Aluminosilicate glass, strengthened glass, glass structures, methods of making and applications

Abstract

The application relates to an aluminosilicate glass which comprises 58-63% of SiO2, 16-20% of Al2O3, 12-15% of Na2O, 0-4% of K2O, 3-6% of MgO and 3.1-5% of B2O3 in percentage by mass. The silica and alumina content in the aluminosilicate glass is suitable and the processing difficulty is low, which is beneficial to obtaining a glass original piece with high strength and a suitable thermal expansion coefficient, the composition further comprises low-cost alkali metal oxides, alkaline earth metal oxides and low-mass percentage boron oxide, which is helpful to improving the efficiency of the ion exchange process in the subsequent strengthening process, obtaining a strengthened glass with high comprehensive mechanical properties and low cost. The application further provides a strengthened glass, a glass structure, a preparation method and an application, the strengthened glass has a deep ion exchange depth, high surface compressive stress and high drop height resistance, and has excellent comprehensive mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silicate glass, in particular to an aluminosilicate glass, a strengthened glass, a glass structure, a preparation method and an application. BACKGROUND

[0002] Glass with good light transmittance, low cost and mechanical properties is a key supporting material for electronic products such as mobile phone screens. With the continuous improvement of electronic product technology, the market has put forward higher requirements for the supporting materials of electronic products. The existing silicate glass is difficult to obtain good drop resistance even after strengthening, which greatly limits the application of silicate glass in electronic products. SUMMARY

[0003] Therefore, the purpose of the present application includes providing an aluminosilicate glass, a strengthened glass, a glass structure, a preparation method and an application. The composition of the aluminosilicate glass has good processing characteristics and mechanical properties, and can obtain a glass product with good comprehensive performance, and the cost is low.

[0004] In a first aspect, the present application provides an aluminosilicate glass, which comprises the following composition according to mass percentage:

[0005] 58% to 63% of SiO2, 16% to 20% of Al2O3, 12% to 15% of Na2O, 0% to 4% of K2O, 3% to 6% of MgO and 3.1% to 5% of B2O3.

[0006] In some embodiments, the aluminosilicate glass satisfies that α is 2.93 to 4.39; wherein; α is the stress decay resistance index of the glass.

[0007]

[0008] W Al , W K , W Mg and W B respectively represent the value obtained by multiplying the mass percentage of Al2O3, K2O, MgO and B2O3 in the aluminosilicate glass by 100.

[0009] In some embodiments, the aluminosilicate glass satisfies one or more of the following characteristics:

[0010] The coefficient of thermal expansion (CTE) is 85x10 -7 ℃ -1 to 91x10 -7 ℃ -1 ;

[0011] The softening temperature is 790℃ to 815℃.

[0012] The melting temperature is 1630-1670℃.

[0013] In a second aspect of the present application, a preparation method of an aluminosilicate glass is provided, comprising the following steps:

[0014] The raw materials are mixed according to the formula to obtain a batch, and the composition of the batch is consistent with the composition of the aluminosilicate glass according to the first aspect;

[0015] The batch is subjected to heating treatment, forming treatment, annealing treatment and cooling treatment to obtain the aluminosilicate glass.

[0016] In some embodiments, the preparation method satisfies one or more of the following characteristics:

[0017] The temperature of the heating treatment is 1650-1680℃;

[0018] The time of the heating treatment is 4-8h;

[0019] The temperature of the annealing treatment is 730-760℃;

[0020] The time of the annealing treatment is 2-4h.

[0021] In a third aspect of the present application, a preparation method of a strengthened glass is provided, comprising the following steps: subjecting a raw glass sheet to chemical strengthening treatment in a molten salt at 415-425℃ for 4-6h to obtain the strengthened glass, wherein the raw glass sheet is the aluminosilicate glass according to any one of claims 1-3 or prepared by the preparation method according to claim 4 or 5.

[0022] In a fourth aspect of the present application, a preparation method of a strengthened glass is provided, comprising the following steps:

[0023] Obtaining a raw glass sheet, and obtaining the value of the stress decay index α of the glass according to the composition of the aluminosilicate glass; wherein, W Al , W K , W Mg and W B respectively represent the value obtained by multiplying the mass percentage of Al2O3, K2O, MgO and B2O3 in the aluminosilicate glass by 100; the raw glass sheet is the aluminosilicate glass according to any one of claims 1-3 or prepared by the preparation method according to claim 4 or 5;

[0024] Subjecting the raw glass sheet to chemical strengthening treatment according to the corresponding process conditions selected according to the interval in which the value of α is located to obtain the strengthened glass;

[0025] wherein,

[0026] when 2.93≤α≤3.72, the original sheet glass is subjected to chemical strengthening treatment at 426℃-434℃ and in molten salt for 2.8h-3.2h;

[0027] when 3.72<α≤4.39, the original sheet glass is subjected to chemical strengthening treatment at 436℃-444℃ and in molten salt for 2.4h-2.6h.

[0028] In a fifth aspect of the present application, a strengthened glass is provided, which is prepared according to the preparation method of the third aspect or the fourth aspect, and satisfies one or more of the following characteristics:

[0029] the surface compressive stress of the strengthened glass is 1000MPa-1250MPa;

[0030] the ion exchange layer depth of the strengthened glass is 38μm-46μm.

[0031] In a sixth aspect of the present application, a glass structure is provided, which comprises the strengthened glass prepared according to the preparation method of the third aspect or the fourth aspect or the strengthened glass of the fifth aspect.

[0032] In a seventh aspect of the present application, the use of the strengthened glass prepared according to the preparation method of the third aspect or the fourth aspect or the strengthened glass of the fifth aspect or the glass structure of the sixth aspect in electronic devices is provided.

[0033] The main components, i.e. silicon oxide and aluminum oxide, in the composition of the aluminosilicate glass provided in the present application are suitable and have low processing difficulty, which is conducive to obtaining a glass sheet with high strength and suitable coefficient of thermal expansion, and the composition further comprises low-cost alkali metal oxide, alkaline earth metal oxide and low-mass percentage boron oxide, which is conducive to improving the efficiency of the ion exchange process in the subsequent strengthening process, obtaining a strengthened glass with high comprehensive mechanical properties and low cost.

