass is all higher than 50000 MPa / mm; in addition, the crystallization upper limit temperature of the base substrate glass is all ≤1310℃, and the viscosity corresponding to the crystallization upper limit temperature is all greater than or equal to 10 2.2 dPa·s, which can meet the continuous melting and casting production process.

[0172] In the comparative example 1, the content of Y2O3+La2O3 is high, which is not within the scope of the present application, resulting in poor acid resistance of the base substrate glass, which does not meet the requirements; in addition, the crystallization upper limit temperature is high, >1360℃, and the viscosity corresponding to the crystallization upper limit is <10 2.0 dPa·s, resulting in poor mass production performance of the glass.

[0173] In the comparative example 2, La2O3 / (Y2O3+La2O3) is high, which is not within the scope of the present application, resulting in a high crystallization upper limit temperature of the base substrate glass, 1355℃, and the viscosity corresponding to the crystallization upper limit is <10 2.0 dPa·s, resulting in poor mass production performance of the glass.

[0174] In the comparative example 3, the content of Y2O3+La2O3 is low, which is not within the scope of the present application, resulting in a high crystallization upper limit temperature of the base substrate glass, >1360℃, and the viscosity corresponding to the crystallization upper limit is <10 2.0 dPa·s, resulting in poor mass production performance of the glass.

[0175] In the comparative example 4, the content of SiO2 and Al2O3 is not within the scope of the present application, and the ratio of Al2O3 / SiO2 is not within the scope of the present application, resulting in a high crystallization upper limit temperature of the base substrate glass, >1360℃, and the viscosity corresponding to the crystallization upper limit is =10 2.1 dPa·s, resulting in poor mass production performance of the glass; and the acid resistance is very poor, which does not meet the requirements.

[0176] In the comparative example 5, the content of Y2O3+La2O3 is low, which is not within the scope of the present application, resulting in a low Young's modulus of the base substrate glass, which does not meet 95GPa, and the bifurcation threshold is ≤49000 MPa / mm.

[0177] The above only describes the preferred embodiments of the present application, and is not intended to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the scope of protection of the present application.

Claims

1. A lithium aluminum silicon substrate glass, characterized in that, The lithium aluminum silicon 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 2.5-8.0 mol%; Li₂O 7.0-12.0 mol%; Na₂O 2.0-5.0 mol%; Y₂O₃ 2.0-3.5 mol%; and La2O3 2.0-4.5 mol%; Among them, Y2O3+La2O3 is 4.5-8.0 mol%, and La2O3 / (Y2O3+La2O3) is 0.45-0.63; The lithium aluminum silicon substrate glass was etched in a 5 wt% HCl solution at 95°C for 24 hours, with an etching amount of 0.2 mg / cm². 2 Up to 1.6 mg / cm 2 ; The upper limit of crystallization temperature for the lithium aluminum silicon substrate glass is 1100℃-1330℃; and The bifurcation threshold of the lithium aluminum silicon substrate glass is 53000MPa / mm-60000MPa / mm.

2. The lithium aluminum silicon substrate glass according to claim 1, characterized in that, The molar percentage of oxides is 63.0-70.0 mol% for SiO2 and / or 8.0-13.0 mol% for Al2O3.

3. The lithium aluminum silicon substrate glass according to claim 2, characterized in that, In terms of the molar percentage of oxides, SiO2 is 63.0-67.0 mol%; and / or Al2O3 is 9.0-12.0 mol%.

4. The lithium aluminum silicon substrate glass according to claim 1, characterized in that, Based on the molar percentage of oxides, Al2O3 / SiO2 ≤ 0.

2.

5. The lithium aluminum silicon substrate glass according to claim 1, characterized in that, The lithium aluminum silicon substrate glass, by molar percentage of oxides, further comprises the following components: K₂O 0.5-2.0 mol%; ZrO2 0-2.0 mol%; B2O3 0-5.0 mol%; P2O5 0.5-5.0 mol%; CaO 0-8.0 mol%; and SrO 0.5-3.0 mol%.

6. The lithium aluminum silicon substrate glass according to any one of claims 1-5, characterized in that, The Young's modulus of the lithium aluminum silicon substrate glass is 95 GPa-130 GPa.

7. The lithium aluminum silicon substrate glass according to claim 6, characterized in that, The Young's modulus of the lithium aluminum silicon substrate glass is 96 GPa-120 GPa.

8. The lithium aluminum silicon substrate glass according to any one of claims 1-5, characterized in that, The bifurcation threshold of the lithium aluminum silicon substrate glass is 53000MPa / mm-58000MPa / mm.