[0034] The preparation method of the aluminosilicate glass provided in the present application adopts a heating, forming, annealing and cooling treatment method to prepare the aluminosilicate glass, and the process is simple, has fewer steps, low processing temperature and low energy consumption.

[0035] The preparation method of the strengthened glass provided in the present application adopts a low strengthening temperature and a short strengthening time, and can prepare a strengthened glass with deep ion exchange depth, high surface compressive stress and high drop height resistance; the preparation process is simple and has low cost.

[0036] The strengthened glass provided in the present application has a deep ion exchange depth, high surface compressive stress and high drop height resistance, and has excellent comprehensive mechanical properties. The deep ion exchange depth is also beneficial to improving the surface hardness and scratch resistance of the glass.

[0037] The glass structure provided in the present application adopts the strengthened glass with a deep ion exchange depth, high surface compressive stress and high drop height resistance, and has good comprehensive mechanical properties.

[0038] The strengthened glass with a deep ion exchange depth, high surface compressive stress and high drop height resistance is used for electronic devices in the present application, which can effectively improve the drop resistance of the electronic devices and also help to improve the service life of the electronic devices. DETAILED DESCRIPTION

[0039] In order to facilitate the understanding of the present application, the present application will be described more fully below, and the preferred embodiments of the present application are given. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the disclosure of the present application more thorough and comprehensive.

[0040] The implementation of the present application will be described in detail below. The present embodiment is implemented on the premise of the technical solution of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the specific embodiments of the present application, and are not intended to limit the present application.

[0042] Terminology

[0043] Unless otherwise stated or contradictory, the terms or phrases used herein have the following meanings:

[0044] In the present application, "a plurality of", "a plurality of" and the like refer to more than two or equal to two in number, unless otherwise specified. For example, "one or more" means one or more than two.

[0045] In the present application, "further", "particularly" and the like are used for description purposes, indicating differences in content, but should not be understood as limiting the scope of protection of the present application.

[0046] In the present application, the technical features described in an open manner include both the closed technical solution consisting of the listed features and the open technical solution containing the listed features.

[0047] In the present application, when a numerical interval (i.e., a numerical range) is involved, the distribution of the selectable numbers in the numerical interval is considered to be continuous and includes both numerical endpoints (i.e., the minimum and maximum values) of the numerical interval and every number between the two numerical endpoints, unless otherwise specified. When a numerical interval refers only to integers within the numerical interval, unless otherwise specified, the two endpoint integers and every integer between the two endpoints are equivalent to a direct recitation of each integer. When multiple numerical ranges are provided to describe a characteristic or property, the numerical ranges can be combined. In other words, unless otherwise indicated, numerical ranges disclosed herein are to be understood to include any and all sub-ranges of the numbers within the range. A "number" in a numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. A "numerical interval" is intended to broadly include numerical interval types such as percentage intervals, ratio intervals, value intervals, etc.

[0048] In the present application, the term "room temperature" generally refers to 4℃ to 35℃, preferably 20℃±5℃. In some embodiments of the present application, room temperature refers to 20℃ to 30℃.

[0049] In the present application, unless otherwise specified, temperature parameters allow both constant temperature treatment and variation within a certain temperature interval. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuation within a range such as ±5℃, ±4℃, ±3℃, ±2℃, ±1℃ is allowed.

[0050] In the present application, the unit of the data range is indicated if only the unit is provided after the right endpoint, which means that the units of the left endpoint and the right endpoint are the same. For example, 2-5h indicates that the units of the left endpoint "2" and the right endpoint "5" are both h (hour).

[0051] Glass with good light transmittance, low cost and mechanical properties is a key supporting material for electronic products such as mobile phone screens. With the continuous improvement of electronic product technology, the market has put forward higher requirements for the supporting materials of electronic products. The existing silicate glass is difficult to obtain good drop resistance performance even after strengthening, which greatly limits the application of silicate glass in electronic products.

[0052] Electronic devices, especially electronic consumer products such as mobile phones and tablet computers, are widely used in daily work and life, but the drop resistance of such electronic devices is poor, especially if the screen is broken after falling, which affects the display effect. At present, the market has put forward higher requirements for the drop resistance of mobile phones and tablet computers, thereby also giving birth to high-strength cover glass. For some models, it is necessary to use high-aluminum glass that is chemically strengthened, and the performance that can be achieved by the current mainstream high-aluminum cover glass is still not ideal and needs to be further optimized.

[0053] Based on this, the purposes of the present application include providing an aluminosilicate glass, a strengthened glass, a glass structure, a preparation method and an application. The composition of the aluminosilicate glass has good processing characteristics and mechanical properties, and can obtain a glass product with good comprehensive performance and low cost.

[0054] In a first aspect, the present application provides an aluminosilicate glass, which comprises the following components in terms of mass percentage:

[0055] 58% to 63% of SiO2, 16% to 20% of Al2O3, 12% to 15% of Na2O, 0% to 4% of K2O, 3% to 6% of MgO and 3.1% to 5% of B2O3.

[0056] The main components in the composition of the aluminosilicate glass provided in the present application, i.e. silicon oxide and aluminum oxide, have suitable contents and low processing difficulty, which is conducive to obtaining a glass sheet with high strength and suitable coefficient of thermal expansion. The composition also includes low-cost alkali metal oxides, alkaline earth metal oxides and a low mass percentage of boron oxide, which helps to improve the efficiency of the ion exchange process in the subsequent strengthening process, obtain a strengthened glass with high comprehensive mechanical properties and low cost.

[0057] In some embodiments, the formula of the aluminosilicate glass comprising 58% to 63% of SiO2, 16% to 20% of Al2O3, 12% to 15% of Na2O, 0% to 4% of K2O, 3% to 6% of MgO and 3.1% to 5% of B2O3 in terms of mass percentage is referred to as "Formula A1".

[0058] In some embodiments, the aluminosilicate glass comprises 58% to 63% of SiO2 in terms of mass percentage, and can also comprise any one of the following mass percentages or a range formed by any two of the following mass percentages: 58%, 58.3%, 58.7%, 59%, 59.7%, 59.8%, 60%, 60.7%, 61%, 61.3%, 61.7%, 62%, 62.5%, 63%, etc.

[0059] Silicon dioxide (SiO2) is the main component for forming the glass framework, which has the effect of improving the strength of the glass, but will increase the viscosity of the glass and reduce the corrosion resistance of the glass to etching liquid. The mass percentage of SiO2 is preferably 58% to 63%. If the mass percentage of SiO2 is less than 58%, the glass forming performance of the glass is poor, and the strength and weather resistance are not enough. If the mass percentage of SiO2 exceeds 63%, the glass becomes difficult to melt, and the tendency to crystallize increases.

[0060] In some embodiments, the aluminosilicate glass includes 16-20% by mass of Al2O3, and can be selected from any one of the following or a range defined by any two of the following: 16%, 16.5%, 17%, 17.5%, 18%, 19%, 20%, etc. Alumina (Al2O3) can improve the strength and etching resistance of the glass, and can greatly increase the ion exchange ability of the glass, but can increase the viscosity of the glass and increase the difficulty of refining, and is a necessary component. The mass percentage is preferably 16-20%. If the content is less than 16%, the etching resistance and ion exchange ability of the glass are insufficient. If it is higher than 20%, the viscosity of the glass is too high, and it is difficult to clarify, the quality of melting is reduced, which will significantly affect the performance of the glass.

[0061] In some embodiments, the aluminosilicate glass includes 12-15% by mass of Na2O, and can be selected from any one of the following or a range defined by any two of the following: 12%, 12.5%, 13%, 13.5%, 14%, 15%, etc. Sodium oxide (Na2O) is a necessary component for ion exchange, and it can also significantly improve the melting of the glass. The mass percentage is preferably 12-16%. If the mass percentage is less than 12%, the melting of the glass is poor; if it is higher than 16%, the weather resistance of the glass is poor.

[0062] In some embodiments, the aluminosilicate glass includes 0-4% by mass of K2O, and can be selected from any one of the following or a range defined by any two of the following: 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, etc. Potassium oxide (K2O) can improve the melting of the glass and increase the DOL value of the glass after strengthening, and is not a necessary component. The mass percentage is preferably 0-4%, and can produce a "mixed alkali effect" with sodium oxide to improve the performance of the glass. If it is higher than 4%, the weather resistance of the glass is poor, and the thermal expansion coefficient of the glass is too large.

[0063] In some embodiments, the aluminosilicate glass includes 3% to 6% of MgO by mass, and can be selected from any one of the following mass percentages or a range between any two of the following mass percentages: 3%, 3.2%, 3.3%, 3.5%, 3.8%, 3.9%, 4.5%, 4.7%, 5%, 5.2%, 5.5%, 6%, etc. Magnesium oxide (MgO) can reduce the viscosity of the glass at high temperatures, promote the melting and fining of the glass, and reduce the coefficient of thermal expansion of the glass, thereby increasing the CS value of the strengthened glass. MgO is a necessary component. If the mass fraction of MgO is less than 3%, the melting property of the glass becomes poor, and it is difficult to achieve the desired CS value after strengthening. If the mass fraction of MgO is greater than 6%, the glass is prone to crystallization, and the melting property of the glass is too short to be formed, and the DOL value of the strengthened glass is low.

[0064] In some embodiments, the aluminosilicate glass includes 3.1% to 5% of B2O3 by mass, and can be selected from any one of the following mass percentages or a range between any two of the following mass percentages: 3.1%, 3.3%, 3.5%, 3.6%, 3.7%, 3.8%, 4%, 4.4%, 4.5%, 5%, etc. Boron oxide (B2O3) can reduce the high-temperature viscosity of the glass and the coefficient of thermal expansion of the glass, but hinders ion exchange, and is a necessary component. If the mass fraction is less than 3.1%, the melting property of the glass is insufficient, and the coefficient of thermal expansion is too large; if the mass fraction is greater than 5%, the ion exchange performance of the glass deteriorates.

[0065] In some embodiments, the aluminosilicate glass satisfies that α is 2.93 to 4.39; wherein; α is the stress decay resistance index of the glass.

[0066]

[0067] W Al , W K , W Mg and W B respectively represent the value obtained by multiplying the mass percentage of Al2O3, K2O, MgO and B2O3 in the aluminosilicate glass by 100.

[0068] In some embodiments, the aluminosilicate glass has a stress decay exponent a of 2.93-4.39, and can be selected from any one of the following values or a range defined by any two of the following values: 2.93, 2.99, 3.33, 3.36, 3.46, 3.5, 3.53, 3.72, 3.75, 3.79, 3.91, 3.99, 4.23, 4.39, etc. The applicant believes that the stress decay exponent a of the glass represents the ability of the glass to resist stress relaxation at a high strengthening temperature. The a of the glass of the present application is preferably 2.93-4.39. If a is too low, the ability of the glass to resist stress relaxation is poor. If a high strengthening temperature is used, the CS decreases significantly, affecting the drop performance. If a is too high, although the ability of the glass to resist stress relaxation is strong, it also indicates that the performance of the glass after different strengthening processes does not differ much, and it is difficult to improve the drop performance by adjusting the process.

[0069] In some embodiments, the aluminosilicate glass has a coefficient of thermal expansion (CTE) of 85x10 -7 ℃ -1 -91x10 -7 ℃ -1 , and can be selected from any one of the following values or a range defined by any two of the following values: 85x10 -7 ℃ -1 , 86.5x10 -7 ℃ -1 , 86.6x10 -7 ℃ -1 , 86.9x10 -7 ℃ -1 , 87x10 -7 ℃ -1 , 87.1x10 -7 ℃ -1 , 87.2x10 -7 ℃ -1 , 87.4x10 -7 ℃ -1 , 87.5x10 -7 ℃ -1 , 87.8x10 -7 ℃ -1 , 88.7x10 -7 ℃ -1 , 88.9x10 -7 ℃ -1 , 89.3x10 -7 ℃ -1 , 90x10 -7 ℃ -1 , 91x10 -7 ℃-1 wait.