9. The lithium aluminum silicon substrate glass according to any one of claims 1-5, characterized in that, The viscosity corresponding to the upper limit of crystallization temperature of the lithium aluminum silicon substrate glass is 10. 2.2 dPa·s or above.

10. The lithium aluminum silicon substrate glass according to claim 9, characterized in that, The viscosity corresponding to the upper limit of crystallization temperature of the lithium aluminum silicon substrate glass is 10. 2.5 dPa·s or above.

11. A chemically strengthened glass, wherein the chemically strengthened glass is obtained by chemically strengthening a lithium aluminum silicon substrate glass as described in any one of claims 1-10.

12. The chemically strengthened glass according to claim 11, characterized in that, Chemical strengthening of lithium aluminum silicon substrate glass includes single-step chemical strengthening or multi-step chemical strengthening.

13. The chemically strengthened glass according to claim 12, characterized in that, The single-step chemical enhancement uses a salt bath containing NaNO3.

14. The chemically strengthened glass according to claim 13, characterized in that, The NaNO3 content in the salt bath is 30-100 wt%.

15. The chemically strengthened glass according to claim 12, characterized in that, The single-step chemical enhancement uses a mixed salt bath containing NaNO3 and KNO3.

16. The chemically strengthened glass according to claim 15, characterized in that, The mixed salt bath contains 80-95 wt% KNO3 and 5-20 wt% NaNO3.

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

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

19. The chemically strengthened glass according to claim 12, 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.

20. The chemically strengthened glass according to claim 12, 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%.

21. The chemically strengthened glass according to claim 12, characterized in that, The multi-step chemical enhancement includes two steps. The first step uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of NaNO3 in the mixed salt bath is 70-95 wt% and the content of KNO3 is 5-30 wt%. The second step uses a mixed salt bath containing NaNO3 and KNO3, wherein the content of KNO3 in the mixed salt bath is 80-95 wt% and the content of NaNO3 is 5-20 wt%.

22. The chemically strengthened glass according to claim 19 or 21, characterized in that, The temperature for the first step of chemical strengthening is 380℃-500℃.

23. The chemically strengthened glass according to claim 19 or 21, characterized in that, The ion exchange time for the first step of chemical enhancement is 3-10 hours.

24. The chemically strengthened glass according to claim 19 or 21, characterized in that, The temperature for the second step of chemical strengthening is 380℃-500℃.

25. The chemically strengthened glass according to claim 19 or 21, characterized in that, The ion exchange time for the second step of chemical enhancement is 1-10 hours.

26. The chemically strengthened glass according to any one of claims 11-21, characterized in that, The CS_50 of the chemically strengthened glass is 100MPa-150MPa, where CS_50 refers to the compressive stress value at a depth of 50μm from the glass surface.

27. The chemically strengthened glass according to claim 26, characterized in that, The CS_50 of the chemically strengthened glass is 105MPa-150MPa.

28. The chemically strengthened glass according to claim 26, characterized in that, The CS_50 of the chemically strengthened glass is 110MPa-140MPa.

29. The chemically strengthened glass according to claim 26, characterized in that, The DOL_0 of the chemically strengthened glass is 0.14t≤DOL_0≤0.25t, where DOL_0 refers to the distance from any surface of the glass to the position near the surface where the compressive stress is zero, and t is the thickness of the chemically strengthened glass in mm.

30. The chemically strengthened glass according to claim 26, characterized in that, The CT_LD of the chemically strengthened glass is 45000MPa / mm-60000MPa / mm, where 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.

31. The chemically strengthened glass according to claim 26, characterized in that, The CT_LD of the chemically strengthened glass is 45000MPa / mm-57000MPa / mm.

32. A method for preparing chemically strengthened glass according to any one of claims 11-31, comprising the following steps: (1) Select the raw materials according to the composition of lithium aluminum silicon substrate glass, mix them, melt and form them, and then cool and anneal them to obtain lithium aluminum silicon substrate glass. (2) Chemically strengthen lithium aluminum silicon substrate glass to obtain chemically strengthened glass.

33. A glass device, characterized in that, It includes lithium aluminum silicon substrate glass according to any one of claims 1-10 or chemically strengthened glass according to any one of claims 11-31.

34. An electronic device, characterized in that, It includes lithium aluminum silicon substrate glass according to any one of claims 1-10 or chemically strengthened glass according to any one of claims 11-31.

35. The electronic device according to claim 34, characterized in that, The electronic device includes one or more of the following: mobile phone, tablet computer, smart wearable device, monitor, or television.

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