[0070] In some embodiments, the softening temperature (Ts) of the aluminosilicate glass is 790°C to 815°C, and can also be selected from any one of the following softening temperature values ​​or an interval consisting of any two softening temperature values: 790°C, 791°C, 792°C, 795°C, 798°C, 800°C, 803°C, 804°C, 805°C, 807°C, 809°C, 811°C, 815°C, etc.

[0071] In this application, unless otherwise specified, the softening temperature refers to the glass viscosity of 10 7.65 dPa×S corresponding temperature; melting temperature refers to the temperature when the glass viscosity is 10 2.0 dPa×S; the softening temperature and melting temperature were measured by the following method: Orton RSV-1600 high temperature viscometer was used to test the high temperature viscosity of the glass to obtain the temperature viscosity curve data, and the VFT formula was used to fit the viscosity of the glass in the full temperature range to determine the softening temperature of the glass (that is, the viscosity is 10 7.65 dPa×S temperature) and melting temperature (i.e., viscosity of 10 2.0 dPa×S temperature).

[0072] In some embodiments, the melting temperature (Tm) of the aluminosilicate glass is 1630°C to 1670°C, and can also be selected from any one of the following melting temperature values ​​or an interval consisting of any two melting temperature values: 1630°C, 1632°C, 1634°C, 1635°C, 1636°C, 1637°C, 1638°C, 1644°C, 1648°C, 1653°C, 1655°C, 1661°C, 1665°C, 1670°C, etc.

[0073] In some embodiments, the aluminosilicate glass has a thermal expansion coefficient (CTE) of 85×10 -7 ℃ -1 ~91×10 -7 ℃ -1 ;

[0074] In a second aspect of the present application, a method for preparing aluminosilicate glass is provided, comprising the following steps:

[0075] S100: Mixing raw materials according to a formula to obtain a batch material, wherein the composition of the batch material is consistent with the composition of the aluminosilicate glass meeting the first aspect;

[0076] S200: subjecting the batch material to heating treatment, forming treatment, annealing treatment and cooling treatment to obtain the aluminosilicate glass.

[0077] The preparation method of the aluminosilicate glass provided in the present application adopts the aluminosilicate glass prepared by the heating, forming, annealing and cooling treatment method, which has simple process, less steps, lower processing temperature and less energy consumption.

[0078] In some embodiments, the temperature of the heating treatment in the preparation method is 1650-1680°C, and can be selected from any one of the following values or an interval formed by any two of the following values: 1650°C, 1660°C, 1670°C, 1680°C, etc.

[0079] In some embodiments, the time of the heating treatment in the preparation method is 4-8h, and can be selected from any one of the following values or an interval formed by any two of the following values: 4h, 5h, 6h, 7h, 8h, etc.

[0080] In some embodiments, the preparation method further comprises a second holding treatment after the heating treatment and before the forming treatment.

[0081] In some embodiments, the temperature of the second holding treatment in the preparation method is 1600-1620°C, and can be selected from any one of the following values or an interval formed by any two of the following values: 1600°C, 1610°C, 1620°C, etc.

[0082] In some embodiments, the time of the second holding treatment in the preparation method is 0.5-1.5h, and can be selected from any one of the following values or an interval formed by any two of the following values: 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, etc.

[0083] In some embodiments, the temperature of the annealing treatment in the preparation method is 730-760°C, and can be selected from any one of the following values or an interval formed by any two of the following values: 730°C, 730°C, 750°C, 760°C, etc.

[0084] In some embodiments, the time of the annealing treatment in the preparation method is 2-4h, and can be selected from any one of the following values or an interval formed by any two of the following values: 2h, 2.5h, 3h, 3.5h, 4h, etc.

[0085] In a third aspect, the present application provides a preparation method of strengthened glass, comprising the following steps: performing chemical strengthening treatment on a raw glass sheet in a molten salt at 415-425°C for 4-6h to obtain the strengthened glass, wherein the raw glass sheet is the aluminosilicate glass according to the first aspect or the aluminosilicate glass prepared by the preparation method according to the second aspect.

[0086] The preparation method of the strengthened glass provided in the present application can prepare the strengthened glass with deep ion exchange depth, high surface compressive stress and high drop height resistance by using low strengthening temperature and short strengthening time. The preparation process is simple and low in cost.

[0087] In some embodiments, in the preparation method of the strengthened glass, the temperature for chemical strengthening treatment is 415-425℃, and can be selected from any one of the following values or an interval formed by any two of the following values: 415℃, 416℃, 417℃, 418℃, 419℃, 420℃, 421℃, 422℃, 423℃, 424℃, 425℃, etc.

[0088] In some embodiments, in the preparation method of the strengthened glass, the time for chemical strengthening treatment is 4-6h, and can be selected from any one of the following values or an interval formed by any two of the following values: 4h, 4.5h, 5h, 5.5h, 6h, etc.

[0089] In some embodiments, in the preparation method of the strengthened glass, the aluminosilicate glass is subjected to chemical strengthening treatment at 420℃ for 5h, the surface compressive stress value of the obtained strengthened glass is denoted as CS1, the surface ion exchange depth of the strengthened glass is denoted as DOL1, and the measured drop height resistance is H1.

[0090] In some embodiments, the CS1 is 1038-1288MPa, and can be selected from any one of the following values or an interval formed by any two of the following values: 1038MPa, 1055MPa, 1069MPa, 1105MPa, 1114MPa, 1135MPa, 1138MPa, 1150MPa, 1156MPa, 1170MPa, 1172MPa, 1180MPa, 1231MPa, 1245MPa, 1288MPa, etc.

[0091] In some embodiments, the DOL1 is 35-42μm, and can be selected from any one of the following values or an interval formed by any two of the following values: 35μm, 35.6μm, 35.8μm, 37.2μm, 37.5μm, 37.7μm, 38.2μm, 38.4μm, 38.7μm, 39.1μm, 39.6μm, 39.8μm, 40.5μm, 41.2μm, 42μm, etc.

[0092] In some embodiments, the H1 is 90mm-110mm, and can be selected from any one of the following values or an interval formed by any two of the following values: 90mm, 92mm, 96mm, 98mm, 99mm, 101mm, 104mm, 105mm, 107mm, 108mm, 110mm, etc.

[0093] In a fourth aspect of the present application, a method for preparing a strengthened glass is provided, comprising the following steps:

[0094] obtaining a raw glass sheet, and obtaining a value of stress decay index α of the aluminosilicate glass according to the composition of the aluminosilicate glass; wherein, W Al , W K , W Mg and W B respectively represent the value of Al2O3, K2O, MgO and B2O3 in the aluminosilicate glass multiplied by 100; the raw glass sheet is the aluminosilicate glass of the first aspect or the aluminosilicate glass prepared by the preparation method of the second aspect;

[0095] obtaining a value of stress decay index α of the aluminosilicate glass according to the composition of the aluminosilicate glass; wherein,

[0096] wherein,

[0097] when 2.93≤α≤3.72, the raw glass sheet is chemically strengthened at 426℃-434℃ and in molten salt for 2.8h-3.2h;

[0098] when 3.72<α≤4.39, the raw glass sheet is chemically strengthened at 436℃-444℃ and in molten salt for 2.4h-2.6h.

[0099] In some embodiments, in the preparation method, when 2.93≤α≤3.72, the aluminosilicate glass is chemically strengthened at 430℃ for 3h. The surface compressive stress value of the strengthened glass is denoted as CS2, the surface ion exchange depth of the strengthened glass is denoted as DOL2, and the measured drop height is H2.

[0100] In some embodiments, the CS2 is 1012MPa-1250MPa, and can be selected from any one of the following values or an interval formed by any two of the following values: 1044MPa, 1012MPa, 1075MPa, 1092MPa, 1110MPa, 1132MPa, 1154MPa, 1250MPa, etc.

[0101] In some embodiments, the DOL2 is 38.1 μm to 42.6 μm, and can be selected from any one of the following values or an interval defined by any two of the following values: 38.1 μm, 38.4 μm, 40.5 μm, 40.7 μm, 41.3 μm, 41.6 μm, 42 μm, 42.6 μm, etc.

[0102] In some embodiments, the H2 is 130 mm to 150 mm, and can be selected from any one of the following values or an interval defined by any two of the following values: 130 mm, 134 mm, 140 mm, 143 mm, 150 mm, etc.

[0103] In some embodiments, in the method for preparing the strengthened glass, when 3.72 < α ≤ 4.39, the aluminosilicate glass is subjected to chemical strengthening treatment at 440 °C for 2.5 h. The surface compressive stress value of the obtained strengthened glass is denoted as CS3, the surface ion exchange depth of the strengthened glass is denoted as DOL3, and the measured drop height resistance is denoted as H3.

[0104] In some embodiments, the CS3 is 1000 MPa to 1211 MPa, and can be selected from any one of the following values or an interval defined by any two of the following values: 1000 MPa, 1070 MPa, 1101 MPa, 1123 MPa, 1140 MPa, 1193 MPa, 1211 MPa, etc.

[0105] In some embodiments, the DOL3 is 39.5 μm to 46 μm, and can be selected from any one of the following values or an interval defined by any two of the following values: 39.5 μm, 42.2 μm, 43.1 μm, 43.4 μm, 44.2 μm, 44.5 μm, 46 μm, etc.

[0106] In some embodiments, the H3 is 133 mm to 160 mm, and can be selected from any one of the following values or an interval defined by any two of the following values: 133 mm, 142 mm, 151 mm, 152 mm, 155 mm, 156 mm, 160 mm, etc.

[0107] In some embodiments, the CS3 is 1000 MPa to 1211 MPa, and the DOL3 is 39.5 μm to 46 μm.

[0108] In the present application, (CS2 x DOL2) / (CS1 x DOL1) or (CS3 x DOL3) / (CS1 x DOL1) is defined as a glass strengthening ratio coefficient (K) without special instructions, which physically means the improvement degree of the glass strengthening degree obtained by selecting a more suitable chemical strengthening method compared with the ordinary chemical strengthening method. It can be understood that the more suitable chemical strengthening method is selected according to the glass stress decay index α, for example, when 2.93 ≤ α ≤ 3.72, the performance of the tempered glass obtained by selecting the more suitable chemical strengthening method of chemically strengthening the original glass at 430 ℃ for 3 h is better than that of the tempered glass obtained by the ordinary chemical strengthening method of chemically strengthening the original glass at 420 ℃ for 5 h ((CS2 x DOL2) > (CS1 x DOL1)); when 3.72 < α ≤ 4.39, the performance of the tempered glass obtained by selecting the more suitable chemical strengthening method of chemically strengthening the original glass at 440 ℃ for 2.5 h is better than that of the tempered glass obtained by the ordinary chemical strengthening method of chemically strengthening the original glass at 420 ℃ for 5 h ((CS2 x DOL2) > (CS1 x DOL1)).

[0109] In some embodiments, the glass strengthening ratio coefficient (K) is 1.045-1.07, and can also be selected from any one of the following numerical values or an interval formed by any two numerical values: 1.045, 1.047, 1.051, 1.052, 1.053, 1.054, 1.056, 1.061, 1.062, 1.063, 1.07, etc.

[0110] In the present application, H2 / H1 or H3 / H1 is defined as a glass drop resistance index (β) without special instructions, which physically means the improvement degree of the glass drop resistance performance obtained by selecting a more suitable chemical strengthening method compared with the ordinary chemical strengthening method. It can be understood that the more suitable chemical strengthening method is selected according to the glass stress decay index α, for example, when 2.93 ≤ α ≤ 3.72, the drop resistance height of the tempered glass obtained by selecting the more suitable chemical strengthening method of chemically strengthening the original glass at 430 ℃ for 3 h is higher than that of the tempered glass obtained by the ordinary chemical strengthening method of chemically strengthening the original glass at 420 ℃ for 5 h (H2 > H1); when 3.72 < α ≤ 4.39, the drop resistance height of the tempered glass obtained by selecting the more suitable chemical strengthening method of chemically strengthening the original glass at 440 ℃ for 2.5 h is higher than that of the tempered glass obtained by the ordinary chemical strengthening method of chemically strengthening the original glass at 420 ℃ for 5 h (H3 > H1).

[0111] In some embodiments, the glass has a drop resistance index (β) of 1.41-1.48, and can be selected from any one of the following values or an interval formed by any two of the following values: 1.41, 1.43, 1.44, 1.45, 1.46, 1.48, etc.

[0112] In a fifth aspect, the present application provides a strengthened glass prepared according to the preparation method of the third aspect or the fourth aspect.

[0113] The strengthened glass provided in the present application has a deep ion exchange depth, a high surface compressive stress, and a high drop resistance height, and has excellent comprehensive mechanical properties. The deep ion exchange depth is also beneficial to improving the surface hardness and scratch resistance of the glass.

[0114] In some embodiments, the strengthened glass has a surface compressive stress of 1000-1250 MPa, and can further have a surface compressive stress of 1038-1288 MPa, 1012-1250 MPa, or 1000-1211 MPa, and can be selected from any one of the following values or an interval formed by any two of the following values: 1000 MPa, 1012 MPa, 1038 MPa, 1044 MPa, 1055 MPa, 1069 MPa, 1070 MPa, 1075 MPa, 1092 MPa, 1101 MPa, 1105 MPa, 1110 MPa, 1114 MPa, 1123 MPa, 1132 MPa, 1135 MPa, 1138 MPa, 1140 MPa, 1150 MPa, 1154 MPa, 1156 MPa, 1170 MPa, 1172 MPa, 1180 MPa, 1193 MPa, 1211 MPa, 1231 MPa, 1245 MPa, 1250 MPa, 1288 MPa, etc.

[0115] In some embodiments, the strengthened glass has an ion exchange layer depth of 38-46 μm, and can further have an ion exchange layer depth of 35-42 μm, 38.1-42.6 μm, or 39.5-46 μm, and can be selected from any one of the following values or an interval formed by any two of the following values: 35 μm, 35.6 μm, 35.8 μm, 37.2 μm, 37.5 μm, 37.7 μm, 38.1 μm, 38.2 μm, 38.4 μm, 38.7 μm, 39.1 μm, 39.5 μm, 39.6 μm, 39.8 μm, 40.5 μm, 40.5 μm, 40.7 μm, 41.2 μm, 41.3 μm, 41.6 μm, 42 μm, 42.2 μm, 42.6 μm, 43.1 μm, 43.4 μm, 44.2 μm, 44.5 μm, 46 μm, etc.

[0116] In some embodiments, the anti-drop height is 90mm-160mm, further can be 90mm-110mm, 130mm-150mm or 133mm-160mm, and can also be selected from any one of the following values or an interval formed by any two of the following values: 90mm, 92mm, 96mm, 98mm, 99mm, 101mm, 104mm, 105mm, 107mm, 108mm, 110mm, 130mm, 133mm, 134mm, 140mm, 142mm, 143mm, 150mm, 151mm, 152mm, 155mm, 156mm, 160mm, etc.

[0117] In a sixth aspect of the present application, a glass structure is provided, which comprises the strengthened glass prepared by the preparation method of the third aspect or the fourth aspect or the strengthened glass of the fifth aspect.

[0118] The glass structure provided in the present application adopts the strengthened glass with a deeper ion exchange depth, a higher surface compressive stress and a higher anti-drop height, and has a better comprehensive mechanical property.

[0119] In a seventh aspect of the present application, the application of the strengthened glass prepared by the preparation method of the third aspect or the fourth aspect or the strengthened glass of the fifth aspect or the glass structure of the sixth aspect in the preparation of electronic devices is provided.

[0120] In the present application, the strengthened glass with a deeper ion exchange depth, a higher surface compressive stress and a higher anti-drop height is used in electronic devices, which can effectively improve the anti-drop performance of electronic devices and also helps to improve the service life of electronic devices.

[0121] In some embodiments, the application relates to the preparation of a protective layer of a cover plate, a window or a view window of a display element of an electronic device.

[0122] In an eighth aspect of the present application, an electronic device is provided, which comprises the strengthened glass prepared by the preparation method of the third aspect or the fourth aspect or the strengthened glass of the fifth aspect or the glass structure of the sixth aspect.

[0123] In order to make the present application more easily understood and implemented, the following provides more specific and detailed examples and comparative examples as references.

[0124] The concept, specific examples and resulting technical effects of the present application will be further described below, so as to fully understand the present application. The purpose of providing these descriptions is to help explain the present application, and should not be used to limit the scope of the claims of the present application.

[0125] Unless otherwise specified, the raw materials used in the following tests can be commonly purchased in the market.

[0126] Example 1

[0127] (1) Preparation method of aluminosilicate:

[0128] According to the composition of the examples in Table 1, the corresponding batch was weighed and calculated based on 1400g of glass liquid, ground and mixed uniformly, placed in a platinum crucible, and heated to 1650-1680°C in an elevator furnace, then lowered to 1600-1620°C for 6h, then lowered to 1600-1620°C for 1h, and then poured into a rectangular graphite mold with dimensions of 195mm x 105mm and heated to 500-550°C. After hardening, it was transferred to an annealing furnace raised to 730-760°C, and annealed for 3h, then cooled to room temperature in the furnace, to obtain an aluminosilicate glass.

[0129] (2) Preparation method of strengthened glass:

[0130] The aluminosilicate glass was subjected to chemical strengthening treatment process by two methods:

[0131] The first method: the aluminosilicate glass was directly subjected to chemical strengthening treatment at 420°C for 5h (the surface compressive stress value of the strengthened glass prepared by this chemical strengthening process is denoted as CS1, the surface ion exchange depth of the tempered glass is denoted as DOL1, and the measured drop height resistance is denoted as H1);

[0132] The second method: according to the interval of the value of the stress decay index α of the glass calculated above, different chemical strengthening processes were selected. The calculation method is as follows: the mass percentage of each component in the aluminosilicate glass is multiplied by 100 to obtain the value, which is brought into the formula of α,

[0133] If 2.93≤α≤3.72, the aluminosilicate glass is subjected to chemical strengthening treatment at 430℃ for 3h (the surface compressive stress value of the strengthened glass prepared by the chemical strengthening process is denoted as CS2, the surface ion exchange depth of the strengthened glass is denoted as DOL2, and the measured drop height resistance is H2; the calculation method of the glass strengthening proportion coefficient K is K=(CS2×DOL2) / (CS1×DOL1), and the calculation method of the glass drop height resistance index is β=H2 / H1); if 3.72<α≤4.39, the aluminosilicate glass is subjected to chemical strengthening treatment at 440℃ for 2.5h (the surface compressive stress value of the strengthened glass prepared by the chemical strengthening process is denoted as CS3, the surface ion exchange depth of the strengthened glass is denoted as DOL3, and the measured drop height resistance is H3; the calculation method of the glass strengthening proportion coefficient K is K=(CS3×DOL3) / (CS1×DOL1), and the calculation method of the glass drop height resistance index is β=H3 / H1). Since the glass stress decay index α of the aluminosilicate glass in Example 1 is 2.93, the second chemical strengthening process is chemical strengthening treatment at 430℃ for 3h to obtain the strengthened glass; and the chemical strengthening molten salt is potassium nitrate.

[0134] (3) Processing and performance testing of the strengthened glass:

[0135] The glass is cut into a thin sheet with a size of 175mm×95mm×0.7mm, polished on both sides, and subjected to CNC processing.

[0136] The marble drop test is performed on the strengthened sample, starting from a height of 30cm, increasing by 5cm each time until the sample is broken, and the height at which the sample is broken is recorded. 20 pieces are tested in each batch, and the average value is taken.

[0137] The sample is cut into a size of 25mm×7mm×1.1mm, and a DIL-402PC horizontal dilatometer is used to test the thermal expansion coefficient (CTE) of the sample. For the glass of the present application, the thermal expansion coefficient is preferably (85-91)×10 -7 ℃ -1 . The thermal expansion coefficient of the mainstream soda-lime glass is about 88×10 -7 ℃ -1 . The matching of the thermal expansion coefficient can make the glass of the present application better used in combination with the soda-lime glass.

[0138] The test results are shown in Table 1.

[0139] In the present application, the surface compressive stress (CS) of strengthened glass and the depth of layer (DOL) of tempered glass are tested by a surface stress tester, which can be selected as FSM-6000LEUV, and the surface stress value and the depth of surface stress layer of tempered glass are tested according to the standard GB / T18144-2008, and the photoelastic coefficient used in the test is 27.5 nm / (cm×MPa), and the refractive index is 1.51. The test method of marble drop height H refers to the standard YD / T 1539-2019 Mobile Communication Handset Reliability Technical Requirements and Test Methods, and the equipment used is a whole machine drop tester with the model of GP-2112-T.

[0140] Examples 2-15

[0141] The preparation method of the aluminosilicate in (1) of Examples 2-15 is basically the same as that in Example 1, except that the composition of the glass is different (see Table 1 for reference).

[0142] The second chemical strengthening treatment process selected in the preparation method of the strengthened glass in (2) of Examples 2-15 is different according to the calculated stress decay resistance index a of the glass.

[0143] The processing and performance testing of the strengthened glass in (3) of Examples 2-15 are the same as those in Example 1 (see Table 1 for relevant parameters and performance values).

[0144] Example 16

[0145] The preparation method of the aluminosilicate in (1) of Example 16 is basically the same as that in Example 1, except that the composition of the glass is different (see Table 1 for reference).

[0146] The second chemical strengthening treatment process selected in the preparation method of the strengthened glass in (2) of Example 16 is chemical strengthening treatment at 430℃ for 3h.

[0147] The processing and performance testing of the strengthened glass in (3) of Example 16 are the same as those in Example 1 (see Table 1 for relevant parameters and performance values).

[0148] Example 17

[0149] The preparation method of the aluminosilicate in (1) of Example 17 is basically the same as that in Example 1, except that the composition of the glass is different (see Table 1 for reference).

[0150] The second chemical strengthening treatment process selected in the preparation method of the strengthened glass in (2) of Example 17 is chemical strengthening treatment at 440℃ for 2.5h.

[0151] (3) Processing and performance test of the strengthened glass in Example 17: same as in Example 1 (see also Table 1 for relevant parameters and performance values).

[0152] Table 1: Aluminosilicate glass compositions, properties and performance of the strengthened glass of Examples 1-15

[0153]

[0154] Table 1 (continued)

[0155]

[0156]

[0157] From the performance data of Examples 1-15 in Table 1, it can be seen that the aluminosilicate glasses provided in the present application have suitable thermal expansion coefficients, which are beneficial for lamination with soda-lime glass. The strengthened glass obtained by using the more optimal chemical strengthening process (second chemical strengthening process), i.e. high temperature and short time chemical strengthening, has an improved drop performance, i.e. a drop resistance of more than 40% (β≥1.40) relative to the common chemical strengthening process (first chemical strengthening process), and is beneficial for energy saving. The strengthening time is shortened by more than 2h relative to the conventional process, and the processing efficiency is improved.

[0158] The compositions of the aluminosilicates in Examples 16 and 17 are within the preferred range of the present application, but the calculated α values are relatively large, and although they have suitable thermal expansion coefficients, the performance of the strengthened glass obtained is not as good as that of Examples 1-15. Specifically, the strengthened glass obtained by using the more optimal chemical strengthening process (second chemical strengthening process), i.e. high temperature and short time chemical strengthening, has a limited improvement in drop performance relative to the common chemical strengthening process (first chemical strengthening process), and Examples 16 and 17 are improved by 22% and 24% (β is equal to 1.22 and 1.24, respectively).

[0159] Comparative Example 1

[0160] The preparation method of the aluminosilicate in (1) of Comparative Example 1 is basically the same as in Example 1, except that the composition of the glass is different (see Table 2).

[0161] The second chemical strengthening process selected in the preparation method of the strengthened glass in (2) of Comparative Example 1 is chemical strengthening at 430°C for 3h.

[0162] (3) Processing and performance test of the strengthened glass in Comparative Example 1: same as in Example 1 (see also Table 2 for relevant parameters and performance values).

[0163] Comparative Example 2

[0164] The method for preparing the aluminosilicate in (1) of Comparative Example 2 was substantially the same as in Example 1, except that the composition of the glass was different (see Table 2).

[0165] The second chemical strengthening process selected in the method for preparing the strengthened glass in (2) of Comparative Example 2 was selected to be chemical strengthening at 440°C for 2.5h.

[0166] (3) Processing and performance testing of the strengthened glass in Comparative Example 2: the same as in Example 1 (see also Table 2 for relevant parameters and performance values).

[0167] Comparative Example 3

[0168] The method for preparing the aluminosilicate in (1) of Comparative Example 3 was substantially the same as in Example 1, except that the composition of the glass was different (see Table 2).

[0169] The second chemical strengthening process selected in the method for preparing the strengthened glass in (2) of Comparative Example 3 was selected to be chemical strengthening at 430°C for 3h.

[0170] (3) Processing and performance testing of the strengthened glass in Comparative Example 3: the same as in Example 1 (see also Table 2 for relevant parameters and performance values).

[0171] Table 2 Aluminosilicate glass composition, performance and performance of strengthened glass of Comparative Examples 1-3

[0172] Performance Comparative Example 1 Comparative Example 2 Comparative Example 3 SiO2(%) 59 58 59 Al2O3(%) 13 17 16 Na20 (%) 15 13 13.5 K2O (%) 3 5.5 1 MgO (%) 5.2 3 3.5 B2O3 (%) 4.8 3.5 7 ∑ (%) 100 100 100 α 2.33 6.13 2.83 CTE (10 -7 C -1 )]]> 88 92 82.4 T s (°C) 762 783 780 T m (°C) 1588 1620 1615 Optimum strengthening process 2# 3# 2# CS1 (MPa) 855 932 1083 DOL1 (pm) 31.0 44.1 33.5 CS2 (MPa) 823 / 1050 DOL2 (pm) 32.8 / 35.2 CS3 (MPa) / 898 / DOL3 (pm) / 46.2 / K 1.018 1.009 1.019 [H1 (mm)] 85 97 86 [H2 (mm)] 115 / 117 [H3 (mm)] / 128 / β 1.35 1.32 1.36

[0173] From the performance data of Examples 1-17 in Table 1, it can be seen that the content of at least one component of the aluminosilicate glass (original glass) in Comparative Examples 1-3 exceeds the aforementioned “Formula A1” (alumina content is lower in Comparative Example 1, magnesium oxide content is higher in Comparative Example 2, and boron oxide content is higher in Comparative Example 3), and the calculated stress decay index α of the glass also deviates from the preferred range of 2.93-4.39 of the present application. In terms of the performance of the strengthened glass obtained by two chemical strengthening processes on the original glass, the performance of the strengthened glass obtained by the chemical strengthening process with higher temperature and shorter time is limited.

[0174] The technical features of the above-described examples can be combined in any manner. To make the description concise, not all possible combinations of the technical features in the above-described examples are described, however, as long as the combinations of the technical features do not contradict each other, they should be considered within the scope of the present disclosure.

[0175] The above embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the patent scope of the application. It should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims, and the description can be used to explain the content of the claims.

Claims

1. A method of making strengthened glass, characterized by, The method comprises the following steps: obtaining a raw sheet glass, wherein the raw sheet glass is an aluminosilicate glass; obtaining a value of a stress decay index α of the aluminosilicate glass according to a composition of the aluminosilicate glass; wherein, W Al , W K , W Mg and W B represent the values obtained by multiplying the mass percentages of Al2O3, K2O, MgO and B2O3, respectively, in the aluminosilicate glass by 100. selecting a corresponding process condition according to an interval in which the value of the α is located to perform a chemical strengthening treatment on the raw sheet glass to obtain the strengthened glass; wherein, when 2.93≤α≤3.72, performing the chemical strengthening treatment on the raw sheet glass at 426℃-434℃ and in a molten salt for 2.8h-3.2h; when 3.72<α≤4.39, performing the chemical strengthening treatment on the raw sheet glass at 436℃-444℃ and in a molten salt for 2.4h-2.6h; According to the mass percentage, the aluminosilicate glass is composed of the following components: 58%-63% of SiO2, 16%-20% of Al2O3, 12%-15% of Na2O, 0%-4% of K2O, 3%-6% of MgO and 3.1%-5% of B2O3.

2. The method of producing strengthened glass according to claim 1, wherein The coefficient of thermal expansion of the aluminosilicate glass is 85 x 10 -7 ℃ -1 ~ 91 x 10 -7 ℃ -1 .

3. The method of producing strengthened glass according to claim 1, wherein The softening temperature of the aluminosilicate glass is 790℃-815℃.

4. The method of producing strengthened glass according to claim 1, wherein The melting temperature of the aluminosilicate glass is 1630℃-1670℃.

5. The method of producing strengthened glass according to any one of claims 1 to 4, characterized in that, The preparation method of the aluminosilicate glass comprises the following steps: mixing raw materials according to a formula to obtain a mixture; performing heating treatment, forming treatment, annealing treatment and cooling treatment on the mixture to obtain the aluminosilicate glass.

6. The method for preparing tempered glass according to claim 5, wherein: The preparation method of the aluminosilicate glass satisfies one or more of the following characteristics: the temperature of the heating treatment is 1650℃-1680℃; the time of the heating treatment is 4h-8h; the temperature of the annealing treatment is 730℃-760℃; the time of the annealing treatment is 2h-4h.

7. A strengthened glass characterized by, The strengthened glass prepared by the preparation method according to any one of claims 1-6 satisfies one or more of the following characteristics: the surface compressive stress of the strengthened glass is 1000MPa-1250MPa; the ion exchange layer depth of the strengthened glass is 38μm-46μm.

8. A glass structure, characterized by, The strengthened glass prepared by the preparation method according to any one of claims 1-6 or the strengthened glass according to claim 7.

9. An application of the strengthened glass prepared by the preparation method according to any one of claims 1-6 or the strengthened glass according to claim 7 or the glass structure according to claim 8 in the preparation of an electronic device.

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